CA1231701A - Process and catalyst for producing polyethylene having a broad molecular weight distribution - Google Patents

Process and catalyst for producing polyethylene having a broad molecular weight distribution

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Publication number
CA1231701A
CA1231701A CA000455866A CA455866A CA1231701A CA 1231701 A CA1231701 A CA 1231701A CA 000455866 A CA000455866 A CA 000455866A CA 455866 A CA455866 A CA 455866A CA 1231701 A CA1231701 A CA 1231701A
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catalyst system
molecular weight
weight distribution
broad
ethylene
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French (fr)
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Howard C. Welborn, Jr.
John A. Ewen
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE
Polyolefins having a broad molecular weight distribution are obtained by polymerizing ethylene or higher alpha-olefins in the presence of a catalyst system comprising two or more metallocenes each having different propagation and termination rate constants and alumoxane.

Description

~Z3~7a~1 .

The present invention concerns ca~alyst and process for the polymerization of etllylene. More particularly, the invention relates to catalysts and process for the polymerization of ethylene to polyethylene having a broad or multimodal molecular weight distribution.
It is known that certain metallocenes such as bis(cyclopentadienyl) titanium or zirconium dialkyls in combination with aluminum alkyl co-catalyst, form homogeneous catalyst systems useful for the polymerization of ethylene. German Patent Application 2,608,863 published 8 September 1977 discloses the use of a catalyst system for the polymerization of ethylene consisting of bis(cyclopentadienyl)titanium dialkyl, aluminum trialkyl and water. German Patent Application 2,608,933 published 8 September 1977 discloses an ethylene polymerization catalyst system consisting of zirconium metallocenes of the general formula (cyclopentadienyl)nZrY4 n' wherein n stands for a number in the range of 1 to 4, Y for R, CH2AlR2l CH2CH2AlR2 and CH2CH(AlR2)2 wherein R stands for alkyl or metallo alkyl;
an aluminum trialkyl cocatalyst and water.
European published Patent Appln. No. 0035242 discloses a process for preparing ethylene and atactic propylene polymers in the presence of a halogen-free Ziegler catalyst system of (1) a cyclopentadienyl compound of the formula (cyclopentadienyl) MeY4 in which n is an integer from 1 to 4, Me is a transition metal, especially zirconium, and Y is either hydrogen, a Cl-C5 alkyl or metallo alkyl group or a group of the general formula CH2AlR2, CH2CH2AlR2 and CH2CH(AlR2)2 in which R represents a Cl-C5 alkyl or metallo alkyl group, and (2) an alumoxane.
3Q The above disclosures demonstrate the usefulness of certain specific metallocer.es in combination with certain aluminum compounds for the polymerization of ethylene and particularly polymerization at a high activity. The above described catalysts comprising titanium and zirconium metallocenes being homogeneous, produce polyethylenes of narrow molecular weight distribution (MWD) i.e. Mw/Mn of from 2-4. Hence, the ~l~;3 3L2317~3~

1 re~erences nei~her disclose polyethylenes having a broad
2 molecular weight distribution and/or a multimodal molecular
3 weight distribution, nor how to obtaln such polyethylenes.
4 U. S. Patent 4,310,648 discloses a catalytic reaction product of a titanium compound, a zirconium compound, an 6 organomagnesium compound and a halide source. The reaction 7 produc~ (a heterogeneous catalyst) when employed in combination 8 wi~h aluminum alkyls is useful for the production at high ~ activity of broad molecular weight polyethylenes.
U. S. Patent 4,361,685 discloses the use of organie soluble 11 chrominum and zirconium compounds to be employed in combination 12 with a supported catalyst system comprising an organometallic 13 activating agent and a trivalent or tetravalent titanium 14 compound. The polymers obtained have a high molecular we~ght and a narrow molecular weight distribution.
16 In " Molecular Weight Distribution And Stereoregularity Of 17 Polypropylenes Obtained With 18 Ti(OC4H914tA12(C2H3)3 Catalyst System"; Polymer, 19 pg. 469-471, 1981, Yol. 22, April, Doi, et al disclose propylene polymerization with a catalyst which at about 41C
21 obtains a soluble catalyst and insoluble catalyst fraction, one 22 w7th "homogeneous catalyt~c centres" and the other with 23 "heterogeneous catalytic centres". The polymerkation at that 24 temperature obtains polypropylene having a bimoda1 mo1ecu7ar weigh$ d~str~bution.
26 It is highly desirable to haYe for many application, such 27 as an extrusion and molding processes, polyethylenes which have 28 a broad molecular weight dlstribution of the unimodal and/or 2 the multimodal typP~ Such polyethylenes evidence excellent 3l processability, i.e., they can be processed at a faster throughput rate with lower energy requirements and at the same 32 time such polymers would evidence reduced melt flow 33 perturbations.
34 In view of the foregoing problems, it would be highly desirable ~o provide a polymer~zation catalyst system of h~gh 36 activ~ty to produce high quality ethylene polymers which ~L~3 ~L~7~iL

1 evidence broad molecular weight distribution. It is 2 furthermore highly desirable to be able tn produce the ethylene 3 polymers d~rectly in a single reactor, i.e., without having to 4 blend polyethylenes having different molecular weights and
5 distr1butions in order to obtain the advantages of this
6 invention-9 The present invention provides polyethylene having a broad ~ molecular we;ght and/or a multimodal molecular weight 11 distribution. The polyethylenes are obtained directly from a ~ single polymerization process, i.e., the polyethylenes of this 13 invention are obtained without requiring blending techniques.
14 The invention furthermore provides a catalyst system for the polymeri7ation of ethy1ene directly to polyethylene having a 16 broad molecular weight distribut~on especially a multimodal 17 molecular weight distribution, and particularly a bimoda1 MWD.
18 The invention further provides a process for polymerizin~
9 ethylene in the presence of the catalyst system.
Accordin~ly~ there is provided catalyst systems and 21 especially systems for the polymerization of ethylene to 22 polyethylene having a broad molecu~ar weight distribution and 23 especially a bimodal or multimodal molecular weight 24 distr~bution; safd catalyst system comprising (a) at least two 2s d~fferent metallocenes each having different propagation and 26 termination rate constants for ethylene polymerizations and ~b) 27 an alumoxane. The metallocenes employed in accordance with 28 this invention are organometallic coordination compounds which 29 are cyclopentadienyl derivatives of a transition metal of Group 4b, 5b and 6b metals of the Periodic Table and include mono, di 31 and tricyclopentadienyls and their derivatives of the 32 transition metals. The metallocenes can be represented by the 33 general formula (CsR m)pR s(C5R m)2MeQ3-P
34 R"s(C5R'm)MeQ', wherein IC5R'm) is a cyclopentadienyl or substituted cyclopentadienyl, each R', which can be the same ~L~3~

1 or different, is hydrogen or a hydrocarbyl radical such as 2 alkyl9 alkenyl, aryl, alkylaryl, or arylalkyl radical having 3 from 1 to 20 carbon atoms or two carbon atoms of the 4 cyclopentadienyl r~ng are joined together to form a C4-C6 ring, R" is a Cl-C4 alkylene radical, a dialkyl germanium 6 or silicone or an alkyl phosphine or amine radical bridging two
7 (C5R'm) rings, Q is a hydrocarbon radical such as aryl,
8 alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1
9 to 20 carbon atoms or halogen and can be the same or differen~, Q' is an alkylidene rad;cal having from 1 to about 20 carbon 11 a$oms, Me is a Group 4b, 5b and 6b metal of the Periodic Table 12 (Chemical Rubber Company's Handbook of Chemistry and Phys~cs, 13 48th Ed1tion), s is O or l, p ~s 0, l or 2; when p = O, s = O;
14 m is 4 when s is 1 and m is 5 when s ~s 0.
The present invention also provides a process for producing 16 polyethylenes having a high molecular weight as well as a broad 17 molecular weight distribution and especially MWD of the bimodal 18 type. The process comprises polymeriz~ng ethylene 19 alone or ethylene with minor amounts of higher alpha-olefins in the presence of the homogeneous catalyst system described above 21 The present invention furthermore provides high molecular 22 weight polyethylene having a ~imodal molecular weight 23 distribution.
24 It is highly surprising that two different metallocenes in combination with an alumoxane can produce polyethylene having a 2~ broad MWD since the individual metal10cenes with an alumoxane 27 generally obtains polyekhylene having a narrow MWD. In 28 acGordance with th~s invention, howeYer, one can advantageously 29 tailor polyethylene ha~ing desired molecular weights and 3 molecuar weight d;stributions by the judicious selection of metallocenes.

33 Figure 1 is a plot of the molecular weight distribution of 34 polyethylene prepared as in Examp7e 1 and in accordance with this invention-3 ~7~

1 Flgure 2 is a plot of the molecular we~ght d~stribution of 2 polyethylene prepared as ~n comparative example IB showing a 3 narrow unimodal MWD.
4 F~gure 3 is a plot of the molecular weight distribution of polyethylene prepared as In comparitive example lA showing a 6 narrow un~modal MWD.
7 Figure 4 is a plot of the mo1ecular weight distr~but~on of 8 polyethylene prepared as in example 2 and showing a b~modal MWD.
9 Figure 5 is a plot of the molecular weight distribution of polyethylene prepared as In example 3 showing a bimodal MWD.

12 The present invention is directed towards a catalytic 13 process for the polymerization of ethylene to high molecular 14 weight polyethylenes evidencing a broad and/or multîmodal molecular weight distribution. The polymers are intended for 16 fabrication into articles by extrusion, injection molding, 17 thermoforming, rotational molding, and the like. In 18 particular, the polymers of this invention are homopo7ymers of 19 ethylene, however, minor amounts of higher alpha-olefins haYing from 3 to about lO carbon atoms and preferably 4 to 8 carbon 21 atoms can be copolymerized with ethylene. IllustratiYe of the 22 higher alpha-olefins are butene-l, hexene-l and octene-l.
23 In the process of the present invention, ethylene, either 24 alone or together with minor amounts of alpha-olefins, is polymerized in the presence of a catalyst system comprising at 26 least two metal~ocenes and an alumoxane.
27 The alumoxanes are well known in the art and are polymeric 28 aluminum compounds which can be represented by the general 29 formulae (R-Al-O)n which is a cyclic compound and R(R-Al-O-)nAlR2, which is a linear compound. In the 31 general formula R is a Cl-C5 alkyl group such as, for 32 example, methyl, ethyl, propy7, buty7 and pentyl and n is an 33 integer ~rom l to about 20. Most preferably, R is methyl.
34 Generally, ~n the preparation of alumoxanes from, for example, ~LZ31~

alumlnum trimethyl and water, a mixture of the linear and 2 cyclic compounds are obta~ned.
3 The alumoxanes can be prepared ~n various ways.
4 Preferab1y, they are prepared by contacting water with a solution of aluminum trialkyl, such as, for example, aluminum 6 trimethyl, in a suitable organic solvent such as benzene or an 7 aliphat~c hydrocarbon. For example, the aluminum alkyl is 8 treated with water in the form of a mo~st solvent or the g aluminum alkyl such as aluminum trimethyl can be desirably contacted with a hydrated salt such as hydrated copper sulfato.
11 Preferably, the alumoxane is prepared in the presence of a 12 hydrated copper sulfate. The method comprises treating a 13 dilute solution of aluminum trimethyl in, for example, toluene, 14 with copper sulfate represented by the general formula CuS04.5H20. The ratio of copper sulfate to aluminum 16 trimethyl is desirably about 1 mole o~ copper sulfate for 5 17 moles of aluminum trimethyl. The reaction is evidenced by the 18 evolution of methane.
19 The metallocenes employed each should have different propagation and termination rate constants with respect to 21 ethy1ene polymerization. Such rate constants can be determined 22 by one of ordinary skill in the art. The metallocenes are the 23 organometallic coo~dination compound which are the mono, di and 24 tricyclopentadienyls and their derivatives of a transltion 2S metal of Group 4b, 5b and 6b metals of the Periodic Tab7e. The 26 more desirable metallocenes employed in accordance with the 27 invention are represented by the general formula 28 (C5R'm)pR"s(C5R'm)MeQ3 p and 29 RUs(C5R'm3~MeQ' wherein (C5R'm) is cyclopentadienyl or substituted cyclopentadienyl, each R' is the same or 31 different and is hydrogen or a hydrocarbyl radical such as 32 alkyl, alkenyl, aryl, alkylaryl7 or arylalkyl radicals 33 containing from 1 to 20 carbon atoms or two adJacent carbon 34 atoms are joined together to form a C4-C6 ring, R" is a Cl-C4 alkylen~ radical, a dialkyl germanium or silicone or 36 an alkyl phosphine or amine radical bridging two ~C5R'm) 1~317~

1 r~ngs, Q ls a hydrocarbyl radical such as aryl, alkyl, alkenyl, 2 alkylaryl, or arylalkyl radical hav~ng from 1-2~ carbon atoms 3 or halogen and can be the same or different, Q' ~s-an 4 alkyl~dene rad~cal havlng from 1 to about 20 carbon atoms, s is 0 or 1? p is 0, 1 or 2; when p is 0, is 0, m is 4 when s is 1 and m is 5 when s is 0 and Me is a Group 4b, 5b or 6b metal of 7 the Periodic Table.
8 Exemplary hydrocarbyl radicals are methyl, ethyl, propyl, 9 ~utyl, amyl, isoamyl, hexyl, isobutyl~ heptyl; octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl, and the like.
11 Exemplary alkylene radicals are methylene, ethylene, 2 propylene, and the like.
13 Exemplary halogen atoms include chlorine, bromine and 14 iodlne and of these halogen atoms, chlorine is preferred.
-15 Exemplary of the alkylid radicals i5 methylidene, 16 ethylidene and propylidene.
17 The multiple metallocene system usefully employed in 18 accordance with this invention are preferably the mono, bi and 19 tricyclopentadienyl or subs$ituted cyclopentadienyl titanium (IV) and zirsonium (lV) compounds represented by the general 21 formula.
22 Illustrative but non-limiting examples of the titanocenes 23 whtch can be usefully employed in accordance with this 24 ; ment;Dn are monocyclopentadienyl titanocenes, such as cyclopentadienyl titanium trichl~ride, 26 pentamethylcyclopentadienyl titanium trichloride;
27 bis(cyclopentadienyl) titanium diphenyl, the carbene 28 represented by the formula Cp2Ti=CH2 Al(CH3)~Cl, 29 and derivatives of th~s reagent such as CP2T; CH2 A~tCH3)3, (cp2TicH2)2~
31 Cp2TiCH2CH~CH3)CH2, Cp2Ti CHCH2C,H2, 32 Cp2Ti=CH2 AlR'!'2Cl, wherein Cp is a cyclopentadienyl 33 or substituted cylopentad~enyl radical, and R "' is an alkyl, 34 aryl or alkylaryl radical having from 1-18 carbon atoms;
subst~tuted bts(Cp)Ti(IY) compounds such as b~s(lndenyl)Tt ~LZ3~L7~

1 d~phenyl or dichlor~de, bis(methylcyclopentadienyl)Ti dipheny~
2 or d~halides and other d~halide complexes; dialkyl~ tr~alkyl, 3 tetra-alkYl and penta-alkyl cyclopentad~enyl titan~um 4 compounds, such as bis(l,2-dimethylcyclopentadienyl)Ti diphenyl or dichloride, bis(l,2-diethylcyclopentadienyl)Ti diphenyl or 6 dichloride and other dihalide complexes.
7 Illustrative but non-limiting examples of the zirconocenes 8 which can be useful1y employed in accordance with th~s 9 invention are monocyclopentadienyl zirconocenes, such as cyclopentadienyl zirconium trichloride, pentamethyl 11 cyclopentadienyl zirconium trichloride;
12 bis(cyclopentadienyl)zirconium diphenyl, 3 bis~cyclopentadienyl)zirconium dimethyl9 the alkyl substituted 14 cyclopentadienes, such as bis(ethyl cyclopentadienyl)~irconium ~ h~l~ bis(B-phenylpropylcyclopentadienyl)zirconium 16 dimethyl, bis(methylcyclopentadienyl)zirconium dimethyl, and 7 dihalide complexes of the above. Di-alkyl, tri-alkyl, 18 tetra-alkyl, and penta-alkyl cyclopentadienes, such as 19 bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis ~1,2-dimethylcyclopentadlenyl)zirconium dimethyl, 21 bis(l~3-diethylcyclopentadienyl)zircofiium dimethyl and dihalide 22 complexes of the above. Silicone~ phosphorus, and carbon 23 bridged cyclopentadiene complexes such as 24 dimethylsilyldicyclopentadienyl zirconium d;methyl or dihalide, methy7phosphine dioyclopentadieQyl zirconium dimethyl or 26 dihalide, and methylene dicyclopentadienyl zirconium dimethyl 27 or dihalide, carbenes represented by the formulae 28 Cp2~r=CH2P(C6H5)20H3, and derivatives of these 29 compounds such as Cp2ZrCH2CH(OH3)CH2.
Bis(cyclopentad;enyl)hafnium d~chloride, 31 bis~cyclopentadienyl)hafnium dimethyl, 32 bis(cyclopentadienyl)vanadium dichloride are illustrative of 33 other metallocenes.
34 The ratio of aluminum in the alumoxane to total metal in the metallocenes can be ~n the range of about 0.5:1 to about 36 105:1, and preferably about 5:1 to about 103:1. The molar 37 ratio of zirconocene to titanocene can vary over a wide range ~ ~23~L7~

1 and in accordance with this ~nvent~on the only limitat~on on ~ the molar ratios is the breadth of the MW distr~butlon or the 3 degree of bi~odal~ty desired in the product polymer.
4 Desirably, the zirconocene to titanocene molar ratio will be about 1:100 to about 100:1, and preferably 1:10 to about 1:1.
6 The solvents used in the preparation of the cata1yst system 7 are inert hydrocarbons, in particular a hydrocarbon that is 8 inert with respect to the catalyst system. Such solvents are ~ well known and include, for example, butane, isobutane, pentane9 hexanè, heptane, octane, cyclohexane, 11 methylcyclohexane, toluene, xylene and the like.
12 The catalyst systems described herein are suitable for the 13 polymerization of ethylene either in solution, slurry or gas 14 phase over a wide range of tempera~ures and pressures. For example, such temperatures may be ~n the range of about -60C
16 to about 280C and especially in the range of about 50C to 17 160C. The pressures employed ~n the process of the present 18 invent~on are those well known for, for example, in the range 19 of about 1 to about 500 atmospheres and even greater.
In a solution phase polymeri7ation the alumoxane and 21 metallocene can be employed as a homogeneous catalyst system.
22 The alumoxane is preferably dissolved in a suitable solven~, 23 typically in inert hydrocarbon solvent such as toluene, ~ylene~
24 and the like in molar concentrations of about O.lM to 3M, 2s however, greater or lesser amounts can be employed.
26 The soluble metallocenes can be converted to supported 27 heterogeneous catalyst by depositing said metallocenes on 28 typical catalyst supports such ~s, for example9 silica, 29 alumina, and polyethylene, The solid catalysts in combination wi~h an alumoxane can be usefully employed in slurry and gas 31 phase olefin polymer~zation.
32 After po1ymerization and deactlvation of the catalyst, the 33 product polymer can be recovered by processes well known in the 34 art for removal of deact~vated catalysts and solut~on. The solvents may be flashed o~f from the polymer solution and the 36 obtained polymer e~truded into water and cut into pellets or 37 other suitable comminuted shapes. Pigments, antioxidants and ~23~
- 10 -1 other additives, as ~s known in the art, may be added to the 2 polymer.
3 The polymer product obtained in accordance with this 4 invention will have an average molecular weight in the range of about 500 to about 2,000,000 and prefèrab7y 10,000 to about 500,000. The polymer will also have concentrations of average 7 molecular weights in the range oP about 500 to about 1009000 8 and 100,000 to 1,000,000 for each sample.
9 The polymers produced by the process of this present invention are capable of being fabricated into a wide variety 1 of articles, as is known for homopolymers of ethylene and 12 copolymers of ethylene and higher alpha-olefins. The present 13 invention is illustrated by the following examples.
14 In the examples following the molecular weights were de~ermined on a Water's Associates Model No. 150C GPC (Gel 16 Permeation Chromatography). The measurements were made by 17 dissolving polymer samples in hot trichlorobenzene ~TCB) and 18 f~ltered. The GPC runs were performed at 14soc in TCB at 1.5 19 ml/min using two Shodex A80 M/S Gel columns of 9.4 ~m internal diameter From Perkin Elmer Inc. 300 milliliter of 3.1 percent 21 solutions in TCB were injected and the chromo~agraphic runs 22 monitored at sensitivity equal -64 and scale factor equal 65.
23 The samples were run in dup1icate. The integration parameters 24 were obtained with a Water's Associates data module. An 25 antioxidant, N-phenyl-2-naphthylamine, was added to all samples.

27 In the examples following the alumoxane was prepared in the 28 following manner:
29 600CC of a 14.5g solution of trimethylaluminum (TMA) in heptane was added ~n 30cc increments at 5 minute intervals, 31 with rapid stirring, to 200cc toluene in a Zippoclave reactor 32 under nitrogen and maintained at 100C. Each increment was 33 immediately followed by the addition of 0.3cc water. The 34 reactor was vented of methane after each addition. Upon - -1 complet~on of the addition, the reactor was stirred for 6 hours 2 while maintaining the temperature at 100C~ The mixture~
3 contains soluble alumoxane and insoluble materials, is allowed 4 to coDl to room temperature and settle. The clear solution con~aining the soluble alumoxane is separated by decantation from the solids.

7 Example 1 8 A l-liter stainless steel pressure vessel, equipped with an g ;ncline blade stirrer, an external water jacket for temperature control~ a septum inlet and vent l~ne, and a regulated supply
11 of dry ethylene and nitrogen, was dried and deoxygenated with a
12 nitrogen flow. 500cc of dry, degassed toluene was intrnduced
13 directly into the pressure vessel. 20~0cc of alumoxane
14 solution ~0.64 molar in total aluminum) was injected into the vessel by a gas tight syringe through the septum inlet and the 16- mixture was stirred a~ 00 rpms and ~0C for ~ minutes at 0 17 ps7g of nitrogen. 0.091 mg bis~pentamethyl 18 cyclopentadienyl)zirconium dimethyl dissolved in l.D ml of dry~
19 distilled toluene ~as injected through the septum inlet into the vessel followed by the injection of 0.906 mg 21 bis(cyclopentadienyl) titanium dipheQyl in 10 ml of toluene.
22 After 1 minute, ethylene at 50 psig was admltted and while the 23 reaction vessel was ma~ntained at 50C. The ethylene was 24 passe~ into the vessel ~or 40 minutes at which time the reaction was stopped by rapidly venting and cooling the 26 reactor. 20.1 gms of powdery white polyethylene having a Mn of 27 5B,600 and a Mw of 323,000 with a molecular weight distribution 28 of 5.51. The GPC as shown in Fig. 1 showed a bimodal molecular 29 weight distribution.

Comparative Example lA
31 Ethylene was polymerized wnder conditions identical to th~t 32 of Example 1 with the exception that the zirconocene only was 33 employed in combination with the alumoxane. 0.102 mg of the 34 zirconocene was empl oyed. 20.6 gm of polyethylene was ~Z39L7~

1 obtained. The polyethylene had a Mn of 42,000 and ~w of 2 139,000 with a MWD of 3.31. The GPC as appears in Figure 3 3 evidenced a unimodal molecular weight distribution.

4 ComparatiYe E~ample lB
Ethylene was polymer~zed under conditions identical to that 6 of Example 1 with the exception that the titanocene only was 7 employed in combination with the alumoxane. 1.02 mg of the 8 titanocene was employed. 13.2gm of polyethylene was obtafned.
9 The polyethylene had a Mn of 184,000 and Mw of 558,000 with a lo MWD of 3.03. The GPC as appears in Figure 2 evidenced a 1 unimodal molecular weight distr~bution.

12 Example 2 13 A l-liter stainless steel pressure vessel, equipped with an 14 incline blade stirrer, an external water jacket for temperature csntrol~ a septum inlet and vent line, and a regulated supply 6 of dry ethylene and nitrogen9 was dried and deoxygenated with a nitrogen flow~ 400cc of dry, degassed toluene was introduoed 18 directly into the pressure vessel. 20.0cc of alumoxane (8 19 mmoles in total aluminum) was Injected into the vessel by a gas tight syringe through the septum inlet and the mixture was 21 stirred at 1,200 rpms and 80~C for 5 minutes at 0 ps~g of 2 nitr~gen. 0.0~5 ~9 b;slcyclopentadienyl) zircon~um dimethyl 23 d~ssolved ~n 1.0 ml of dry, distilled toluene was injected 4 through the septum inlet into the vessel followed by the injection of 5.18 mg bis~cyc7Opentadienyl)titanium d7phenyl in 26 10 ml of toluene. After 1 minute, e~hylene at 60 psig was 27 admitted for 40 minutes while maintaining the reaction vessel 28 at 80C. The reaction was stopped by rapidly venting and 29 cool~ng. 10.7 gms of powdery white polyethylene having a Mn of 63,000 and a Mw of 490,000 with a molecular weight distribution 31 of 7.8. The GPC as shown in Fig. 4 showed a bimodal molecular 32 wei ght di stribution.

1~3~1l7~3:~L

1 Example 3 2 A l-liter stainless steel pressure vessel, equ~pped with an 3 incline blade st;rrer, an external water jacket for temperature 4 control, a septum inlet and vent line~ and a reguiated supply of dry ethylene and nitrogen, was dried and deoxygenated with a 6 n~trogen flow. 400cc of dry, de~assed toluene was introduced 7 directly into the pressure vessel. 2Q.Occ of alumoxane (8 8 mmoles in total aluminum) was injected into the vessel by a gas 9 tight syringe through the septum inlet and the mixture was lo stirred at 1,200 rpms and 50C for 5 minutes at 0 psig of 11 nitrogen. 0.1~1 mg bis(cyclopentadienyl) zirconium d;methyl 12 dissolved in 1.0 ml of dry, distilled toluene was inject~d 13 through the septum inlet into the vessel followed by the 14 injection of 5.5 mg bis(cyclopentadienyl) titanium diphenyl in 10 ml of toluene. After 1 minute, ethylene at 60 psig was 16 admitted for 40 minutes while maintaining the reaction vessel 17 at 50C. The reaction was stopped by rapidly venting and 18 cooling. 13.8 gms of powdery white polyethylene having a Mn of 19 16,500 and a Mw of 89,000 with a molecular weight d~stribution of 5.4. The GPC as shown in Fig. 5 showed a bimodal molecular 21 we~ght distribut~on.
22 Example 4 23 A l-liter stainless steel pressure vessel, e~uipped with an 24 incline blade stirrer, an external water jacket for temperature control, a septum inlet and vent line, and a regulated supply 26 of dry ethylene and nitrogen, was dried and deoxygenated with a 27 nitrogen flow. 400cc of dry, degassed toluene was introduced 28 direct1y into the pressure vessel. 20.0cc of alumoxane (15 29 mmoles in total aluminum) was injected into the vessel by a gas tight syringe through the s~ptum inlet ~nd the mixture was 31 stirred at 1,200 rpms and 80C for 5 minutes at 0 psig of 32 nitrogen. 0.231 mg bislcyclopentadienyl) ~irconium dimethyl 33 and 0.260 bis(ethylcyclopentadienyl)zirconium dimethyl, each 34 dissolved in 1.0 ml of dry distilled toluene, were injected ~hrough the septum inlet into the vessel followed by the 7~
~ 14 -1 ~n~ect~on of 0.535 mg bis(cyclopentadienyl)titanium diphenyl In 2 10 ml of toluene. After 1 minute, ethylene at 60 psig was 3 admitted for 40 minutes while maintaining the reaction vessel 4 at 80~C. The reaction was stopped by rapidly venting and cooling. 24.0 gms of powdery white polyethylene having a Mn of 6 43,000 and a Mw of 191,000 with a molecular weight distribut~on 7 of 4.4.

8 Example 5 9 A l-liter stainless steel pressure vessel9 equipped with an lo incline blade stirrer, an external water jacket for temperature 11 control, a septum inlet and vent lineJ and a regulated supply 12 of dry ethylene and nitrogen, was dried and deoxygenated with a 13 nitrogen flow. 400cc of dry, degassed toluene was introduced 14 directly into the pressure vessel. 20.0cc of alumoxane (15 mmoles in total aluminum~ was injected into the vessel by a gas 16 tight syringe through the septum inlet and the m~xture was 17 stirred at 1,200 rpms and 80C for 5 minutes at 0 ps~g of 18 nitrogen. .201 mg bis(cyclopentad~enyl)~irconium dimethyl and 9 0.216 mg bis(ethyl cyc1Opentad~enyl)zirconium dimethyl each dissolved in 1.0 ml of dry distilled toluene were injected 21 through the septum inlet into the vessel followed by the 22 inject~on of 0.506 mg bis(cyclopentadienyl) titanium diphenyl 23 in 10 ml of toluene. After 1 minute, ethylene at 50 psig was 24 admltted for 40 minutes while maintain~ng the reaction vessel at 80C. The reaction was stopped by rapidly venting and 26 cooling. 25.2 gms of powdery white polyethylene having a Mn of 27 3917 and a Mw of 168,000 with a molecular weight distribution 28 of 4.2 and bimodal Mw distribution.

29 Example 6 A l-liter stainless steel pressure vessel, equipped with an 31 incline b7ade stirrer, an external water jacket for temperature 32 control, a septum inlet and vent line, and a regulated supply 33 of dry ethylene and nitrogen, was dried and deoxygenated with a 34 nitrogen flow. 50Qcc of dry, degassed toluene was introduced ~L23~
- 15 -1 directly into the pressure vessel. lO.Occ of alumoxane (8 2 moles total aluminum) was injected into the vessel by a gas 3 tight syringe through the septum inlet and the mixture was 4 stirred at l,200 rpms and 80C for 5 minutes at 0 psly of nitrogen. 0.260 mg bis(cyclopentadienyl)zircon;um dimethyl and 6 0.204 mg bis(ethyl cyclopentadienyl)zirconlum dimethyl each 7 dissolved in l.0 ml of dry distilled toluene were injected 8 through the septum inlet into the vessel. After l minute, 9 ethylene at 60 psig was a~mitted for 12 minutes while maintaining the reaction vessel at 80C. The reaction was 11 stopped by rapidly venting and cooling. 32.0 gms of powdery 12 white polyethylene having a Mn of 47,100 and a Mw of 183,000 13 wlth a molecular weight distribution of 3.9.

Claims (7)

    THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
    OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
    1. A catalyst system for the (co)polymerization of ethylene to polyethylene having a broad molecular weight distribution, said catalyst comprising (a) at least two different metallocenes selected from mono, di or tricyclopentadienyls and their derivatives of a Group 4b, 5b and 6b transition metal each having different propagation and termination rate constants for ethylene polymerizations and (b) an alumoxane.

    2. The catalyst system of claim 1 wherein the transition metals are selected from titanium and zirconium.

    3. A catalyst system for the (co)polymerization of ethylene to polyethylene having a broad and/or multimodal molecular weight distribution; said catalyst comprising:
    (a) at least two or more metallocenes represented by the general formula (C5R')pR"s(C5R'm)MeQ3-p or R"s(C5R'm)2MeQ', each having a different propagation and termination rate constant, and (b) an alumoxane wherein (C5R'm) is a cyclopentadieny1 or substituted eyclopentadienyl, each R' wh;ch can be the same or different is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyt radicals having from 1 to 20 carbon atoms or two carbon atoms of the cyclopentadienyl ring are joined together to form a C4-C6 ring, R" is a C1-C4 alkylene radical, a dialkyl germanium or silicone or alkyl phosphine or amine radical bridging two (C5R'm) rings, Q is a hydrocarbon radical such as aryl, alkyl, alkenyl, alkylaryl, or arylakyl radicals having from 1-20 carbon atoms or halogen and can be the same or different, Q' is an alkylidene radical having from 1 to about 20 carbon atoms, Me is a Group 4b, 5b or 6b metal, s is 0 or 1, p is 0, 1 or 2, when p is 0, s is 0; m is 4 when s is 1 and m is 5 when s is 0.

    4. The catalyst system of claim 3 comprising two zirconocenes.

    5. The catalyst system of claim 3 comprising two titanocenes.

    6. The catalyst system of claim 4 comprising at least 2 zirconocenes and 1 titanocene.

    7. The homogeneous catalyst system of claim 5 comprising at least 2 titanocenes and 1 zirconocene.

    8. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  1. claim 1.

    9. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  2. claim 2.

    10. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  3. claim 3.

    11. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  4. claim 4.

    12. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  5. claim 5.

    13. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  6. claim 6.

    14. A process for producing polyethylene having a broad and/or multimodal molecular weight distribution comprising polymerizing ethylene in the presence of the catalyst system of
  7. claim 7.
CA000455866A 1983-06-06 1984-06-05 Process and catalyst for producing polyethylene having a broad molecular weight distribution Expired CA1231701A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5703180A (en) * 1992-11-19 1997-12-30 Mitsui Petrochemical Industries, Ltd. Catalyst for olefin polymerization, process for olefin polymerization using the same, ethylene/α-olefin copolymer, graft modified ethylene/α-olefin copolymer, and ethylene copolymer composition
US6001941A (en) * 1992-11-19 1999-12-14 Mitsui Chemicals, Inc. Ethylene α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin
US11325342B2 (en) 2016-12-27 2022-05-10 Eneos Corporation Adhesive tape

Families Citing this family (365)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5580939A (en) * 1983-06-06 1996-12-03 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US4937299A (en) * 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
ZA844157B (en) * 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
CA1231702A (en) * 1983-06-06 1988-01-19 John A. Ewen Process and catalyst for producing reactor blend polyolefins
FR2570381B1 (en) * 1984-09-17 1987-05-15 Bp Chimie Sa PROCESS FOR THE POLYMERIZATION OF ETHYLENE OR OF THE COPOLYMERIZATION OF ETHYLENE AND ALPHA-OLEFIN IN A FLUIDIZED BED IN THE PRESENCE OF A CATALYST BASED ON CHROMIUM OXIDE
JPH0788403B2 (en) * 1984-11-01 1995-09-27 昭和電工株式会社 Method for producing polyolefin
DE3443087A1 (en) * 1984-11-27 1986-05-28 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING POLYOLEFINES
US4704491A (en) * 1985-03-26 1987-11-03 Mitsui Petrochemical Industries, Ltd. Liquid ethylene-alpha-olefin random copolymer, process for production thereof, and use thereof
JPH0639496B2 (en) * 1985-06-03 1994-05-25 旭化成工業株式会社 Olefin Polymerization Method
CA1268754A (en) * 1985-06-21 1990-05-08 Howard Curtis Welborn, Jr. Supported polymerization catalyst
US4808561A (en) * 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4897455A (en) * 1985-06-21 1990-01-30 Exxon Chemical Patents Inc. Polymerization process
US4701432A (en) * 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
US5124418A (en) * 1985-11-15 1992-06-23 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4791180A (en) * 1985-12-12 1988-12-13 Exxon Chemical Patents Inc. New polymerization catalyst
US4752597A (en) * 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
IL80888A (en) * 1985-12-12 1991-12-12 Exxon Chemical Patents Inc Olefin polymerization catalysts,their preparation and use thereof
US6013743A (en) * 1985-12-24 2000-01-11 Mitsui Chemicals Inc. Process for polymerization of alpha-olefins
US5641843A (en) * 1985-12-24 1997-06-24 Mitsui Petrochemical Industries, Ltd. Process for polymerization of alpha-olefins
JPH0780930B2 (en) * 1985-12-26 1995-08-30 三井石油化学工業株式会社 Method for polymerizing α-olefin
US5700750A (en) * 1985-12-26 1997-12-23 Mitsui Petrochemical Industries, Ltd. Process for polymerization of alpha-olefins
US4658078A (en) * 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
KR920001353B1 (en) * 1986-08-26 1992-02-11 미쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 Catalyst for polymerizing alpha-olefin and polymerization process
US5654248A (en) * 1986-08-26 1997-08-05 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing alpha-olefins and process for polymerization
US5077255A (en) * 1986-09-09 1991-12-31 Exxon Chemical Patents Inc. New supported polymerization catalyst
US5084534A (en) * 1987-06-04 1992-01-28 Exxon Chemical Patents, Inc. High pressure, high temperature polymerization of ethylene
US5700749A (en) * 1986-09-24 1997-12-23 Mitsui Petrochemical Industries, Ltd. Process for polymerizing olefins
DE3786013T2 (en) 1986-09-24 1993-09-02 Mitsui Petrochemical Ind POLYMERIZATION PROCESS FOR OLEFINS.
JPH03503674A (en) * 1986-11-20 1991-08-15 エヌディーイー・テクノロジー・インコーポレーテッド Volume leak detection system for underground storage tanks, etc.
JPH0780933B2 (en) * 1986-11-20 1995-08-30 三井石油化学工業株式会社 Olefin Polymerization Method
DE3640924A1 (en) * 1986-11-29 1988-06-01 Hoechst Ag 1-OLEFIN STEREOBLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
KR910008277B1 (en) * 1986-12-03 1991-10-12 미쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 Solid catalyst olefin polymerization and process its preparation
JP2618384B2 (en) * 1986-12-27 1997-06-11 三井石油化学工業株式会社 Solid catalyst for olefin polymerization and its preparation
JPH0742301B2 (en) * 1987-02-14 1995-05-10 三井石油化学工業株式会社 Particulate aluminoxane, its manufacturing method and its use
US5003019A (en) * 1987-03-02 1991-03-26 Mitsui Petrochemical Industries, Ltd. Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers
US4874880A (en) * 1987-03-10 1989-10-17 Chisso Corporation Bis(di-, tri- or tetra-substituted-cyclopentadienyl)-zirconium dihalides
US4794096A (en) * 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US5064797A (en) * 1987-04-03 1991-11-12 Phillips Petroleum Company Process for producing polyolefins and polyolefin catalysts
ES2082745T3 (en) 1987-04-03 1996-04-01 Fina Technology METALLOCAN CATALYTIC SYSTEMS FOR THE POLYMERIZATION OF OLEFINS PRESENTING A SILICON HYDROCARBON BRIDGE.
US4939217A (en) * 1987-04-03 1990-07-03 Phillips Petroleum Company Process for producing polyolefins and polyolefin catalysts
JP2538588B2 (en) * 1987-04-03 1996-09-25 三井石油化学工業株式会社 Method for producing solid catalyst for olefin polymerization
DE3726067A1 (en) 1987-08-06 1989-02-16 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
US4975403A (en) * 1987-09-11 1990-12-04 Fina Technology, Inc. Catalyst systems for producing polyolefins having a broad molecular weight distribution
DE3750776T2 (en) * 1987-09-11 1995-04-27 Fina Technology Catalyst system for polyolefin production with a broad molecular weight distribution.
JPH0713075B2 (en) * 1988-06-20 1995-02-15 チッソ株式会社 Zirconium compounds with bridged bis-substituted cyclopentadienyl ligands
US4931417A (en) * 1987-11-09 1990-06-05 Chisso Corporation Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure
JPH0720973B2 (en) * 1988-06-20 1995-03-08 チッソ株式会社 Hafnium compounds with bridged bis-substituted cyclopentadienyl ligands
US4912075A (en) * 1987-12-17 1990-03-27 Exxon Chemical Patents Inc. Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization
DE3808267A1 (en) * 1988-03-12 1989-09-21 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
US5120867A (en) * 1988-03-21 1992-06-09 Welborn Jr Howard C Silicon-bridged transition metal compounds
US5017714A (en) * 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
US5008228A (en) * 1988-03-29 1991-04-16 Exxon Chemical Patents Inc. Method for preparing a silica gel supported metallocene-alumoxane catalyst
KR100197327B1 (en) * 1988-07-15 1999-06-15 치어즈 엠. 노우드 Syndiotactic polypropylene
US4892851A (en) * 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5043515A (en) * 1989-08-08 1991-08-27 Shell Oil Company Ethylene oligomerization catalyst and process
DE3840772A1 (en) * 1988-12-03 1990-06-07 Hoechst Ag METHOD FOR PRODUCING A HETEROGENIC METALLOCENE CATALYST COMPONENT
EP0685496A1 (en) 1988-12-26 1995-12-06 Mitsui Petrochemical Industries, Ltd. Olefin copolymers and processes for preparing same
US5830087A (en) * 1995-06-26 1998-11-03 Lisco, Inc. Multi-layer golf ball
DE3907964A1 (en) * 1989-03-11 1990-09-13 Hoechst Ag METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN
DE3916553A1 (en) 1989-05-20 1990-11-22 Hoechst Ag SYNDIO ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
US5004820A (en) * 1989-08-07 1991-04-02 Massachusetts Institute Of Technology Preparation of chiral metallocene dihalides
US6025448A (en) * 1989-08-31 2000-02-15 The Dow Chemical Company Gas phase polymerization of olefins
US6075077A (en) * 1989-08-31 2000-06-13 The Dow Chemical Company Asphalt, bitumen, and adhesive compositions
US6686488B2 (en) 1989-08-31 2004-02-03 The Dow Chemical Company Constrained geometry addition polymerization catalysts
NZ235032A (en) * 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
US7041841B1 (en) 1989-09-13 2006-05-09 Exxonmobil Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5026798A (en) 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5547675A (en) * 1989-09-13 1996-08-20 Exxon Chemical Patents Inc. Modified monocyclopentadienyl transition metal/alumoxane catalyst system for polymerization of olefins
US5036034A (en) * 1989-10-10 1991-07-30 Fina Technology, Inc. Catalyst for producing hemiisotactic polypropylene
US5151204A (en) * 1990-02-01 1992-09-29 Exxon Chemical Patents Inc. Oleaginous compositions containing novel ethylene alpha-olefin polymer viscosity index improver additive
MY141000A (en) * 1990-04-18 2010-02-12 Mitsui Chemicals Inc Process for the preparation of an ethylene copolymer and an olefin polymer, and catalysts for olefin polymerization
DE4015254A1 (en) * 1990-05-12 1991-11-14 Hoechst Ag METHOD FOR PRODUCING A POLYOLEFIN
US5070055A (en) * 1990-06-29 1991-12-03 Union Carbide Chemicals And Plastics Technology Corporation Novel coimpregnated vanadium-zirconium catalyst for making polyethylene with broad or bimodal MW distribution
US6538080B1 (en) 1990-07-03 2003-03-25 Bp Chemicals Limited Gas phase polymerization of olefins
US5272236A (en) * 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5169818A (en) * 1991-01-12 1992-12-08 Hoechst Aktiengesellschaft Metallocene (co)polymers, process for their preparation and their use as catalysts
US5262498A (en) * 1991-01-12 1993-11-16 Hoechst Aktiengesellschaft Metallocene (co)polymers, process for their preparation and their use as catalysts
CA2060019A1 (en) * 1991-03-04 1992-09-05 Phil Marvin Stricklen Process for producing polyolefins having a bimodal molecular weight distribution
ES2182929T3 (en) 1991-03-09 2003-03-16 Basell Polyolefine Gmbh METALOCENE AND CATALYST.
JP3117231B2 (en) * 1991-03-11 2000-12-11 三井化学株式会社 Method for producing syndiotactic poly-α-olefin having a broad molecular weight distribution
US5418200A (en) * 1991-03-29 1995-05-23 Chevron Chemical Company Cyclopentadienyl group 6B metal α-olefin polymerization catalysts and process for polymerizing α-olefins
US5436305A (en) * 1991-05-09 1995-07-25 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
US5466766A (en) * 1991-05-09 1995-11-14 Phillips Petroleum Company Metallocenes and processes therefor and therewith
US5399636A (en) * 1993-06-11 1995-03-21 Phillips Petroleum Company Metallocenes and processes therefor and therewith
EP0702030B1 (en) * 1991-05-27 2001-03-21 TARGOR GmbH Process for preparing olefin polymers with large molecular weight distribution
DE59204800D1 (en) * 1991-05-27 1996-02-08 Hoechst Ag Process for the production of syndiotactic polyolefins with a broad molecular weight distribution
US5693583A (en) * 1991-06-10 1997-12-02 Mobil Oil Corporation High activity polyethylene catalysts which produce bimodal or trimodal product molecular weight distributions
US5409874A (en) * 1991-06-20 1995-04-25 Mitsui Petrochemical Industries, Ltd. Catalyst for olefin polymerization, process for the polymerization of olefin, and transition metal compound employable for the catalyst
US5594078A (en) * 1991-07-23 1997-01-14 Phillips Petroleum Company Process for producing broad molecular weight polyolefin
US5411925A (en) * 1993-02-12 1995-05-02 Phillips Petroleum Company Organo-aluminoxy product and use
US5250612A (en) * 1991-10-07 1993-10-05 The Dow Chemical Company Polyethylene films exhibiting low blocking force
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
US5525695A (en) * 1991-10-15 1996-06-11 The Dow Chemical Company Elastic linear interpolymers
US5783638A (en) * 1991-10-15 1998-07-21 The Dow Chemical Company Elastic substantially linear ethylene polymers
US5674342A (en) * 1991-10-15 1997-10-07 The Dow Chemical Company High drawdown extrusion composition and process
US5582923A (en) * 1991-10-15 1996-12-10 The Dow Chemical Company Extrusion compositions having high drawdown and substantially reduced neck-in
US5677383A (en) * 1991-10-15 1997-10-14 The Dow Chemical Company Fabricated articles made from ethylene polymer blends
US5847053A (en) * 1991-10-15 1998-12-08 The Dow Chemical Company Ethylene polymer film made from ethylene polymer blends
JP3378598B2 (en) * 1991-10-28 2003-02-17 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー Catalyst composition
US5286694A (en) * 1991-12-11 1994-02-15 Phillips Petroleum Company Lanthanide halide catalyst, method of producing the catalyst, and polymerization process employing the catalyst
US5182244A (en) * 1991-12-19 1993-01-26 Phillips Petroleum Company Transition metal/rare earth catalyst and olefin polymerization process
US5260244A (en) * 1991-12-19 1993-11-09 Phillips Petroleum Company Transition metal/rare earth catalyst, olefin polymeration process, and polymer produced
ES2095037T3 (en) 1991-12-30 1997-02-01 Dow Chemical Co POLYMERIZATIONS OF ETHYLENE INTERPOLYMERS.
US6184326B1 (en) 1992-03-20 2001-02-06 Fina Technology, Inc. Syndiotactic polypropylene
US6143854A (en) * 1993-08-06 2000-11-07 Exxon Chemical Patents, Inc. Polymerization catalysts, their production and use
US5308817A (en) * 1992-05-18 1994-05-03 Fina Technology, Inc. Metallocene catalyst component with good catalyst efficiency after aging
US6043401A (en) * 1992-05-26 2000-03-28 Bp Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US5688887A (en) * 1992-05-26 1997-11-18 Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US5710222A (en) 1992-06-22 1998-01-20 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
DE69326463T2 (en) * 1992-07-01 2000-05-04 Exxon Chemical Patents Inc OLEFIN POLYMERIZATION CATALYSTS BASED ON TRANSITIONAL METALS
US5332707A (en) * 1992-07-31 1994-07-26 Amoco Corporation Olefin polymerization and copolymerization catalyst
US5317036A (en) * 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
CA2103380C (en) * 1992-11-19 2002-07-02 Mitsui Chemicals, Inc. Ethylene/.alpha.-olefin copolymer composition, graft modified ethylene/.alpha.-olefin copolymer composition, ethylene copolymer composition, and multi-stage olefin polymerization process
GB9224876D0 (en) † 1992-11-27 1993-01-13 Exxon Chemical Patents Inc Improved processing polyolefin blends
US5608019A (en) * 1992-12-28 1997-03-04 Mobil Oil Corporation Temperature control of MW in olefin polymerization using supported metallocene catalyst
US5420220A (en) * 1993-03-25 1995-05-30 Mobil Oil Corporation LLDPE films
US5332706A (en) * 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
US5602067A (en) * 1992-12-28 1997-02-11 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
PT681592E (en) * 1993-01-29 2001-01-31 Dow Chemical Co ETHYLENE INTERPOLIMERIZATIONS
US5350807A (en) * 1993-06-25 1994-09-27 Phillips Petroleum Company Ethylene polymers
CA2129794A1 (en) * 1993-08-10 1995-02-11 Toshiyuki Tsutsui Olefin polymerization catalysts and methods of olefin polymerization
US5459117A (en) * 1993-08-27 1995-10-17 Ewen; John A. Doubly-conformationally locked, stereorigid catalysts for the preparation of tactiospecific polymers
US5631202A (en) 1993-09-24 1997-05-20 Montell Technology Company B.V. Stereospecific metallocene catalysts with stereolocking α-CP substituents
DE4333128A1 (en) * 1993-09-29 1995-03-30 Hoechst Ag Process for the preparation of polyolefins
US5455741A (en) * 1993-10-26 1995-10-03 Pulse Engineering, Inc. Wire-lead through hole interconnect device
ZA948934B (en) * 1993-11-15 1996-05-10 Mobil Oil Corp Catalyst composition for use in the polymerization and copolymerization of ethylene
US5614456A (en) * 1993-11-15 1997-03-25 Mobil Oil Corporation Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers
US5399622A (en) * 1993-11-17 1995-03-21 Phillips Petroleum Company System of chromium catalyst and yttrium catalyst, olefin polymerization process, and polymer
DE69419893T2 (en) * 1993-12-27 1999-12-02 Mitsui Chemicals Inc Catalyst and process for olefin polymerization
US5543376A (en) * 1994-02-25 1996-08-06 Phillips Petroleum Company Process for producing polyolefins
US5624877A (en) * 1994-02-25 1997-04-29 Phillips Petroleum Company Process for producing polyolefins
US5648438A (en) * 1994-04-01 1997-07-15 Exxon Chemical Patents, Inc. Process for producing polymers with multimodal molecular weight distributions
US5541272A (en) 1994-06-03 1996-07-30 Phillips Petroleum Company High activity ethylene selective metallocenes
IT1270253B (en) * 1994-06-20 1997-04-29 Spherilene Srl ETHYLENE COPOLYMERS AND PROCEDURE FOR THE PREPARATION OF ETHYLENE POLYMERS
EP0766702B1 (en) * 1994-06-24 2001-10-17 ExxonMobil Chemical Patents Inc. Polymerization catalyst systems, their production and use
US5453471B1 (en) 1994-08-02 1999-02-09 Carbide Chemicals & Plastics T Gas phase polymerization process
KR100221164B1 (en) * 1994-08-18 1999-09-15 야마모토 카즈모토 High-density ethylene polymer and method for producing the same
EP0779837B1 (en) 1994-09-08 2001-08-01 Mobil Oil Corporation Catalytic control of the mwd of a broad/bimodal resin in a single reactor
US5525678A (en) * 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
US5741195A (en) * 1994-09-30 1998-04-21 Lisco, Inc. High visibility inflated game ball
US5773106A (en) * 1994-10-21 1998-06-30 The Dow Chemical Company Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus
US5549867A (en) * 1994-11-03 1996-08-27 Fiberweb North America, Inc. Distribution enhanced polyolefin meltspinning process and product
US6506866B2 (en) 1994-11-17 2003-01-14 Dow Global Technologies Inc. Ethylene copolymer compositions
US5543484A (en) * 1994-11-18 1996-08-06 The Penn State Research Foundation α-olefin/para-alkylstyrene copolymers
US5625015A (en) 1994-11-23 1997-04-29 Exxon Chemical Patents Inc. Method for making supported catalyst systems and catalyst systems therefrom
ES2116188B1 (en) 1994-12-30 1999-04-01 Repsol Quimica Sa PROCESS OF OBTAINING POLYOLEFINES WITH WIDE, BIMODAL OR MULTIMODAL MOLECULAR WEIGHT DISTRIBUTIONS.
US5670589A (en) * 1995-02-08 1997-09-23 Phillips Petroleum Company Organoaluminoxy product, catalyst systems, preparation, and use
DE59503159D1 (en) * 1995-02-17 1998-09-17 Witco Gmbh Process for the preparation of transition metal complexes with 1,3-disubstituted cyclopentadienyl ligands
US5593931A (en) * 1995-03-03 1997-01-14 Chevron Chemical Company Cyclopentadienyl group 6b metal alpha-olefin polymerization catalysts and process for polymerizing alpha-olefins
BE1009186A3 (en) * 1995-03-13 1996-12-03 Solvay Solid catalyst for the (co) polymerization of ethylene, preparation process for system catalyst for the (co) polymerization of ethylene and method (co) polymerization of ethylene.
US5830958A (en) * 1995-05-12 1998-11-03 Phillips Petroleum Company Polynuclear metallocene preparation and use
US5882750A (en) * 1995-07-03 1999-03-16 Mobil Oil Corporation Single reactor bimodal HMW-HDPE film resin with improved bubble stability
US5869575A (en) * 1995-08-02 1999-02-09 The Dow Chemical Company Ethylene interpolymerizations
WO1997006187A1 (en) 1995-08-10 1997-02-20 Exxon Chemical Patents Inc. Metallocene stabilized alumoxane
US5652202A (en) * 1995-08-15 1997-07-29 Exxon Chemical Patents Inc. Lubricating oil compositions
US6403772B1 (en) * 1995-09-11 2002-06-11 Montell Technology Company, Bv Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom
US5558802A (en) * 1995-09-14 1996-09-24 Exxon Chemical Patents Inc Multigrade crankcase lubricants with low temperature pumpability and low volatility
EP0768319A1 (en) * 1995-09-29 1997-04-16 Nippon Oil Co. Ltd. Process for the production of polyolefins
US5795941A (en) * 1995-10-03 1998-08-18 The Dow Chemical Company Crosslinkable bimodal polyolefin compositions
US6486089B1 (en) 1995-11-09 2002-11-26 Exxonmobil Oil Corporation Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution
EP0866081A4 (en) * 1995-12-08 2000-12-20 Kaneka Corp Grafted polyolefin resin and thermoplastic resin composition containing the same
TR199601005A2 (en) 1995-12-15 1997-07-21 Union Carbide Chem Plastic The method for the production of long chain, branched polyolefins.
US6395669B1 (en) * 1996-01-18 2002-05-28 Equistar Chemicals, Lp Catalyst component and system
NO960350A (en) 1996-01-26 1997-04-28 Borealis As Process and catalyst system for the polymerization of ethylene, optionally together with <alpha> olefins, and prepared polymeric material
US6417130B1 (en) 1996-03-25 2002-07-09 Exxonmobil Oil Corporation One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization
US5644007A (en) * 1996-04-26 1997-07-01 Minnesota Mining And Manufacturing Company Continuous process for the production of poly(1-alkenes)
JPH09309926A (en) * 1996-05-17 1997-12-02 Dow Chem Co:The Production of ethylene copolymer
CN1113900C (en) * 1996-06-17 2003-07-09 埃克森美孚化学专利公司 Mixed transition metal catalyst system for olefin polymerization
GB9613814D0 (en) * 1996-07-02 1996-09-04 Bp Chem Int Ltd Supported polymerisation catalysts
US6248837B1 (en) 1996-07-15 2001-06-19 The Penn State Research Foundation Process for preparing polyolefin diblock copolymers involving borane chain transfer reaction in transition metal-mediated olefin polymerization
AU3505497A (en) * 1996-07-15 1998-02-09 Mobil Oil Corporation Comonomer pretreated bimetallic catalyst for blow molding and film applications
US5849823A (en) * 1996-09-04 1998-12-15 The Dow Chemical Company Homogeneously branched ethylene α-olefin interpolymer compositions for use in gasket applications
RU2194708C2 (en) * 1996-11-15 2002-12-20 Монтелл Текнолоджи Компани Б.В. Metallocene, ligand, catalytic system, method of polymerization
US6177377B1 (en) * 1996-12-18 2001-01-23 Amherst Polymer Technology, Inc. Polymer blends and process for preparation
US6005463A (en) * 1997-01-30 1999-12-21 Pulse Engineering Through-hole interconnect device with isolated wire-leads and component barriers
ES2187005T3 (en) 1997-02-07 2003-05-16 Exxonmobil Chem Patents Inc PROPYLENE POLYMERS THAT INCLUDE POLYETHYLENE MACROMERS.
ES2277381T5 (en) 1997-02-07 2014-02-06 Exxonmobil Chemical Patents Inc. Preparation of vinyl containing macromers
US6552126B2 (en) 1997-03-03 2003-04-22 Spalding Sports Worldwide, Inc. Golf ball cover containing a blend of ionomer and plastomer, and method of making same
US6143683A (en) * 1997-04-09 2000-11-07 Fina Technology, Inc. Metallocene catalyst and catalyst system for polymerizing an olefin having at least 3 carbon atoms
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
US6153551A (en) * 1997-07-14 2000-11-28 Mobil Oil Corporation Preparation of supported catalyst using trialkylaluminum-metallocene contact products
US6051525A (en) * 1997-07-14 2000-04-18 Mobil Corporation Catalyst for the manufacture of polyethylene with a broad or bimodal molecular weight distribution
WO1999010389A1 (en) 1997-08-21 1999-03-04 Sumitomo Chemical Company, Limited Modified particles, carrier prepared therefrom, olefin polymerization catalyst component prepared therefrom, olefin polymerization catalyst prepared therefrom, and process for preparing olefin polymer
US6114483A (en) * 1997-08-27 2000-09-05 E. I. Du Pont De Nemours And Company Polymerization of olefins
US6184327B1 (en) 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers
US6117962A (en) * 1997-12-10 2000-09-12 Exxon Chemical Patents Inc. Vinyl-containing stereospecific polypropylene macromers
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
ES2198098T3 (en) 1998-03-09 2004-01-16 Basell Poliolefine Italia S.P.A. MULTIETAPE PROCEDURE FOR POLYMERIZATION OF OLEFINS.
JP4440355B2 (en) 1998-03-25 2010-03-24 住友化学株式会社 Modified particle, carrier comprising the same, catalyst component for olefin polymerization comprising the same, catalyst for olefin polymerization comprising the same, and method for producing olefin polymer
US6306960B1 (en) 1998-05-13 2001-10-23 Exxonmobil Chemical Patents Inc. Articles formed from foamable polypropylene polymer
US6784269B2 (en) 1998-05-13 2004-08-31 Exxonmobil Chemical Patents Inc. Polypropylene compositions methods of making the same
EP1078009B1 (en) 1998-05-13 2004-06-16 ExxonMobil Chemical Patents Inc. Propylene homopolymers and methods of making the same
US6207606B1 (en) * 1998-05-15 2001-03-27 Univation Technologies, Llc Mixed catalysts and their use in a polymerization process
US6245868B1 (en) 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
DE69911128T2 (en) * 1998-07-21 2004-07-08 Japan Polychem Corp. Olefin polymerization catalyst and process for making olefin polymers
CA2245375C (en) 1998-08-19 2006-08-15 Nova Chemicals Ltd. Dual reactor polyethylene process using a phosphinimine catalyst
CA2341167A1 (en) 1998-08-26 2000-03-09 Exxon Chemical Patents Inc. Branched polypropylene compositions
CA2247703C (en) 1998-09-22 2007-04-17 Nova Chemicals Ltd. Dual reactor ethylene polymerization process
US6258903B1 (en) * 1998-12-18 2001-07-10 Univation Technologies Mixed catalyst system
US6291608B1 (en) * 1998-12-23 2001-09-18 Phillips Petroleum Company Polymerization catalyst system and polymerization process
US6174930B1 (en) 1999-04-16 2001-01-16 Exxon Chemical Patents, Inc. Foamable polypropylene polymer
TW444043B (en) 1999-05-11 2001-07-01 Ind Tech Res Inst Resin compositions for electric circuit boards
DE19929809A1 (en) 1999-06-30 2001-01-04 Ticona Gmbh Continuous process for the production of an amorphous polyolefin with a broad molar mass distribution and uniform glass temperature
CA2278042C (en) 1999-07-19 2008-12-16 Nova Chemicals Corporation Mixed phosphinimine catalyst
US6265493B1 (en) 1999-07-21 2001-07-24 The Penn State Research Foundation Polyolefin graft copolymers derived from linear copolymers of alpha-olefins and divinylbenzene having narrow molecular weight and composition distributions and process for preparing same
US6096849A (en) * 1999-07-21 2000-08-01 The Penn State Research Foundation Linear copolymers of alpha-olefins and divinylbenzene having narrow molecular weight and composition distributions and process for preparing same
US6369176B1 (en) * 1999-08-19 2002-04-09 Dupont Dow Elastomers Llc Process for preparing in a single reactor polymer blends having a broad molecular weight distribution
US6403520B1 (en) 1999-09-17 2002-06-11 Saudi Basic Industries Corporation Catalyst compositions for polymerizing olefins to multimodal molecular weight distribution polymer, processes for production and use of the catalyst
US6274684B1 (en) * 1999-10-22 2001-08-14 Univation Technologies, Llc Catalyst composition, method of polymerization, and polymer therefrom
US6294626B1 (en) 1999-11-15 2001-09-25 Equistar Chemicals, Lp Olefin polymerization catalysts containing modified boraaryl ligands
ES2239631T3 (en) * 1999-12-10 2005-10-01 Exxonmobil Chemical Patents Inc. COMPOLIMERIZED PROPYLENE AND DIENO POLYMERS.
US6809168B2 (en) * 1999-12-10 2004-10-26 Exxonmobil Chemical Patents Inc. Articles formed from propylene diene copolymers
US6977287B2 (en) * 1999-12-10 2005-12-20 Exxonmobil Chemical Patents Inc. Propylene diene copolymers
US6444605B1 (en) 1999-12-28 2002-09-03 Union Carbide Chemicals & Plastics Technology Corporation Mixed metal alkoxide and cycloalkadienyl catalysts for the production of polyolefins
US6399531B1 (en) 1999-12-28 2002-06-04 Union Carbide Chemicals & Plastics Technology Corporation Hybrid ziegler-natta and cycloalkadienyl catalysts for the production of polyolefins
ATE239057T1 (en) 2000-02-15 2003-05-15 Asahi Chemical Ind POLYAMIDE COMPOSITION
US6455638B2 (en) 2000-05-11 2002-09-24 Dupont Dow Elastomers L.L.C. Ethylene/α-olefin polymer blends comprising components with differing ethylene contents
US6444765B1 (en) 2000-06-14 2002-09-03 Equistar Chemicals, Lp Olefin polymerization process for producing broad MWD polymers
US6812304B2 (en) 2000-06-14 2004-11-02 Equistar Chemicals, Lp Process for producing improved premixed supported boraaryl catalysts
US6518445B1 (en) 2000-12-15 2003-02-11 Albemarle Corporation Methylaluminoxane compositions, enriched solutions of such compositions, and the preparation thereof
US6388051B1 (en) 2000-12-20 2002-05-14 Union Carbide Chemicals & Plastics Technology Corporation Process for selecting a polyethylene having improved processability
US6479600B2 (en) 2001-01-08 2002-11-12 The Penn State Research Foundation Polyolefin containing a terminal phenyl or substituted phenyl group and process for preparing same
MY137183A (en) * 2001-03-16 2009-01-30 Dow Global Technologies Inc Method of making interpolymers and products made therefrom
GB0111443D0 (en) * 2001-05-10 2001-07-04 Borealis Tech Oy Olefin polymerisation process
CA2347410C (en) 2001-05-11 2009-09-08 Nova Chemicals Corporation Solution polymerization process catalyzed by a phosphinimine catalyst
SG96700A1 (en) * 2001-09-27 2003-06-16 Sumitomo Chemical Co Catalyst component for addition polymerization, process for producing catalyst for addition polymerization and process for producing addition polymer
WO2003048213A1 (en) * 2001-11-30 2003-06-12 Exxonmobil Chemical Patents, Inc. Ethylene/alpha-olefin copolymer made with a non-single-site/single-site catalyst combination, its preparation and use
US6916892B2 (en) * 2001-12-03 2005-07-12 Fina Technology, Inc. Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropylene
CN1304120C (en) * 2002-03-19 2007-03-14 英国石油化学品有限公司 Separation of gases and solids using a cyclone
WO2003087114A1 (en) * 2002-04-12 2003-10-23 Dow Global Technologies Inc. Azaborolyl group 4 metal complexes, catalysts and olefin polymerization process
ES2291639T3 (en) * 2002-06-04 2008-03-01 UNION CARBIDE CHEMICALS &amp; PLASTICS TECHNOLOGY CORPORATION POLYMER COMPOSITIONS AND METHOD TO PREPARE PIPES OF THEM.
US20030236365A1 (en) * 2002-06-24 2003-12-25 Fina Technology, Inc. Polyolefin production with a high performance support for a metallocene catalyst system
KR101021433B1 (en) * 2002-08-16 2011-03-15 존슨 앤드 존슨 비젼 케어, 인코포레이티드 A mold for producing contact lenses, a method of making a lens, a lens, and a method for making a coated lenses
EP1546223A2 (en) * 2002-09-20 2005-06-29 ExxonMobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US8008412B2 (en) * 2002-09-20 2011-08-30 Exxonmobil Chemical Patents Inc. Polymer production at supersolution conditions
US20080153997A1 (en) * 2006-12-20 2008-06-26 Exxonmobil Research And Engineering Polymer production at supercritical conditions
US7183364B2 (en) * 2002-12-20 2007-02-27 University Of Maryland, College Park Process for preparation of polyolefins via degenerative transfer polymerization
US7541412B2 (en) * 2002-12-20 2009-06-02 University Of Maryland, College Park Process for preparation of polyolefins via degenerative transfer polymerization
US7199072B2 (en) * 2002-12-31 2007-04-03 Univation Technologies, Llc Process of producing a supported mixed catalyst system and polyolefins therefrom
US7195806B2 (en) * 2003-01-17 2007-03-27 Fina Technology, Inc. High gloss polyethylene articles
CN100351275C (en) 2003-03-21 2007-11-28 陶氏环球技术公司 Morphology controlled olefin polymerization process
US7119153B2 (en) * 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
DE102004008313B4 (en) * 2004-02-20 2014-01-16 Wankel Super Tec Gmbh Rotary piston internal combustion engine with an improved inner gasket
DE602004006223T2 (en) * 2004-03-12 2008-01-17 Saudi Basic Industries Corp. A catalyst composition for the polymerization of olefins and polymerization processes using the same
CN1938341B (en) * 2004-04-07 2011-08-10 尤尼威蒂恩技术有限责任公司 Method of controlling olefin polymerization
US20050234198A1 (en) * 2004-04-20 2005-10-20 Fina Technology, Inc. Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system
KR100677869B1 (en) * 2004-07-01 2007-02-02 대림산업 주식회사 Multinuclear metal compound, catalyst system including the same, and olefin polymerization process using the same
BRPI0513057A (en) * 2004-07-08 2008-04-22 Exxonmobil Chem Patents Inc polymer production under supercritical conditions
US20060052540A1 (en) 2004-09-09 2006-03-09 Maria Ellul Thermoplastic vulcanizates
EP1650232A1 (en) * 2004-10-25 2006-04-26 Total Petrochemicals Research Feluy LDPE-Like polymers with bisindenyl-based ligands having different rings
US7169864B2 (en) * 2004-12-01 2007-01-30 Novolen Technology Holdings, C.V. Metallocene catalysts, their synthesis and their use for the polymerization of olefins
US7323523B2 (en) * 2004-12-07 2008-01-29 Nova Chemicals (International) S.A. Adjusting polymer characteristics through process control
US7321015B2 (en) * 2004-12-07 2008-01-22 Nova Chemicals (International) S.A. Adjusting polymer characteristics through process control
US7064096B1 (en) * 2004-12-07 2006-06-20 Nova Chemicals (International) Sa Dual catalyst on a single support
WO2006065651A2 (en) 2004-12-17 2006-06-22 Dow Global Technologies Inc. Rheology modified polyethylene compositions
JP5154754B2 (en) * 2005-01-31 2013-02-27 三井化学株式会社 Ethylene polymer and molded product obtained therefrom
US20060205898A1 (en) * 2005-03-08 2006-09-14 Goyal Shivendra K Dual reactor polyethylene resins with balanced physical properties
US7868088B2 (en) * 2005-03-17 2011-01-11 University Of Maryland, College Park Methods for modulated degenerative transfer living polymerization and isotactic-atactic stereoblock and stereogradient poly(olefins) thereby
WO2006102106A1 (en) * 2005-03-17 2006-09-28 University Of Maryland, College Park Methods for modulated degenerative transfer living polymerization and isotactic-atactic stereoblock and stereogradient poly(olefins) thereby
US20060235147A1 (en) * 2005-04-14 2006-10-19 Nova Chemicals (International) S.A. Dual reactor polyethylene resins for food packaging - films, bags and pouches
JP5158304B2 (en) * 2005-04-21 2013-03-06 東ソー株式会社 Method for producing polyethylene
US20060247373A1 (en) * 2005-04-28 2006-11-02 Nova Chemicals (International) S.A. Dual reactor polyethylene resins for electronic packaging-films, tapes, bags and pouches
US7232869B2 (en) * 2005-05-17 2007-06-19 Novolen Technology Holdings, C.V. Catalyst composition for olefin polymerization
WO2007025556A1 (en) * 2005-08-30 2007-03-08 Pirelli & C. S.P.A. Process for manufacturing a thermoplastic elastomeric material
US7714082B2 (en) * 2005-10-04 2010-05-11 Univation Technologies, Llc Gas-phase polymerization process to achieve a high particle density
US7531602B2 (en) * 2005-10-05 2009-05-12 Nova Chemicals (International) S.A. Polymer blends
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
KR100886681B1 (en) 2006-03-31 2009-03-04 주식회사 엘지화학 Process for preparing linear low density polyethylene
EP1847555A1 (en) * 2006-04-18 2007-10-24 Borealis Technology Oy Multi-branched Polypropylene
RU2008122073A (en) * 2006-05-02 2009-12-10 Дау Глобал Текнолоджиз Инк. (Us) COMPOSITIONS OF HIGH DENSITY POLYETHYLENE, THE METHOD OF PRODUCING THEM, THE WIRING AND CABLES SHAPED, PRODUCED FROM THEM, AND THE METHOD OF PRODUCING SUCH WIRING AND CABLES
US7456244B2 (en) * 2006-05-23 2008-11-25 Dow Global Technologies High-density polyethylene compositions and method of making the same
US7662894B2 (en) * 2006-12-19 2010-02-16 Saudi Bosic Industries Corporation Polymer supported metallocene catalyst composition for polymerizing olefins
US8242237B2 (en) * 2006-12-20 2012-08-14 Exxonmobil Chemical Patents Inc. Phase separator and monomer recycle for supercritical polymerization process
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
US7754834B2 (en) * 2007-04-12 2010-07-13 Univation Technologies, Llc Bulk density promoting agents in a gas-phase polymerization process to achieve a bulk particle density
ATE450569T1 (en) 2007-05-02 2009-12-15 Dow Global Technologies Inc HIGH DENSITY POLYETHYLENE COMPOSITIONS, METHOD FOR PRODUCING THEREOF, INJECTION MOLDED ARTICLES MADE THEREFROM AND METHOD FOR PRODUCING SUCH ARTICLES
US8487033B2 (en) * 2007-05-16 2013-07-16 Exxonmobil Chemical Patents Inc. Thermoplastic elastomer compositions, methods for making the same, and articles made therefrom
US8470939B2 (en) * 2007-06-01 2013-06-25 Equistar Chemicals, Lp Preparation of polyethylene
JP2010529253A (en) * 2007-06-04 2010-08-26 エクソンモービル・ケミカル・パテンツ・インク Very homogeneous solution polymerization of propylene
WO2008154068A1 (en) * 2007-06-13 2008-12-18 Advanced Elastomer Systems, L.P. Thermoplastic polymer compositions, methods for making the same, and articles made therefrom
US7981517B2 (en) * 2007-08-28 2011-07-19 Dow Global Technologies Inc. Bituminous compositions and methods of making and using same
EP2201042B1 (en) * 2007-09-13 2012-06-27 ExxonMobil Research and Engineering Company In-line blending of plasticizers with a base polymer
EP2195349B1 (en) * 2007-09-13 2012-07-11 ExxonMobil Research and Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
TW200936619A (en) * 2007-11-15 2009-09-01 Univation Tech Llc Polymerization catalysts, methods of making, methods of using, and polyolefin products made therefrom
WO2011087520A1 (en) 2009-12-22 2011-07-21 Univation Technologies, Llc Catalyst systems having a tailored hydrogen response
JP5308797B2 (en) 2007-12-11 2013-10-09 住友化学株式会社 Olefin polymerization reaction apparatus, polyolefin production system, and polyolefin production method
JP5249730B2 (en) 2007-12-11 2013-07-31 住友化学株式会社 Olefin polymerization reaction apparatus and polyolefin production method
JP5308794B2 (en) 2007-12-11 2013-10-09 住友化学株式会社 Polyolefin production method using spouted bed apparatus
JP5308795B2 (en) 2007-12-11 2013-10-09 住友化学株式会社 Polyolefin production method and polyolefin production system provided with spouted bed apparatus
JP5427396B2 (en) 2007-12-11 2014-02-26 住友化学株式会社 Powder transfer apparatus and polyolefin production method
EP2223802B1 (en) 2007-12-19 2015-09-09 Japan Polyethylene Corporation Resin for foamable layered product, foamable layered product, and foamed converted paper and heat-insulating container both obtained from the same
CN103254497B (en) 2007-12-20 2015-11-18 埃克森美孚研究工程公司 Produce the online blend method of the blend of polypropylene and ethylene-propylene copolymer
US7910679B2 (en) * 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
CN101945942B (en) * 2007-12-20 2012-08-08 埃克森美孚研究工程公司 In-line process to produce pellet-stable polyolefins
US8318875B2 (en) 2008-01-18 2012-11-27 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization and polypropylenes made therefrom
EP2083046A1 (en) 2008-01-25 2009-07-29 ExxonMobil Chemical Patents Inc. Thermoplastic elastomer compositions
EP2172490A1 (en) 2008-10-03 2010-04-07 Ineos Europe Limited Controlled polymerisation process
WO2010050570A1 (en) 2008-10-30 2010-05-06 三井・デュポンポリケミカル株式会社 Multilayer sheet, solar cell element sealing material and solar cell module
WO2010071798A1 (en) 2008-12-18 2010-06-24 Univation Technologies, Llc Method for seed bed treatment for a polymerization reaction
RU2011135979A (en) 2009-01-30 2013-03-10 ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи COMPOSITIONS OF HIGH DENSITY POLYETHYLENE, THE METHOD OF PRODUCING THEREOF, PRODUCED FROM THEM, CUPS AND THE METHOD OF MANUFACTURING SUCH CARE PRODUCTS
WO2010095603A1 (en) 2009-02-17 2010-08-26 三井・デュポンポリケミカル株式会社 Solar cell sealing sheet and solar cell module
PL2414087T3 (en) 2009-03-30 2019-06-28 Toray Industries, Inc. Microporous membranes, method for making such membranes, and the use of such membranes as battery separator film
JP5588433B2 (en) 2009-05-13 2014-09-10 三井・デュポンポリケミカル株式会社 Solar cell encapsulant sheet and solar cell module
CN102414228B (en) 2009-05-14 2014-05-07 尤尼威蒂恩技术有限责任公司 Mixed metal catalyst systems having a tailored hydrogen response
JP5545800B2 (en) 2009-06-08 2014-07-09 住友化学株式会社 Jet-fluidized bed type olefin polymerization reactor, polyolefin production system, and polyolefin production method
ES2547867T3 (en) 2009-06-29 2015-10-09 Chevron Phillips Chemical Company Lp The use of hydrogen elimination catalysts to control the molecular weight of the polymer and hydrogen levels in a polymerization reactor
KR101741855B1 (en) 2009-06-29 2017-05-30 셰브론 필립스 케미컬 컴퍼니 엘피 Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates
US8710147B2 (en) 2009-12-18 2014-04-29 Chevron Oronite Company Llc. Carbonyl-ene functionalized polyolefins
EP2357035A1 (en) 2010-01-13 2011-08-17 Ineos Europe Limited Polymer powder storage and/or transport and/or degassing vessels
EP2383298A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
EP2383301A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
WO2011159400A1 (en) 2010-06-15 2011-12-22 Exxonmobil Chemical Patents Inc. Nonwoven fabrics made from polymer blends and methods for making same
RU2608124C2 (en) 2010-11-29 2017-01-13 Инеос Коммершиал Сервисиз Юк Лимитед Method of controlling polymerisation
CA2824771A1 (en) 2011-01-14 2012-07-19 W.R. Grace & Co.-Conn. Process of making modified metallocene catalyst, catalyst produced and use thereof
SG184672A1 (en) 2011-03-25 2012-10-30 Sumitomo Chemical Co Olefin polymerization reactor, polyolefin production system, and polyolefin production process
US8383740B1 (en) 2011-08-12 2013-02-26 Ineos Usa Llc Horizontal agitator
EP2573091A1 (en) 2011-09-23 2013-03-27 Lummus Novolen Technology Gmbh Process for recycling of free ligand from their corresponding metallocene complexes
RU2608615C2 (en) 2011-10-17 2017-01-23 Инеос Юроуп Аг Control over polymers degassing process
KR101339550B1 (en) * 2011-11-24 2013-12-10 삼성토탈 주식회사 A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same
KR101331556B1 (en) 2012-03-30 2013-11-20 대림산업 주식회사 Multimodal polyolefin resin and article prepared with the same
US8940842B2 (en) * 2012-09-24 2015-01-27 Chevron Phillips Chemical Company Lp Methods for controlling dual catalyst olefin polymerizations
US8865846B2 (en) * 2012-09-25 2014-10-21 Chevron Phillips Chemical Company Lp Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers
KR101437509B1 (en) 2012-12-03 2014-09-03 대림산업 주식회사 Catalyst composition for preparing multimodal polyolefin resin having superior moldability and mechanical properties and polymerization method using the same
EP2938620B1 (en) 2012-12-28 2020-09-02 Univation Technologies, LLC Methods of integrating aluminoxane production into catalyst production
US9938361B2 (en) 2013-01-14 2018-04-10 Univation Technologies, Llc Methods for preparing catalyst systems with increased productivity
WO2016094843A2 (en) 2014-12-12 2016-06-16 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system comprising mesoporous organosilica support
US10351639B2 (en) 2014-12-12 2019-07-16 Exxonmobil Research And Engineering Company Organosilica materials for use as adsorbents for oxygenate removal
EP3274380B1 (en) 2015-04-20 2020-08-19 ExxonMobil Chemical Patents Inc. Catalyst composition comprising fluorided support and processes for use thereof
US10618989B2 (en) 2015-04-20 2020-04-14 Exxonmobil Chemical Patents Inc. Polyethylene composition
JP6621845B2 (en) 2015-05-08 2019-12-18 エクソンモービル ケミカル パテンツ インコーポレイテッド Polymerization method
JP6499927B2 (en) 2015-06-10 2019-04-10 Ｊｘｔｇエネルギー株式会社 Network structure
KR101850985B1 (en) 2015-06-15 2018-04-20 주식회사 엘지화학 Method for preparing supported metallocene catalyst
KR101810740B1 (en) 2015-09-25 2017-12-20 롯데케미칼 주식회사 Method for preparing polyolefin and polyolefin prepared therefrom
WO2018063764A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018063765A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018063767A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018118155A1 (en) 2016-12-20 2018-06-28 Exxonmobil Chemical Patents Inc. Polymerization process
US11193008B2 (en) 2017-04-10 2021-12-07 Exxonmobil Chemical Patents Inc. Methods for making polyolefin polymer compositions
WO2018208414A1 (en) 2017-05-10 2018-11-15 Exxonmobil Chemical Patents Inc. Catalyst systems and processes for using the same
KR20190063794A (en) 2017-11-30 2019-06-10 롯데케미칼 주식회사 Polyolefin composition having imporoved stress resistance
WO2019118073A1 (en) 2017-12-13 2019-06-20 Exxonmobil Chemical Patents Inc. Deactivation methods for active components from gas phase polyolefin polymerization process
WO2019173030A1 (en) 2018-03-08 2019-09-12 Exxonmobil Chemical Patents Inc. Methods of preparing and monitoring a seed bed for polymerization reactor startup
WO2019213227A1 (en) 2018-05-02 2019-11-07 Exxonmobil Chemical Patents Inc. Methods for scale-up from a pilot plant to a larger production facility
WO2019217173A1 (en) 2018-05-02 2019-11-14 Exxonmobil Chemical Patents Inc. Methods for scale-up from a pilot plant to a larger production facility
WO2020014138A1 (en) 2018-07-09 2020-01-16 Exxonmobil Chemical Patents Inc. Polyethylene cast films and methods for making the same
US11383483B2 (en) 2018-07-26 2022-07-12 Exxonmobil Chemical Patents Inc. Multilayer foam films and methods for making the same
US20200087495A1 (en) 2018-09-14 2020-03-19 Fina Technology, Inc. Polyethylene and controlled rheology polypropylene polymer blends and methods of use
US20220025135A1 (en) 2018-11-13 2022-01-27 Exxonmobil Chemical Patents Inc. Polyethylene Films
CN113207293B (en) 2018-11-13 2023-08-04 埃克森美孚化学专利公司 Polyethylene blends and films
KR102474477B1 (en) 2018-11-29 2022-12-05 롯데케미칼 주식회사 Polyolefin composition having imporoved stress resistance
KR102116476B1 (en) 2019-01-18 2020-05-28 대림산업 주식회사 Catalyst composition for polymerizing polyolefin, method for producing polyolefin, and polyolefin resin
WO2020163079A1 (en) 2019-02-06 2020-08-13 Exxonmobil Chemical Patents Inc. Films and backsheets for hygiene articles
CA3121960A1 (en) 2019-02-20 2020-08-27 Fina Technology, Inc. Polymer compositions with low warpage
EP3970934A4 (en) 2019-05-13 2022-06-29 Asahi Kasei Kabushiki Kaisha Low-pore pellets and method for producing molded body
KR102203007B1 (en) 2019-06-05 2021-01-14 대림산업 주식회사 Method for manufacturing multimodal polyolefins using multistage continuous polymerization process
EP4050066A4 (en) 2019-10-24 2022-12-21 Asahi Kasei Kabushiki Kaisha Polyamide-cellulose resin composition
WO2021126458A1 (en) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Films made of polyethylene blends for improved sealing performance and mechanical properties
WO2021183337A1 (en) 2020-03-12 2021-09-16 Exxonmobil Chemical Patents Inc. Films made of polyethylene blends for improved bending stiffness and high md tear resistance
EP4289887A4 (en) 2021-02-03 2024-04-17 Asahi Chemical Ind Method for producing resin composition
US20240124690A1 (en) 2021-02-22 2024-04-18 Asahi Kasei Kabushiki Kaisha Composition Containing Cellulose Nanofibers
CN117222697A (en) 2021-04-26 2023-12-12 弗纳技术股份有限公司 Single site catalyzed polymer sheet
EP4330294A1 (en) 2021-04-30 2024-03-06 ExxonMobil Chemical Patents Inc. Processes for transitioning between different polymerization catalysts in a polymerization reactor
EP4353782A1 (en) 2021-06-10 2024-04-17 Asahi Kasei Kabushiki Kaisha Resin composition and method for producing same

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3306919A (en) * 1958-01-15 1967-02-28 Union Carbide Corp Cyclopentadienyl titanium compounds
US3013002A (en) * 1960-04-05 1961-12-12 Hercules Powder Co Ltd Polymerization of ethylene with dicyclopentadienyl chromium-metal alkylcatalysts
US3135809A (en) * 1960-07-21 1964-06-02 Southern Res Inst Isomerization process
NL296404A (en) * 1962-08-08
GB1233599A (en) * 1966-04-04 1971-05-26
BE737574A (en) * 1968-09-05 1970-02-02
DE2043515A1 (en) * 1970-09-02 1972-04-20 Hoechst Ag Olefins polymn catalyst - consisting of titanium trichloride prod
DE2608933A1 (en) * 1976-03-04 1977-09-08 Basf Ag Ethylene polymerisation using Ziegler catalyst system - contg. cyclopentadienyl zirconium cpd., aluminium tri-alkyl cpd. and opt. water
DE2608863A1 (en) * 1976-03-04 1977-09-08 Basf Ag Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water
JPS54134792A (en) * 1978-04-11 1979-10-19 Mitsui Petrochem Ind Ltd Polymerization or copolymerization of ethylene
JPS55151010A (en) * 1979-05-16 1980-11-25 Mitsui Petrochem Ind Ltd Polymerization or copolymerization olefin
IT1193358B (en) * 1980-01-18 1988-06-15 Montedison Spa COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS AND CATALYSTS FROM THEM OBTAINED
DE3007725A1 (en) * 1980-02-29 1981-09-17 Hansjörg Prof. Dr. 2000 Hamburg Sinn METHOD FOR PRODUCING POLYETHYLENE, POLYPROPYLENE AND COPOLYMERS
US4310648A (en) * 1980-10-20 1982-01-12 The Dow Chemical Company Polymerization of olefins in the presence of a catalyst containing titanium and zirconium
DE3127133A1 (en) * 1981-07-09 1983-01-27 Hoechst Ag, 6000 Frankfurt METHOD FOR PRODUCING POLYOLEFINS AND THEIR COPOLYMERISATS
CA1231702A (en) * 1983-06-06 1988-01-19 John A. Ewen Process and catalyst for producing reactor blend polyolefins
ZA844157B (en) * 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5703180A (en) * 1992-11-19 1997-12-30 Mitsui Petrochemical Industries, Ltd. Catalyst for olefin polymerization, process for olefin polymerization using the same, ethylene/α-olefin copolymer, graft modified ethylene/α-olefin copolymer, and ethylene copolymer composition
US6001941A (en) * 1992-11-19 1999-12-14 Mitsui Chemicals, Inc. Ethylene α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin
US6303713B1 (en) 1992-11-19 2001-10-16 Mitsui Chemicals Inc Graft modified ethylene α-olefin copolymer obtained by graft copolymerzing an ethylene/α-olefin copolymer with a polar monomer
US11325342B2 (en) 2016-12-27 2022-05-10 Eneos Corporation Adhesive tape

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