CA2158868A1 - Block copolymers from ionic catalysts - Google Patents
Block copolymers from ionic catalystsInfo
- Publication number
- CA2158868A1 CA2158868A1 CA002158868A CA2158868A CA2158868A1 CA 2158868 A1 CA2158868 A1 CA 2158868A1 CA 002158868 A CA002158868 A CA 002158868A CA 2158868 A CA2158868 A CA 2158868A CA 2158868 A1 CA2158868 A1 CA 2158868A1
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- copolymers
- tapered
- ethylene
- block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
Abstract
A process for the production of block copolymers of ethylene and an .alpha.-olefin such as propylene by using an ionic catalyst system including a metallocene component and a component having a cation capable of donating a proton and a compatible non-coordination anion.
Novel block copolymers are produced.
Novel block copolymers are produced.
Description
-1- 215886~
APPLICATION FOR PATENT
Title: BLOCK COPOLYMERS FROM IONIC CATALYSTS
FIELD OF THE INVENTION
This invention relates to a method for preparing block and tapered copolymers by polymerizing ethylene and other olefins in the presence of an activated cyclopentadienyl transition metal catalyst system. More particularly, this invention relates to a process for the production of multiblock and tapered copolymers of ethylenically unsaturated monomers. The invention also relates to the multiblock and tapered copolymers produced.
REPLACEMENTPAGE
~N~E~ S~EE~
W094l21700 215 8 ~ 6 8 PCT~S94/03060 APPLICATION FOR PATENT
Title: BLOCK COPOLYMERS FROM IONIC CATALYSTS
SPECIFICATION
Cross-Reference to Related Ap~lications This application is a Continuation-In-Part of Copending USSN 477,791 filed February 9, 1990 which is a Continuation-In-Part of copending U.S. Patent Application Nos. 133,052 filed December 21, 1987 and 133,480 filed December 22, 1987. Copending U.S. Patent Application No.
lS 133,052 is in turn a Continuation-In-Part of U.S. Patent Application No. 011,471 filed January 30, 1987.
Copending U.S. Patent Application No. 133,480 is in turn a Continuation-In-Part of U.S. Patent Application No.
008,800 filed January 30, 1987 all of which are incorporated by reference. This application is also related to copending USSN 07/917,008.
FIELD OF THE IN V ~ N~1~1ON
2S This invention relates to a method for preparing block and tapered copolymers by polymerizing ethylene and other olefins in the presence of an activated cyclopentadienyl transition metal catalyst system. More particularly, this invention relates to a process for the production of multiblock and tapered copolymers of ethylenically unsaturated monomers. The invention also related to the multiblock and tapered copolymers produced.
W094/21700 PCT~S94/03060 BACKGROUND OF THE INVENTION
Block copolymers are well known and have been used commercially as components in adhesives, as melt processable rubbers, impact resistant thermoplastics, and as compatibilizers, or "surfactants", for emulsifying polymer-polymer blends.
A block copolymer is created when two or more polymeric segments, or blocks, of different chemical composition are covalently bonded in an end-to-end fashion. Block copolymers have certain advantages over blends. Firstly, the segments are covalently bonded to each other, thereby eliminating the interface problem.
Secondly, block copolymers can be used to strengthen blends of immiscible polymers by serving as "emulsifiers," which encourage physical connections between the phase, and thus improve the interfacial adhesion and load transferring capability of the components.
While a wide variety of block copolymer architectures are possible, most block copolymers of interest involve the covalent bonding of hard plastic segments which are crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber, glass-glass, and glass-crystalline block copolymers are also possible and may have commercial importance. Two common types of block copolymer structures are the diblock and triblock forms. However, multiblock copolymers, in which more than three segments are bonded together, are also desirable.
Block copolymers are similar to, yet distinct from, tapered polymers. In a tapered copolymer the composition of comonomer is gradually varied from one end of the polymer to the other. Tapered copolymers are WO94/21700 215 8 8 6 8 PCT~S94/03060 commercially used as viscosity modifiers, oil additives, thermoplastic elastomers, and impact-resistant plastics.
Block copolymers have been made by anionic polymerization routes. Butadiene-isoprene block copolymers have been synthesized using the sequential addition technique. In sequential addition, a certain amount of one of the monomers is contacted with the catalyst. Once the monomer has reacted to extinction, forming the first block, a certain amount of the second monomer species is introduced and allowed to react to form the second block. The process may be repeated as desired using the same or other anionically polymerizable monomers.
Likewise, olefin based block copolymers have not been successfully synthesized through coordination catalysis. Several difficulties arise in the use of known coordination catalysts for the block copolymerization of olefins. Among those are the fact that conventional catalysts are typically multi-sited, and a significant fraction of the active sites are unstable. This leads to random chain initiation and termination which, in turn, lowers the theoretical block copolymer yield. What is desired, and what practice of this invention provides, is a catalyst system with well-characterized structure and reactivity which has a single active site. The system should have well-defined and stable polymerization kinetics and be free of aluminum alkyls or other chain transfer agents.
SUMMARY OF THE INVENTION
-The invention comprises a process for the production of novel block copolymers of ethylene with an a-olefin and the polymers obtained therefrom. The process includes sequentially contacting ethylene with an a-W094l21700 PCT~S94/03060 2ls~868 olefin monomer in a suitable solvent at 0C in thepresence of an activated cyclopentadienyl catalyst system to produce a block or tapered block copolymer. The activated catalyst will polymerize a-olefins to form tapered polymers and multiblock polymçr~;such as di- and tri-block homopolymers and copolymers of ethylene and propylene with one or more other alpha-olefins.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a graph of the percent insolubles vs.
polymerization time in minutes.
Figure 2 is graph of the tensile strength of EP/PP
block copolymers at 100 and 120 degrees C.
Figure 3 is a graph of the effect of EP block polymerization time on blocking efficiency.
DESCRIPTION OF PREFERRED EMBODIMENTS
The invention provides (1) novel di, tri-, and multi-block copolymers and tapered copolymers of ethylene, l-olefins, diolefins, cyclic olefins, acetylenes and other unsaturated monomers; and (2) the processes for polymerizing said block copolymers.
Activated Catalyst System - General System The process of this invention is practiced with that class of catalyst referred to, disclosed, and described in U.S. Patents 5,055,438; 5,057,475; 5,096,867;
5,017,714; 5,153,157; copending USSN's 542,236 filed June 22, 1990; 468,382 filed May 21, 1991; 885,170 filed May 18, 1992; 737,611 filed July 19, 1991; 926,006 filed August 5, 1992; 07/133,052 and 07/133,480 and EPA's 277,003, 277,004, published June 3, 1988; EPA 129,368 WO94/21700 ! PCT~S94103060 2~S5886~
published December 22, 1984, EPA 520,732 published December 30, 1992 all of which are incorporated by - reference herein. The activated catalyst is prepared by combining at least two components. The first of these is a mono or bis(cyclopentadienyl) derivative of a Group IV-B metal compound containing at least one ligand which will combine with the second activator component or at least a portion thereof such as a cation portion thereof.
The second component may be an alumoxane or a noncoordinating anion.
Choice of Group IV Metal ComPonent In general, most Group IVB metal components may be combined with most activator components to produce an active olefin polymerization catalyst.
To obtain block copolymer with a hard segment and a soft segment, it is important to choose a catalyst capable of producing both. For example, a chiral activated catalyst will produce stereoregular polyolefins while an achiral activated catalyst typically produces non-stereoregular, even amorphous polyolefins. As an example, a chiral cyclopentadienyl hafnium based catalyst could be used to produce hard blocks of isotactic polypropylene and at different reaction conditions the same catalyst could then produce soft "elastomer" blocks of EP.
Anionic coordination complexes containing perfluorphenyl-, trifluoromethylphenyl-, or bis-trifluormethylphenyl rings are preferred. When the non-coordinating anion contains a plurality of bor'on atoms, more effective catalysts are obtained with activator compounds containing larger anions.
WO94/21700 ~ lS 8 8 6 9 6 - PCT~S94103060 Preferred CatalYsts for the~Production of Block and Tapered~CoPolymers Preferred catalyst systems for the production of block copolymers are single-sited living catalysts.
Living catalysts are those systems in which chain transfer is substantially nonexistent and the rate of initiation is fast compared to propagation. Catalysts which have finite chain transfer rates may also be useful for the production of block and tapered copolymers if the rate of propagation is fast relative to termination. It is also important that the average chain lifetimes are reasonably long (minutes to hours) in order to permit adequate time for modifications of the reactor conditions (e.g. changing monomer feed streams). While most reasonably stable ionic catalysts described above will under suitable conditions produce block and/or tapered copolymers of nonpolar olefins, it is preferred that the catalyst be: l) thermally stable (recoverable as a single organometallic complex), 2) versatile in terms of random copolymer synthesis (i.e. capable of preparing HDPE, i-PP, s-PP, EP-rubber, LLDPE etc.), 3) capable of producing high molecular weight polymers at reasonable temperatures and pressures, 4) high activity (fast propagation catalysts) and 5) slow in chain termination reactions so that few chains of polymer product are produced per hour per site.
Preferred activated biscyclopentadienyl catalysts are represented by the formulae:
[ (A-CP)MXl] [ (C2B9Hll) 2C]
[(A-CP)MXl(L')][B(c6F5)3(x3)]
[(A-Cp)MXl)2Xl][B']
WO94/2170U 2 1 ~88 68 PCT~594/03060 wherein: M is titanium, zirconium or hafnium; (A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*; and Cp and Cp* are the same or different substituted or unsubstituted cyclopentadienyl radicals; A' is a covalent bridging - 5 group containing a Group IV-A element; L' is a neutral Lewis base; Xl is a hydride radical, hydrocarbyl radical having from l to 20 carbon atoms, substituted-hydrocarbyl radical, wherein l or more of the hydrogen atoms are replaced with a halogen atom, having from l to 20 carbon atoms, or organo-metalloid radical comprising a Group IV-A element wherein each of the hydrocarbyl substituents contained in the organo portion of said organo-metalloid, independently, contain from l to 20 carbon atoms; X3 is a hydride, halide, hydrocarbyl radical, a Cl - C20 hydrocarbyl radical wherein one or more of the hydrogen atoms is replaced by a halogen atoms, organometalloid radical wherein each hydrocarbyl substitution in the organo portion contains from l to 20 carbon atoms and the metal is a Group IVA metal and B' is a noncoordinating anion. In another preferred embodiment B' can be replaced with an alumoxane, preferably methylalumoxane.
These catalysts are preferred catalysts for the production of block and tapered copolymers of ethylene, l-olefins, dienes, cyclic olefins and other unsaturated monomers. Ionic catalysts of this form where M= Hf are the most preferred. Polymerizations using hafnium systems of this form under standard random copolymer conditions as described in our copending U.S. Patent Application No. 133,480 produce high molecular weight HDPE, LLDPE, a-PP, i-PP, s-PP, and EP-rubber at rates comparable to similar Zr-based catalysts. In another embodiment on of the Cp rings could be replaced by a heteroatom ligand as described in US 5,055,438, incorporated by reference above. Tapered and block copolymers containing the above segments can be produced using the appropriate hafnium ionic catalysts using the WO94/21700 PCT~S94/03060 ~ a~ ~8 6~ - 8 -techniques and process conditions set forth in the following sections.
Processes for the Production of Block and TaPered CopolYmers Many procedures for modifying the reactor conditions and monomer feeds for the production of block copolymers have been developed and applied using conventional Ziegler-Natta catalysts. The processes include batch reactors and sequential additions techniques, series batch reactors, loop and tubular reactors, and fluidized bed reactors. A review of the processes and patents is given in chapter 4 of "Block Copolymers" [D. C. Allport and W. H. James; John Wiley and Sons, New York 1973]. In principle, the catalysts of this invention can be used in any of the processes described above for the production of well-defined block copolymers.
The most demanding process, that is the process which requires the longest chain lifetimes, is sequential addition. In the first step of the sequential addition process, the catalyst is placed in a well stirred batch reactor in a suitable solvent and first segment of the block copolymer is grown by adding a specific number of molar equivalents of monomer(s). The catalyst consumes all of the monomer(s) prior to addition of the second monomer(s) (a different set of monomers than in the first step). This procedure can be repeated to prepare multiblock copolymers. As an added step the polymerization vessel can be vacuumed free of substantially all leftover monomer or vented of monomer and/or purged with nitrogen or other suitable inert dry gases in between some or all of the monomer addition steps.
i, 2158~68 WO94/21700 PCT~S94/03060 g Sequential Addition Conditions: Solvent Preferably, the solvent should normally disperse or dissolve the catalyst to form a well-mixed system. The most preferred catalysts for block copolymer synthesis, (ACpHfMe(L')][B(C6F5)4], are prepared in toluene and form non-miscible, toluene-dispersible phases. The concentration of toluene in the catalyst phase depends on lo temperature and the structUre of the catalyst. While aliphatic hydrocarbons, fluorinated hydrocarbons, and chlorinated aromatic hydrocarbons may be used in this invention, the preferred solvents for the preparation of block copolymers from the most preferred catalysts are IS aromatic hydrocarbons such as toluene, xylene, ethyl benzene and the like.
Tem~erature The reactor temperature strongly affects the yield of block copolymer and must be adjusted depending on the type and concentration of monomers and catalyst used.
The general procedure for determining this condition is to 1) find the maximum temperature where high molecular weight polymer segments can be prepared and 2) confirm the molecular weight is controlled by the catalyst-to-monomer ratio at this temperature. The general trend is that higher temperatures cause chain transfer to be more rapid relative to propagation and therefore give lower block copolymer yields. The process may be carried out at temperatures of -80C to 80C, however, it is preferred that the temperature be in the range of -10C
to 20C.
215 8 8 6 8 PCT~S94/03060 Concentration of Catalyst The concentration should be high enough to produce significant rates of polymerization under the generally low pressure conditions of sequential addition. The concentration should not be so high as to produce uncontrollable exotherms upon exposure to the monomer.
The exotherm can be controlled, however, by adjusting the rate of monomer addition during the formation of a block segment. This level of control allows for a large range of acceptable catalysts concentrations. The process may be carried out at catalyst concentrations ranging from 6 x 10-6 to 6 x 1o~2 moles of catalyst/liter of solution, however it is preferred that catalyst levels be in the range of 1 x 10-4 to 3 x 10-3 moles of catalyst/liter of solution.
Monomer Concentration The amount of monomer added depends on the molecular weight of the targeted polymer and the moles of active catalyst in the reactor. Molar ratios of monomer to catalyst may be in the range of 10:1 to 10,000:1. The monomers may be added quickly or may be metered in to the reactor to control exotherms.
Order of Monomer Addition Precipitation of polymer (with catalyst attached) causes undesirable broadening of the molecular weight distribution due to mass transport limitations and poor mixing. It is therefore preferred to prepare the soluble block (generally the elastomeric segment) in the first stage of the reaction. Thus, as indicated in the examples, when ethylene is added in the first step in the synthesis of a HDPE-b-atactic-PP diblock copolymer the W094/21700 ~ 21 5 8 ~ 6 8 PCT~S94/03060 initially formed polyethylene precipitates with the catalyst and the final molecular weight distribution of crude block copolymer product is rather broad (Mw/Mn =
APPLICATION FOR PATENT
Title: BLOCK COPOLYMERS FROM IONIC CATALYSTS
FIELD OF THE INVENTION
This invention relates to a method for preparing block and tapered copolymers by polymerizing ethylene and other olefins in the presence of an activated cyclopentadienyl transition metal catalyst system. More particularly, this invention relates to a process for the production of multiblock and tapered copolymers of ethylenically unsaturated monomers. The invention also relates to the multiblock and tapered copolymers produced.
REPLACEMENTPAGE
~N~E~ S~EE~
W094l21700 215 8 ~ 6 8 PCT~S94/03060 APPLICATION FOR PATENT
Title: BLOCK COPOLYMERS FROM IONIC CATALYSTS
SPECIFICATION
Cross-Reference to Related Ap~lications This application is a Continuation-In-Part of Copending USSN 477,791 filed February 9, 1990 which is a Continuation-In-Part of copending U.S. Patent Application Nos. 133,052 filed December 21, 1987 and 133,480 filed December 22, 1987. Copending U.S. Patent Application No.
lS 133,052 is in turn a Continuation-In-Part of U.S. Patent Application No. 011,471 filed January 30, 1987.
Copending U.S. Patent Application No. 133,480 is in turn a Continuation-In-Part of U.S. Patent Application No.
008,800 filed January 30, 1987 all of which are incorporated by reference. This application is also related to copending USSN 07/917,008.
FIELD OF THE IN V ~ N~1~1ON
2S This invention relates to a method for preparing block and tapered copolymers by polymerizing ethylene and other olefins in the presence of an activated cyclopentadienyl transition metal catalyst system. More particularly, this invention relates to a process for the production of multiblock and tapered copolymers of ethylenically unsaturated monomers. The invention also related to the multiblock and tapered copolymers produced.
W094/21700 PCT~S94/03060 BACKGROUND OF THE INVENTION
Block copolymers are well known and have been used commercially as components in adhesives, as melt processable rubbers, impact resistant thermoplastics, and as compatibilizers, or "surfactants", for emulsifying polymer-polymer blends.
A block copolymer is created when two or more polymeric segments, or blocks, of different chemical composition are covalently bonded in an end-to-end fashion. Block copolymers have certain advantages over blends. Firstly, the segments are covalently bonded to each other, thereby eliminating the interface problem.
Secondly, block copolymers can be used to strengthen blends of immiscible polymers by serving as "emulsifiers," which encourage physical connections between the phase, and thus improve the interfacial adhesion and load transferring capability of the components.
While a wide variety of block copolymer architectures are possible, most block copolymers of interest involve the covalent bonding of hard plastic segments which are crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber, glass-glass, and glass-crystalline block copolymers are also possible and may have commercial importance. Two common types of block copolymer structures are the diblock and triblock forms. However, multiblock copolymers, in which more than three segments are bonded together, are also desirable.
Block copolymers are similar to, yet distinct from, tapered polymers. In a tapered copolymer the composition of comonomer is gradually varied from one end of the polymer to the other. Tapered copolymers are WO94/21700 215 8 8 6 8 PCT~S94/03060 commercially used as viscosity modifiers, oil additives, thermoplastic elastomers, and impact-resistant plastics.
Block copolymers have been made by anionic polymerization routes. Butadiene-isoprene block copolymers have been synthesized using the sequential addition technique. In sequential addition, a certain amount of one of the monomers is contacted with the catalyst. Once the monomer has reacted to extinction, forming the first block, a certain amount of the second monomer species is introduced and allowed to react to form the second block. The process may be repeated as desired using the same or other anionically polymerizable monomers.
Likewise, olefin based block copolymers have not been successfully synthesized through coordination catalysis. Several difficulties arise in the use of known coordination catalysts for the block copolymerization of olefins. Among those are the fact that conventional catalysts are typically multi-sited, and a significant fraction of the active sites are unstable. This leads to random chain initiation and termination which, in turn, lowers the theoretical block copolymer yield. What is desired, and what practice of this invention provides, is a catalyst system with well-characterized structure and reactivity which has a single active site. The system should have well-defined and stable polymerization kinetics and be free of aluminum alkyls or other chain transfer agents.
SUMMARY OF THE INVENTION
-The invention comprises a process for the production of novel block copolymers of ethylene with an a-olefin and the polymers obtained therefrom. The process includes sequentially contacting ethylene with an a-W094l21700 PCT~S94/03060 2ls~868 olefin monomer in a suitable solvent at 0C in thepresence of an activated cyclopentadienyl catalyst system to produce a block or tapered block copolymer. The activated catalyst will polymerize a-olefins to form tapered polymers and multiblock polymçr~;such as di- and tri-block homopolymers and copolymers of ethylene and propylene with one or more other alpha-olefins.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a graph of the percent insolubles vs.
polymerization time in minutes.
Figure 2 is graph of the tensile strength of EP/PP
block copolymers at 100 and 120 degrees C.
Figure 3 is a graph of the effect of EP block polymerization time on blocking efficiency.
DESCRIPTION OF PREFERRED EMBODIMENTS
The invention provides (1) novel di, tri-, and multi-block copolymers and tapered copolymers of ethylene, l-olefins, diolefins, cyclic olefins, acetylenes and other unsaturated monomers; and (2) the processes for polymerizing said block copolymers.
Activated Catalyst System - General System The process of this invention is practiced with that class of catalyst referred to, disclosed, and described in U.S. Patents 5,055,438; 5,057,475; 5,096,867;
5,017,714; 5,153,157; copending USSN's 542,236 filed June 22, 1990; 468,382 filed May 21, 1991; 885,170 filed May 18, 1992; 737,611 filed July 19, 1991; 926,006 filed August 5, 1992; 07/133,052 and 07/133,480 and EPA's 277,003, 277,004, published June 3, 1988; EPA 129,368 WO94/21700 ! PCT~S94103060 2~S5886~
published December 22, 1984, EPA 520,732 published December 30, 1992 all of which are incorporated by - reference herein. The activated catalyst is prepared by combining at least two components. The first of these is a mono or bis(cyclopentadienyl) derivative of a Group IV-B metal compound containing at least one ligand which will combine with the second activator component or at least a portion thereof such as a cation portion thereof.
The second component may be an alumoxane or a noncoordinating anion.
Choice of Group IV Metal ComPonent In general, most Group IVB metal components may be combined with most activator components to produce an active olefin polymerization catalyst.
To obtain block copolymer with a hard segment and a soft segment, it is important to choose a catalyst capable of producing both. For example, a chiral activated catalyst will produce stereoregular polyolefins while an achiral activated catalyst typically produces non-stereoregular, even amorphous polyolefins. As an example, a chiral cyclopentadienyl hafnium based catalyst could be used to produce hard blocks of isotactic polypropylene and at different reaction conditions the same catalyst could then produce soft "elastomer" blocks of EP.
Anionic coordination complexes containing perfluorphenyl-, trifluoromethylphenyl-, or bis-trifluormethylphenyl rings are preferred. When the non-coordinating anion contains a plurality of bor'on atoms, more effective catalysts are obtained with activator compounds containing larger anions.
WO94/21700 ~ lS 8 8 6 9 6 - PCT~S94103060 Preferred CatalYsts for the~Production of Block and Tapered~CoPolymers Preferred catalyst systems for the production of block copolymers are single-sited living catalysts.
Living catalysts are those systems in which chain transfer is substantially nonexistent and the rate of initiation is fast compared to propagation. Catalysts which have finite chain transfer rates may also be useful for the production of block and tapered copolymers if the rate of propagation is fast relative to termination. It is also important that the average chain lifetimes are reasonably long (minutes to hours) in order to permit adequate time for modifications of the reactor conditions (e.g. changing monomer feed streams). While most reasonably stable ionic catalysts described above will under suitable conditions produce block and/or tapered copolymers of nonpolar olefins, it is preferred that the catalyst be: l) thermally stable (recoverable as a single organometallic complex), 2) versatile in terms of random copolymer synthesis (i.e. capable of preparing HDPE, i-PP, s-PP, EP-rubber, LLDPE etc.), 3) capable of producing high molecular weight polymers at reasonable temperatures and pressures, 4) high activity (fast propagation catalysts) and 5) slow in chain termination reactions so that few chains of polymer product are produced per hour per site.
Preferred activated biscyclopentadienyl catalysts are represented by the formulae:
[ (A-CP)MXl] [ (C2B9Hll) 2C]
[(A-CP)MXl(L')][B(c6F5)3(x3)]
[(A-Cp)MXl)2Xl][B']
WO94/2170U 2 1 ~88 68 PCT~594/03060 wherein: M is titanium, zirconium or hafnium; (A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*; and Cp and Cp* are the same or different substituted or unsubstituted cyclopentadienyl radicals; A' is a covalent bridging - 5 group containing a Group IV-A element; L' is a neutral Lewis base; Xl is a hydride radical, hydrocarbyl radical having from l to 20 carbon atoms, substituted-hydrocarbyl radical, wherein l or more of the hydrogen atoms are replaced with a halogen atom, having from l to 20 carbon atoms, or organo-metalloid radical comprising a Group IV-A element wherein each of the hydrocarbyl substituents contained in the organo portion of said organo-metalloid, independently, contain from l to 20 carbon atoms; X3 is a hydride, halide, hydrocarbyl radical, a Cl - C20 hydrocarbyl radical wherein one or more of the hydrogen atoms is replaced by a halogen atoms, organometalloid radical wherein each hydrocarbyl substitution in the organo portion contains from l to 20 carbon atoms and the metal is a Group IVA metal and B' is a noncoordinating anion. In another preferred embodiment B' can be replaced with an alumoxane, preferably methylalumoxane.
These catalysts are preferred catalysts for the production of block and tapered copolymers of ethylene, l-olefins, dienes, cyclic olefins and other unsaturated monomers. Ionic catalysts of this form where M= Hf are the most preferred. Polymerizations using hafnium systems of this form under standard random copolymer conditions as described in our copending U.S. Patent Application No. 133,480 produce high molecular weight HDPE, LLDPE, a-PP, i-PP, s-PP, and EP-rubber at rates comparable to similar Zr-based catalysts. In another embodiment on of the Cp rings could be replaced by a heteroatom ligand as described in US 5,055,438, incorporated by reference above. Tapered and block copolymers containing the above segments can be produced using the appropriate hafnium ionic catalysts using the WO94/21700 PCT~S94/03060 ~ a~ ~8 6~ - 8 -techniques and process conditions set forth in the following sections.
Processes for the Production of Block and TaPered CopolYmers Many procedures for modifying the reactor conditions and monomer feeds for the production of block copolymers have been developed and applied using conventional Ziegler-Natta catalysts. The processes include batch reactors and sequential additions techniques, series batch reactors, loop and tubular reactors, and fluidized bed reactors. A review of the processes and patents is given in chapter 4 of "Block Copolymers" [D. C. Allport and W. H. James; John Wiley and Sons, New York 1973]. In principle, the catalysts of this invention can be used in any of the processes described above for the production of well-defined block copolymers.
The most demanding process, that is the process which requires the longest chain lifetimes, is sequential addition. In the first step of the sequential addition process, the catalyst is placed in a well stirred batch reactor in a suitable solvent and first segment of the block copolymer is grown by adding a specific number of molar equivalents of monomer(s). The catalyst consumes all of the monomer(s) prior to addition of the second monomer(s) (a different set of monomers than in the first step). This procedure can be repeated to prepare multiblock copolymers. As an added step the polymerization vessel can be vacuumed free of substantially all leftover monomer or vented of monomer and/or purged with nitrogen or other suitable inert dry gases in between some or all of the monomer addition steps.
i, 2158~68 WO94/21700 PCT~S94/03060 g Sequential Addition Conditions: Solvent Preferably, the solvent should normally disperse or dissolve the catalyst to form a well-mixed system. The most preferred catalysts for block copolymer synthesis, (ACpHfMe(L')][B(C6F5)4], are prepared in toluene and form non-miscible, toluene-dispersible phases. The concentration of toluene in the catalyst phase depends on lo temperature and the structUre of the catalyst. While aliphatic hydrocarbons, fluorinated hydrocarbons, and chlorinated aromatic hydrocarbons may be used in this invention, the preferred solvents for the preparation of block copolymers from the most preferred catalysts are IS aromatic hydrocarbons such as toluene, xylene, ethyl benzene and the like.
Tem~erature The reactor temperature strongly affects the yield of block copolymer and must be adjusted depending on the type and concentration of monomers and catalyst used.
The general procedure for determining this condition is to 1) find the maximum temperature where high molecular weight polymer segments can be prepared and 2) confirm the molecular weight is controlled by the catalyst-to-monomer ratio at this temperature. The general trend is that higher temperatures cause chain transfer to be more rapid relative to propagation and therefore give lower block copolymer yields. The process may be carried out at temperatures of -80C to 80C, however, it is preferred that the temperature be in the range of -10C
to 20C.
215 8 8 6 8 PCT~S94/03060 Concentration of Catalyst The concentration should be high enough to produce significant rates of polymerization under the generally low pressure conditions of sequential addition. The concentration should not be so high as to produce uncontrollable exotherms upon exposure to the monomer.
The exotherm can be controlled, however, by adjusting the rate of monomer addition during the formation of a block segment. This level of control allows for a large range of acceptable catalysts concentrations. The process may be carried out at catalyst concentrations ranging from 6 x 10-6 to 6 x 1o~2 moles of catalyst/liter of solution, however it is preferred that catalyst levels be in the range of 1 x 10-4 to 3 x 10-3 moles of catalyst/liter of solution.
Monomer Concentration The amount of monomer added depends on the molecular weight of the targeted polymer and the moles of active catalyst in the reactor. Molar ratios of monomer to catalyst may be in the range of 10:1 to 10,000:1. The monomers may be added quickly or may be metered in to the reactor to control exotherms.
Order of Monomer Addition Precipitation of polymer (with catalyst attached) causes undesirable broadening of the molecular weight distribution due to mass transport limitations and poor mixing. It is therefore preferred to prepare the soluble block (generally the elastomeric segment) in the first stage of the reaction. Thus, as indicated in the examples, when ethylene is added in the first step in the synthesis of a HDPE-b-atactic-PP diblock copolymer the W094/21700 ~ 21 5 8 ~ 6 8 PCT~S94/03060 initially formed polyethylene precipitates with the catalyst and the final molecular weight distribution of crude block copolymer product is rather broad (Mw/Mn =
3.0). Addition of propylene in the first step produces a system which remains homogenous throughout the block copolymer synthesis, yielding a crude product having a much narrower Mw/Mn = tl.7-l.8).
Method of Monomer Addition Monomer may be added and removed in such a way that the resulting block copolymer has excellent properties, such as blocking efficiency. This is accomplished by applying a 5 to lO psi (_ 34kPa to _ 69 kPa) vacuum and purging-the reactor with a dry inert gas, such as nitrogen, between monomer addition steps. In a preferred embodiment a minimum vacuum needed is 5 psi. The dry inert gas purge may be at 5 psi or above, preferably at or above 15 psi even more preferably between 5 and 25 psi in a two liter reactor. As is well known to those of ordinary skill in the art the pressures will vary with the size and other conditions of the reactor. Thus these numbers are a guide and not meant to be absolute.
Preparation of Tapered and Random Copolymers Addition of stoichiometric amounts of a mixture of two olefins to the reactor under block copolymer conditions will naturally produce tapered copolymer because the monomers will generally have different reactivities with the catalyst. Thus, the head of the polymer will be rich in the more reactive comonomer while the polymer tail will contain larger amounts of the slower reacting comonomer. The extent of tapering will depend on magnitude of the difference of monomer reactivity. The extent of tapering can be controlled by 215 8 8 6 8 PCT~S94/03060 metering the two monomers into the reactor at different rates.
Random copolymers such as non-crystalline ethylene-S propylene rubber can be made under block copolymerconditions by adding the fast monomer (ethylene) to the catalyst/propylene mixture at a rate where the desired amount of ethylene has been added when all the propylene has been consumed. This procedure is exemplified for a o ethylene-propylene elastomer containing 50 mole %
propylene.
In a preferred embodiment, tapered block copolymers having properties typical of thermoplastic elastomers (TPE's)can be produced. These particular tapered block copolymers typically strong and elastic, having a low modulus at low strain, high tensile strengths, up to 2500 psi or more, and a tension set of 14 to 25. These tapered copolymers are also characterized by an ethylene content of 15 to 25 mole %, preferably 18 to 23 mole %.
These tapered block copolymers can be produced by using a chiral hafnium catalyst, such as those used in the examples below, at a reaction temperature of -10 degrees C to 20 degrees C, preferably -5 degrees C to 10 degrees C. However, higher temperatures could be used, depending on the heat dissipation system utilized. These tapered block copolymers apparently have long steroregular segments of crystalline polypropylene that are probably formed when the concentration of ethylene in the feed drops to a low level. The DSC melting curves of these polymers typically show a broad melting peak with a sharp crystallization peak at low temperatures.
Block CopolYmer Products The novel polymer products of this invention are olefinic block and tapered copolymers having narrow WO94/21700 215 8 8 6 8 PCT~S94/03060 molecular weight distributions and well defined di-, tri-, multiblock or tapered structures. The polymer segments which can be incorporated into these architectures include 1) elastomers such as atactic polypropylene, atactic poly-l-olefins, and ethyle-le/1-olefin copolymers wherein the ethylene comonomer is a C3-C18 _-olefin such as ethylene-propylene, ethylene butene, and ethylene-octene copolymers ethylene-propylene-diene terpolymers and other crosslinkable elastomeric olefins; 2) thermoplastics such as high density polyethylene, linear low density polyethylene having melting points from 80-135C (e.g. ethylene-propylene and other ethylene-l-olefin copolymers wherein each l-olefin has from 4 to 20 carbon atoms), ethylene/diene copolymers such as ethylene/ethyldiene-norbornene copolymers, isotactic polypropylene having melting points from lOO-C-165-C, syndiotactic polypropylenes having melting points from lOO-C-165-C, semi-isotactic polypropylenes and other crystalline l-olefin homo and copolymers; and 3) glasses such as homo-polycyclopentene, homopolynorbornene and the like. The average molecular weight of the polymer segments included in the novel block copolymers of this invention can be in the range of from 100-1,000,000 daltons, preferably from 30,000 to 200,000 daltons. The molecular weight distributions (Mw/Mn) of the crude and/or fractionated block copolymer are preferably 5 or less, even more preferably 3 or less, even more preferably 2.5 or less, and even more preferably 2 or less. As indicated above and in the examples following the percentage of block copolymer in the crude product can vary from 1% to 100%, preferably from 50% to 90%
depending on the application and the conditions of the experiment. Furthermore, preferred block copolymers of this invention have blocking efficiencies of 30% or greater, preferably 50% or greater, more preferably 70~
or greater, even more preferably 90% or greater, and most preferably 95% or greater. In a preferred embodiment WO94/21700 PCT~S94103060 shorter reaction times and lower reactor temperatures are used to produce block copolymers having enhanced blocking efflciency.
The block copolymers of this ~vention can also be formulated into a wide variety of adhesives by blending the block copolymers with one or more solid or liquid tackifiers and optionally other known components such as oils, plasticizers, fillers, antioxidants, coloring agents, and the like. Useful tackifiers include natural rosins, hydrogenated or non-hydrogenated linear, branched or cyclic aliphatics or aromatics and mixtures thereof. The tackifiers may be present at from 5 weight percent to 95 weight percent based upon the weight of the IS composition. Fillers and other additives may be present at up to 150 weight percent based upon the weight of the copolymer and the tackifiers.
The block copolymers may also be molded or shaped into articles such as bumpers, shoe soles, dash boards, automotive parts, containers, sheeting and the like by methods known in the art. Fillers and other additives known in the art, such as carbon black, silica, talc, glass, glass fibers, antioxidants, plasticizers, oils, waxes, coloring agents, and the like nay further be added to the compositions before or after molding or shaping.
The block copolymers can also be used in foams, sealants, coatings, weather strippings, sound absorbers and the like with the appropriate additives known to those of ordinary skill in the art, such as foaming agents, tackifiers, oils, plasticizers, films and the like.
The block copolymers of this invention can be represented by the following general formula:
(Al)(A2)(A3)--- (An) W094/2l700 215 8 8 6 8 PCT~S94/03060 wherein each A is a polymer segment having an average molecular weight from lOO to l,OOO,OOO daltons chosen independently from homopolymers consisting of HDPE, homo and copolymers of cyclic olefins, such as polycyclopentene and polynorbornene, and isotactic, atactic, and syndiotactic poly-l-olefins such as atactic-PP, isotactic-PP, syndiotactic-PP; random copolymers of l-olefins and diolefins such as ethylene-propylene rubber, ethylene-propylene-hexadiene rubber, ethylene-lo butene rubber, linear low density polyethylenes, suchthat no adjacent segments are the same polymer composition.
Novel block copolymers of this invention include but are not limited to diblock copolymers such as (HDPE)(EP), (i-PP)(EP), (LLDPE)(a-PP), (HDPE)(a-PP), (LLDPE)(HDPE) and the like, and triblock copolymers such as (HDPE)(EP)(HDPE), (HDPE)(EP)(LLDPE), (LLDPE)(a-PP)(LLDPE), (HDPE)(a-PP)(LLDPE), (i-PP)(EP)(i-PP), (s-PP)(EP)(s-pp) and the like. It will be recognized to those well versed in the field that the isotactic polypropylene segments contained in the block copolymers of this invention have microstructure defects which are not observed in conventional i-PP materials prepared using titanium Ziegler-Natta catalyst. The microstructure defects which are unique to isotactic polypropylenes prepared using metallocene catalysts arise from 1-3 and 2-1 additions to propylene. The melting points of such materials can vary from 60C to 165C
depending on the total number total defects.
The tapered copolymers can be represented by similar general formula where the transitions between idealized polymer segments An are gradual. These gradient transitions between segments are represented by arrows.
(Al)---'(A2)---'(A3)--->..... (An).
WO94/21700 PCT~S94/03060 ` 215 8868 - 16 -An example of this would be a polymer prepared by reacting a 50-50 mixture of ethylene and propylene with a living catalyst which has a high preference for ethylene over propylene. The tapered polymer obtained in such an S experiment would be designated by the following formula:
HDPE--->EP--->a-PP
The GPC data was obtained on a Waters 150 GPC
instrument (MCL, Baytown) equipped with an RI detector.
The samples were run at ca. 140C in triclorobenzene solvent. The molecular weights were calculated from the PP calibration curves. The thermal behavior of the polymers was recorded by DuPont 912 Differential Scanning lS Calorimeter. The room temperature and the high temperature tensile properties of polymers were tested on Instron 4505. The polymers were compression molded on a Carver Press into thin sheets and allowed to condition for 24 hours. The micro-tensile specimens were cut and pulled at a crosshead speed of either 2 or 20 in/min.
The samples were equilibrated for 5-lO minutes in an environmental chamber prior to testing for high temperature tensile properties. The tension set was measured in terms of % residual strain after holding the sample at 100% strain for lO minutes followed by relaxation.
Example l: First EthYlene then PropYlene The reactor was cooled to 0C and charged with 400 mls of toluene and 0.20 mmoles of catalyst (bis cyclopentadienyl hafnium dimethyl and N,N, dimethylanilinium tetrakis(pentaflurophenyl)boron.
Ethylene (4.0 grams; 0.143 moles) was added to 0C and 2 psig over 25 minutes. After all the ethylene was consumed, propylene (6 grams; 0.139 moles) was added;
after 30 minutes the reactor was dropped and the product wo 94/zl7on ~ 1 5 8 8 6 8 PcTn~s94/o3n60 collected. The crude product contained 50 mole %
propylene, had a Mn = 87,000 with a molecular weight distribution of 3Ø The crude product was washed with hexane at room temperature to remove any a-PP which was not in the form of block copolymer. The hexane insoluble material contained crystalline HPDE (as determined by IR) and 30 mole % propylene; the Mn was 144,000 with a molecular weight distribution of 1.89. The hexane soluble fraction was a-PP, did not contain ethylene (by IR), and had a Mn of 63,000 with a molecular weight distribution of 1.47. Based on the extraction studies, it was concluded that 50-60% of the a-PP chains were incorporated into a block copolymer under these conditions.
IS
Exam~le 2: First Propylene then Ethylene The procedure of Example 1 was repeated except propylene was added first. The crude product had 41 mole % propylene (IR), a Mn of 170,000 with a molecular weight distribution of 1.78. A pad was pressed and extracted with hexane for 4 hours. At this point, the material contained 37 mole % propylene and very crystalline HDPE.
The pad was further extracted with toluene at room temperature for 50 hours with no loss of weight. The extracted "diblock" had a Mn f 230,000 and a molecular weight distribution of 1.48 (the hexane solubles were a-PP having a Mn f 125,000 and a molecular weight distribution of 1.72).
Exam~le 3: Mw Control in Block CoPolymer SYnthesis Using the procedure in Example 2, 3.0 grams of propylene (0.070 moles) were added to 0.20 mmole of the catalyst. After the propylene (0.071 moles) was completely consumed, 2.0 grams of ethylene were added to the system. The resulting product was washed with hexane wog4nl700 PCT~S94/03060 at room temperature to remove any a-PP. The resulting block copolymer had a Mn f 107,000 and a molecular weight distribution of 1.68, and c,ontained 42 mole %
propylene by IR spectroscopy. ~'-~
Example 4: Effect of Tem~erature The procedure of Example 1 was followed except thetemperature was varied. If the temperature is raised the effect is to lower the efficiency of the block formation.
The temperature was raised from O-C to lO C and the blocking efficiency was reduced to less than 10%. When the temperature was lowered to -5C, the blocking efficiency improved 78%.
IS
Example 5: Increasin~ Time Between Monomer Addition A series of block copolymerizations were run at O-C
and the time between the addition of propylene and ethylene was varied from 6 to 42 minutes. The crude products were collected, analyzed by GPC and IR, then extracted with hexane at room temperature for 65 hours to remove unblocked a-PP. In a well-behaved system wherein the extraction technique removes all of the a-PP, a logrithmically increase in the percent of hexane extractables with time would be expected. The data of this example is shown in Fig. 1 in graphical form. The Y-axis represents the percent of polypropylene which is incorporated into the block copolymer. The extractables were isolated and analyzed by GPC and IR; they were all pure a-PP. The correlation is close to the linear result expected so that this technique can be used to evaluate the kinetics of chain loss under a variety of conditions.
This result confirms the ability to make true block copolymers, and confirms that hexane extraction is a good measure of block copolymer efficiency for this polymer system.
W094/21700 21 5 8 8 6 8 PCT~S94/03060 Example 6: Preparation of EP
The procedure of Example 1 was followed except where 5 noted. In this example, 1.6 grams of propylene (0.037 moles) were added to [Cp2HfMe2][B(pfp)4] (0.30 mmole) in 400 cc of toluene at O-C. Immediately after the propylene addition, 1.1 grams of ethylene (0.039 moles) was metered in over 3 minutes. After six minutes, the product was recovered yielding 2.7 grams of amorphous EP
rubber. The product was non-crystalline by IR; the polymer had a Mn f 96,000 and a molecular weight distribution of 1.69.
ExamPle 7: PreDaration of EP
The procedure of Example 1 was followed except where noted. In this example 3.2 grams of propylene (0.074 moles) was added to [Cp2HfMe2][B(pfp)4] (0.30 mmole) in 400 cc of toluene at OoC. Ethylene (2.2 grams; 0.078 moles) was added to the reactor over 5.5 minutes. The product was recovered yielding 5.7 grams of EP rubber having a Mn of 155,000, and molecular weight distribution of 1.48. The IR showed some degree of PE-crystallinity.
ExamPle 8: Preparation of EP-b-HDPE
Example 6 was repeated to prepare "living" EP-rubber. After all the monomer had been consumed, ethylene (1.1 grams) was added to prepare the desired block copolymer. The product was recovered yielding 4.25 grams of copolymer. The IR showed PE crystallinity and the polymer had thermoplastic-like properties. The onset of Tg was -52.9C and the product had a melting point of 119C. The Mn of the crude product was 161,000 with a molecular weight distribution of 1.59.
W094/21700 215 8 8 6 8 PCT~S94/03060 ExamPle 9: aPP-HDPE di-Block CoPolYmer Blocks were synthesized as follows:
To 400 ml. of toluene containing 0.29 mmoles of Cp2Hf(Me)2 DMA(B(pfp)4), 2.3 g. of propylene was added first to a two liter zipperclave-reactor at O-C.
(DMA(B(pfp)4) = N,N-dimethylanilinium terakis (pentaflourophenyl) boron.) After 6 minutes of polymerization, the pressu_ dropped to approximately l psi. The reactor was then vented through a Nujol bubbler. A 5-6 psi vacuum was applied at the end of the PP reaction, followed by purging with 20 psi of N2. 20 psi of N2 was charged into the reactor while stirring and then vented to aid in removing any remaining propylene monomer dissolved in the solution. After venting N2, l.5 gm. of ethylene was added slowly and allowed 1-3 minutes for complete reaction. The resulting polymer was precipitated in the methanol and then extracted with hexane for 24 hours at room temperature. Soluble aPP was extracted by hexane whereas HDPE of aPP-HDPE block copolymer remained insoluble. Both hexane-soluble and insoluble species were then subjected to GPC and FTIR
analysis for MW and composition. This vacuum/N2 purging technique produced an end product with a high degree of HDPE formation. Characterization results are summarized in table l.
Mechanical properties (tensile, elongation, and tension set) were also measured for the aPP-HDPE di-block copolymers made. All measurements were done on an Instron model 4505 with crosshead speed set at 20 inches/minute. Test conditions for the tension set measurements were as follows: 100% elongation for lO
minutes at room temperature, then released. Percent deformation was measured immediately and after lO
minutes.
Table 1 ~PP-HDPEDi-BlockCopolymers ~e No.17005- 87-41 _ 95-45 97-46 101-48 103-49 Y~d ~n) 4.87-- 4.03 4.04 S~Z4 4.56 H~ In~nl--b~
~% 76 80 86 91 78 PP CQ1,t~ .-t, ~9O 36 44 57 49 43 Mc~ psi 1673 21S0 2820 2467 2217 F1O~E~I; n,% 602 400 382 567 476 Tcns~e, psi 1308 998 933 1345 1134 Ten~on Se~ % _ 46 57 53 S9 Tn4C 107 108 117 119 116 Mn~ x 1000 218 29S 245 2S5 239 M~ n 135 1.61 1.S4 1.93 1.69 ~ e Solubles Mn,~ 1000 _ 114 101 112 102 Mw~n 1.76 1.72 2.12 1.6 C~=asaPP 47 36 22 17 40 ~t A~A~
Molcr~-bloc~uolccaL 0.059 0.038 0.0049 0.065 0.051 ~olcaPP~molccaL - 0.025 0.019 0.014 0.034 A~h~ oat Mole % - 6.3% 6.8% 7.9% 8.5qo WO94/21700 PCT~S94/03060 ~ 2lS 8868 _ 22 -Example 10: HDPE-aPP-HDPE Tri-Blocks Synthesis of tri-block copolymers was performed under the same conditions as Example 9. In order to avoid precipitation of the first ~DPE block in the toluene solution, a small amount of gas phase C3= was charged into the reactor and polymerized prior to adding the first block C2= monomer. We applied 10 psi vacuum, followed with a 20 psi N2 purge between each monomer sequence before addition of a new monomer. The final products were precipitated in methanol and dried in a vacuum oven. In order to analyze the product composition, samples were extracted in hexane for 24 hours at room temperature. Block copolymers of HDPE-aPP
or HDPE-aPP-HDPE would remain insoluble, whereas aPP
would be extracted in this solvent. All soluble as well as insoluble samples were then subjected to MW and compositional analysis by GPC and FTIR. The results for total yields, weight percent of hexane extraction, MW and propylene content are summarized in the following table 2.
Table 2 HDPE-aPP-HDPE Tri-block CoPolymers Reac. I Reac. II Reac. III
(17005-159) (17005-161)fl7005-163) Total Yield (qm)2.41 6.97 9.03 Hexane insoluble wt% 95 59 92 Propylene content,wt% 25.851.9 50.4 Modulus, psi - 21S7 2444 Elongation, % - 670 638 Tensile, psi - 2398 2256 35 Tension set, %
(10 min at 100%) - 28 32 Mn, (x10-3) 125 346 331 Mw/Mn 2.1 1.8 2.1 Hexane Soluble Mn (x10-3) ~ 121 115 Mw/Mn - 2.4 3.1 WO94/21700 2 I 5 8 8 6 8 PCT~S94/03060 Results of FTIR analysis show that all of the hexane soluble are 100% aPP.
In order to assess the mechanical properties of the linear tri-block copolymers, we synthesized six more samples according to the same reaction conditions as previously described. Table 3 summarizes the data.
Samples #51, #53 and #54 were run with block ratios of l:3:l. Samples #55, #56 and #52 were run with a block ratio of l:6:l. Sample #52 was run with twice the ~mount of monomers charged and with the same level of cat~ yst concentration. We obtained a Mn=306,000 (almost double) with a similar narrow Mw/Mn=2Ø
588~8 - 24 -Tabl e 3 ' C G _ o C~ o ~`
_ ~ o o ~ CO CC CC -- ~ ~ -- ~ ~ --o U
O~ I~ ~'~ ~, C' ,~, ~ ~ -- O ~ --O ~ O O
G ~D q' 1-- C` o~ ~ --I~ V~ X ~D `' ~' -- ~'`I -- O -- ~ O O
3 . ~ u c u O ~ - = u o ~ c:~ 2 ~, O
o ~ _ K 5 O _ -- - _ 3 O x _ 3 O O
W094/21700 2 I 5 8 8 6 8 PCT~S94/03060 Example 11: HDPE-EP-HDPE Tri-block Copolymers The procedure set out in Example 9 was followed.
Three reactions were run with each reaction being terminated at the end of each blocking sequence. Samples of the hexane-soluble and insoluble fractions for each of these reactions were sub~ected to MW and compositional analysis by GPC and FTIR. Table 4 below summarizes the results.
l Table 4 Reactions I II III
Total Yields(g)2.06 9.06 9.80 Mn (x10-3) 237 190 299 Mw/Mn 2.05 2.70 2.19 lS
Hexane Insoluble Wt% 99.6 36.2 51.8 PP Content, wt%5.4 * *
Mn (x10-3) 189 324 297 Mw/Mn 2.28 1.94 2.37 Hexane Solubles**
Wt% 0.4 63.8 48.2 Mn (x10-3) - 164 Mw/Mn - 2.44 * The FTIR PP content was too high to be accurately calculated.
** FTIR shows hexane solubles contain both aPP and EP.
Three additional reactions were run using the same reaction conditions as previously described but varying the block ratio and the middle block E/P composition.
Table 5 summarizes results from these runs.
W094/21700 PCT~S94/03060 2i5 88 6 8 _ 26 -Table 5 HDPE-EP-HDPE Block CopolYmers (same reaction conditions as in Example 1) s Charge No. 17005-125-57 127-58 129-59 Block Ratio, by wt. 1:2.5:1 - 1:3.6:1 1:13:1 E/P Ratio, by wt.1:1 1:6 1:12 Total Yield, g 7.2 8.2 13.6 lO Exotherm, C 1 5 20 Hexane Insolubles Wt % 97 (30) 36 Propylene content, wt% 45.9 85.2 Modulus, psi 1560 3107 550 Elongation, % 509 290 885 Tensile, psi 1046 1204 688 Tension set, % 26 45 46 (10;, 100%) Mn(K) 510 544 156 Mw/Mn 1.8 2.1 3.4 Mol. polymer/
Mol. catalyst 0.047 0.016 0.108 Hexane Solubles Wt % 3 70 64 Mn, 1000 309 470 121 Mw/Mn 2.0 2.3 4.1 Mol. polymer/
Mol. catalyst 0.0024 0.042 0.248 Example 12: EP-RCP Block Copol~mers Sequential monomer addition technique was used to synthesize (A) EP-b-RCP Block Copolymers and (B) EP-b-iPP
Block Copolymers. (RCP is a tapered or random copolymer of propylene and an alpha olefin preferably ethylene. In the tapered RCP, the polymer chain is amorphous in one end and gradually becomes semi-crystalline toward the other end.) Removal of the residual ethylene of the "EP"
block by vacuum technique was used to synthesize EP/PP
block copolymers consisting of isotactic "PP" block and tapered copolymers (147-1,149-1, 150-1). The catalyst used was MeSi2(bis-indeneyl) hafnium dimethyl, indicated in the tables as"Hf-*", with DMAH(B(pfp)4).
WO94nl700 21 5 8 8 6 8 PCT~S94/03060 -The procedure of example 9 was used except where noted. The polymerization runs were carried out in a 1 L
autoclave reactor using toluene diluent. The "EP" block was formed first followed by the "PP" block. In between monomer addition steps the reactor was vented completely (O psi pressure) or subjected to vacuum/nitrogen purge cycle. The yield was determined by completely drying the crude product in the vacuum oven at lOO'C for at least 24 hours. The crude product was then subjected to heptane lo extraction at RT/50 C for 24 hours. The heptane soluble fraction is the unblocked EP copolymer and heptane insoluble part is EP-b-PP block copolymer.
A. Synthesis and Characterization of EP-block-RCP
(Random Co-Polymer):
Sequential monomer addition technique was employed.
"EP" block was formed first followed by the "PP" block.
The reactor was vented in between monomer addition steps.
The details of the polymerization conditions and the characterization data of block copolymers are reported in Table 7. A control "EP" run was carried out under similar conditions to simulate "EP" block of EP/PP block copolymer. The crude product obtained in the block run was subjected to the heptane extraction at room temperature.
(B) SYnthesis and Characterization of EP-block-iPP:
We followed the procedure in Example 12A above, however, by applying vacuum in between the "EP" and "PP"
block, we were able to remove the residual C2 of "EP"
block. The resultant block copolymers exhibited a sharp melting peak in the range of 135-138C corresponding to the "iPP" block. The polymerization conditions and the characterization of EP-b-ipp block copolymers and tapered copolymers are reported in Table 8 and A. The crude W094/21700 PCT~S94/03060 product formed in the block run was subjected to heptane extraction at 50C to insure complete removal of the unblocked EP copolymer. The heptane insoluble fraction was considered to be the block copolymer. The wt% EP in the block copolymer is calculated,from the results obtained in the heptane extraction studies. Mechanical properties are listed in tables 9 and 10.
WO 94/2l700 215 8 8 6 ~ PCT/US94/03060 TABLE A
~' ~ ~ ~ ' -- ~ _ o o ,j o o o U .D
- 2 co ~ ~ ~t G eo U CC
~ _ Z ~ ~ O ~ CO ~
' -- E
' ~ o 8 o o ~ ¢ ~e O 0 0 g ~O C?. ~
o E e o '~ v~ o o o ~, o ~ ~ o~ CO ~
", E U o -- o o o S:
U r ~0 eo ~, ~ ~ ~ _ O _ O
r~ ~ ~r7 0 H
p r o o~ 0~ C~
_ tO o o o _ _ _ '2 a 2 ~
O ~ O _ ~ eo ' ? ~r ~ eo ~ 3 ~ ~, o v~ v~
, X
8 8 't g 8 8 m & ~,, a~ ~ t ~" 8 8 8 Q ~ 3 o o '^
, b r X ~l E
. ~ :-, ~ _ ~ _ _ _ _ . = '' ~ ~ ~ o o U~~
. _ r~ eo éi r CO ~ ~ CO
' ~ g ~ O ~ ~ O O -- O O ~ ~ O
c.~ o'? _ O O c O O c O c r ~ . &
~ ~ ~o ~ co eo eo o~
~ o ~ _ _ a ~ ~ 2 ~ ~ a 33 ~
x ~ 8 ~ ~5 8 ~,C ~ ~e 8 8 8 m ~ n ~ o O ,~
3a E E ' . o ~
', 3 o oO ~ o ~ ~ ~o ~ ~ o o - o o o - o o - o æ O - O = Yo s ,~ ~ & ~ ~
21S8868 _ 32 -TABLE 8 ( cont ) ~ O _ _ _ a ~ 2 ~ a ~
CO, ~ 0~0 ~ O~ ~ 00 .
.~- E 3 Y~
X ~ ca ~ 8 " 8 ", 8 8 8 ", ,~ ~
~_ ~ 8 C~ o Q Q ~o ''O ~ O
E E ' , o ~ o X
, ' ~ o ~ ~o ~ c . _ ~ ~ O
. ~ E ~ o 3 ~ o 3 o o -- d ~ o ~'~ c U~
~ oo -- Y eo oo Y ~o c c c c c c b O
__321~;8868 m # Stre~J 95 St~ln T~il- * S~ T~
~ Yleld ~ Yl~d Streo~th O Br lc (l~
(p~l) (p-t) 14-3 2,364 17 4~1 n4 l ~o 17-3 2~883 16 3.2~4 S26 12,160 19-3 3,264 13 S.~lS 714 ~ "~0 24-3 1.931 19 3,900 774 17,660 29-3 3.0S1 16 4,489 7C0 19310 15MD - 237 K 3.688 S2 3.440 470 12.100 MWD - 2.16 Table 10 ID # 100% 300% T-n~lle % Str~ % l~eco-er~
Modulu~ Modulu~ Strength ~ Bre lc ~Iter (p-l) (p-l) (p~l) 100% strJIn 147-1 268 333 1,S00 1.320 90 149-1 459 SS8 1.587 870 8S
1S0-1 427 S03 1.7S0 1.03S 8S
146-3 8S9 979 2.734 822 6 148-3 983 l.l27 2.616 n6 SS
lS1-3 961 1.100 3.100 788 SS
Method of Monomer Addition Monomer may be added and removed in such a way that the resulting block copolymer has excellent properties, such as blocking efficiency. This is accomplished by applying a 5 to lO psi (_ 34kPa to _ 69 kPa) vacuum and purging-the reactor with a dry inert gas, such as nitrogen, between monomer addition steps. In a preferred embodiment a minimum vacuum needed is 5 psi. The dry inert gas purge may be at 5 psi or above, preferably at or above 15 psi even more preferably between 5 and 25 psi in a two liter reactor. As is well known to those of ordinary skill in the art the pressures will vary with the size and other conditions of the reactor. Thus these numbers are a guide and not meant to be absolute.
Preparation of Tapered and Random Copolymers Addition of stoichiometric amounts of a mixture of two olefins to the reactor under block copolymer conditions will naturally produce tapered copolymer because the monomers will generally have different reactivities with the catalyst. Thus, the head of the polymer will be rich in the more reactive comonomer while the polymer tail will contain larger amounts of the slower reacting comonomer. The extent of tapering will depend on magnitude of the difference of monomer reactivity. The extent of tapering can be controlled by 215 8 8 6 8 PCT~S94/03060 metering the two monomers into the reactor at different rates.
Random copolymers such as non-crystalline ethylene-S propylene rubber can be made under block copolymerconditions by adding the fast monomer (ethylene) to the catalyst/propylene mixture at a rate where the desired amount of ethylene has been added when all the propylene has been consumed. This procedure is exemplified for a o ethylene-propylene elastomer containing 50 mole %
propylene.
In a preferred embodiment, tapered block copolymers having properties typical of thermoplastic elastomers (TPE's)can be produced. These particular tapered block copolymers typically strong and elastic, having a low modulus at low strain, high tensile strengths, up to 2500 psi or more, and a tension set of 14 to 25. These tapered copolymers are also characterized by an ethylene content of 15 to 25 mole %, preferably 18 to 23 mole %.
These tapered block copolymers can be produced by using a chiral hafnium catalyst, such as those used in the examples below, at a reaction temperature of -10 degrees C to 20 degrees C, preferably -5 degrees C to 10 degrees C. However, higher temperatures could be used, depending on the heat dissipation system utilized. These tapered block copolymers apparently have long steroregular segments of crystalline polypropylene that are probably formed when the concentration of ethylene in the feed drops to a low level. The DSC melting curves of these polymers typically show a broad melting peak with a sharp crystallization peak at low temperatures.
Block CopolYmer Products The novel polymer products of this invention are olefinic block and tapered copolymers having narrow WO94/21700 215 8 8 6 8 PCT~S94/03060 molecular weight distributions and well defined di-, tri-, multiblock or tapered structures. The polymer segments which can be incorporated into these architectures include 1) elastomers such as atactic polypropylene, atactic poly-l-olefins, and ethyle-le/1-olefin copolymers wherein the ethylene comonomer is a C3-C18 _-olefin such as ethylene-propylene, ethylene butene, and ethylene-octene copolymers ethylene-propylene-diene terpolymers and other crosslinkable elastomeric olefins; 2) thermoplastics such as high density polyethylene, linear low density polyethylene having melting points from 80-135C (e.g. ethylene-propylene and other ethylene-l-olefin copolymers wherein each l-olefin has from 4 to 20 carbon atoms), ethylene/diene copolymers such as ethylene/ethyldiene-norbornene copolymers, isotactic polypropylene having melting points from lOO-C-165-C, syndiotactic polypropylenes having melting points from lOO-C-165-C, semi-isotactic polypropylenes and other crystalline l-olefin homo and copolymers; and 3) glasses such as homo-polycyclopentene, homopolynorbornene and the like. The average molecular weight of the polymer segments included in the novel block copolymers of this invention can be in the range of from 100-1,000,000 daltons, preferably from 30,000 to 200,000 daltons. The molecular weight distributions (Mw/Mn) of the crude and/or fractionated block copolymer are preferably 5 or less, even more preferably 3 or less, even more preferably 2.5 or less, and even more preferably 2 or less. As indicated above and in the examples following the percentage of block copolymer in the crude product can vary from 1% to 100%, preferably from 50% to 90%
depending on the application and the conditions of the experiment. Furthermore, preferred block copolymers of this invention have blocking efficiencies of 30% or greater, preferably 50% or greater, more preferably 70~
or greater, even more preferably 90% or greater, and most preferably 95% or greater. In a preferred embodiment WO94/21700 PCT~S94103060 shorter reaction times and lower reactor temperatures are used to produce block copolymers having enhanced blocking efflciency.
The block copolymers of this ~vention can also be formulated into a wide variety of adhesives by blending the block copolymers with one or more solid or liquid tackifiers and optionally other known components such as oils, plasticizers, fillers, antioxidants, coloring agents, and the like. Useful tackifiers include natural rosins, hydrogenated or non-hydrogenated linear, branched or cyclic aliphatics or aromatics and mixtures thereof. The tackifiers may be present at from 5 weight percent to 95 weight percent based upon the weight of the IS composition. Fillers and other additives may be present at up to 150 weight percent based upon the weight of the copolymer and the tackifiers.
The block copolymers may also be molded or shaped into articles such as bumpers, shoe soles, dash boards, automotive parts, containers, sheeting and the like by methods known in the art. Fillers and other additives known in the art, such as carbon black, silica, talc, glass, glass fibers, antioxidants, plasticizers, oils, waxes, coloring agents, and the like nay further be added to the compositions before or after molding or shaping.
The block copolymers can also be used in foams, sealants, coatings, weather strippings, sound absorbers and the like with the appropriate additives known to those of ordinary skill in the art, such as foaming agents, tackifiers, oils, plasticizers, films and the like.
The block copolymers of this invention can be represented by the following general formula:
(Al)(A2)(A3)--- (An) W094/2l700 215 8 8 6 8 PCT~S94/03060 wherein each A is a polymer segment having an average molecular weight from lOO to l,OOO,OOO daltons chosen independently from homopolymers consisting of HDPE, homo and copolymers of cyclic olefins, such as polycyclopentene and polynorbornene, and isotactic, atactic, and syndiotactic poly-l-olefins such as atactic-PP, isotactic-PP, syndiotactic-PP; random copolymers of l-olefins and diolefins such as ethylene-propylene rubber, ethylene-propylene-hexadiene rubber, ethylene-lo butene rubber, linear low density polyethylenes, suchthat no adjacent segments are the same polymer composition.
Novel block copolymers of this invention include but are not limited to diblock copolymers such as (HDPE)(EP), (i-PP)(EP), (LLDPE)(a-PP), (HDPE)(a-PP), (LLDPE)(HDPE) and the like, and triblock copolymers such as (HDPE)(EP)(HDPE), (HDPE)(EP)(LLDPE), (LLDPE)(a-PP)(LLDPE), (HDPE)(a-PP)(LLDPE), (i-PP)(EP)(i-PP), (s-PP)(EP)(s-pp) and the like. It will be recognized to those well versed in the field that the isotactic polypropylene segments contained in the block copolymers of this invention have microstructure defects which are not observed in conventional i-PP materials prepared using titanium Ziegler-Natta catalyst. The microstructure defects which are unique to isotactic polypropylenes prepared using metallocene catalysts arise from 1-3 and 2-1 additions to propylene. The melting points of such materials can vary from 60C to 165C
depending on the total number total defects.
The tapered copolymers can be represented by similar general formula where the transitions between idealized polymer segments An are gradual. These gradient transitions between segments are represented by arrows.
(Al)---'(A2)---'(A3)--->..... (An).
WO94/21700 PCT~S94/03060 ` 215 8868 - 16 -An example of this would be a polymer prepared by reacting a 50-50 mixture of ethylene and propylene with a living catalyst which has a high preference for ethylene over propylene. The tapered polymer obtained in such an S experiment would be designated by the following formula:
HDPE--->EP--->a-PP
The GPC data was obtained on a Waters 150 GPC
instrument (MCL, Baytown) equipped with an RI detector.
The samples were run at ca. 140C in triclorobenzene solvent. The molecular weights were calculated from the PP calibration curves. The thermal behavior of the polymers was recorded by DuPont 912 Differential Scanning lS Calorimeter. The room temperature and the high temperature tensile properties of polymers were tested on Instron 4505. The polymers were compression molded on a Carver Press into thin sheets and allowed to condition for 24 hours. The micro-tensile specimens were cut and pulled at a crosshead speed of either 2 or 20 in/min.
The samples were equilibrated for 5-lO minutes in an environmental chamber prior to testing for high temperature tensile properties. The tension set was measured in terms of % residual strain after holding the sample at 100% strain for lO minutes followed by relaxation.
Example l: First EthYlene then PropYlene The reactor was cooled to 0C and charged with 400 mls of toluene and 0.20 mmoles of catalyst (bis cyclopentadienyl hafnium dimethyl and N,N, dimethylanilinium tetrakis(pentaflurophenyl)boron.
Ethylene (4.0 grams; 0.143 moles) was added to 0C and 2 psig over 25 minutes. After all the ethylene was consumed, propylene (6 grams; 0.139 moles) was added;
after 30 minutes the reactor was dropped and the product wo 94/zl7on ~ 1 5 8 8 6 8 PcTn~s94/o3n60 collected. The crude product contained 50 mole %
propylene, had a Mn = 87,000 with a molecular weight distribution of 3Ø The crude product was washed with hexane at room temperature to remove any a-PP which was not in the form of block copolymer. The hexane insoluble material contained crystalline HPDE (as determined by IR) and 30 mole % propylene; the Mn was 144,000 with a molecular weight distribution of 1.89. The hexane soluble fraction was a-PP, did not contain ethylene (by IR), and had a Mn of 63,000 with a molecular weight distribution of 1.47. Based on the extraction studies, it was concluded that 50-60% of the a-PP chains were incorporated into a block copolymer under these conditions.
IS
Exam~le 2: First Propylene then Ethylene The procedure of Example 1 was repeated except propylene was added first. The crude product had 41 mole % propylene (IR), a Mn of 170,000 with a molecular weight distribution of 1.78. A pad was pressed and extracted with hexane for 4 hours. At this point, the material contained 37 mole % propylene and very crystalline HDPE.
The pad was further extracted with toluene at room temperature for 50 hours with no loss of weight. The extracted "diblock" had a Mn f 230,000 and a molecular weight distribution of 1.48 (the hexane solubles were a-PP having a Mn f 125,000 and a molecular weight distribution of 1.72).
Exam~le 3: Mw Control in Block CoPolymer SYnthesis Using the procedure in Example 2, 3.0 grams of propylene (0.070 moles) were added to 0.20 mmole of the catalyst. After the propylene (0.071 moles) was completely consumed, 2.0 grams of ethylene were added to the system. The resulting product was washed with hexane wog4nl700 PCT~S94/03060 at room temperature to remove any a-PP. The resulting block copolymer had a Mn f 107,000 and a molecular weight distribution of 1.68, and c,ontained 42 mole %
propylene by IR spectroscopy. ~'-~
Example 4: Effect of Tem~erature The procedure of Example 1 was followed except thetemperature was varied. If the temperature is raised the effect is to lower the efficiency of the block formation.
The temperature was raised from O-C to lO C and the blocking efficiency was reduced to less than 10%. When the temperature was lowered to -5C, the blocking efficiency improved 78%.
IS
Example 5: Increasin~ Time Between Monomer Addition A series of block copolymerizations were run at O-C
and the time between the addition of propylene and ethylene was varied from 6 to 42 minutes. The crude products were collected, analyzed by GPC and IR, then extracted with hexane at room temperature for 65 hours to remove unblocked a-PP. In a well-behaved system wherein the extraction technique removes all of the a-PP, a logrithmically increase in the percent of hexane extractables with time would be expected. The data of this example is shown in Fig. 1 in graphical form. The Y-axis represents the percent of polypropylene which is incorporated into the block copolymer. The extractables were isolated and analyzed by GPC and IR; they were all pure a-PP. The correlation is close to the linear result expected so that this technique can be used to evaluate the kinetics of chain loss under a variety of conditions.
This result confirms the ability to make true block copolymers, and confirms that hexane extraction is a good measure of block copolymer efficiency for this polymer system.
W094/21700 21 5 8 8 6 8 PCT~S94/03060 Example 6: Preparation of EP
The procedure of Example 1 was followed except where 5 noted. In this example, 1.6 grams of propylene (0.037 moles) were added to [Cp2HfMe2][B(pfp)4] (0.30 mmole) in 400 cc of toluene at O-C. Immediately after the propylene addition, 1.1 grams of ethylene (0.039 moles) was metered in over 3 minutes. After six minutes, the product was recovered yielding 2.7 grams of amorphous EP
rubber. The product was non-crystalline by IR; the polymer had a Mn f 96,000 and a molecular weight distribution of 1.69.
ExamPle 7: PreDaration of EP
The procedure of Example 1 was followed except where noted. In this example 3.2 grams of propylene (0.074 moles) was added to [Cp2HfMe2][B(pfp)4] (0.30 mmole) in 400 cc of toluene at OoC. Ethylene (2.2 grams; 0.078 moles) was added to the reactor over 5.5 minutes. The product was recovered yielding 5.7 grams of EP rubber having a Mn of 155,000, and molecular weight distribution of 1.48. The IR showed some degree of PE-crystallinity.
ExamPle 8: Preparation of EP-b-HDPE
Example 6 was repeated to prepare "living" EP-rubber. After all the monomer had been consumed, ethylene (1.1 grams) was added to prepare the desired block copolymer. The product was recovered yielding 4.25 grams of copolymer. The IR showed PE crystallinity and the polymer had thermoplastic-like properties. The onset of Tg was -52.9C and the product had a melting point of 119C. The Mn of the crude product was 161,000 with a molecular weight distribution of 1.59.
W094/21700 215 8 8 6 8 PCT~S94/03060 ExamPle 9: aPP-HDPE di-Block CoPolYmer Blocks were synthesized as follows:
To 400 ml. of toluene containing 0.29 mmoles of Cp2Hf(Me)2 DMA(B(pfp)4), 2.3 g. of propylene was added first to a two liter zipperclave-reactor at O-C.
(DMA(B(pfp)4) = N,N-dimethylanilinium terakis (pentaflourophenyl) boron.) After 6 minutes of polymerization, the pressu_ dropped to approximately l psi. The reactor was then vented through a Nujol bubbler. A 5-6 psi vacuum was applied at the end of the PP reaction, followed by purging with 20 psi of N2. 20 psi of N2 was charged into the reactor while stirring and then vented to aid in removing any remaining propylene monomer dissolved in the solution. After venting N2, l.5 gm. of ethylene was added slowly and allowed 1-3 minutes for complete reaction. The resulting polymer was precipitated in the methanol and then extracted with hexane for 24 hours at room temperature. Soluble aPP was extracted by hexane whereas HDPE of aPP-HDPE block copolymer remained insoluble. Both hexane-soluble and insoluble species were then subjected to GPC and FTIR
analysis for MW and composition. This vacuum/N2 purging technique produced an end product with a high degree of HDPE formation. Characterization results are summarized in table l.
Mechanical properties (tensile, elongation, and tension set) were also measured for the aPP-HDPE di-block copolymers made. All measurements were done on an Instron model 4505 with crosshead speed set at 20 inches/minute. Test conditions for the tension set measurements were as follows: 100% elongation for lO
minutes at room temperature, then released. Percent deformation was measured immediately and after lO
minutes.
Table 1 ~PP-HDPEDi-BlockCopolymers ~e No.17005- 87-41 _ 95-45 97-46 101-48 103-49 Y~d ~n) 4.87-- 4.03 4.04 S~Z4 4.56 H~ In~nl--b~
~% 76 80 86 91 78 PP CQ1,t~ .-t, ~9O 36 44 57 49 43 Mc~ psi 1673 21S0 2820 2467 2217 F1O~E~I; n,% 602 400 382 567 476 Tcns~e, psi 1308 998 933 1345 1134 Ten~on Se~ % _ 46 57 53 S9 Tn4C 107 108 117 119 116 Mn~ x 1000 218 29S 245 2S5 239 M~ n 135 1.61 1.S4 1.93 1.69 ~ e Solubles Mn,~ 1000 _ 114 101 112 102 Mw~n 1.76 1.72 2.12 1.6 C~=asaPP 47 36 22 17 40 ~t A~A~
Molcr~-bloc~uolccaL 0.059 0.038 0.0049 0.065 0.051 ~olcaPP~molccaL - 0.025 0.019 0.014 0.034 A~h~ oat Mole % - 6.3% 6.8% 7.9% 8.5qo WO94/21700 PCT~S94/03060 ~ 2lS 8868 _ 22 -Example 10: HDPE-aPP-HDPE Tri-Blocks Synthesis of tri-block copolymers was performed under the same conditions as Example 9. In order to avoid precipitation of the first ~DPE block in the toluene solution, a small amount of gas phase C3= was charged into the reactor and polymerized prior to adding the first block C2= monomer. We applied 10 psi vacuum, followed with a 20 psi N2 purge between each monomer sequence before addition of a new monomer. The final products were precipitated in methanol and dried in a vacuum oven. In order to analyze the product composition, samples were extracted in hexane for 24 hours at room temperature. Block copolymers of HDPE-aPP
or HDPE-aPP-HDPE would remain insoluble, whereas aPP
would be extracted in this solvent. All soluble as well as insoluble samples were then subjected to MW and compositional analysis by GPC and FTIR. The results for total yields, weight percent of hexane extraction, MW and propylene content are summarized in the following table 2.
Table 2 HDPE-aPP-HDPE Tri-block CoPolymers Reac. I Reac. II Reac. III
(17005-159) (17005-161)fl7005-163) Total Yield (qm)2.41 6.97 9.03 Hexane insoluble wt% 95 59 92 Propylene content,wt% 25.851.9 50.4 Modulus, psi - 21S7 2444 Elongation, % - 670 638 Tensile, psi - 2398 2256 35 Tension set, %
(10 min at 100%) - 28 32 Mn, (x10-3) 125 346 331 Mw/Mn 2.1 1.8 2.1 Hexane Soluble Mn (x10-3) ~ 121 115 Mw/Mn - 2.4 3.1 WO94/21700 2 I 5 8 8 6 8 PCT~S94/03060 Results of FTIR analysis show that all of the hexane soluble are 100% aPP.
In order to assess the mechanical properties of the linear tri-block copolymers, we synthesized six more samples according to the same reaction conditions as previously described. Table 3 summarizes the data.
Samples #51, #53 and #54 were run with block ratios of l:3:l. Samples #55, #56 and #52 were run with a block ratio of l:6:l. Sample #52 was run with twice the ~mount of monomers charged and with the same level of cat~ yst concentration. We obtained a Mn=306,000 (almost double) with a similar narrow Mw/Mn=2Ø
588~8 - 24 -Tabl e 3 ' C G _ o C~ o ~`
_ ~ o o ~ CO CC CC -- ~ ~ -- ~ ~ --o U
O~ I~ ~'~ ~, C' ,~, ~ ~ -- O ~ --O ~ O O
G ~D q' 1-- C` o~ ~ --I~ V~ X ~D `' ~' -- ~'`I -- O -- ~ O O
3 . ~ u c u O ~ - = u o ~ c:~ 2 ~, O
o ~ _ K 5 O _ -- - _ 3 O x _ 3 O O
W094/21700 2 I 5 8 8 6 8 PCT~S94/03060 Example 11: HDPE-EP-HDPE Tri-block Copolymers The procedure set out in Example 9 was followed.
Three reactions were run with each reaction being terminated at the end of each blocking sequence. Samples of the hexane-soluble and insoluble fractions for each of these reactions were sub~ected to MW and compositional analysis by GPC and FTIR. Table 4 below summarizes the results.
l Table 4 Reactions I II III
Total Yields(g)2.06 9.06 9.80 Mn (x10-3) 237 190 299 Mw/Mn 2.05 2.70 2.19 lS
Hexane Insoluble Wt% 99.6 36.2 51.8 PP Content, wt%5.4 * *
Mn (x10-3) 189 324 297 Mw/Mn 2.28 1.94 2.37 Hexane Solubles**
Wt% 0.4 63.8 48.2 Mn (x10-3) - 164 Mw/Mn - 2.44 * The FTIR PP content was too high to be accurately calculated.
** FTIR shows hexane solubles contain both aPP and EP.
Three additional reactions were run using the same reaction conditions as previously described but varying the block ratio and the middle block E/P composition.
Table 5 summarizes results from these runs.
W094/21700 PCT~S94/03060 2i5 88 6 8 _ 26 -Table 5 HDPE-EP-HDPE Block CopolYmers (same reaction conditions as in Example 1) s Charge No. 17005-125-57 127-58 129-59 Block Ratio, by wt. 1:2.5:1 - 1:3.6:1 1:13:1 E/P Ratio, by wt.1:1 1:6 1:12 Total Yield, g 7.2 8.2 13.6 lO Exotherm, C 1 5 20 Hexane Insolubles Wt % 97 (30) 36 Propylene content, wt% 45.9 85.2 Modulus, psi 1560 3107 550 Elongation, % 509 290 885 Tensile, psi 1046 1204 688 Tension set, % 26 45 46 (10;, 100%) Mn(K) 510 544 156 Mw/Mn 1.8 2.1 3.4 Mol. polymer/
Mol. catalyst 0.047 0.016 0.108 Hexane Solubles Wt % 3 70 64 Mn, 1000 309 470 121 Mw/Mn 2.0 2.3 4.1 Mol. polymer/
Mol. catalyst 0.0024 0.042 0.248 Example 12: EP-RCP Block Copol~mers Sequential monomer addition technique was used to synthesize (A) EP-b-RCP Block Copolymers and (B) EP-b-iPP
Block Copolymers. (RCP is a tapered or random copolymer of propylene and an alpha olefin preferably ethylene. In the tapered RCP, the polymer chain is amorphous in one end and gradually becomes semi-crystalline toward the other end.) Removal of the residual ethylene of the "EP"
block by vacuum technique was used to synthesize EP/PP
block copolymers consisting of isotactic "PP" block and tapered copolymers (147-1,149-1, 150-1). The catalyst used was MeSi2(bis-indeneyl) hafnium dimethyl, indicated in the tables as"Hf-*", with DMAH(B(pfp)4).
WO94nl700 21 5 8 8 6 8 PCT~S94/03060 -The procedure of example 9 was used except where noted. The polymerization runs were carried out in a 1 L
autoclave reactor using toluene diluent. The "EP" block was formed first followed by the "PP" block. In between monomer addition steps the reactor was vented completely (O psi pressure) or subjected to vacuum/nitrogen purge cycle. The yield was determined by completely drying the crude product in the vacuum oven at lOO'C for at least 24 hours. The crude product was then subjected to heptane lo extraction at RT/50 C for 24 hours. The heptane soluble fraction is the unblocked EP copolymer and heptane insoluble part is EP-b-PP block copolymer.
A. Synthesis and Characterization of EP-block-RCP
(Random Co-Polymer):
Sequential monomer addition technique was employed.
"EP" block was formed first followed by the "PP" block.
The reactor was vented in between monomer addition steps.
The details of the polymerization conditions and the characterization data of block copolymers are reported in Table 7. A control "EP" run was carried out under similar conditions to simulate "EP" block of EP/PP block copolymer. The crude product obtained in the block run was subjected to the heptane extraction at room temperature.
(B) SYnthesis and Characterization of EP-block-iPP:
We followed the procedure in Example 12A above, however, by applying vacuum in between the "EP" and "PP"
block, we were able to remove the residual C2 of "EP"
block. The resultant block copolymers exhibited a sharp melting peak in the range of 135-138C corresponding to the "iPP" block. The polymerization conditions and the characterization of EP-b-ipp block copolymers and tapered copolymers are reported in Table 8 and A. The crude W094/21700 PCT~S94/03060 product formed in the block run was subjected to heptane extraction at 50C to insure complete removal of the unblocked EP copolymer. The heptane insoluble fraction was considered to be the block copolymer. The wt% EP in the block copolymer is calculated,from the results obtained in the heptane extraction studies. Mechanical properties are listed in tables 9 and 10.
WO 94/2l700 215 8 8 6 ~ PCT/US94/03060 TABLE A
~' ~ ~ ~ ' -- ~ _ o o ,j o o o U .D
- 2 co ~ ~ ~t G eo U CC
~ _ Z ~ ~ O ~ CO ~
' -- E
' ~ o 8 o o ~ ¢ ~e O 0 0 g ~O C?. ~
o E e o '~ v~ o o o ~, o ~ ~ o~ CO ~
", E U o -- o o o S:
U r ~0 eo ~, ~ ~ ~ _ O _ O
r~ ~ ~r7 0 H
p r o o~ 0~ C~
_ tO o o o _ _ _ '2 a 2 ~
O ~ O _ ~ eo ' ? ~r ~ eo ~ 3 ~ ~, o v~ v~
, X
8 8 't g 8 8 m & ~,, a~ ~ t ~" 8 8 8 Q ~ 3 o o '^
, b r X ~l E
. ~ :-, ~ _ ~ _ _ _ _ . = '' ~ ~ ~ o o U~~
. _ r~ eo éi r CO ~ ~ CO
' ~ g ~ O ~ ~ O O -- O O ~ ~ O
c.~ o'? _ O O c O O c O c r ~ . &
~ ~ ~o ~ co eo eo o~
~ o ~ _ _ a ~ ~ 2 ~ ~ a 33 ~
x ~ 8 ~ ~5 8 ~,C ~ ~e 8 8 8 m ~ n ~ o O ,~
3a E E ' . o ~
', 3 o oO ~ o ~ ~ ~o ~ ~ o o - o o o - o o - o æ O - O = Yo s ,~ ~ & ~ ~
21S8868 _ 32 -TABLE 8 ( cont ) ~ O _ _ _ a ~ 2 ~ a ~
CO, ~ 0~0 ~ O~ ~ 00 .
.~- E 3 Y~
X ~ ca ~ 8 " 8 ", 8 8 8 ", ,~ ~
~_ ~ 8 C~ o Q Q ~o ''O ~ O
E E ' , o ~ o X
, ' ~ o ~ ~o ~ c . _ ~ ~ O
. ~ E ~ o 3 ~ o 3 o o -- d ~ o ~'~ c U~
~ oo -- Y eo oo Y ~o c c c c c c b O
__321~;8868 m # Stre~J 95 St~ln T~il- * S~ T~
~ Yleld ~ Yl~d Streo~th O Br lc (l~
(p~l) (p-t) 14-3 2,364 17 4~1 n4 l ~o 17-3 2~883 16 3.2~4 S26 12,160 19-3 3,264 13 S.~lS 714 ~ "~0 24-3 1.931 19 3,900 774 17,660 29-3 3.0S1 16 4,489 7C0 19310 15MD - 237 K 3.688 S2 3.440 470 12.100 MWD - 2.16 Table 10 ID # 100% 300% T-n~lle % Str~ % l~eco-er~
Modulu~ Modulu~ Strength ~ Bre lc ~Iter (p-l) (p-l) (p~l) 100% strJIn 147-1 268 333 1,S00 1.320 90 149-1 459 SS8 1.587 870 8S
1S0-1 427 S03 1.7S0 1.03S 8S
146-3 8S9 979 2.734 822 6 148-3 983 l.l27 2.616 n6 SS
lS1-3 961 1.100 3.100 788 SS
Claims (17)
1. A process for producing block copolymers comprising the steps of:
(i) contacting under polymerization conditions in a polymerization reactor a first olefinic monomer(s) with an activated catalyst complex which is the reaction product of:
(a) a cyclopentadienyl Group IVB metal component, and (b) a second component of an alumoxane to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a block copolymer; and (iii) recovering a block copolymer having a molecular weight distribution of 3 or less.
(i) contacting under polymerization conditions in a polymerization reactor a first olefinic monomer(s) with an activated catalyst complex which is the reaction product of:
(a) a cyclopentadienyl Group IVB metal component, and (b) a second component of an alumoxane to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a block copolymer; and (iii) recovering a block copolymer having a molecular weight distribution of 3 or less.
2. A process for producing tapered copolymers comprising the steps of:
(i) contacting under polymerization conditions in a polymerization reactor a first olefinic monomer(s) with an activated catalyst complex which is the reaction product of:
(a) a cyclopentadienyl Group IVB metal component, and (b) a second component of an alumoxane to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a tapered copolymer; and (iii) recovering a tapered copolymer having a molecular weight distribution of 3 or less.
(i) contacting under polymerization conditions in a polymerization reactor a first olefinic monomer(s) with an activated catalyst complex which is the reaction product of:
(a) a cyclopentadienyl Group IVB metal component, and (b) a second component of an alumoxane to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a tapered copolymer; and (iii) recovering a tapered copolymer having a molecular weight distribution of 3 or less.
3. A process for producing tapered copolymers comprising the steps of:
(i) contacting under polymerization conditions in a polymerization reactor a first olefinic monomer(s) with an activated catalyst complex which is the reaction product of:
(a) a cyclopentadienyl Group IVB metal component, and (b) a second component of a compatible non-coordinating anion to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a tapered copolymer; and (iii) recovering a tapered copolymer having a molecular weight distribution of 3 or less.
(i) contacting under polymerization conditions in a polymerization reactor a first olefinic monomer(s) with an activated catalyst complex which is the reaction product of:
(a) a cyclopentadienyl Group IVB metal component, and (b) a second component of a compatible non-coordinating anion to produce a first living polymer; and (ii) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a tapered copolymer; and (iii) recovering a tapered copolymer having a molecular weight distribution of 3 or less.
4. The process of claim 1 wherein the block copolymer is a diblock or triblock copolymer.
5. The process of claim 1, 2 or 3 wherein the polymerization is vented or purged with a dry gas in between steps (i) and (ii).
6. The process of claim 1, 2 or 3 wherein the polymerization reactor is vented or subjected to a vacuum and purged with a dry gas in between steps (i) and (ii).
7. The process of claim 3 wherein the activated catalyst complex product is represented by the formulae:
[A-CpMX1] [(C2B9H11) 2Co]
[A-CpMX1(L')][B(C6F5)3(X3)]
[(A-CpMX1)2X1][B']
wherein: M is titanium, zirconium or hafnium; (A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp; and Cp and Cp* are the same or different substituted or unsubstituted cyclopentadienyl radicals; A' is a covalent bridging group containing a Group IV-A element; L' is a neutral Lewis base; X1 is a hydride radical, hydrocarbyl radical having from 1 to 20 carbon atoms, substituted-hydrocarbyl radical, wherein 1 or more of the hydrogen atoms are replaced with a halogen atom, having from 1 to 20 carbon atoms, or organo-metalloid radical comprising a Group IV-A element wherein each of the hydrocarbyl substituents contained in the organo portion of said organo-metalloid, independently, contain from 1 to 20 carbon atoms; X3 is a hydride, halide, hydrocarbyl radical, a C1 - C20 hydrocarbyl radical wherein one or more of the hydrogen atoms is replaced by a halogen atoms, organometalloid radical wherein each hydrocarbyl substitution in the organic portion contains from 1 to 20 carbon atoms and the metal is a Group IVA metal and B' is a noncoordinating anion.
[A-CpMX1] [(C2B9H11) 2Co]
[A-CpMX1(L')][B(C6F5)3(X3)]
[(A-CpMX1)2X1][B']
wherein: M is titanium, zirconium or hafnium; (A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp; and Cp and Cp* are the same or different substituted or unsubstituted cyclopentadienyl radicals; A' is a covalent bridging group containing a Group IV-A element; L' is a neutral Lewis base; X1 is a hydride radical, hydrocarbyl radical having from 1 to 20 carbon atoms, substituted-hydrocarbyl radical, wherein 1 or more of the hydrogen atoms are replaced with a halogen atom, having from 1 to 20 carbon atoms, or organo-metalloid radical comprising a Group IV-A element wherein each of the hydrocarbyl substituents contained in the organo portion of said organo-metalloid, independently, contain from 1 to 20 carbon atoms; X3 is a hydride, halide, hydrocarbyl radical, a C1 - C20 hydrocarbyl radical wherein one or more of the hydrogen atoms is replaced by a halogen atoms, organometalloid radical wherein each hydrocarbyl substitution in the organic portion contains from 1 to 20 carbon atoms and the metal is a Group IVA metal and B' is a noncoordinating anion.
8. The process of claim 3, wherein the catalyst is the reaction product bis(cyclopentadienyl) hafnium dimethyl and N,N-dimethylanilinium terakis(pentaflouropheny)boron.
9. The process of claim 1, 2 or 3 wherein said steps (i) and (ii) are carried out at a temperature of from -5°C to 10°C.
10. The process of claim 1, 2 or 3 wherein any of said monomers is selected from the group consisting of ethylene, propylene, and 1-butene.
11. The product of the method of claim 1 characterized by a blocking efficiency of 30% or greater.
12. The product of the process of claim 2, wherein the product is a tapered copolymer comprising from 15 to 25 mole percent ethylene and having a molecular weight distribution of 2.5 or less.
13. The product of the process of claim 3, wherein the product is a tapered copolymer comprising from 15 to 25 mole percent ethylene and having a molecular weight distribution of 2.5 or less.
14. Olefinic tapered copolymers having a Mw/Mn 3 or less represented by the formula:
(A1) (A2) (A3) (An) wherein n is an integer, each A represent a polymer segment having an average of Mw of from 100 to 1,000,000 daltons and adjacent A represent different olefinic polymer segments, A being selected from the group consisting of: atactic, syndiotactic or isotactic polymers of one or more of olefins, diolefins, .alpha.-olefins, cyclic olefins and polymers of one or more of olefins, diolefins, .alpha.-olefins, cyclic olefins.
(A1) (A2) (A3) (An) wherein n is an integer, each A represent a polymer segment having an average of Mw of from 100 to 1,000,000 daltons and adjacent A represent different olefinic polymer segments, A being selected from the group consisting of: atactic, syndiotactic or isotactic polymers of one or more of olefins, diolefins, .alpha.-olefins, cyclic olefins and polymers of one or more of olefins, diolefins, .alpha.-olefins, cyclic olefins.
15. The copolymers of claim 14 wherein each A is selected from atactic-polypropylene, isotactic-polypropylene, syndiotactic-polypropylene, polyethylene, ethylene propylene copolymers, ethylene butene copolymer, ethylene .alpha.-olefin copolymer, HDPE, LLDPE.
16. An adhesive comprising a copolymer of claim 14 and a tackifier.
17. A molded article or a foam comprising a copolymer of claim 14.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/035,021 US5391629A (en) | 1987-01-30 | 1993-03-22 | Block copolymers from ionic catalysts |
US035,021 | 1993-03-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2158868A1 true CA2158868A1 (en) | 1994-09-29 |
Family
ID=21880132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002158868A Abandoned CA2158868A1 (en) | 1993-03-22 | 1994-03-21 | Block copolymers from ionic catalysts |
Country Status (5)
Country | Link |
---|---|
US (1) | US5391629A (en) |
EP (1) | EP0738290A1 (en) |
JP (1) | JPH09500150A (en) |
CA (1) | CA2158868A1 (en) |
WO (1) | WO1994021700A1 (en) |
Families Citing this family (181)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995027741A1 (en) * | 1994-04-11 | 1995-10-19 | Mitsui Petrochemical Industries, Ltd. | Process for producing propylene polymer composition, and propylene polymer composition |
WO1995027740A1 (en) * | 1994-04-11 | 1995-10-19 | Mitsui Petrochemical Industries, Ltd. | Process for producing propylene polymer composition, and propylene polymer composition |
US6291389B1 (en) | 1994-04-28 | 2001-09-18 | Exxonmobil Chemical Patents Inc. | Cationic polymerization catalysts |
JP3357186B2 (en) * | 1994-07-14 | 2002-12-16 | 三菱化学株式会社 | Method for producing propylene block copolymer |
US5883144A (en) | 1994-09-19 | 1999-03-16 | Sentinel Products Corp. | Silane-grafted materials for solid and foam applications |
US5929129A (en) | 1994-09-19 | 1999-07-27 | Sentinel Products Corp. | Crosslinked foamable compositions of silane-grafted, essentially linear polyolefins blended with polypropylene |
DE69528941T2 (en) | 1994-09-19 | 2003-09-18 | Sentinel Products Corp | Cross-linked foam structures of mainly linear polyolefins and manufacturing processes |
US5932659A (en) | 1994-09-19 | 1999-08-03 | Sentinel Products Corp. | Polymer blend |
JP3275223B2 (en) * | 1994-09-22 | 2002-04-15 | 科学技術振興事業団 | Polypropylene-b-poly (ethylene-co-propylene) and method for producing the same |
US6114443A (en) * | 1995-04-14 | 2000-09-05 | Exxon Research And Engineering Co. | Polyolefin blends compatibilized with a diblock copolymer |
US5677381A (en) * | 1995-07-07 | 1997-10-14 | Exxon Research And Engineering Company | Ethylene copolymer-monofunctional ionomer compositions |
US6225426B1 (en) * | 1996-04-10 | 2001-05-01 | Uniroyal Chemical Company, Inc. | Process for producing polyolefin elastomer employing a metallocene catalyst |
CA2203595A1 (en) | 1996-04-26 | 1997-10-26 | Robert F. Hurley | Cross-linked polyolefin tape |
US5844009A (en) | 1996-04-26 | 1998-12-01 | Sentinel Products Corp. | Cross-linked low-density polymer foam |
US5882776A (en) | 1996-07-09 | 1999-03-16 | Sentinel Products Corp. | Laminated foam structures with enhanced properties |
US5876813A (en) * | 1996-07-09 | 1999-03-02 | Senitnel Products Corp | Laminated foam structures with enhanced properties |
US5938878A (en) | 1996-08-16 | 1999-08-17 | Sentinel Products Corp. | Polymer structures with enhanced properties |
US6329459B1 (en) | 1996-09-23 | 2001-12-11 | Bridgestone Corporation | Extended syndiotactic polystyrene-elastomeric block copolymers |
US6191197B1 (en) | 1996-09-23 | 2001-02-20 | Bridgestone Corporation | Extended polymer compostion derived from blends of elastomers and syndiotactic polystyrene |
DE19641223A1 (en) * | 1996-09-27 | 1998-04-02 | Daramic Inc | Shoe and method for its manufacture |
KR100503523B1 (en) | 1997-02-07 | 2005-07-25 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Preparation of vinyl-containing macromers |
US6660809B1 (en) * | 1997-02-07 | 2003-12-09 | Exxonmobil Chemical Patents Inc. | Propylene polymers incorporating polyethylene macromers |
US5889128A (en) | 1997-04-11 | 1999-03-30 | Massachusetts Institute Of Technology | Living olefin polymerization processes |
WO1998046675A1 (en) * | 1997-04-14 | 1998-10-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Olefinic thermoplastic elastomer composition |
US6921794B2 (en) | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
US7026404B2 (en) * | 1997-08-12 | 2006-04-11 | Exxonmobil Chemical Patents Inc. | Articles made from blends made from propylene ethylene polymers |
US6635715B1 (en) | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US7232871B2 (en) * | 1997-08-12 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US6209227B1 (en) * | 1997-10-31 | 2001-04-03 | Kimberly-Clark Worldwide, Inc. | Shoe cover with slip-resistant sole |
US6184327B1 (en) | 1997-12-10 | 2001-02-06 | Exxon Chemical Patents, Inc. | Elastomeric propylene polymers |
US6197910B1 (en) | 1997-12-10 | 2001-03-06 | Exxon Chemical Patents, Inc. | Propylene polymers incorporating macromers |
DE69929678T2 (en) | 1998-03-04 | 2006-09-21 | Exxonmobil Chemical Patents Inc., Baytown | METHOD FOR INCREASING THE REVENUE IN EPDM POLYMERIZATIONS |
US6319998B1 (en) | 1998-03-04 | 2001-11-20 | Exxon Mobil Chemical Patents Inc. | Method for making polymer blends by using series reactors |
US6211300B1 (en) | 1998-04-10 | 2001-04-03 | Chisso Corporation | Propylene-ethylene block copolymer compositions and processes for production thereof |
DE69935815T2 (en) * | 1998-07-01 | 2007-12-27 | Exxonmobil Chemical Patents Inc., Baytown | Elastic mixture with crystal polymers and crystallizable polymers of propene |
CN1309670A (en) * | 1998-07-17 | 2001-08-22 | 拜尔公司 | Process for polymerizing cationically polymerizable olefin |
US6225427B1 (en) | 1998-10-15 | 2001-05-01 | Uniroyal Chemical Company, Inc. | Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst |
US20040002420A1 (en) * | 1998-10-23 | 2004-01-01 | Feng-Jung Wu | Stable catalysts and co-catalyst compositions formed from hydroxyaluminoxane and their use |
US6555494B2 (en) | 1998-10-23 | 2003-04-29 | Albemarle Corporation | Transition metal compounds having conjugate aluminoxate anions, their preparation and their use as catalyst components |
US6492292B2 (en) | 1998-10-23 | 2002-12-10 | Albemarle Corporation | Gelatinous compositions formed from hydroxyaluminoxane, solid compositions formed therefrom, and the use of such compositions as catalyst components |
US6160145A (en) * | 1998-10-23 | 2000-12-12 | Albemarle Corporation | Transition metal compounds having conjugate aluminoxate anions and their use as catalyst components |
US6812182B2 (en) | 1998-10-23 | 2004-11-02 | Albemarle Corporation | Compositions formed from hydroxyaluminoxane and their use as catalyst components |
US6462212B1 (en) | 1998-10-23 | 2002-10-08 | Albemarle Corporation | Transition metal compounds having conjugate aluminoxate anions and their use as catalyst components |
FR2791991B1 (en) * | 1999-03-24 | 2003-08-29 | Atochem Elf Sa | COPOLYMERIZATION PROCESS AND COPOLYMERS THUS OBTAINED |
EP1209171A4 (en) * | 1999-05-10 | 2004-04-21 | Jp Agency Of Industrialscience | Process for producing olefin living polymer |
US6271325B1 (en) | 1999-05-17 | 2001-08-07 | Univation Technologies, Llc | Method of polymerization |
WO2001016228A1 (en) | 1999-09-01 | 2001-03-08 | Exxon Chemical Patents Inc. | Breathable films and method for making |
US6380328B1 (en) | 1999-12-10 | 2002-04-30 | Univation Technologies, Llc | Catalyst systems and their use in a polymerization process |
US6265505B1 (en) | 1999-11-18 | 2001-07-24 | Univation Technologies, Llc | Catalyst system and its use in a polymerization process |
US6271323B1 (en) | 1999-10-28 | 2001-08-07 | Univation Technologies, Llc | Mixed catalyst compounds, catalyst systems and their use in a polymerization process |
US6300438B1 (en) | 1999-10-22 | 2001-10-09 | Univation Technolgies, Llc | Hafnium transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
US6300439B1 (en) | 1999-11-08 | 2001-10-09 | Univation Technologies, Llc | Group 15 containing transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
US6417304B1 (en) | 1999-11-18 | 2002-07-09 | Univation Technologies, Llc | Method of polymerization and polymer produced therefrom |
US6624107B2 (en) | 1999-10-22 | 2003-09-23 | Univation Technologies, Llc | Transition metal catalyst compounds having deuterium substituted ligand and catalyst systems thereof |
US6274684B1 (en) | 1999-10-22 | 2001-08-14 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US6281306B1 (en) * | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
CN1333032C (en) | 1999-12-22 | 2007-08-22 | 埃克森美孚化学专利公司 | Adhesive alpha-olefin inter-polymers |
CN1188435C (en) | 2000-01-26 | 2005-02-09 | 三井化学株式会社 | Olefin polymers and production process thereof |
FR2812645B1 (en) * | 2000-08-07 | 2003-09-19 | Solvay | OLEFIN POLYMER COMPOSITION, PROCESS FOR OBTAINING SAME, AND USE |
JP2002206007A (en) * | 2000-11-08 | 2002-07-26 | National Institute Of Advanced Industrial & Technology | Method for manufacturing olefinic block copolymer |
WO2002066540A2 (en) * | 2001-01-10 | 2002-08-29 | Basell Poliolefine Italia S.P.A. | Block copolymers and process for their preparation |
CA2332203A1 (en) * | 2001-01-24 | 2002-07-24 | Bayer Inc. | Process for making high molecular weight isobutylene polymers |
JP5156167B2 (en) * | 2001-04-12 | 2013-03-06 | エクソンモービル・ケミカル・パテンツ・インク | Propylene-ethylene polymer and production method |
DE60221834T2 (en) * | 2001-06-13 | 2008-06-26 | Beta Technologie Ag | MASS POLYMERIZATION REACTORS AND METHOD OF POLYMERIZATION |
WO2003000790A1 (en) * | 2001-06-22 | 2003-01-03 | Exxonmobil Chemical Patents, Inc. | Metallocene-produced very low density polyethylenes or linear lowdensity polyethylenes as impact modifiers |
US6833171B2 (en) | 2002-04-03 | 2004-12-21 | Kimberly-Clark Worldwide, Inc. | Low tack slip-resistant shoe cover |
US20040052690A1 (en) * | 2002-09-12 | 2004-03-18 | Eaton Gerald B. | Polymerization reactant injection system |
DE10244213A1 (en) | 2002-09-23 | 2004-04-01 | Bayer Ag | Process for the preparation of homo-, copolymers and / or block copolymers with metallocenes with a donor-acceptor interaction after living polymerization |
US20040096626A1 (en) * | 2002-11-14 | 2004-05-20 | Epoli-Espumas De Polietileno Sa | Layered structures with enhanced properties |
US7541412B2 (en) * | 2002-12-20 | 2009-06-02 | University Of Maryland, College Park | Process for preparation of polyolefins via degenerative transfer polymerization |
US7947776B2 (en) | 2003-08-25 | 2011-05-24 | Dow Global Technologies Llc | Aqueous dispersion, its production method, and its use |
US8779053B2 (en) | 2003-08-25 | 2014-07-15 | Dow Global Technologies Llc | Coating compositions |
US8722787B2 (en) | 2003-08-25 | 2014-05-13 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US9169406B2 (en) | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
US7803865B2 (en) * | 2003-08-25 | 2010-09-28 | Dow Global Technologies Inc. | Aqueous dispersion, its production method, and its use |
US8357749B2 (en) * | 2003-08-25 | 2013-01-22 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US8349929B2 (en) * | 2003-08-25 | 2013-01-08 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US8946329B2 (en) | 2003-08-25 | 2015-02-03 | Dow Global Technologies Llc | Coating compositions |
US7763676B2 (en) * | 2003-08-25 | 2010-07-27 | Dow Global Technologies Inc. | Aqueous polymer dispersions and products from those dispersions |
US8158711B2 (en) * | 2003-08-25 | 2012-04-17 | Dow Global Technologies Llc | Aqueous dispersion, its production method, and its use |
TW200517426A (en) | 2003-08-25 | 2005-06-01 | Dow Global Technologies Inc | Aqueous dispersion, its production method, and its use |
JP2005099712A (en) * | 2003-08-28 | 2005-04-14 | Sharp Corp | Driving circuit of display device, and display device |
US20050107559A1 (en) * | 2003-11-14 | 2005-05-19 | Coates Geoffrey W. | Ethylene-C4-C20-alkene copolymers |
CA2546075C (en) * | 2003-11-14 | 2010-12-14 | Exxonmobil Chemical Patents Inc. | Propylene-based elastomers and uses thereof |
BRPI0508173B1 (en) * | 2004-03-17 | 2016-03-15 | Dow Global Technologies Inc | multiblock copolymers, polymer, copolymer, a functional derivative, homogeneous polymer blend, process for preparing a propylene-containing multiblock copolymer and process for preparing a 4-methyl-1-pentene multiblock copolymer |
US7579408B2 (en) * | 2004-03-17 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins |
AR053693A1 (en) | 2004-03-17 | 2007-05-16 | Dow Global Technologies Inc | COMPOSITIONS OF ETHYLENE / ALFA-OLEFINE INTERPOLIMERO MULTIBLOCK SUITABLE FOR FILMS |
US7622179B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof |
US7863379B2 (en) * | 2004-03-17 | 2011-01-04 | Dow Global Technologies Inc. | Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers |
US7662881B2 (en) * | 2004-03-17 | 2010-02-16 | Dow Global Technologies Inc. | Viscosity index improver for lubricant compositions |
SG151301A1 (en) * | 2004-03-17 | 2009-04-30 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene multi- block copolymer formation |
US7687442B2 (en) * | 2004-03-17 | 2010-03-30 | Dow Global Technologies Inc. | Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils |
US7666918B2 (en) * | 2004-03-17 | 2010-02-23 | Dow Global Technologies, Inc. | Foams made from interpolymers of ethylene/α-olefins |
US7897689B2 (en) * | 2004-03-17 | 2011-03-01 | Dow Global Technologies Inc. | Functionalized ethylene/α-olefin interpolymer compositions |
US7622529B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility |
US7741397B2 (en) * | 2004-03-17 | 2010-06-22 | Dow Global Technologies, Inc. | Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof |
US7795321B2 (en) * | 2004-03-17 | 2010-09-14 | Dow Global Technologies Inc. | Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom |
BRPI0508148B1 (en) * | 2004-03-17 | 2015-09-01 | Dow Global Technologies Inc | ETHYLENE INTERPOLYMER IN MULTI-BLOCK, CROSS-LINKED DERIVATIVE AND COMPOSITION” |
US7608668B2 (en) * | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
US7582716B2 (en) * | 2004-03-17 | 2009-09-01 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack |
US7355089B2 (en) * | 2004-03-17 | 2008-04-08 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
US8273838B2 (en) * | 2004-03-17 | 2012-09-25 | Dow Global Technologies Llc | Propylene/α-olefins block interpolymers |
US7671131B2 (en) | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom |
US7671106B2 (en) * | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Cap liners, closures and gaskets from multi-block polymers |
US7803728B2 (en) * | 2004-03-17 | 2010-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of ethylene/α-olefins |
US7714071B2 (en) * | 2004-03-17 | 2010-05-11 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom |
US20060084755A1 (en) * | 2004-10-19 | 2006-04-20 | Good David J | Reactive hot melt adhesive with block acrylic copolymer |
EP1805229A1 (en) | 2004-10-28 | 2007-07-11 | Dow Gloval Technologies Inc. | Method of controlling a polymerization reactor |
US7300994B2 (en) * | 2004-11-22 | 2007-11-27 | Cornell Research Foundation, Inc. | Isotactic polypropylene containing polymers |
MY157904A (en) * | 2005-03-17 | 2016-08-15 | Dow Global Technologies Inc | FORMS MADE FROM INTERPOLYMERS OF ETHYLENE/a-OLEFINS |
US7989543B2 (en) * | 2005-03-17 | 2011-08-02 | Dow Global Technologies Llc | Adhesive and marking compositions made from interpolymers of ethylene/α-olefins |
KR101319131B1 (en) * | 2005-03-17 | 2013-10-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Fibers made from copolymers of ethylene/alpha-olefins |
US8084537B2 (en) * | 2005-03-17 | 2011-12-27 | Dow Global Technologies Llc | Polymer blends from interpolymers of ethylene/α-olefin with improved compatibility |
AU2006227619A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Llc | Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates |
CN101248135B (en) | 2005-06-24 | 2013-03-27 | 埃克森美孚化学专利公司 | Plasticized functionalized propylene copolymer adhesive composition |
CN101248133B (en) | 2005-06-24 | 2012-11-21 | 埃克森美孚化学专利公司 | Functionalized propylene copolymer adhesive composition |
SG165384A1 (en) * | 2005-09-15 | 2010-10-28 | Dow Global Technologies Inc | Control of polymer architecture and molecular weight distribution via multi-centered shuttling agent |
RU2008110052A (en) * | 2005-09-15 | 2009-09-20 | Дау Глобал Текнолоджиз Инк. (Us) | OLEPHIN BLOCK COPOLYMERS OBTAINED BY CATALYTIC USE OF POLYMERIZABLE Shuttle AGENT |
AR058496A1 (en) * | 2005-10-26 | 2008-02-06 | Dow Global Technologies Inc | ELASTIC ARTICLES OF MULTIPLE LAYERS |
US7709577B2 (en) | 2005-12-07 | 2010-05-04 | Exxonmobil Chemical Patents Inc. | Process of making polymer blends |
US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
KR20080080526A (en) * | 2005-12-09 | 2008-09-04 | 다우 글로벌 테크놀로지스 인크. | Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions |
US7601255B2 (en) | 2006-09-06 | 2009-10-13 | Chemtura Corporation | Process for removal of residual catalyst components |
CN101542031A (en) * | 2006-09-06 | 2009-09-23 | 陶氏环球技术公司 | Knit fabrics comprising olefin block interpolymers |
FR2905951A1 (en) * | 2006-09-20 | 2008-03-21 | Arkema France | PROCESS FOR THE PREPARATION OF A TRIBLOC COPOLYMER COMPRISING A SEMI-CRYSTALLINE AND / OR HYDROLYSABLE BLOCK, AN ELASTOMERIC BLOCK AND AN AMORPHOUS BLOCK |
EP2094753A2 (en) | 2006-11-30 | 2009-09-02 | Dow Global Technologies Inc. | Stretch fabrics with wrinkle resistance and garment |
CN101636530B (en) * | 2006-11-30 | 2013-04-17 | 陶氏环球技术有限责任公司 | Elastic fiber fabric comprising crosslinked ethylene polymer |
US7928022B2 (en) * | 2006-11-30 | 2011-04-19 | Dow Global Technologies Llc | Olefin block compositions for heavy weight stretch fabrics |
US7256240B1 (en) | 2006-12-22 | 2007-08-14 | Exxonmobil Chemical Patents Inc. | Process of making polymer blends |
CA2674991A1 (en) * | 2007-01-16 | 2008-07-24 | Dow Global Technologies Inc. | Cone dyed yarns of olefin block compositions |
ATE477923T1 (en) * | 2007-01-16 | 2010-09-15 | Dow Global Technologies Inc | ELASTIC FIBERS AND GARMENTS MADE OF OLEFIN BLOCK POLYMERS |
TW200900545A (en) * | 2007-01-16 | 2009-01-01 | Dow Global Technologies Inc | Colorfast fabrics and garments of olefin block compositions |
KR20100041818A (en) * | 2007-07-09 | 2010-04-22 | 다우 글로벌 테크놀로지스 인크. | Olefin block interpolymer composition suitable for fibers |
JP5996162B2 (en) * | 2007-07-13 | 2016-09-21 | ダウ グローバル テクノロジーズ エルエルシー | Catalytic olefin block copolymer having controlled block sequence distribution and at least one low crystalline hard block |
US20120184676A1 (en) * | 2007-08-31 | 2012-07-19 | Stichting Dutch Polymer Institute | Compatiblised polyolefin compositions |
EP2195349B1 (en) | 2007-09-13 | 2012-07-11 | ExxonMobil Research and Engineering Company | In-line process for producing plasticized polymers and plasticized polymer blends |
EP2203512A1 (en) * | 2007-09-28 | 2010-07-07 | Dow Global Technologies Inc. | Thermoplastic olefin composition with improved heat distortion temperature |
EP2799235A1 (en) * | 2007-10-22 | 2014-11-05 | Dow Global Technologies LLC | Multilayer films |
US7906588B2 (en) * | 2007-10-26 | 2011-03-15 | Exxonmobil Chemical Patents Inc. | Soft heterogeneous isotactic polypropylene compositions |
US9127151B2 (en) | 2009-04-28 | 2015-09-08 | Exxonmobil Chemical Patents Inc. | Polymer compositions having improved properties as viscosity index improvers and use thereof in lubricating oils |
US20120028865A1 (en) | 2010-07-28 | 2012-02-02 | Sudhin Datta | Viscosity Modifiers Comprising Blends of Ethylene-Based Copolymers |
US8378042B2 (en) | 2009-04-28 | 2013-02-19 | Exxonmobil Chemical Patents Inc. | Finishing process for amorphous polymers |
US20110059277A1 (en) * | 2009-09-04 | 2011-03-10 | Rainer Kolb | Elastomeric Surface Coatings for Plastic Articles |
US20100316808A1 (en) * | 2009-06-16 | 2010-12-16 | Gregory Keith Hall | Polyolefin Compositions for Coating Applications |
US20100316820A1 (en) * | 2009-06-16 | 2010-12-16 | Rainer Kolb | Composite Materials Comprising Propylene-Based Polymer Blend Coatings |
US9017593B2 (en) | 2009-06-16 | 2015-04-28 | Exxonmobil Chemical Patents Inc. | Composite materials comprising propylene-based polymer blend coatings |
WO2011011124A1 (en) | 2009-07-23 | 2011-01-27 | Exxonmobil Chemical Patents Inc. | Polypropylene-based elastomer coating compositions |
US9005739B2 (en) * | 2009-07-23 | 2015-04-14 | Exxonmobil Chemical Patents Inc. | Laminated articles and their production |
US8067652B2 (en) | 2009-08-13 | 2011-11-29 | Chemtura Corporation | Processes for controlling the viscosity of polyalphaolefins |
US9879160B2 (en) | 2009-10-29 | 2018-01-30 | Exxonmobil Chemical Patents Inc. | Pressure-sensitive hot melt adhesive compositions |
US8425924B2 (en) * | 2009-11-24 | 2013-04-23 | Exxonmobil Chemical Patents Inc. | Propylene compositions containing a pyrethroid and products made therefrom |
SG182320A1 (en) | 2010-01-22 | 2012-08-30 | Exxonmobil Chem Patents Inc | Ethylene copolymers, methods for their production, and use |
EP2528957B1 (en) | 2010-01-27 | 2014-10-22 | ExxonMobil Chemical Patents Inc. | Copolymers, compositions thereof, and methods for making them |
JP5753264B2 (en) | 2010-07-28 | 2015-07-22 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Viscosity modifiers containing blends of ethylene-based copolymers |
JP5651243B2 (en) | 2010-07-28 | 2015-01-07 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Viscosity modifiers containing blends of ethylene-based copolymers |
CN103025823B (en) | 2010-07-28 | 2016-05-25 | 埃克森美孚化学专利公司 | As ethene-base co-polymer composition and the manufacture method thereof of viscosity modifier |
US8557906B2 (en) | 2010-09-03 | 2013-10-15 | Exxonmobil Chemical Patents Inc. | Flame resistant polyolefin compositions and methods for making the same |
CN103154123B (en) | 2010-10-15 | 2016-01-27 | 埃克森美孚化学专利公司 | polypropylene-based adhesive compositions |
WO2013022103A1 (en) | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | Method for producing olefin block polymer using group 4 transition metal complex |
WO2013081080A1 (en) | 2011-12-02 | 2013-06-06 | 住友化学株式会社 | Method for producing olefin block polymer using plurality of types of transition metal catalysts |
JP6088548B2 (en) * | 2012-02-03 | 2017-03-01 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Method for producing a polymer composition useful as an oil modifier |
US10316176B2 (en) | 2012-02-03 | 2019-06-11 | Exxonmobil Chemical Patents Inc. | Polymer compositions and methods of making them |
US9139794B2 (en) | 2012-02-03 | 2015-09-22 | Exxonmobil Chemical Patents Inc. | Process for the production of polymeric compositions useful as oil modifiers |
BR112015015408B1 (en) | 2012-12-28 | 2021-07-20 | Dow Global Technologies Llc | COATING COMPOSITION, E, COATED ARTICLE |
WO2014105466A2 (en) | 2012-12-28 | 2014-07-03 | Dow Global Technologies Llc | A coating composition and articles made therefrom |
WO2015122414A1 (en) | 2014-02-13 | 2015-08-20 | 三井化学株式会社 | Method for producing ethylene/alpha-olefin copolymer |
JP6702854B2 (en) | 2014-02-28 | 2020-06-03 | 三井化学株式会社 | CROSSLINKED PRODUCT, PRODUCTION METHOD AND USE THEREOF, AND ETHYLENE COPOLYMER |
JP6253765B2 (en) | 2014-03-28 | 2017-12-27 | 三井化学株式会社 | Olefin resin and process for producing the same |
KR101814320B1 (en) | 2014-03-28 | 2018-01-02 | 미쓰이 가가쿠 가부시키가이샤 | ETHYLENE/α-OLEFIN COPOLYMER AND LUBRICATING OIL |
CN106795449B (en) | 2014-09-10 | 2020-08-07 | 三井化学株式会社 | Lubricating oil composition |
KR101889669B1 (en) | 2014-09-11 | 2018-08-17 | 미쓰이 가가쿠 가부시키가이샤 | Method for producing olefin (co)polymer containing constituent unit derived from 1-butene |
KR101720920B1 (en) | 2014-12-09 | 2017-03-28 | 미쯔이가가꾸가부시끼가이샤 | Propylene-based resin composition |
KR101840993B1 (en) | 2015-03-20 | 2018-03-21 | 미쓰이 가가쿠 가부시키가이샤 | Thermoplastic elastomer composition, use thereof, production method thereof, ethylene /? - olefin / non-conjugated polyene copolymer and uses thereof |
SG11201802756QA (en) | 2015-12-16 | 2018-06-28 | Exxonmobil Chemical Patents Inc | Low crystalline polymer compositions |
JP2019513307A (en) | 2016-03-30 | 2019-05-23 | エクソンモービル・ケミカル・パテンツ・インク | Thermoplastic vulcanizate composition for solar cell applications |
CA3018952C (en) | 2016-03-31 | 2023-06-27 | Exxonmobil Chemical Patents Inc. | Low crystalline polymer compositions prepared in a dual reactor |
CN110072981B (en) | 2017-01-16 | 2022-02-25 | 三井化学株式会社 | Lubricating oil composition for automobile gears |
EP3584075A4 (en) | 2017-02-20 | 2020-12-30 | Mitsui Chemicals, Inc. | Laminate |
EP3714025A1 (en) | 2017-11-21 | 2020-09-30 | ExxonMobil Chemical Patents Inc. | Bimodal copolymer compositions useful as oil modifiers |
US20190177639A1 (en) | 2017-12-13 | 2019-06-13 | Chevron Oronite Company Llc | Bimodal copolymer compositions useful as oil modifiers and lubricating oils comprising the same |
US11905348B2 (en) | 2018-03-20 | 2024-02-20 | Mitsui Chemicals, Inc. | Ethylene/alpha-olefin/non-conjugated polyene copolymer, method for producing the same, and use thereof |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4141847A (en) * | 1977-05-11 | 1979-02-27 | Shell Oil Company | Star-shaped polymer reacted with dicarboxylic acid and amine as dispersant viscosity index improver |
DE3171570D1 (en) * | 1980-06-02 | 1985-09-05 | Hercules Inc | Preparation of block copolymers using dimethyl-bis(methylcyclopentadienyl)titanium |
US4408019A (en) * | 1981-06-11 | 1983-10-04 | Hercules Incorporated | Block copolymers of ethylene and propylene |
JPS58162620A (en) * | 1982-03-23 | 1983-09-27 | Mitsubishi Petrochem Co Ltd | Olefin block copolymer |
US4522982A (en) * | 1983-06-06 | 1985-06-11 | Exxon Research & Engineering Co. | Isotactic-stereoblock polymers of alpha-olefins and process for producing the same |
US4959436A (en) * | 1983-06-15 | 1990-09-25 | Exxon Research And Engineering Co. | Narrow MWD alpha-olefin copolymers |
JPH0826108B2 (en) * | 1986-09-03 | 1996-03-13 | 三菱化学株式会社 | Method for producing propylene block copolymer |
DE3640924A1 (en) * | 1986-11-29 | 1988-06-01 | Hoechst Ag | 1-OLEFIN STEREOBLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
PL276385A1 (en) * | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
IL85097A (en) * | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
US5155080A (en) * | 1988-07-15 | 1992-10-13 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
DE3826075A1 (en) * | 1988-07-30 | 1990-02-01 | Hoechst Ag | 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
CA2027145C (en) * | 1989-10-10 | 2002-12-10 | Michael J. Elder | Metallocene catalysts with lewis acids and aluminum alkyls |
DE69026679T3 (en) * | 1989-10-30 | 2005-10-06 | Fina Technology, Inc., Houston | Addition of alkylaluminum to improve a metallocene catalyst |
ATE120768T1 (en) * | 1989-10-30 | 1995-04-15 | Fina Technology | PRODUCTION OF METALLOCE CATALYSTS FOR OLEFIN POLYMERIZATION. |
DE3942364A1 (en) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | METHOD FOR PRODUCING A POLYPROPYLENE MOLDING MATERIAL |
DE3942365A1 (en) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | METHOD FOR PRODUCING A POLYPROPYLENE MOLDING MATERIAL |
CA2075035A1 (en) * | 1990-02-09 | 1991-08-10 | Howard W. Turner | Block copolymers from ionic catalysts |
DE4130429A1 (en) * | 1991-09-13 | 1993-03-18 | Basf Ag | METHOD FOR PRODUCING MULTI-PHASE BLOCK COPOLYMERISATS BASED ON ALK-1-ENEN |
-
1993
- 1993-03-22 US US08/035,021 patent/US5391629A/en not_active Expired - Lifetime
-
1994
- 1994-03-21 JP JP6521310A patent/JPH09500150A/en active Pending
- 1994-03-21 EP EP94912830A patent/EP0738290A1/en not_active Withdrawn
- 1994-03-21 WO PCT/US1994/003060 patent/WO1994021700A1/en not_active Application Discontinuation
- 1994-03-21 CA CA002158868A patent/CA2158868A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO1994021700A1 (en) | 1994-09-29 |
US5391629A (en) | 1995-02-21 |
JPH09500150A (en) | 1997-01-07 |
EP0738290A1 (en) | 1996-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5391629A (en) | Block copolymers from ionic catalysts | |
JP4218988B2 (en) | Thermoplastic elastomer composition derived from branched olefin copolymer | |
EP0987279B1 (en) | Branched polypropylene | |
EP3489264B1 (en) | Chain shuttling agents and their use for the preparation of block copolymers | |
JP2888639B2 (en) | Ethylene / branched olefin copolymer | |
EP0513216B1 (en) | Block copolymers from ionic catalysts | |
US6613845B1 (en) | Propylene/ethylene-α-olefin block copolymer and process for producing the same | |
CN108047568B (en) | Molded article and propylene resin composition | |
US6414102B2 (en) | Linear copolymers of alpha-olefins and divinylbenzene having narrow molecular weight and composition distributions, graft copolymers derived therefrom, and process for preparing same | |
CN101331164B (en) | Control of polymer architecture and molecular weight distribution via multi-centered shuttling agent | |
JPH09316147A (en) | Propylene/ethylene-alpha-olefin block copolymer and its production | |
MXPA06010481A (en) | Catalyst composition comprising shuttling agent for higher olefin multi-block copolymer formation. | |
JP2003516452A (en) | Method for preparing crosslinked blend of amorphous polymer and crystalline polymer | |
KR101850233B1 (en) | Olefin-based resin, method for producing same and propylene-based resin composition | |
US7851540B2 (en) | Resin composition and molded body made from same | |
EP0476148B1 (en) | Propylene copolymer | |
JPS62121711A (en) | Lowly crystalline ethylene random copolymer and its production | |
US6479600B2 (en) | Polyolefin containing a terminal phenyl or substituted phenyl group and process for preparing same | |
JPH11504973A (en) | Polymerization of crystalline copolymers of olefins and cyclic olefins | |
US6319990B1 (en) | Functionalized thermoplastic elastomer | |
JP4226088B2 (en) | Propylene copolymer | |
JPH10158351A (en) | Propylene/ethylene-alpha-olefin-based block copolymer | |
JPH02135243A (en) | Highly rigid polypropylene composition | |
US6617410B2 (en) | Propylene copolymers containing styrene units | |
WO2020257627A1 (en) | Synthesis of long-chain branched polypropylene using heterogenous ziegler-natta catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Dead |