CA1188044A - Process for producing random ethylene terpolymers - Google Patents
Process for producing random ethylene terpolymersInfo
- Publication number
- CA1188044A CA1188044A CA000337801A CA337801A CA1188044A CA 1188044 A CA1188044 A CA 1188044A CA 000337801 A CA000337801 A CA 000337801A CA 337801 A CA337801 A CA 337801A CA 1188044 A CA1188044 A CA 1188044A
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- CA
- Canada
- Prior art keywords
- mole
- carbon atoms
- titanium
- alpha
- ethylene
- 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.)
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Classifications
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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
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
Abstract
Abstract of the Disclosure A process for producing a random terpolymer of ethylene and alpha-olefins having at least 3 carbon atoms in the presence of a catalyst composed of (1) a titanium catalyst component containing at least magnesium and titanium and (2) an organoaluminum catalyst component in a hydrocarbon solvent at a temperature above the melting point of the terpolymer formed, under such condi-tions that the resulting copolymer dissolves in the hydrocarbon solvent;
characterized in that said terpolymer consists essentially of (A) more than 90 mole% to 99.5 mole% of ethylene, (B) 0.2 mole% to 9.8 mole% of an alpha-olefin with 3 or 4 carbon atoms, and (C) 0.2 mole% to 9.8 mole% of an alpha-olefin with 5 to 18 carbon atoms, the total of the proportions of the monomers (A), (B) and (C) being 100 mole%.
characterized in that said terpolymer consists essentially of (A) more than 90 mole% to 99.5 mole% of ethylene, (B) 0.2 mole% to 9.8 mole% of an alpha-olefin with 3 or 4 carbon atoms, and (C) 0.2 mole% to 9.8 mole% of an alpha-olefin with 5 to 18 carbon atoms, the total of the proportions of the monomers (A), (B) and (C) being 100 mole%.
Description
PROCESS FOR PRODUCING RANDOM ET~YLENE TERPOLYMERS
This invention relates to a process for producing a random ethylene terpolymer whic]l has non-rubbery and plastic properties, and excellent tear strength, impact strength and transparency without a substantial deterioration in its favorable mechanical properties, and which is suitable for production of melt-shaped articles such as films or hollow containers.
Iligh-pressure polyethylene has been considered to possess relatively good transparency and used in the production of melt-shaped articles such as films, sheets and hollow containers. Films of high-pressure polyethylene, how-10 ever, have only limited applications because of their unsatisfactory tearstrength and impact strength and their difficulty of attaining small thicknesses.
Furthermore, films having superior transparency are difficult to obtain from high-pressure polyethylene by an inflation molding technique. It has been de-sired therefore to develop olefinic resins having improved transparency.
Generally, copolymers of ethylene with alpha-olefins having at least 3 carbon atoms which are produced by using Ziegler-type catalysts have much the same density as high-pressure polyethylene, and exhibit relatively good mechani-cal strength. When produced by using vanadium-containing Ziegler catalysts, these copolymers have relatively low melting points, and their thermal resist-20 ance is unsatisfactory. ritanium-containing Ziegler catalysts, on the other hand, lead to copolymers having poor transparency.
Copolymers having much the same transparency as high-pressure poly-ethylene could be produced in the presence of the titanium-containing Ziegler catalysts if the polymerization conditions or the catalysts are properly modi-fied (as disclosed in Canadian Patent No. 9~6,250 assigned to Mitsui Petrochemical Indus-tries, Ltd., issued on March 23, 1976; corresponding to British Patent No. 1,355,245 published on October 2, 1974). In practice, how-F7130-K163(Sanseki)/MS
~,
This invention relates to a process for producing a random ethylene terpolymer whic]l has non-rubbery and plastic properties, and excellent tear strength, impact strength and transparency without a substantial deterioration in its favorable mechanical properties, and which is suitable for production of melt-shaped articles such as films or hollow containers.
Iligh-pressure polyethylene has been considered to possess relatively good transparency and used in the production of melt-shaped articles such as films, sheets and hollow containers. Films of high-pressure polyethylene, how-10 ever, have only limited applications because of their unsatisfactory tearstrength and impact strength and their difficulty of attaining small thicknesses.
Furthermore, films having superior transparency are difficult to obtain from high-pressure polyethylene by an inflation molding technique. It has been de-sired therefore to develop olefinic resins having improved transparency.
Generally, copolymers of ethylene with alpha-olefins having at least 3 carbon atoms which are produced by using Ziegler-type catalysts have much the same density as high-pressure polyethylene, and exhibit relatively good mechani-cal strength. When produced by using vanadium-containing Ziegler catalysts, these copolymers have relatively low melting points, and their thermal resist-20 ance is unsatisfactory. ritanium-containing Ziegler catalysts, on the other hand, lead to copolymers having poor transparency.
Copolymers having much the same transparency as high-pressure poly-ethylene could be produced in the presence of the titanium-containing Ziegler catalysts if the polymerization conditions or the catalysts are properly modi-fied (as disclosed in Canadian Patent No. 9~6,250 assigned to Mitsui Petrochemical Indus-tries, Ltd., issued on March 23, 1976; corresponding to British Patent No. 1,355,245 published on October 2, 1974). In practice, how-F7130-K163(Sanseki)/MS
~,
- 2 ~
ever, it has beell impossible to provide ethylene copolymers having better trans-parency as well as higher tear resistance and impact resistance than high-pressure polyethylene films. Moreover, the Canadian Patent does not specific-ally disclose terpolymers of ethylene, alplla-olefins ~ith 3 or ~ carbon atoms and alpha-olefins having 5 to 18 carbon a-toms.
Random copolymers of ethylene or propylene having novel characteristic features which exhibit improved transparency while retaining their good mechani-cal properties have been suggested in -the past (see, for e~ample, German OLS
Nos. 2,757,863 and 2,803~5g8)~
The above-cited German OLS No. 2,757,863 discloses a random propylene copolymer having novel characteristic features consisting essentially of 40 to 90 mole% of propylene and 60 to 10 mole% of l-butene, and the cited German OLS
No. 2,803,598 discloses an ethylene copolymer having novel characteristic fea-tures consisting essentially of a major proportion of ethylene and a minor pro-portion of an alpha-olefin having 5 to 18 carbon atoms, which have unique struc-tural characteristics. Fhese patent documents, however, do not at all refer to terpolymers derived from ethylene, and alpha-olefin having 3 or 4 carbon atoms and an alpha-olefin having 5 to 18 carbon atoms.
U. S. Patent No. 3,222,332 discloses the preparation of copolymers of ethylene with propylene and/or butene-l, in which an alpha-olefin with at least 5 carbon atoms is used as comonomer, preferably an alpha olefin with at least 8 and at most 16 carbon atoms.
'l~le process disclosed in the U. S. Patent leads to products with special properties, in particular to rubber-like products which are completely or almost completely amorphous and which possess hysterisis properties after vulcanization. In the U. S. Patent, an ethylene content of 50 to 90 mole% in the copolymer is recommended, and only a titanium trihalide is disclosed as a
ever, it has beell impossible to provide ethylene copolymers having better trans-parency as well as higher tear resistance and impact resistance than high-pressure polyethylene films. Moreover, the Canadian Patent does not specific-ally disclose terpolymers of ethylene, alplla-olefins ~ith 3 or ~ carbon atoms and alpha-olefins having 5 to 18 carbon a-toms.
Random copolymers of ethylene or propylene having novel characteristic features which exhibit improved transparency while retaining their good mechani-cal properties have been suggested in -the past (see, for e~ample, German OLS
Nos. 2,757,863 and 2,803~5g8)~
The above-cited German OLS No. 2,757,863 discloses a random propylene copolymer having novel characteristic features consisting essentially of 40 to 90 mole% of propylene and 60 to 10 mole% of l-butene, and the cited German OLS
No. 2,803,598 discloses an ethylene copolymer having novel characteristic fea-tures consisting essentially of a major proportion of ethylene and a minor pro-portion of an alpha-olefin having 5 to 18 carbon atoms, which have unique struc-tural characteristics. Fhese patent documents, however, do not at all refer to terpolymers derived from ethylene, and alpha-olefin having 3 or 4 carbon atoms and an alpha-olefin having 5 to 18 carbon atoms.
U. S. Patent No. 3,222,332 discloses the preparation of copolymers of ethylene with propylene and/or butene-l, in which an alpha-olefin with at least 5 carbon atoms is used as comonomer, preferably an alpha olefin with at least 8 and at most 16 carbon atoms.
'l~le process disclosed in the U. S. Patent leads to products with special properties, in particular to rubber-like products which are completely or almost completely amorphous and which possess hysterisis properties after vulcanization. In the U. S. Patent, an ethylene content of 50 to 90 mole% in the copolymer is recommended, and only a titanium trihalide is disclosed as a
- 3 --titanium catalyst component o:E the catalyst used in the copolymerization. No description is given in the Patent as to a titanium catalyst component contain-ing a~ least magnesium and titanium. In addition, the resulting copolymers are rubber-like products which exhibit their useful properties only after vulcaniza-tion.
We made investigations in order to provide ethylene copolymers having improved properties over the ethylene copolymers disclosed in the above-cited German OLS No. 2,803,598, particularly having better transparency without in-volving a deterioration in mechanical properties.
These investigations have led to the discovery that the desired improvements can be achieved by using (B) 0.2 to 9.8 mole% of an alpha-olefin with 3 or 4 carbon atoms and ~C) 0.2 to 9.8 mole% of an alpha-olefin with 5 to 18 carbon atoms as comonomers to be copolymerized with (A) a major proportion (more tha~ 90 mole% to 99.5 mole%) of ethylene, the total of the proportions of the monomers (A), (B) and (C) being 100 mole%. It has also been found that the resul~ing terpolymer can be melt-shaped, without the need for vulcanization, into articles having superior properties, for example packaginc~ films having superior transparency, tear strength, impact strength and heat-sealing property;
or can be melt-extruded on other plastic films to form superior laminate films;
or exhibit excellent properties as blending resins to be blended with other thermoplastic synthetic resins.
It is an object of this invention therefore to provide a process for producing a random ethylene terpolymer having improved properties.
The above and other objects and advantages of this invention will be-come more apparent from the following description.
The pressnt invention provides a process for producing a random ethylene terpolymer of ethylene with an alpha-olefin having at least 3 carbon ~0
We made investigations in order to provide ethylene copolymers having improved properties over the ethylene copolymers disclosed in the above-cited German OLS No. 2,803,598, particularly having better transparency without in-volving a deterioration in mechanical properties.
These investigations have led to the discovery that the desired improvements can be achieved by using (B) 0.2 to 9.8 mole% of an alpha-olefin with 3 or 4 carbon atoms and ~C) 0.2 to 9.8 mole% of an alpha-olefin with 5 to 18 carbon atoms as comonomers to be copolymerized with (A) a major proportion (more tha~ 90 mole% to 99.5 mole%) of ethylene, the total of the proportions of the monomers (A), (B) and (C) being 100 mole%. It has also been found that the resul~ing terpolymer can be melt-shaped, without the need for vulcanization, into articles having superior properties, for example packaginc~ films having superior transparency, tear strength, impact strength and heat-sealing property;
or can be melt-extruded on other plastic films to form superior laminate films;
or exhibit excellent properties as blending resins to be blended with other thermoplastic synthetic resins.
It is an object of this invention therefore to provide a process for producing a random ethylene terpolymer having improved properties.
The above and other objects and advantages of this invention will be-come more apparent from the following description.
The pressnt invention provides a process for producing a random ethylene terpolymer of ethylene with an alpha-olefin having at least 3 carbon ~0
- 4 ~
atoms in the presence of a catalyst composed of a titaniwn ca-talyst component containing at least magnesium ancl titanium and all organoaluminum catalyst com-ponent in a hydrocarbon solvent at a temperature above the melting point of the terpolymer formed, under SUCil conditions that the resulting terpolymer dissolves in the hydrocarbon solvent; characterized in that said terpolymer consists essentially of ~A) more than 90 mole% to 99.S mole% of ethylene, (B) 0.2 mole% to 9.8 mole% of an alpha-olefin with 3 to 4 carbon atoms, and ~C) 0.2 mole% to 9.8 mole% of an alpha-olefin with 5 to 1~ carbon atoms, the total of the proportions of the monomers ~A), ~B) and ~C) being 100 mole%.
The catalyst used in this invention composed of the aforesaid titanium catalyst component containing at least magnesium and titanium and the aforesaid organoaluminum catalyst component is known.
In the titanium cata]yst component, the titanium compound is present in the form supported on a magnesium compound in many cases. Or it is present in the form of a complex formed of a soluble magnesium compound complex and a titanium compound. In the aforesaid supported catalyst component, a magnesium halide is present either alone or as a complex with another metal compound. For example, when the magnesium halide is used as a starting material, the magnesium halide supports the titanium compound while it is rendered non-crystalline by mechanical pulverization or by the aid of an electron donor. When other magne-sium compounds are used as the starting material, a halogenating agent ~which may be a titanium compound) is caused to act on the magnesium compound in the step of catalyst preparation to convert it partly or wholly into -the correspond-ing magnesium halide. By supporting the titaniwn compound on the resulting magnesium halide, a catalyst component having high activity can be obtained.
,~
PreferablyJ the catalys-t used in this invention is composed of a solid, magnesium-containillg titanium catalyst component and an organoaluminulTI compo~nd.
It is preferred that such a catalyst should have the ability to Eorm a ter-polymer in an amount of at least 50g per mg of Ti in the catalyst. Especially preferred catalysts are those in which the solid titanium catalyst component is obtained by supporting titanium on a compound containing a magnesium halide, especially magnesium chloride and has a Cl/Ti weight ratio of from 3 to 200, pre-ferably from 5 to 150, an ~Ig/Ti mole ratio of from 3 to 90> and a surface area of at least 20 m /g, preferably at least 70 m /g, more pre-ferably at least 150 m /g.
The solid titanium catalyst component preferably contains 0.5 to 10 parts by weight of titanium, 15 to 30 parts by weight of magnesium, and 50 to 70 parts by weight of halogen, the total proportion of these components being 100 parts by weight. It may also contain more than 0.01, pre-ferably about 0.1 to 50 parts by weight of an electron donor and/or other elements.
Examples of the electron donor that may be included in the solid titanium catalyst component include alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropyl benzyl alcohol; organic acid esters having 2 to 18 carbon atoms such as methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, methyl methacrylate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, amyl toluate, ethyl ethylb3nzoate, ethyl anisate, ethyl ethoxy-benzoate, gammabutyrolactone and coumarin; carboxylic acids having 2 to 18 carbon atoms; phenols having 6 to 15 carbon atoms; aldehydes having 2 -to 15 - 6 _ ~ L~ ~
carbon a-toms; ketones having 3 to 15 carbon atoms; ethers having 2 to 20 carbon atoms; acid amides; amines; and nitriles.
Some suitable titanium catalyst components are disclosed, for example, in Japanese Patent Publication No~ 26383/72 ~U. S. Patent ~o. 3,705,886), Japanese Patent Publication No. 41676/72 (British Patent No. 1,2g6,867), Japanese Patent Publication No. 32270/75 (U. S. Patent No. 4,071,67~, and Britlsh Patent No. 1,433,537), Japanese Laid-Open Patent Publication No.
88983/74 (U. S. Patent No. 4,071,672), and Japanese Laid-Open Patent Publication No. 95382/75 (British Patent No. 1,485,520). These patents do not give a speci-fic example of terpolymerizing ethylene, an alpha-olefin with 3 or 4 carbon atoms and an alpha-olefin with 5 to 18 carbon atoms.
A solid titanium catalyst component which is disclosed in the above-cited British Patent 1,433,537 and has the surface area specified hereinabove can be synthesized, for example, by adding about 3 to about 7 moles of a lower alcohol such as ethanol to 1 mole of magnesium chloride, reacting the adduct with an amount of an organoaluminum compound which is sufficient to react with the alcohol, and then reacting the resulting product with titanium tetra-chloride or its solution in an inert hydrocarbon.
Preferred organoaluminum compounds include~ for e~ample, compounds of formula M AIR4 wherein R is a hydrocarbon group~ M is lithium, sodium or potassium, compounds of formula R 3 AlX wherein Rl is the same as defined above, X is a halogen atom, and m is zero or a positive number of not greater than 3, compounds of formula R13 Al(OR2) wherein Rl i.s the same as defined above, R2 is a hydrocarbon group, whicil is identical to, or different from, Rl, and n is a positive number greater than 0 but not greater than 3, and compounds of formula RlAl(OR2)X wherein Rl, R2 ~ld X are the same as defined above.
If there are two or more groups Rl, R2 and X in each of the above DL~
formula, they may be the Sallle or dii-~Eerent. Prcferrc?d hydrocarbon groups repre-sented by Rl or R contalll 1 to 15 carbon atoms. X is preferably chlorine or bromine. Examples of the hydroca.rbon groups R1 and R2 are alkyl and aryl groups. Of the organoalumillum compounds exemplified above, compounds of the formula R 3 mAlX are especially preferred.
The solid titanium catalyst component disclosed in the British Patent No. 1,'i85,520 can be prepared by reacting the soli.d titanium cata.lyst component obtained by the method of the British Patent No. 1,433,537 with small amounts of titanium terrachloride and an organoaluminum compound. The organoaluminum compounds exemplified above can also be used in this process.
The solid titanium catalyst components obtained by these two methods contain titanium, magnc?sium, halogen and aluminum, and have a surface area o:E
at least 70 m2/g, preferably more than 150 m2/g bu-t not exceeding 500 m2/g.
Examples of suitable organoaluminum catalyst components are compoullds having an Al-C bond in the molecule, such as ~i) organoaluminum compounds of the following formula R Al~OR ) ~I X
m n p q wherein Rl and R are indentical or different, and represent a hydro-carbon radical containing usually 1 -to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number defined by 0 < m < 3, n :is a number defined by 0 < Jl < 3, p is a number de-fi.ned by O < p < 3, and q is a number defined by O < q < 3 provided that m + n -~ p -~ q = 3, and ~ii) complex alkyl compounds of metals of Group I and aluminum having the general formula ~1 AlR A
wherein ~ represents Li, Na or K, and Rl is as defined above.
,.S~ ~D
Examples o:E the hydrocarbon groups Rl and R are alkyl, alkenyl and aryl groups.
Examples of the organoaluminum compound within the group (i) are those of the general formulae R Al(OR )3 (wherein R and R are the same as defined above, and m is preferably a number defined by 1.5 < m < 3), Rl AlX3 m (wherein R is as defined above, X is halogen, and m ls preferably a number de-fined by 0 < m < 3), Rl AlH3 (wherein Rl is as defined aboveJ and m is prefer-ably 2 < m < 3), and R mAl(OR )nXq (wherein R and R are as defined above, X
is halogen, 0 < m < 3, 0 < n c 3, 0 < q < 3, and m + n + q = 3).
Specific examples of the aluminum compounds which fall into the group (i) include trialkyl aluminums such as triethylaminium and tributyl aluminum;
trialkenyl aluminums such as triisoprenyl aluminum; partially alkoxylated alkyl aluminums, for example, dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesqùiethoxide and butyl aluminum sesquibutoxide; cvmpounds hav-ing an average composition expressed by R12 5Al(OR2)o 5; partially halogenated alkyl aluminums, for example, dialkyl aluminum halogenides such as diethyl aluminum chlorideg dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalogenides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminums dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; partially hydrogenated alkyl aluminums, for example, dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride, alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alcoholated and halogena-ted alkyl aluminums, for exampleJ alkyl aluminum alkoxyhalides such as ethyl aluminum ethoxychloride, butyl aluminum butoxychloride and ethyl aluminum ethoxybromide, .~
~ ~&~3~
_ 9 _ OrganoalUlllillUIII colllpOUndS iTI which two or more aluminum atoms are bonded through on oxygen or nitrogen atom may also be used as compounds analo-gous to the compounds of group (i). Examples of such compounds are 2 5)2 ( 2 5)2' (C4~lg)2AloAl(c4~l9)2~ and (C2H5)2AINAl(C2H5) ~ xamples of compounds of formula (ii) are LiAl(C2H5)~ cmd LiAl(C7H15)~.
Among the above organoaluminum compounds, those represented by the general formula R'nAlX3 m and having the average composition 1 < m < 2.7, pre-ferably 1.5 > m > 2.3 are preferred because they lead to terpolymers having good transparency. Especially suitable organoaluminum compounds are alkyl aluminum sesquihalogenides and dialkyl aluminum halogenides, alkyl aluminum sesquichlorides and dialkyl aluminum chlorides being most preferred.
In the process of this invention, the terpolymerization reaction is carried out in the presence of the above-illustrated catalyst in a hydrocarbon solvent at a temperature above the melting point of the terpolymer formed, under such conditions that the solvent and the resulting terpolymer form a homo-geneous phase.
The polymerization solvent is an inert hydrocarbon solvent or the monomers themselves may be used as the solvent. Examples of the inert solvent are aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, isohexane, isooctane, n-decane and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexanc and methylcyclohexane; and aromatic hydro-carbons such as benzene, toluene, xylene and ethylbenzene.
The copolymer should dissolve in the polymerization medium. The re-sulting solution may separate into a phase rich in the terpolymer~ and a phase poor in the terpolymer. Preferably, however, the polymerization is carried out under such conditions that the resulting terpolymer and the polymerization sol-.j~
vent form a homogeneous phase. The conditions for forming the homogeneous phase vary depending upon the type of the solvent, the concentrations (pressure) of the monomers in the solvent and hydrogen, the polymeri.zation temperature, the molecular weight (intrinsic viscosity) of the terpolymer. The concentra-tion of the terpolymer should be adjusted according to the individual condi-tions so that it dissolves in the hydrocarbon solvent.
The concentration of the terpolymer varies also depending upon the polymerization conditions. Usually, it is preferably maintained at about 50 to 300g per liter of solution. The polymerization temperature is above the melt-ing point of the terpolymer, usually 125 to 240 C, preferably 130 to 220 C.
The terpolymerization can be performed either batchwise or continuously. The continuous method is preferred for obtaining terpolymers having good transpar-ency.
The amount of the titanium catalyst component used is for, for exampleJ 0.0005 to 1 millimole, preferably 0.001 to 0.1 millimole, calculated as titanium atom. The amount of the organoaluminum catalyst component is for example 0.01 to lQ millimoles, preferably 0.05 to 1 millimoles, calculated as aluminum. Preferably, the Al/Ti mole ratio is adjusted to about 1 to 1000.
In the present invention, ethylene, an alpha-olefin having 3 or 4 carbon atoms and an alpha-olefin having 5 to 18 carbon atoms are terpolymerized under the aforesaid polymerization conditions so as to form a terpolymer con-sisting essentially of more than 90 mole% to 99.5 mole%, preferably 92 to 99 mole%, of ethylene, 0.2 to 9.8 mole%, preferably 0.3 to 7 mole%, of the alpha-olefin having 3 or 4 carbon atom, and 0.2 to 9.8 mole%, preferably 0.3 to 7 mole%, of the alpha-olefin having 5 to 18 carbon atoms.
The alpha-olefin with 3 or 4 carbon atoms to be terpolymerized with ethylene in this invention is propylene or butene-l. ~xamples of the alpha-olefin with 5 to 18 carbon atoms include l-pentene, l-hexane, 4-methyl-1-pentene, 3-methyl-1-pentene, l-heptene, l-octene, l-decene, l~dodecene, l-tetradecene, l-octadecene, and mixtures of these. Alpha-ole~ins having 6 to 12 carbon atoms are preferred, and 4-methyl-1-pentene is especially preferred.
Adjustment of the proportions of the monomers (A), (B) and (C) in the process of this invention to the ranges specified above can be performed by ad-justing the proportLons of the alpha-olefins fed. The proportions of the alpha-olefins may vary according to the types of the alpha-olefins, the polymeriza-tion temperature, the partial pressure of ethylene in the polymerization vessel,and other polymerization conditions. For example, the alpha-olefin having 3 or 4 carbon atom is fed in an amount of 0.003 to 2.0 moles, preferably about 0.005 to 1.0 mole, and the alpha-olefin having 5 to 18 carbon atoms is fed in an amount of from 0.005 to 10 molesJ preferably from 0.01 to 3.0 moles, both per mole of ethylene.
The terpolymerization is carried out preferably under elevated pres-sures, for example under about 2 to about 100 kg/cm2, preferably from about 10 to about 50 kg/cm2. Generally, hydrogen is used for control of molecular weight.
The ethylene copolymer of the aforesaid composition obtained by the process of this invention have a density of generally 0.900 to 0.945 g/cm3, pre-ferably 0.910 to 0.940 g/cm3. The suitable molecular weight of the copolymer is O.S to 4.0 dl/g, especially 1.0 to 3.0 dl/g, expressed by intrinsic viscositymeasured in decalin at 135C.
The terpolymer obtained by this invention has superior transparency, tear strength and impact strength, and is suitable for use as a film. Since it also has very good heat sealing property, films prepared from this copolymer aresuitable as packaging films. Films prepared from the terpolymer by a T-die method and an inflation method all have 'nigh transparency.
The terpolymer obtained by this invention can also be shaped into various articles by blow molding~ injection molding, extrusion molding, etc.
lt can also be extrusion-coated on other films to Eorm coated films. Or it can be blended with other polyolefins such as polyethylene, polypropyleneJ poly-l-butene, poly-4-methyl-1-pentene, an ethylene-propylene copolymer, an ethylene-l-butene copolymer and a propylene-l-butene copolymer. Moreover, it may be used after :incorporating petroleum resins, waxes, stabilizers, antistatic agents, ultraviolet absorbers, natural or synthetic rubbers, lubricants, inorganic fillers, etc.
Example 1 Preparation of a Ti catalyst component:-~ nder a nitrogen stream, 10 moles of anhydrous magnesium dichloride~commercially available) was suspended in 30 liters of dehydrated and puxified hexane. With stirring, 60 moles of ethanol was added dropwise over 1 hour, and reacted at 30C for 1 hour. Then, 27 moles of diethyl aluminum chloride was added dropwise at room temperature~ cmd the mixture was stirred for 1 hour.
Subsequently, 30 moles of titanium tetrachloride was added. The mi.xture was heated to 80C, and reacted for 3 hours with stirring. The resulting solid was separated by decantation, and repeatedly washed with purified hexane to form a hexane suspension of the solid. The concentration of titanium was determined by titration.
Polymerization:-A 200-liter continuous polymerization reactor was charged continu-ously with dehydrated and purified hexane, diethyl aluminum chloride and the supported Ti catalyst component prepared as above a-t a rate of 80 liters/ilr, 20 mmoles/hr, and 0.3 mmole/hr ~calculated as titanium), respectively. Then, ethylene, propylene, 4-methyl-1-pentene and hydrogen were simultaneously -fed D~L
continuously into the polymerization reactor at a rate of 13 kg/hr, 2.5 kg/hr, and 9.0 kg/hr, and 100 liters/hr, respectively. The monomers \.~ere polymerized at a polymerizatiorl temperature of 150C under a total pressure of 30 kg/cm G
with a residence time of 1 hour. The concelltration of the resulting terpolymer was maintained at 110 g/liter of the solution during the polymerization.
The resulting copol~ner had a density of 0.923 g/cm3 and a melt index (MI) of 2.13, and contained 95.5 mole% of ethylene3 2.~ mole% of propylene, and 2.1 molc% of 4-methyl-1-pentene.
The terpolymer was molded by a commercially available tubular film-Eorming machine (a product of Modern Machinery Company) designed for high-pressure polyethylene to form a film having a width of 350 mm and a thickness of 40 microns. The film-forming conditions were as follows:
Resin temperature: 180 C
Rotating speed of the screw: 100 rpm Diameter of the die: 100 mm Die slit width: 0.8 mm The properties of the resulting film are shown in Table 1. The film had good transparency and strength.
~xample 2 A 200-liter continuous polymerization reactor was charged continuously with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component obtained in Example 1 at a rate of 80 liters/hr, 20 mmoles/hr, and 0.3 mmole/hr (calculated as titanium~, respectively. Then, ethylene, pro-pylene, 4-methyl-1-pentene, and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13 kg/hr~ 1 kg/hr, 12.0 kg/hr, and 90 liters~hr, respectively. The monomers were polymerized at a polymerlzation temperature of 150C under a -total pressure o~ 30 kg/cm2-G with a residence time '.~f of 1 hour. The concentration of the terpolymer was maintained at 102 g/liter of the solution during the polymerization.
The resulting terpolymer had a density of 0.920 g/cm , and an MI of 1.94, and contained 95.9 mole% oE ethylene, 0.9 mole% of propylene, and 3.2 mole% of 4-methyl-l-pentene.
The terpolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Example 3 A 200-liter continuous polymerization reactor was charged continu-ously with dehydrated and purified hexane, diethyl aluminum chloride, diethyl aluminum sesquichloride, and the Ti catalyst component described in Example 1 at a rate of 80 liters/hr, 12 mmoles/hr, 12 mmoles/hr, and 0.8 mmole/hr (calcu-lated as titanium), respectively. Then, ethylene, l-butene, 4-methyl-1-pentene, and hydrogen were simultaneously Eed continuously into the polymerization reactor at a rate of 13.5 kg/hr~ 4 kg/hr~ 10 kg/hr, and 90 liters/hr, respec-tively. The monomers were polymerized at a polymerization temperature of 150C
under a total pressure of 30 kg/cm G with a residence time of 1 hour. The con-centration of the resulting copolymer was maintained at 108 g/liter of tlle solu-tion during the polymerization.
The resulting terpolymer had a density of 0.921 g/cm3 and an MI of 1.75, and contained 95.1 mole% of ethylene, 2.6 mole% of l-butene, and 2.3 mole% of 4-methyl-1-pentene.
The terpolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Example 4 Preparation of Ti catalyst component:-Under a nitrogen stream, 5 moles of anhydrous magnesium chloride (com-mercially avaikable) was suspended in 10 liters of dehydrated and purified hexane, and with stirring, 30 moles of ethanol was added dropwise over 1 hour.
Then, 14.2 moles of diet]lyl alumimlm chloride was added dropwise at room temperature, and the mixture was stirred for 1 hour. ~urther, 2 moles oE
titanium tetrachloride and 2 moles of triethylaluminium were added. The mix-ture was subjected to a reducing reaction while being stirred at room tempera-ture for 4 hours. The color oE the solid por-tion changed to light brown peculiar to trivalent titanium. The titanium concentration in the resulting hexane suspension was determined by -titration.
Polymerization:-The same continuous polymerization reactor as used in Example 1 was continuous~y charged with dehydrated and purified hexane, diethyl aluminum chloride, and the supported titanium catalyst component obtained as described above at a rate of 80 liters/hr, 24 mmoles/hr, and 0.4 mmole/hr ~calculated as titanium), respectively. Then, ethylene, l-butene, 4-methyl-1-pentene and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13.0 kg/hr, 1.5 kg/hr, 12.0 kg/hr, and 90 liters/hr, respectively.
The monomers were polymerized at a polymerization temperature of 145C under a total pressure of 30 kg/cm2-G with a residence time of 1 hour. The concentra-tion of the terpolymer was maintained at 115 g/liter of -the solution during the polymerization.
The resulting terpolymer had a density of 0.925 g/cm3 and an MI of 2.80, and contained 96.7 mole% of ethylene, 0.6 mole% of l-butene and 2.7 mole%
of 4-methyl-1-pentene. The terpolymer had good transparency.
~ y the same method as in Example 1, a film having a high tear strength was obtained. The results are shown in Table 1.
,~1 8~3~
Example 5 The same continuous polymerization reactor was charged continuously with dehydrated and purified he~ane, ethyl al~nninum ses~uichloride, and the sup-ported I`i catalyst component described in Example 4 at a rate of 80 liters/IIr, 2L~ mmoles/IIr, and 1.5 nDIloles/hr ~calculated as titanium), respectively. Then, ethylene, propylene, 4-met}lyl-1-peIltelle, and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13 kg/hr, 2 kg/hr, 10 kg/hr, and 100 liters/hr, respectively. The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm2 G with a residence time of l hour. The concentration of the terpolymer was maintained at 118 g/liter of the solution during the polymerization.
The resulting terpolymer had a density of 0.922 g/cm3 and an ~II of 2.35, and contained 96.0 mole% of ethyleIle, 1.6 mole% of propylene and 2.4 mole% of 4-methyl-1-pentene.
The copolymer was formed into a film under the same conditions as in E~ample 1. The results are shown in Table 1.
E~ample 6 A 200-liter continuous polymerization reactor was charged continuously with dehydratcd and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in E~ample l at a rate of 80 liters/hr, 20 mmoles/
hr, and 0.3 mmole/hr (calculated as titanium) respectively. Then, ethylene, pro-pylene, l-octene and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13 kg/hr, 2 kg/hr, 12 kg/hr, and 100 liters/
hr, respectively. The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm2-G with a residence time of 1 hour.
The concentration of the terpolymer was maintained at 99 g/liter of the solution during the polymerization.
.~
The resulting terpolymer had a density of 0.923 g/cm3 and an ~li of 2.45, and contained 97.2 mole% of ethylene, 1.2 mole% of propylene, and 1.6 mole% of l-octene.
I`he copolymer was formed lnto a film uncler the same conditions as in Example 1. The results are sho~ in Tlble 1.
Compclratlve Example 1 A 200-liter continuous polymerization reactor was charged continu-ously with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in Example 1 at a rate of 8~ liters/hr, 20 mmoles/hr, and 0.3 mmole/hr (calculatecl as titanium) respectively. Then, ethylene, propylene and hydrogen were simultaneously fed con~iIluously into the polymerization reactor at a rate of 13 kg/hr, 5.0 k~/hr, and 80 liters/hr, respectively. I`he monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm2-G with a residence time of 1 hour.
The concentration of the copolymer was maintaiIled at 118 g/liter of the solu-tion during the polymerization.
The resultin~ copolymer had a density of 0.924 g/cm and an ~II of 2.50, and contained 94.5 mole% of ethylene and 5.5 mole% of propylene.
The copolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Comparative Example 2 A 200-liter continuous polymerization reactor was continuously charged with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described i-n Example 1 at a rate of 80 liters/hr, 20 mmoles/
hr, and 0.3 mmole/hr (calculated as titanium), respectively. Then~ ethylene, l-butene and hydrogen l~cre simultaneously fed continuously into the polymeriza-tion reactor at a rate of 13 kg/hr, 7.0 kg/hr, and 90 liters/hr, respectively.
",,~, ,f~
.lL ~&~
The monomers were polymerized at a polymerization temperature of 150C under a total pressure o:E 30 kg/cm2-G with a residence time of 1 hour. The concentra-tion of the copolymer was maintained at 110 g/liter of the solutior. during the polymerization.
The resulting copolymer had a density of 0.929 g/cm3 and an MI of 2.15, and contained 95.4 mole% of ethylene and 4.6 mole% of l-butene.
The copolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Comparative Example 3 A 200-liter continuous polymerization reactor was charged with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in Example 1 at a rate of 80 liters/hr, 20 mmoles/hr, and 0.4 mmole/hr ~calculated as ti.tanium), respectively. Then, ethylene, 4-methyl-l-pentene, and hydrogen were simultaneously fed continuously into the polymer-ization reactor at a rate of 13 kg/hr, 13 kg/hr, and 110 liters/hr, respecti.vely.
The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm G with a residence time of 1 hour. The concentra-tion of the copolymer was maintained at 107 g/liter of the solution during the polymerization.
The resulting copolymer had a density of 0.922 g/cm and an MI of 3.0~, and contained 96.7 mole% of ethylene, and 3.3 mole% of 4-methyl-1-pentene.
The copolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Comparative Example ~
A 200-liter continuous polymerization reactor was charged continuously with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in Example 1 at a rate of 80 liters/hr, 20 mmoles/
~i ~&~
hr, and 0.4 mmole/hr (calculated as titanium), respectively. Then, ethylene, l-octene, and hydrogen were simultaneously fed continuously into the polymeriza-tion reactor at a rate of 13 kg/hr, 14 kg/hr, and 100 kg/hr, respectively. The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm G with a residence time of l hour. The concentra-tion of the copolymer was maintained at lll g/liter of the solution during the polymerization.
The resulting copolymer had a density of 0.926 g/cm3 and an MI of 2.90, and contained 97.5 mole% of ethylene and 2.5 mole% of l-octene.
The copolymer was formed into a film under the same conditions as in Example l. The results are shown in Table 1.
~.~,"
-Table 1 Example ~Ex.~ and Ex 1 Ex 2 Ex 3 Ex. 4 Ex. 5Cvmparative Example (CEx.) -Propylene Propylene l-Butene l-Butene Propylene B (2.4) (0.9) (2.6) (0.6) (1.6 Comonomers (content, mole%) 4-Methyl- 4-Methyl- 4-Methyl- 4-Melhyl- 4-~le~hyl-C i-pentene l-pentene l-pentene l-pentene l-pentene (2.1) (3.2) (2.3) (2.7) (2.~) Melt index 2.13 1.94 1.75 2.80 2.35 Density (g/cm ) 0.923 0.920 0.921 0.925 0.922 ~aze (%) 2.0 2.5 1.5 2.5 0.9 Properties Impact strength 1700 2200 1800 2400 2000 of 40 ~- (kg.cm/cm) thick injection Elemendorf MD 77 128 88 120 79 film tear strength (kg/cm) TD 153 190 162 194 148 æ
Table 1 ~continued) Example (Ex.) and Ex. 6 CEx.l CEx.2 CEx.3 CEx.4Comparative Example (CEx.) B Propylene Propylene l-Butene - -(1.2) (5.5) ~4.6 Comonomers (content, mole%) l-Octene - - 4-Methyl- l-Octene C (1.6) l-pen~ene (2.5) (3.3) Melt index 2.45 2.50 2.15 3.04 2.90 Density (g/cm3) 0.923 0.924 0.929 0.922 0.926 Haze (%) 3.0 2.5 3.0 5.0 6.0 Properties Impact strength 2100 1200 1400 2500 2600 of 40 ~- (kg.cm/cm) thick injection Elemendorf MD 81 28 33 153 130 ~
film tear strength '~b (kg/cm) TD 159 83 101 195 175 Q~
Qa ~P
atoms in the presence of a catalyst composed of a titaniwn ca-talyst component containing at least magnesium ancl titanium and all organoaluminum catalyst com-ponent in a hydrocarbon solvent at a temperature above the melting point of the terpolymer formed, under SUCil conditions that the resulting terpolymer dissolves in the hydrocarbon solvent; characterized in that said terpolymer consists essentially of ~A) more than 90 mole% to 99.S mole% of ethylene, (B) 0.2 mole% to 9.8 mole% of an alpha-olefin with 3 to 4 carbon atoms, and ~C) 0.2 mole% to 9.8 mole% of an alpha-olefin with 5 to 1~ carbon atoms, the total of the proportions of the monomers ~A), ~B) and ~C) being 100 mole%.
The catalyst used in this invention composed of the aforesaid titanium catalyst component containing at least magnesium and titanium and the aforesaid organoaluminum catalyst component is known.
In the titanium cata]yst component, the titanium compound is present in the form supported on a magnesium compound in many cases. Or it is present in the form of a complex formed of a soluble magnesium compound complex and a titanium compound. In the aforesaid supported catalyst component, a magnesium halide is present either alone or as a complex with another metal compound. For example, when the magnesium halide is used as a starting material, the magnesium halide supports the titanium compound while it is rendered non-crystalline by mechanical pulverization or by the aid of an electron donor. When other magne-sium compounds are used as the starting material, a halogenating agent ~which may be a titanium compound) is caused to act on the magnesium compound in the step of catalyst preparation to convert it partly or wholly into -the correspond-ing magnesium halide. By supporting the titaniwn compound on the resulting magnesium halide, a catalyst component having high activity can be obtained.
,~
PreferablyJ the catalys-t used in this invention is composed of a solid, magnesium-containillg titanium catalyst component and an organoaluminulTI compo~nd.
It is preferred that such a catalyst should have the ability to Eorm a ter-polymer in an amount of at least 50g per mg of Ti in the catalyst. Especially preferred catalysts are those in which the solid titanium catalyst component is obtained by supporting titanium on a compound containing a magnesium halide, especially magnesium chloride and has a Cl/Ti weight ratio of from 3 to 200, pre-ferably from 5 to 150, an ~Ig/Ti mole ratio of from 3 to 90> and a surface area of at least 20 m /g, preferably at least 70 m /g, more pre-ferably at least 150 m /g.
The solid titanium catalyst component preferably contains 0.5 to 10 parts by weight of titanium, 15 to 30 parts by weight of magnesium, and 50 to 70 parts by weight of halogen, the total proportion of these components being 100 parts by weight. It may also contain more than 0.01, pre-ferably about 0.1 to 50 parts by weight of an electron donor and/or other elements.
Examples of the electron donor that may be included in the solid titanium catalyst component include alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropyl benzyl alcohol; organic acid esters having 2 to 18 carbon atoms such as methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, methyl methacrylate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, amyl toluate, ethyl ethylb3nzoate, ethyl anisate, ethyl ethoxy-benzoate, gammabutyrolactone and coumarin; carboxylic acids having 2 to 18 carbon atoms; phenols having 6 to 15 carbon atoms; aldehydes having 2 -to 15 - 6 _ ~ L~ ~
carbon a-toms; ketones having 3 to 15 carbon atoms; ethers having 2 to 20 carbon atoms; acid amides; amines; and nitriles.
Some suitable titanium catalyst components are disclosed, for example, in Japanese Patent Publication No~ 26383/72 ~U. S. Patent ~o. 3,705,886), Japanese Patent Publication No. 41676/72 (British Patent No. 1,2g6,867), Japanese Patent Publication No. 32270/75 (U. S. Patent No. 4,071,67~, and Britlsh Patent No. 1,433,537), Japanese Laid-Open Patent Publication No.
88983/74 (U. S. Patent No. 4,071,672), and Japanese Laid-Open Patent Publication No. 95382/75 (British Patent No. 1,485,520). These patents do not give a speci-fic example of terpolymerizing ethylene, an alpha-olefin with 3 or 4 carbon atoms and an alpha-olefin with 5 to 18 carbon atoms.
A solid titanium catalyst component which is disclosed in the above-cited British Patent 1,433,537 and has the surface area specified hereinabove can be synthesized, for example, by adding about 3 to about 7 moles of a lower alcohol such as ethanol to 1 mole of magnesium chloride, reacting the adduct with an amount of an organoaluminum compound which is sufficient to react with the alcohol, and then reacting the resulting product with titanium tetra-chloride or its solution in an inert hydrocarbon.
Preferred organoaluminum compounds include~ for e~ample, compounds of formula M AIR4 wherein R is a hydrocarbon group~ M is lithium, sodium or potassium, compounds of formula R 3 AlX wherein Rl is the same as defined above, X is a halogen atom, and m is zero or a positive number of not greater than 3, compounds of formula R13 Al(OR2) wherein Rl i.s the same as defined above, R2 is a hydrocarbon group, whicil is identical to, or different from, Rl, and n is a positive number greater than 0 but not greater than 3, and compounds of formula RlAl(OR2)X wherein Rl, R2 ~ld X are the same as defined above.
If there are two or more groups Rl, R2 and X in each of the above DL~
formula, they may be the Sallle or dii-~Eerent. Prcferrc?d hydrocarbon groups repre-sented by Rl or R contalll 1 to 15 carbon atoms. X is preferably chlorine or bromine. Examples of the hydroca.rbon groups R1 and R2 are alkyl and aryl groups. Of the organoalumillum compounds exemplified above, compounds of the formula R 3 mAlX are especially preferred.
The solid titanium catalyst component disclosed in the British Patent No. 1,'i85,520 can be prepared by reacting the soli.d titanium cata.lyst component obtained by the method of the British Patent No. 1,433,537 with small amounts of titanium terrachloride and an organoaluminum compound. The organoaluminum compounds exemplified above can also be used in this process.
The solid titanium catalyst components obtained by these two methods contain titanium, magnc?sium, halogen and aluminum, and have a surface area o:E
at least 70 m2/g, preferably more than 150 m2/g bu-t not exceeding 500 m2/g.
Examples of suitable organoaluminum catalyst components are compoullds having an Al-C bond in the molecule, such as ~i) organoaluminum compounds of the following formula R Al~OR ) ~I X
m n p q wherein Rl and R are indentical or different, and represent a hydro-carbon radical containing usually 1 -to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number defined by 0 < m < 3, n :is a number defined by 0 < Jl < 3, p is a number de-fi.ned by O < p < 3, and q is a number defined by O < q < 3 provided that m + n -~ p -~ q = 3, and ~ii) complex alkyl compounds of metals of Group I and aluminum having the general formula ~1 AlR A
wherein ~ represents Li, Na or K, and Rl is as defined above.
,.S~ ~D
Examples o:E the hydrocarbon groups Rl and R are alkyl, alkenyl and aryl groups.
Examples of the organoaluminum compound within the group (i) are those of the general formulae R Al(OR )3 (wherein R and R are the same as defined above, and m is preferably a number defined by 1.5 < m < 3), Rl AlX3 m (wherein R is as defined above, X is halogen, and m ls preferably a number de-fined by 0 < m < 3), Rl AlH3 (wherein Rl is as defined aboveJ and m is prefer-ably 2 < m < 3), and R mAl(OR )nXq (wherein R and R are as defined above, X
is halogen, 0 < m < 3, 0 < n c 3, 0 < q < 3, and m + n + q = 3).
Specific examples of the aluminum compounds which fall into the group (i) include trialkyl aluminums such as triethylaminium and tributyl aluminum;
trialkenyl aluminums such as triisoprenyl aluminum; partially alkoxylated alkyl aluminums, for example, dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesqùiethoxide and butyl aluminum sesquibutoxide; cvmpounds hav-ing an average composition expressed by R12 5Al(OR2)o 5; partially halogenated alkyl aluminums, for example, dialkyl aluminum halogenides such as diethyl aluminum chlorideg dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalogenides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminums dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; partially hydrogenated alkyl aluminums, for example, dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride, alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alcoholated and halogena-ted alkyl aluminums, for exampleJ alkyl aluminum alkoxyhalides such as ethyl aluminum ethoxychloride, butyl aluminum butoxychloride and ethyl aluminum ethoxybromide, .~
~ ~&~3~
_ 9 _ OrganoalUlllillUIII colllpOUndS iTI which two or more aluminum atoms are bonded through on oxygen or nitrogen atom may also be used as compounds analo-gous to the compounds of group (i). Examples of such compounds are 2 5)2 ( 2 5)2' (C4~lg)2AloAl(c4~l9)2~ and (C2H5)2AINAl(C2H5) ~ xamples of compounds of formula (ii) are LiAl(C2H5)~ cmd LiAl(C7H15)~.
Among the above organoaluminum compounds, those represented by the general formula R'nAlX3 m and having the average composition 1 < m < 2.7, pre-ferably 1.5 > m > 2.3 are preferred because they lead to terpolymers having good transparency. Especially suitable organoaluminum compounds are alkyl aluminum sesquihalogenides and dialkyl aluminum halogenides, alkyl aluminum sesquichlorides and dialkyl aluminum chlorides being most preferred.
In the process of this invention, the terpolymerization reaction is carried out in the presence of the above-illustrated catalyst in a hydrocarbon solvent at a temperature above the melting point of the terpolymer formed, under such conditions that the solvent and the resulting terpolymer form a homo-geneous phase.
The polymerization solvent is an inert hydrocarbon solvent or the monomers themselves may be used as the solvent. Examples of the inert solvent are aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, isohexane, isooctane, n-decane and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexanc and methylcyclohexane; and aromatic hydro-carbons such as benzene, toluene, xylene and ethylbenzene.
The copolymer should dissolve in the polymerization medium. The re-sulting solution may separate into a phase rich in the terpolymer~ and a phase poor in the terpolymer. Preferably, however, the polymerization is carried out under such conditions that the resulting terpolymer and the polymerization sol-.j~
vent form a homogeneous phase. The conditions for forming the homogeneous phase vary depending upon the type of the solvent, the concentrations (pressure) of the monomers in the solvent and hydrogen, the polymeri.zation temperature, the molecular weight (intrinsic viscosity) of the terpolymer. The concentra-tion of the terpolymer should be adjusted according to the individual condi-tions so that it dissolves in the hydrocarbon solvent.
The concentration of the terpolymer varies also depending upon the polymerization conditions. Usually, it is preferably maintained at about 50 to 300g per liter of solution. The polymerization temperature is above the melt-ing point of the terpolymer, usually 125 to 240 C, preferably 130 to 220 C.
The terpolymerization can be performed either batchwise or continuously. The continuous method is preferred for obtaining terpolymers having good transpar-ency.
The amount of the titanium catalyst component used is for, for exampleJ 0.0005 to 1 millimole, preferably 0.001 to 0.1 millimole, calculated as titanium atom. The amount of the organoaluminum catalyst component is for example 0.01 to lQ millimoles, preferably 0.05 to 1 millimoles, calculated as aluminum. Preferably, the Al/Ti mole ratio is adjusted to about 1 to 1000.
In the present invention, ethylene, an alpha-olefin having 3 or 4 carbon atoms and an alpha-olefin having 5 to 18 carbon atoms are terpolymerized under the aforesaid polymerization conditions so as to form a terpolymer con-sisting essentially of more than 90 mole% to 99.5 mole%, preferably 92 to 99 mole%, of ethylene, 0.2 to 9.8 mole%, preferably 0.3 to 7 mole%, of the alpha-olefin having 3 or 4 carbon atom, and 0.2 to 9.8 mole%, preferably 0.3 to 7 mole%, of the alpha-olefin having 5 to 18 carbon atoms.
The alpha-olefin with 3 or 4 carbon atoms to be terpolymerized with ethylene in this invention is propylene or butene-l. ~xamples of the alpha-olefin with 5 to 18 carbon atoms include l-pentene, l-hexane, 4-methyl-1-pentene, 3-methyl-1-pentene, l-heptene, l-octene, l-decene, l~dodecene, l-tetradecene, l-octadecene, and mixtures of these. Alpha-ole~ins having 6 to 12 carbon atoms are preferred, and 4-methyl-1-pentene is especially preferred.
Adjustment of the proportions of the monomers (A), (B) and (C) in the process of this invention to the ranges specified above can be performed by ad-justing the proportLons of the alpha-olefins fed. The proportions of the alpha-olefins may vary according to the types of the alpha-olefins, the polymeriza-tion temperature, the partial pressure of ethylene in the polymerization vessel,and other polymerization conditions. For example, the alpha-olefin having 3 or 4 carbon atom is fed in an amount of 0.003 to 2.0 moles, preferably about 0.005 to 1.0 mole, and the alpha-olefin having 5 to 18 carbon atoms is fed in an amount of from 0.005 to 10 molesJ preferably from 0.01 to 3.0 moles, both per mole of ethylene.
The terpolymerization is carried out preferably under elevated pres-sures, for example under about 2 to about 100 kg/cm2, preferably from about 10 to about 50 kg/cm2. Generally, hydrogen is used for control of molecular weight.
The ethylene copolymer of the aforesaid composition obtained by the process of this invention have a density of generally 0.900 to 0.945 g/cm3, pre-ferably 0.910 to 0.940 g/cm3. The suitable molecular weight of the copolymer is O.S to 4.0 dl/g, especially 1.0 to 3.0 dl/g, expressed by intrinsic viscositymeasured in decalin at 135C.
The terpolymer obtained by this invention has superior transparency, tear strength and impact strength, and is suitable for use as a film. Since it also has very good heat sealing property, films prepared from this copolymer aresuitable as packaging films. Films prepared from the terpolymer by a T-die method and an inflation method all have 'nigh transparency.
The terpolymer obtained by this invention can also be shaped into various articles by blow molding~ injection molding, extrusion molding, etc.
lt can also be extrusion-coated on other films to Eorm coated films. Or it can be blended with other polyolefins such as polyethylene, polypropyleneJ poly-l-butene, poly-4-methyl-1-pentene, an ethylene-propylene copolymer, an ethylene-l-butene copolymer and a propylene-l-butene copolymer. Moreover, it may be used after :incorporating petroleum resins, waxes, stabilizers, antistatic agents, ultraviolet absorbers, natural or synthetic rubbers, lubricants, inorganic fillers, etc.
Example 1 Preparation of a Ti catalyst component:-~ nder a nitrogen stream, 10 moles of anhydrous magnesium dichloride~commercially available) was suspended in 30 liters of dehydrated and puxified hexane. With stirring, 60 moles of ethanol was added dropwise over 1 hour, and reacted at 30C for 1 hour. Then, 27 moles of diethyl aluminum chloride was added dropwise at room temperature~ cmd the mixture was stirred for 1 hour.
Subsequently, 30 moles of titanium tetrachloride was added. The mi.xture was heated to 80C, and reacted for 3 hours with stirring. The resulting solid was separated by decantation, and repeatedly washed with purified hexane to form a hexane suspension of the solid. The concentration of titanium was determined by titration.
Polymerization:-A 200-liter continuous polymerization reactor was charged continu-ously with dehydrated and purified hexane, diethyl aluminum chloride and the supported Ti catalyst component prepared as above a-t a rate of 80 liters/ilr, 20 mmoles/hr, and 0.3 mmole/hr ~calculated as titanium), respectively. Then, ethylene, propylene, 4-methyl-1-pentene and hydrogen were simultaneously -fed D~L
continuously into the polymerization reactor at a rate of 13 kg/hr, 2.5 kg/hr, and 9.0 kg/hr, and 100 liters/hr, respectively. The monomers \.~ere polymerized at a polymerizatiorl temperature of 150C under a total pressure of 30 kg/cm G
with a residence time of 1 hour. The concelltration of the resulting terpolymer was maintained at 110 g/liter of the solution during the polymerization.
The resulting copol~ner had a density of 0.923 g/cm3 and a melt index (MI) of 2.13, and contained 95.5 mole% of ethylene3 2.~ mole% of propylene, and 2.1 molc% of 4-methyl-1-pentene.
The terpolymer was molded by a commercially available tubular film-Eorming machine (a product of Modern Machinery Company) designed for high-pressure polyethylene to form a film having a width of 350 mm and a thickness of 40 microns. The film-forming conditions were as follows:
Resin temperature: 180 C
Rotating speed of the screw: 100 rpm Diameter of the die: 100 mm Die slit width: 0.8 mm The properties of the resulting film are shown in Table 1. The film had good transparency and strength.
~xample 2 A 200-liter continuous polymerization reactor was charged continuously with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component obtained in Example 1 at a rate of 80 liters/hr, 20 mmoles/hr, and 0.3 mmole/hr (calculated as titanium~, respectively. Then, ethylene, pro-pylene, 4-methyl-1-pentene, and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13 kg/hr~ 1 kg/hr, 12.0 kg/hr, and 90 liters~hr, respectively. The monomers were polymerized at a polymerlzation temperature of 150C under a -total pressure o~ 30 kg/cm2-G with a residence time '.~f of 1 hour. The concentration of the terpolymer was maintained at 102 g/liter of the solution during the polymerization.
The resulting terpolymer had a density of 0.920 g/cm , and an MI of 1.94, and contained 95.9 mole% oE ethylene, 0.9 mole% of propylene, and 3.2 mole% of 4-methyl-l-pentene.
The terpolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Example 3 A 200-liter continuous polymerization reactor was charged continu-ously with dehydrated and purified hexane, diethyl aluminum chloride, diethyl aluminum sesquichloride, and the Ti catalyst component described in Example 1 at a rate of 80 liters/hr, 12 mmoles/hr, 12 mmoles/hr, and 0.8 mmole/hr (calcu-lated as titanium), respectively. Then, ethylene, l-butene, 4-methyl-1-pentene, and hydrogen were simultaneously Eed continuously into the polymerization reactor at a rate of 13.5 kg/hr~ 4 kg/hr~ 10 kg/hr, and 90 liters/hr, respec-tively. The monomers were polymerized at a polymerization temperature of 150C
under a total pressure of 30 kg/cm G with a residence time of 1 hour. The con-centration of the resulting copolymer was maintained at 108 g/liter of tlle solu-tion during the polymerization.
The resulting terpolymer had a density of 0.921 g/cm3 and an MI of 1.75, and contained 95.1 mole% of ethylene, 2.6 mole% of l-butene, and 2.3 mole% of 4-methyl-1-pentene.
The terpolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Example 4 Preparation of Ti catalyst component:-Under a nitrogen stream, 5 moles of anhydrous magnesium chloride (com-mercially avaikable) was suspended in 10 liters of dehydrated and purified hexane, and with stirring, 30 moles of ethanol was added dropwise over 1 hour.
Then, 14.2 moles of diet]lyl alumimlm chloride was added dropwise at room temperature, and the mixture was stirred for 1 hour. ~urther, 2 moles oE
titanium tetrachloride and 2 moles of triethylaluminium were added. The mix-ture was subjected to a reducing reaction while being stirred at room tempera-ture for 4 hours. The color oE the solid por-tion changed to light brown peculiar to trivalent titanium. The titanium concentration in the resulting hexane suspension was determined by -titration.
Polymerization:-The same continuous polymerization reactor as used in Example 1 was continuous~y charged with dehydrated and purified hexane, diethyl aluminum chloride, and the supported titanium catalyst component obtained as described above at a rate of 80 liters/hr, 24 mmoles/hr, and 0.4 mmole/hr ~calculated as titanium), respectively. Then, ethylene, l-butene, 4-methyl-1-pentene and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13.0 kg/hr, 1.5 kg/hr, 12.0 kg/hr, and 90 liters/hr, respectively.
The monomers were polymerized at a polymerization temperature of 145C under a total pressure of 30 kg/cm2-G with a residence time of 1 hour. The concentra-tion of the terpolymer was maintained at 115 g/liter of -the solution during the polymerization.
The resulting terpolymer had a density of 0.925 g/cm3 and an MI of 2.80, and contained 96.7 mole% of ethylene, 0.6 mole% of l-butene and 2.7 mole%
of 4-methyl-1-pentene. The terpolymer had good transparency.
~ y the same method as in Example 1, a film having a high tear strength was obtained. The results are shown in Table 1.
,~1 8~3~
Example 5 The same continuous polymerization reactor was charged continuously with dehydrated and purified he~ane, ethyl al~nninum ses~uichloride, and the sup-ported I`i catalyst component described in Example 4 at a rate of 80 liters/IIr, 2L~ mmoles/IIr, and 1.5 nDIloles/hr ~calculated as titanium), respectively. Then, ethylene, propylene, 4-met}lyl-1-peIltelle, and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13 kg/hr, 2 kg/hr, 10 kg/hr, and 100 liters/hr, respectively. The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm2 G with a residence time of l hour. The concentration of the terpolymer was maintained at 118 g/liter of the solution during the polymerization.
The resulting terpolymer had a density of 0.922 g/cm3 and an ~II of 2.35, and contained 96.0 mole% of ethyleIle, 1.6 mole% of propylene and 2.4 mole% of 4-methyl-1-pentene.
The copolymer was formed into a film under the same conditions as in E~ample 1. The results are shown in Table 1.
E~ample 6 A 200-liter continuous polymerization reactor was charged continuously with dehydratcd and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in E~ample l at a rate of 80 liters/hr, 20 mmoles/
hr, and 0.3 mmole/hr (calculated as titanium) respectively. Then, ethylene, pro-pylene, l-octene and hydrogen were simultaneously fed continuously into the polymerization reactor at a rate of 13 kg/hr, 2 kg/hr, 12 kg/hr, and 100 liters/
hr, respectively. The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm2-G with a residence time of 1 hour.
The concentration of the terpolymer was maintained at 99 g/liter of the solution during the polymerization.
.~
The resulting terpolymer had a density of 0.923 g/cm3 and an ~li of 2.45, and contained 97.2 mole% of ethylene, 1.2 mole% of propylene, and 1.6 mole% of l-octene.
I`he copolymer was formed lnto a film uncler the same conditions as in Example 1. The results are sho~ in Tlble 1.
Compclratlve Example 1 A 200-liter continuous polymerization reactor was charged continu-ously with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in Example 1 at a rate of 8~ liters/hr, 20 mmoles/hr, and 0.3 mmole/hr (calculatecl as titanium) respectively. Then, ethylene, propylene and hydrogen were simultaneously fed con~iIluously into the polymerization reactor at a rate of 13 kg/hr, 5.0 k~/hr, and 80 liters/hr, respectively. I`he monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm2-G with a residence time of 1 hour.
The concentration of the copolymer was maintaiIled at 118 g/liter of the solu-tion during the polymerization.
The resultin~ copolymer had a density of 0.924 g/cm and an ~II of 2.50, and contained 94.5 mole% of ethylene and 5.5 mole% of propylene.
The copolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Comparative Example 2 A 200-liter continuous polymerization reactor was continuously charged with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described i-n Example 1 at a rate of 80 liters/hr, 20 mmoles/
hr, and 0.3 mmole/hr (calculated as titanium), respectively. Then~ ethylene, l-butene and hydrogen l~cre simultaneously fed continuously into the polymeriza-tion reactor at a rate of 13 kg/hr, 7.0 kg/hr, and 90 liters/hr, respectively.
",,~, ,f~
.lL ~&~
The monomers were polymerized at a polymerization temperature of 150C under a total pressure o:E 30 kg/cm2-G with a residence time of 1 hour. The concentra-tion of the copolymer was maintained at 110 g/liter of the solutior. during the polymerization.
The resulting copolymer had a density of 0.929 g/cm3 and an MI of 2.15, and contained 95.4 mole% of ethylene and 4.6 mole% of l-butene.
The copolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Comparative Example 3 A 200-liter continuous polymerization reactor was charged with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in Example 1 at a rate of 80 liters/hr, 20 mmoles/hr, and 0.4 mmole/hr ~calculated as ti.tanium), respectively. Then, ethylene, 4-methyl-l-pentene, and hydrogen were simultaneously fed continuously into the polymer-ization reactor at a rate of 13 kg/hr, 13 kg/hr, and 110 liters/hr, respecti.vely.
The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm G with a residence time of 1 hour. The concentra-tion of the copolymer was maintained at 107 g/liter of the solution during the polymerization.
The resulting copolymer had a density of 0.922 g/cm and an MI of 3.0~, and contained 96.7 mole% of ethylene, and 3.3 mole% of 4-methyl-1-pentene.
The copolymer was formed into a film under the same conditions as in Example 1. The results are shown in Table 1.
Comparative Example ~
A 200-liter continuous polymerization reactor was charged continuously with dehydrated and purified hexane, diethyl aluminum chloride, and the Ti catalyst component described in Example 1 at a rate of 80 liters/hr, 20 mmoles/
~i ~&~
hr, and 0.4 mmole/hr (calculated as titanium), respectively. Then, ethylene, l-octene, and hydrogen were simultaneously fed continuously into the polymeriza-tion reactor at a rate of 13 kg/hr, 14 kg/hr, and 100 kg/hr, respectively. The monomers were polymerized at a polymerization temperature of 150C under a total pressure of 30 kg/cm G with a residence time of l hour. The concentra-tion of the copolymer was maintained at lll g/liter of the solution during the polymerization.
The resulting copolymer had a density of 0.926 g/cm3 and an MI of 2.90, and contained 97.5 mole% of ethylene and 2.5 mole% of l-octene.
The copolymer was formed into a film under the same conditions as in Example l. The results are shown in Table 1.
~.~,"
-Table 1 Example ~Ex.~ and Ex 1 Ex 2 Ex 3 Ex. 4 Ex. 5Cvmparative Example (CEx.) -Propylene Propylene l-Butene l-Butene Propylene B (2.4) (0.9) (2.6) (0.6) (1.6 Comonomers (content, mole%) 4-Methyl- 4-Methyl- 4-Methyl- 4-Melhyl- 4-~le~hyl-C i-pentene l-pentene l-pentene l-pentene l-pentene (2.1) (3.2) (2.3) (2.7) (2.~) Melt index 2.13 1.94 1.75 2.80 2.35 Density (g/cm ) 0.923 0.920 0.921 0.925 0.922 ~aze (%) 2.0 2.5 1.5 2.5 0.9 Properties Impact strength 1700 2200 1800 2400 2000 of 40 ~- (kg.cm/cm) thick injection Elemendorf MD 77 128 88 120 79 film tear strength (kg/cm) TD 153 190 162 194 148 æ
Table 1 ~continued) Example (Ex.) and Ex. 6 CEx.l CEx.2 CEx.3 CEx.4Comparative Example (CEx.) B Propylene Propylene l-Butene - -(1.2) (5.5) ~4.6 Comonomers (content, mole%) l-Octene - - 4-Methyl- l-Octene C (1.6) l-pen~ene (2.5) (3.3) Melt index 2.45 2.50 2.15 3.04 2.90 Density (g/cm3) 0.923 0.924 0.929 0.922 0.926 Haze (%) 3.0 2.5 3.0 5.0 6.0 Properties Impact strength 2100 1200 1400 2500 2600 of 40 ~- (kg.cm/cm) thick injection Elemendorf MD 81 28 33 153 130 ~
film tear strength '~b (kg/cm) TD 159 83 101 195 175 Q~
Qa ~P
Claims (7)
- WHAT IS CLAIMED IS:
l. A process for producing a random terpolymer of ethylene and alpha-olefins having at least 3 carbon atoms in the presence of a catalyst composed of (1 a titanium catalyst component containing at least magnesium and titanium and (2) an organoaluminum catalyst component in a hydrocarbon solvent at a temperature above the melting point of the terpolymer formed, under such conditions that the resulting copolymer dissolves in the hydrocarbon solvent; characterized in that said terpolymer consists essentially of (A) more than 90 mole% to 99.5 mole% of ethylene, (B) 0.2 mole% to 9.8 mole% of an alpha-olefin with 3 or 4 carbon atoms, and (C) 0.2 mole% to 9.8 mole% of an alpha-olefin with 5 to 18 carbon atoms, the total of the proportions of the monomers (A), (B) and (C) being 100 mole%. - 2. The process of claim 1 wherein said titanium catalyst component is a solid reaction product of (a) the reaction product between an adduct of magnesium chloride with a lower alcohol and an organoaluminum compound, with (b) titanium tetrachloride or titanium tetrachloride and an organoaluminum compound.
- 3. The process of claim 2 wherein the organo-aluminum compound used in preparing the reaction product (a) and optionally also in the reaction between (a) and (b) is at least one organoaluminum compound selected from compounds of formula M1AlR? wherein R1 is a hydrocarbon group having 1 to 15 carbon atoms, M1 is lithium, sodium or potassium, compounds of formula R13-mAlX wherein R1 is as defined herein, X is a halogen atom, and m is zero or a positive number of not greater than 3, compounds of formula R1 3-n Al (OR2)n wherein R1 is as defined herein, R2 is a hydrocarbon group, which is identical to, or different from, R1, and n is a positive number greater than 0 but not greater than 3, and compound of formula R1A1(OR2)X wherein R1, R2 and X are as defined herein.
- 4. The process of claim 1, 2 or 3 wherein the organoaluminum catalyst component (2) is an organoaluminum compound of the general formula R1mAl(OR2)nHpXq wherein R1 and R2 are identical or different, and each repre-sents a hydrocarbon radical having 1 to 15 carbon atoms, X is halogen, m is a number defined by 0 < m ? 3, n is a number defined by 0 < n ? 3, p is a number defined by 0 < p ? 3, and q is a number defined by 0 ? q < 3, provided that m + n + p + q = 3.
- 5. The process of claim 1 wherein the amount of the titanium catalyst com-ponent (1) is 0.0005 to 1 millimole, calculated as Ti atom, per litre of the hydrocarbon solvent, and the amount of the organoaluminum catalyst component (2) is 0.01 to 10 millimoles, calculated as Al atom, per litre of the hydrocarbon solvent.
- 6. The process of claim 5 wherein the Al/Ti mole ratio is from 1 to 1,000.
- 7. The process of claim 1 wherein the alpha-olefin with 5 to 18 carbon atoms is 4-methyl-1-pentene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP127,305/78 | 1978-10-18 | ||
| JP53127305A JPS6011925B2 (en) | 1978-10-18 | 1978-10-18 | Method for producing ethylene copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1188044A true CA1188044A (en) | 1985-05-28 |
Family
ID=14956654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000337801A Expired CA1188044A (en) | 1978-10-18 | 1979-10-17 | Process for producing random ethylene terpolymers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4438243A (en) |
| EP (1) | EP0010428B1 (en) |
| JP (1) | JPS6011925B2 (en) |
| AT (1) | ATE4990T1 (en) |
| CA (1) | CA1188044A (en) |
| DE (1) | DE2966309D1 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA802850B (en) * | 1979-06-18 | 1981-05-27 | Union Carbide Corp | High tear strength polymers |
| JPS56155226A (en) * | 1980-05-02 | 1981-12-01 | Nippon Oil Co Ltd | Manufacture of radiation-bridged polyolefin |
| JPS5738837A (en) * | 1980-08-19 | 1982-03-03 | Mitsubishi Chem Ind Ltd | Production of polyolefin film |
| EP0131617A1 (en) * | 1983-01-10 | 1985-01-23 | Crown Zellerbach Corporation | Films of linear low density polyethylene having improved impact strength |
| FI68632C (en) * | 1983-06-22 | 1985-10-10 | Neste Oy | FOER FARING FRAMSTAELLNING AV SAMPOLYMER AV ETEN OCH LANGKEDJADE ALFA-OLEFINER |
| JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| JPS60195108A (en) * | 1984-03-16 | 1985-10-03 | Mitsui Petrochem Ind Ltd | Titanium-based catalytic component for olefin polymerization |
| FR2563833B1 (en) * | 1984-05-02 | 1986-09-05 | Bp Chimie Sa | PROCESS OF COPOLYMERIZATION IN A FLUIDIZED BED OF ETHYLENE, PROPYLENE AND / OR BUTENE-1 AND ALPHA-OLEFINS CONTAINING 5 TO 8 CARBON ATOMS |
| JPS6136447A (en) * | 1984-07-26 | 1986-02-21 | 元旦ビューティ工業株式会社 | Traverse shingling roof |
| CA2003882C (en) * | 1988-12-19 | 1997-01-07 | Edwin Rogers Smith | Heat shrinkable very low density polyethylene terpolymer film |
| JP2775804B2 (en) * | 1989-02-03 | 1998-07-16 | 東ソー株式会社 | Polyethylene manufacturing method |
| US6025448A (en) * | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
| US5324799A (en) * | 1990-03-06 | 1994-06-28 | Akihiro Yano | Polyethylene and process of production thereof |
| US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
| US6006745A (en) * | 1990-12-21 | 1999-12-28 | Minnesota Mining And Manufacturing Company | Device for delivering an aerosol |
| US5525695A (en) | 1991-10-15 | 1996-06-11 | The Dow Chemical Company | Elastic linear interpolymers |
| US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
| US5395471A (en) * | 1991-10-15 | 1995-03-07 | The Dow Chemical Company | High drawdown extrusion process with greater resistance to draw resonance |
| US5674342A (en) * | 1991-10-15 | 1997-10-07 | The Dow Chemical Company | High drawdown extrusion composition and process |
| US5783638A (en) * | 1991-10-15 | 1998-07-21 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
| US5582923A (en) * | 1991-10-15 | 1996-12-10 | The Dow Chemical Company | Extrusion compositions having high drawdown and substantially reduced neck-in |
| US5180702A (en) * | 1991-12-11 | 1993-01-19 | Phillips Petroleum Company | Metal halide catalyst, method of producing the catalyst, polymerization process employing the catalyst, and polymer produced by the polymerization process |
| US5792534A (en) * | 1994-10-21 | 1998-08-11 | The Dow Chemical Company | Polyolefin film exhibiting heat resistivity, low hexane extractives and controlled modulus |
| BR9609280A (en) * | 1995-05-31 | 1999-05-11 | Sasol Tech Pty Ltd | Polymer process for producing a polymer and polymer composition |
| DE19827328A1 (en) * | 1998-06-19 | 1999-12-23 | Targor Gmbh | Propene terpolymers with a low content of xylene-soluble material, useful for the production of film, fibers, molded products and sealing layer materials |
| EP1112294A1 (en) * | 1998-07-20 | 2001-07-04 | Sasol Technology (Proprietary) Limited | Ethylene terpolymers and process for their preparation |
| CN111662402B (en) * | 2019-03-08 | 2023-02-28 | 浙江大学 | Polyolefin composition and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL302003A (en) * | 1964-02-07 | |||
| CA849081A (en) * | 1967-03-02 | 1970-08-11 | Du Pont Of Canada Limited | PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES |
| FI57264C (en) * | 1972-09-14 | 1980-07-10 | Mitsui Petrochemical Ind | SAETT ATT HOMOPOLYMERISERA ELLER COPOLYMERISERA ETHYL PROPYLEN ELLER ETHLEN OCH ALPHA-OLEFIN OCH / ELLER EN DIOLEFIN SAMT EN CATALYST COMPOSITION FOR ANALYZING VID SAETTET |
| JPS5719122B2 (en) * | 1973-12-26 | 1982-04-21 | ||
| JPS5952643B2 (en) | 1977-01-27 | 1984-12-20 | 三井化学株式会社 | ethylene copolymer |
| US4363904A (en) | 1979-06-18 | 1982-12-14 | Union Carbide Corporation | High tear strength polymers |
-
1978
- 1978-10-18 JP JP53127305A patent/JPS6011925B2/en not_active Expired
-
1979
- 1979-10-17 EP EP79302239A patent/EP0010428B1/en not_active Expired
- 1979-10-17 CA CA000337801A patent/CA1188044A/en not_active Expired
- 1979-10-17 DE DE7979302239T patent/DE2966309D1/en not_active Expired
- 1979-10-17 AT AT79302239T patent/ATE4990T1/en active
-
1981
- 1981-05-14 US US06/263,721 patent/US4438243A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6011925B2 (en) | 1985-03-29 |
| US4438243A (en) | 1984-03-20 |
| DE2966309D1 (en) | 1983-11-17 |
| JPS5554309A (en) | 1980-04-21 |
| ATE4990T1 (en) | 1983-10-15 |
| EP0010428B1 (en) | 1983-10-12 |
| EP0010428A1 (en) | 1980-04-30 |
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