WO1997011098A1 - Olefin polymers which contain polar groups, and a method for their manufacture - Google Patents

Olefin polymers which contain polar groups, and a method for their manufacture Download PDF

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Publication number
WO1997011098A1
WO1997011098A1 PCT/FI1996/000494 FI9600494W WO9711098A1 WO 1997011098 A1 WO1997011098 A1 WO 1997011098A1 FI 9600494 W FI9600494 W FI 9600494W WO 9711098 A1 WO9711098 A1 WO 9711098A1
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Prior art keywords
polymerization
zrcl
ethylene
olefin
bis
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Application number
PCT/FI1996/000494
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French (fr)
Inventor
Barbro LÖFGREN
Päivi Aaltonen
Pekka Knuuttila
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Borealis A/S
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Priority to AU69899/96A priority Critical patent/AU6989996A/en
Publication of WO1997011098A1 publication Critical patent/WO1997011098A1/en

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    • 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
    • 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
    • C08F210/02—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
    • 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

Definitions

  • Olefin polymers which contain polar groups, and a method for their manufacture
  • the invention relates to novel olefin copolymers which contain functional groups and to a method for their manufacture.
  • the linking of monomers which contain functional groups to a hydrocarbon polymer chain signifies the creating of a usable method for the modification of the chemical and physical properties of olefins.
  • monomers containing functional groups it is possible to improve properties such as adhesion, dyeability, printability and permeability.
  • a functional group provides a possibility for graft polymerization and thereby for uses such as compatibilization of blends containing polyolefins.
  • the Ziegler-Natta catalyst system is commonly used in the polymerization and copolymerization of olefins, but one of the major limitations of these conventional catalysts is that they are not suited for use in conjunction with monomers containing polar groups. Ziegler-Natta catalysts rather form a complex with the electron pair of a heteroatom, and thus in polymerization they rapidly deactivate the active centers by forming a stable complex with the functional group.
  • a polar monomer resembles alpha-olefin, the greater is its potential for becoming polymerized by the same active centers as olefins.
  • the inventors have shown that comonomers which contain heteroatoms can be used for the polymerization of polyolefin. It is known that Lewis acid components (Zr, Al) present in the catalyst tend to form a complex with the unbound electron pairs of heteroatoms, thus causing deactivation of the catalyst.
  • this non-desirable interaction can be minimized by certain methods, such as (a) by isolating the double bond from the heteroatoms by means of a longer hydrocarbon chain; (b) by adding a steric barrier around the heteroatom; (c) by decreasing the electron donor character of the heteroatom, for example, by linking to it or in its vicinity a group which attracts electrons; (d) by selecting catalyst components which are inert to functional groups; (e) by precomplexing the functional monomer by using a Lewis acid; or (f) by using a polar solvent which becomes polarized with the active center but allows the polymerization of the vinyl monomer.
  • US patent publication 5, 286, 800 discloses the polymerization, with alpha-olefins, of comonomers containing functional groups. In these polymerizations there are used borane monomers which are converted, by reactions after the polymerization step, into polyolefins which contain functional groups.
  • An object of the present invention is to provide novel copolymers of olefins and monomers containing functional groups. Furthermore, one object of the invention is a method in which the catalyst system has as high an activity as possible in the presence of a polar group. One object of the invention is also to provide for the copolymerization of olefins a method in which the copolymerization with a polar comonomer takes place in one step, without any pretreatment or postmodif ication. A further object according to the invention is to provide functional polyolefins in which the molar masses remain relatively high and the molar mass distributions are wide. In the Applicant's previous application FI 951970, this object was achieved by using as the functional monomer 2-methyl-3-buten-l-ol, 3-methyl-3-buten-l-ol and 5- hexen-1-ol.
  • the olefin copolymer according to the invention prepared by polymerizing an olefin which contains 2—5 carbon atoms with a monomer which contains a functional group, is characterized in that the functional monomer is 9-methyl decenoate.
  • the olefin used in the manufacture of copolymers according to the invention consists of olefins containing 2—6 carbon atoms.
  • ethylene or propylene is used, but olefins having a longer carbon chain, such as l-butene, pentene and 1 -hexene, may be used just as well.
  • the catalyst used is a metallocene-type catalyst.
  • the metallocene may be a metallocene of any type.
  • suitable metallocene compounds include compounds having the formula (Cp) m R n MR' 0 X p , where Cp is an unsubstituted or substituted and/or fused homo- or heterocyclopentadienyl, R is a group containing 1-4 carbon atoms and serving as a bridge between two Cp rings, M is a transition metal belonging to group 4A, 5A or 6A (Hubbard), R' is a C j -C 2 hydrocarbyl or hydroxy- carbyl group, and X is a halogen, m being 1—3, n being 0 or p being 0—3, and the sum m+n+p corresponding to the state of oxidation of the transition metal M.
  • the transition metal is preferably zirconium or hafnium, most preferably zirconium.
  • metallocene compounds include bis(n-butylcyclopentadienyl) zirconium dichloride, 1 ,2-ethylene-bis(indenyl) zirconium dichloride, and 1,2- ethylene-bis(indenyl) hafnium dichloride.
  • the polymerization activity of the catalyst can also be increased by using activators such as alumoxane.
  • activators such as alumoxane.
  • One method is to add the alumoxane to the metallocene compo ⁇ nent either before, simultaneously or after the metallocene.
  • Another method is to add the activator directly into the polymerization reactor.
  • Suitable activators include alumoxane compounds having the formula R-(Al(R)-O) n - A1R2 or (-Al(R)-O-) m ,where n is 1-40, m is 3-40, and R is a C r C 8 alkyl group.
  • R is a methyl group.
  • the support used may be any porous or inert support, such as silica or alumina or mixtures thereof.
  • the polymerization may be carried out by any method, for example by slurry polymerization or gas phase polymerization.
  • the polymerization may be carried out, for example, at a temperature of 60-100 °C and under a pressure of 1-100 bar.
  • the partial pressure of olefin in the reactor may vary within the range 1-3 bar and the amount of comonomer within the range 0.5—10 mmol.
  • n-butylcyclopentadienyl) zirconium dichloride (n-butCp) 2 )ZrCl 2 dicyclopenta- dienyl zirconium dichloride Cp 2 ZrCl 2 , l,2-ethylene-bis(indenyl) zirconium di ⁇ chloride Et(Ind) 2 ZrCl 2 , (dimethylsilyl-bis(lH-indenyl)) zirconium dichloride Me Si(Ind) 2 ZrCl 2 and methylalumoxane (MAO) were of a commercial grade and were not purified separately.
  • n-butCp) 2 )ZrCl 2 dicyclopenta- dienyl zirconium dichloride Cp 2 ZrCl 2 , l,2-ethylene-bis(indenyl) zirconium di ⁇ chloride Et(Ind) 2 ZrCl 2 , (dimethylsilyl-bis(lH-in
  • Polymerization-grade ethylene and propylene and the n-heptane and toluene serving as the medium were purified by feeding them through a column series to eliminate any moisture and oxygen residues.
  • the comonomer methy 1-9-decenoate was of own production.
  • Ethylene copolymerizations were carried out in a 0.5 dm 3 autoclave at a temperature of 60 °C for 40 minutes, and the reaction medium used was n-heptane.
  • the medium n-heptane (350 cm 3 ) was fed into a vacuumized reactor, blanketed with nitrogen and equipped with a stirrer. The rotation velocity of the stirrer was con ⁇ stantly 400 rotations per minute.
  • ethylene was monitored by means of a mass flow controller. After equilibrium had been reached, polymerization was started by pumping the catalyst into the reactor. The partial pressure of ethylene or propylene was maintained constant (2.5 bar ethylene overpressure) by means of an electronic pressure controller and a solenoid valve, and the reactor temperature was maintained constant ( ⁇ 0.1 °C). The conver ⁇ sion was maintained low in order that it could be assumed that the concentration in the reactor remained constant. At 40 minutes, reactor pressure was released and the obtained polymer product was washed with a solution of ethanol and hydrochloric acid, and was dried.
  • Propylene copolymerizations were carried in the same manner as ethylene copolymerizations except that the medium used was toluene in an amount of 300 cm 3 , the polymerization time was 60 minutes and the polymerization tempera- ture was 30 °C, and the propylene overpressure was 3.0 bar.
  • the catalyst used was l,2-ethylene-bis(indenyl) zirconium dichloride.
  • compositions of the copolymers of ethylene and the functional monomer were determined by using a Jeol NMR spectrometer.
  • the melting points and enthalpies were determined from the peak of the DSC curve by using a Perkin Elmer DSC-7 instrument.
  • the DSC measurements were carried out by reheating the sample to 180 °C at heating rates of 2 and 10 °C/min.
  • the molar masses and the molar mass distributions were measured using a Waters- type ALC/GPC 150 instrument in which there had been installed 3 TOSOH mixed- bed columns in which the polystyrene barrier limit was 4 x 10 8 at a temperature of 135 °C.
  • the solvent used was 1,2,4-trichlorobenzene having a flow rate of 1.0 ml/min.
  • Ethylene was copolymerized with methyl-9-decenoate.
  • the catalysts used were combinations (n-butCp) 2 ZrCl 2 /MAO, Cp 2 ZrCl 2 /MAO, Et(Ind) 2 ZrCl 2 /MAO and Me 2 Si(Ind) 2 ZrCl 2 /MAO.
  • the polymerization conditions and some product properties are shown in Table 1.
  • Copolymerizations of propylene and methyl-9-decenoate were carried out by using the combination l ,2-ethylene-bis(indenyl) zirconium chloride/MAO.
  • the polymerization conditions and some properties of the product are shown in Table 2.

Abstract

An olefin copolymer prepared by polymerizing an olefin which contains 2-5 carbon atoms with a monomer which contains a functional group, the functional monomer being 9-methyl decenoate.

Description

Olefin polymers which contain polar groups, and a method for their manufacture
The invention relates to novel olefin copolymers which contain functional groups and to a method for their manufacture.
The linking of monomers which contain functional groups to a hydrocarbon polymer chain signifies the creating of a usable method for the modification of the chemical and physical properties of olefins. By using monomers containing functional groups it is possible to improve properties such as adhesion, dyeability, printability and permeability. Furthermore, a functional group provides a possibility for graft polymerization and thereby for uses such as compatibilization of blends containing polyolefins.
The Ziegler-Natta catalyst system is commonly used in the polymerization and copolymerization of olefins, but one of the major limitations of these conventional catalysts is that they are not suited for use in conjunction with monomers containing polar groups. Ziegler-Natta catalysts rather form a complex with the electron pair of a heteroatom, and thus in polymerization they rapidly deactivate the active centers by forming a stable complex with the functional group.
The more a polar monomer resembles alpha-olefin, the greater is its potential for becoming polymerized by the same active centers as olefins. The inventors have shown that comonomers which contain heteroatoms can be used for the polymerization of polyolefin. It is known that Lewis acid components (Zr, Al) present in the catalyst tend to form a complex with the unbound electron pairs of heteroatoms, thus causing deactivation of the catalyst. In practice this non-desirable interaction can be minimized by certain methods, such as (a) by isolating the double bond from the heteroatoms by means of a longer hydrocarbon chain; (b) by adding a steric barrier around the heteroatom; (c) by decreasing the electron donor character of the heteroatom, for example, by linking to it or in its vicinity a group which attracts electrons; (d) by selecting catalyst components which are inert to functional groups; (e) by precomplexing the functional monomer by using a Lewis acid; or (f) by using a polar solvent which becomes polarized with the active center but allows the polymerization of the vinyl monomer.
If deactivation can be successfully prevented by one or several of the above-men¬ tioned methods, the copolymerization of functional monomers will become more popular than it is today.
US patent publication 5, 286, 800 discloses the polymerization, with alpha-olefins, of comonomers containing functional groups. In these polymerizations there are used borane monomers which are converted, by reactions after the polymerization step, into polyolefins which contain functional groups.
In Japanese patent publication 61 72 447, the comonomer used is 10-undecen-l-ol which has been pretreated with tri-isobutyl aluminum for 3 hours at room tempera¬ ture before polymerization.
An object of the present invention is to provide novel copolymers of olefins and monomers containing functional groups. Furthermore, one object of the invention is a method in which the catalyst system has as high an activity as possible in the presence of a polar group. One object of the invention is also to provide for the copolymerization of olefins a method in which the copolymerization with a polar comonomer takes place in one step, without any pretreatment or postmodif ication. A further object according to the invention is to provide functional polyolefins in which the molar masses remain relatively high and the molar mass distributions are wide. In the Applicant's previous application FI 951970, this object was achieved by using as the functional monomer 2-methyl-3-buten-l-ol, 3-methyl-3-buten-l-ol and 5- hexen-1-ol.
The olefin copolymer according to the invention, prepared by polymerizing an olefin which contains 2—5 carbon atoms with a monomer which contains a functional group, is characterized in that the functional monomer is 9-methyl decenoate.
The olefin used in the manufacture of copolymers according to the invention consists of olefins containing 2—6 carbon atoms. Preferably, ethylene or propylene is used, but olefins having a longer carbon chain, such as l-butene, pentene and 1 -hexene, may be used just as well.
The catalyst used is a metallocene-type catalyst. The metallocene may be a metallocene of any type. Thus, suitable metallocene compounds include compounds having the formula (Cp)mRnMR'0Xp, where Cp is an unsubstituted or substituted and/or fused homo- or heterocyclopentadienyl, R is a group containing 1-4 carbon atoms and serving as a bridge between two Cp rings, M is a transition metal belonging to group 4A, 5A or 6A (Hubbard), R' is a Cj-C2 hydrocarbyl or hydroxy- carbyl group, and X is a halogen, m being 1—3, n being 0 or p being 0—3, and the sum m+n+p corresponding to the state of oxidation of the transition metal M. The transition metal is preferably zirconium or hafnium, most preferably zirconium.
Examples of suitable metallocene compounds include bis(n-butylcyclopentadienyl) zirconium dichloride, 1 ,2-ethylene-bis(indenyl) zirconium dichloride, and 1,2- ethylene-bis(indenyl) hafnium dichloride.
The polymerization activity of the catalyst can also be increased by using activators such as alumoxane. One method is to add the alumoxane to the metallocene compo¬ nent either before, simultaneously or after the metallocene. Another method is to add the activator directly into the polymerization reactor. Suitable activators include alumoxane compounds having the formula R-(Al(R)-O)n- A1R2 or (-Al(R)-O-)m,where n is 1-40, m is 3-40, and R is a CrC8 alkyl group. Preferably R is a methyl group.
The support used may be any porous or inert support, such as silica or alumina or mixtures thereof.
The polymerization may be carried out by any method, for example by slurry polymerization or gas phase polymerization. Thus the polymerization may be carried out, for example, at a temperature of 60-100 °C and under a pressure of 1-100 bar. The partial pressure of olefin in the reactor may vary within the range 1-3 bar and the amount of comonomer within the range 0.5—10 mmol.
The invention is described below in greater detail, with reference to the accompany - ing examples.
Materials
Bis(n-butylcyclopentadienyl) zirconium dichloride (n-butCp)2)ZrCl2, dicyclopenta- dienyl zirconium dichloride Cp2ZrCl2, l,2-ethylene-bis(indenyl) zirconium di¬ chloride Et(Ind)2ZrCl2, (dimethylsilyl-bis(lH-indenyl)) zirconium dichloride Me Si(Ind)2ZrCl2 and methylalumoxane (MAO) were of a commercial grade and were not purified separately. Polymerization-grade ethylene and propylene and the n-heptane and toluene serving as the medium were purified by feeding them through a column series to eliminate any moisture and oxygen residues. The comonomer methy 1-9-decenoate was of own production.
Polymerization
Ethylene copolymerizations were carried out in a 0.5 dm3 autoclave at a temperature of 60 °C for 40 minutes, and the reaction medium used was n-heptane. The medium n-heptane (350 cm3) was fed into a vacuumized reactor, blanketed with nitrogen and equipped with a stirrer. The rotation velocity of the stirrer was con¬ stantly 400 rotations per minute. The comonomer was added in one batch under nitrogen blanket, and the cocatalyst MAO (Al/Zr = 3000 mol/mol) was added at the beginning of the polymerization by using a pump. After the polymerization tempera¬ ture had been reached, ethylene was fed into the reactor. The consumption of ethylene was monitored by means of a mass flow controller. After equilibrium had been reached, polymerization was started by pumping the catalyst into the reactor. The partial pressure of ethylene or propylene was maintained constant (2.5 bar ethylene overpressure) by means of an electronic pressure controller and a solenoid valve, and the reactor temperature was maintained constant (±0.1 °C). The conver¬ sion was maintained low in order that it could be assumed that the concentration in the reactor remained constant. At 40 minutes, reactor pressure was released and the obtained polymer product was washed with a solution of ethanol and hydrochloric acid, and was dried.
Propylene copolymerizations were carried in the same manner as ethylene copolymerizations except that the medium used was toluene in an amount of 300 cm3, the polymerization time was 60 minutes and the polymerization tempera- ture was 30 °C, and the propylene overpressure was 3.0 bar. The catalyst used was l,2-ethylene-bis(indenyl) zirconium dichloride.
Characterization of the polymers
The compositions of the copolymers of ethylene and the functional monomer were determined by using a Jeol NMR spectrometer.
The melting points and enthalpies were determined from the peak of the DSC curve by using a Perkin Elmer DSC-7 instrument. The DSC measurements were carried out by reheating the sample to 180 °C at heating rates of 2 and 10 °C/min. The molar masses and the molar mass distributions were measured using a Waters- type ALC/GPC 150 instrument in which there had been installed 3 TOSOH mixed- bed columns in which the polystyrene barrier limit was 4 x 108 at a temperature of 135 °C. The solvent used was 1,2,4-trichlorobenzene having a flow rate of 1.0 ml/min.
Examples
Ethylene was copolymerized with methyl-9-decenoate. The catalysts used were combinations (n-butCp)2ZrCl2/MAO, Cp2ZrCl2/MAO, Et(Ind)2ZrCl2/MAO and Me2Si(Ind)2ZrCl2/MAO. The polymerization conditions and some product properties are shown in Table 1.
Table 1
Ex. Catalyst Comonomer Activity Molar mass Mv/Mn Tm
No. 2 mg amount kg/g cat h Mw 10"3 °C mmol
1 (n-butCp)2ZrCl2 1 5,0 98 3, 1 131 ,5
2 » 2 4, 1 139 3,8 134,5
3 » 3 2, 1 131 3,9 134,0
* 4 « 4 0,2 60 5,2 133,3
5 Cp2ZrCl2 1 2,5 120 4,6 130,4
6 Et(Ind)2ZrCl2 1 1.9 265 4,8 130,8
7 Me2Si(Ind)2ZrCl2 1 1 , 1 104 2,9 128, 1
polymerization temperature 60 °C polymerization time 40 min ethylene pressure 2.5 bar
Zr = 4.94 x IO"2 mol
Al (as MAO) = 1.98 x IO"2 mol
* Composition of the ethylene copolymer Comonomer Comonomer feed In the copolymer mmol % wt. molar %
methyl-9-decenoate 4 1.1 0.2
Activity decreases as the amount of comonomer fed in increases.
Copolymerizations of propylene and methyl-9-decenoate were carried out by using the combination l ,2-ethylene-bis(indenyl) zirconium chloride/MAO. The polymerization conditions and some properties of the product are shown in Table 2.
Table 2
Ex. Catalyst Comonomer Activity Molar mass Mv/Mn Tm No. 2 mg amount kg/g cat h Mw- 10"3 °C mmol
8 Et(Ind)2ZrCl2 0,5 3,9 33 1 ,8 135,5
Al/Zr 4000 mol/mol
MAO solution 12.4 ml (7.0 cm) from burette
Propylene 3.0 bar
30 °C
300 ml (261 g) toluene
400 rpm
60 min

Claims

Claims
1. An olefin copolymer prepared by polymerizing an olefin containing 2—5 carbon atoms with a monomer containing a functional group, characterized in that the functional monomer is 9-methyl decenoate.
2. An olefin copolymer according to Claim 1, characterized in that the olefin has been selected from the group ethylene and propylene.
3. An olefin copolymer according to Claim 1—2, characterized in that it has been prepared by using a metallocene catalyst.
4. An olefin copolymer according to any of the above claims, characterized in that the metallocene is selected from the group bis(n-butylcyclopentadienyl) zirconium chloride (n-butCp)2)ZrCl2, dicyclopentadienyl zirconium dichloride Cp2ZrCl2, 1,2- ethylene-bis(indenyl) zirconium dichloride Et(Ind)2ZrCl2, (dimethylsilyl-bis(lH- indenyl) zirconium dichloride Me2Si(Ind)2ZrCl2.
5. An olefin copolymer according to Claim 4, characterized in that the polymerization has been carried out using methylalumoxane (MAO) as an activator.
PCT/FI1996/000494 1995-09-21 1996-09-19 Olefin polymers which contain polar groups, and a method for their manufacture WO1997011098A1 (en)

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FI954475 1995-09-21
FI954475A FI954475A (en) 1995-09-21 1995-09-21 Olefin polymers containing polar groups and processes for their preparation

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EP1186619A2 (en) * 2000-09-07 2002-03-13 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition contaning the copolymer, and uses thereof
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
WO2009123663A1 (en) 2007-12-20 2009-10-08 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
US7741420B2 (en) 2004-07-14 2010-06-22 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US8138269B2 (en) 2007-12-20 2012-03-20 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
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US9012385B2 (en) 2012-02-29 2015-04-21 Elevance Renewable Sciences, Inc. Terpene derived compounds
US9315748B2 (en) 2011-04-07 2016-04-19 Elevance Renewable Sciences, Inc. Cold flow additives
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EP1186619A2 (en) * 2000-09-07 2002-03-13 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition contaning the copolymer, and uses thereof
EP1186619A3 (en) * 2000-09-07 2003-10-29 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition contaning the copolymer, and uses thereof
US7393907B2 (en) 2000-09-07 2008-07-01 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof
US7714087B2 (en) 2000-09-07 2010-05-11 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US7354979B2 (en) 2002-09-20 2008-04-08 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7807769B2 (en) 2002-09-20 2010-10-05 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
US7741420B2 (en) 2004-07-14 2010-06-22 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
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