WO2001046276A1 - Catalyseurs metallocenes a geometrie contrainte mutli-nucleaire et copolymeres de compose aromatique ethylene/vinyle ainsi obtenus - Google Patents

Catalyseurs metallocenes a geometrie contrainte mutli-nucleaire et copolymeres de compose aromatique ethylene/vinyle ainsi obtenus Download PDF

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WO2001046276A1
WO2001046276A1 PCT/KR2000/001486 KR0001486W WO0146276A1 WO 2001046276 A1 WO2001046276 A1 WO 2001046276A1 KR 0001486 W KR0001486 W KR 0001486W WO 0146276 A1 WO0146276 A1 WO 0146276A1
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ethylene
copolymer
styrene
aluminum
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PCT/KR2000/001486
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English (en)
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Sung Cheol Yoon
Xuequan Zhang
Jae Gon Lim
Hyun Joon Kim
Young Sub Lee
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Samsung General Chemicals Co., Ltd.
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Priority to AU20311/01A priority Critical patent/AU2031101A/en
Publication of WO2001046276A1 publication Critical patent/WO2001046276A1/fr

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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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—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

Definitions

  • the present mvention relates to metaUocene catalysts for copolymerization of ethylene/vinyl aromatic compound. More particularly, the present invention relates to the constrained geometry metaUocene catalysts having a structure linked with more than two ligands of transition metal complex, isotactic-alternating- ethylene/vinyl aromatic compound copolymers having high isotacticity, alternating index and improved physical properties, which are copolymerized using said catalysts, and a method of preparing the copolymers.
  • olefm or styrene polymers are prepared by radical polymerization, ion polymerization, or coordination polymerization using Ziegler-Natta Catalysts.
  • radical polymerization or ion polymerization atactic polymers are obtained and by coordination polymerization using a Ziegler-Natta Catalyst, isotactic polymers are mainly obtained.
  • the polymers are classified into an atactic, an isotactic and a syndiotactic structure depending on the position of benzene rings as side chains.
  • An atactic structure has an irregular arrangement of the benzene rings and an isotactic polystyrene has an arrangement that the benzene rings are positioned at one side of the polymer main chain.
  • a syndiotactic structure has a regularly alternating arrangement of the benzene rings.
  • Copolymerization of ethylene and a vinyl aromatic compound such as styrene has been studied for a couple of decades.
  • a polymerization method using a heterogeneous Ziegler-Natta catalyst was introduced (Polymer Bulletin 20, 237-241 (1988)).
  • the conventional method has shortcomings in that the catalyst has poor activity, the copolymer has a low content of styrene and poor uniformity, and the copolymer is mostly a homopolymer.
  • a copolymer of ethylene and styrene has been prepared using a homogeneous Ziegler-Natta catalyst system comprising a transition metal compound and an organoaluminum compound.
  • Japanese Patent Laid-Open Nos. 3-163088 and 7-53618 disclose a pseudo-random styrene/ethylene copolymer prepared by using a catalyst with a constrained geometrical structure, which does not have any head-to-tail bonds.
  • the phenyl groups in the alternating structure of the pseudo-random styrene/ethylene copolymer do not have stereoregularity.
  • the copolymer shows the same properties as an amo ⁇ hous resin with no crystallinity.
  • Japanese Patent Laid-Open No. 6-49132 and Polymer Preprints disclose a method for producing a styrene/ethylene copolymer which is a pseudo random copolymer with no head-to-tail bonds.
  • the styrene/ethylene copolymer is prepared a bridged indenyl zirconium complex and a cocatalyst.
  • the Polymer Preprints the ethylene/styrene alternating structure in the pseudo random copolymer does not show stereoregularity.
  • the copolymer has a styrene/ethylene alternating structure but has neither an ethylene chain nor styrene chains including head-to-head bonds and tail-to-tail bonds.
  • the copolymer is a perfect alternating copolymer with an alternating degree of at least 70, preferably at least 90.
  • the phenyl groups form isotactic streroregularity of which isotactic diad index is 0.92.
  • the copolymer has a molecular weight of 20,000 or below, the physical properties are poor.
  • the catalyst has poor activity and a homopolymer such as syndiotactic polystyrene is obtained. Therefore, the polymerization method is not successfully commercialized.
  • Eur. Polym. J., 31, 79(1995) discloses a polymerization of ethylene and styrene using a catalyst of CpTiBz 3 . According to the process, homopolymers such as polystyrene and syndiotactic polystyrene are obtained instead of copolymers of styrene/ethylene.
  • Macromolecules, 29, 1158 (1996) discloses polymerization of ethylene/styrene using CpTiC13 as a catalyst and a boron type cocatalyst, resulting to prepare a mixture of a copolymer having a high degree of alternating structure, a syndiotactic polystyrene and a polyethylene.
  • the publication does not mention about stereoregularity of the phenyl groups .
  • U.S. Patent No. 5,883,213 discloses an ethylene/styrene copolymer having a weight average molecular weight of at least 81,000, having a styrene content of from 1 to less than 55 % by mole fraction, wherein the stereoregularity of phenyl groups in the alternating structure of ethylene and styrene is represented by an isotactic diad index of more than 0.75.
  • the yield of copolymer per metal unit is low, a larger amount of an organoaluminum compound is used, the polymerization process is carried out at a high temperature and a high pressure, and the polymer is amo ⁇ hous due to lack of stereoregularity. Further, the polymer has a pseudo-random structure.
  • the present inventors have developed new constrained geometry metaUocene catalysts for olef ⁇ n/styrene copolymerization, which are superior to a conventional Ziegler-Natta catalyst in activity ofthe catalyst, content of styrene, amount of homopolymer prepared, and heterogeneous proportion ofthe polymer.
  • a feature ofthe present invention is the provision of a metaUocene catalyst of preparing ethylene/vinyl aromatic compound copolymer which is designed to improve low activity of catalyst, a low styrene content, an excess amount of homopolymer by-products and ununiform composition in the heterogeneous Ziegler-Natta catalyst system.
  • Another feature of the present invention is the provision of a metaUocene catalyst of preparing a large amount of ethylene/vinyl aromatic compound copolymer using a small amount of a cocatalyst.
  • a further feature ofthe present invention is the provision of a constrained geometry metaUocene catalyst with high activity.
  • a further feature ofthe present invention is the provision of a process of preparing an ethylene/vinyl aromatic compound copolymer using the metaUocene catalyst.
  • the metaUocene catalyst according to the present invention contains in one molecule 2 to 4 transition metals that are bonded with ligands.
  • the metaUocene catalyst is used for preparing an ethylene/vinyl aromatic compound copolymer.
  • the metaUocene catalyst is employed with a cocatalyst such as organometallic compound or a mixture of non-coordinated Lewis acid and alkyl aluminum.
  • the ethylene/vinyl aromatic compound copolymer prepared by using the metaUocene catalyst shows an isotacticity of at least 60 %, and especially an alternating index of at least 80 % measured by 13 C NMR analysis.
  • Fig. 1 is a chemical formula showing a microstructure of an ethylene/styrene copolymer
  • Fig. 2 is a graph of the peak values of ethylene/styrene copolymers prepared in Example 7 and Comparative Example 1 measured by means of 13 C NMR analysis;
  • Fig. 3 is a chemical formula of an ethylene/styrene copolymer having an isotactic alternating structure.
  • the multi-nuclear constrained geometry catalyst according to the present invention is represented by the following formula (1), and the multi -nuclear constrained geometry catalysts containing 2, 3, or 4 transition metals are represented by the following formulae (2), (3) and (4), respectively:
  • M is the same or different Ti, Zr or Hf;
  • Cp 1 is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a substituted indenyl group; a tetrahydroindenyl group; a substituted tetrahydroindenyl group; a fluorenyl group; an octahydrofluorenyl group; a substituted fluorenyl group; an octahydrofluorenyl group; or a substituted octahydrofluorenyl group;
  • Y is a hydrogen atom or a silyl group of C ⁇ _ I0 , an alkyl group of C ⁇ _ 10 , an aryl group of Cj.io, or a combination thereof;
  • A is a hetero atom such as N, O, P, and S;
  • X is selected from the group consistmg of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group;
  • G is an alkyl group of cycloalkyl group of C ⁇ . 30 , an aryl group of C ⁇ . 30 , or an alkyl aryl group of C ⁇ . 30; and
  • n is 2, 3, or 4.
  • the metaUocene catalyst is used with a cocatalyst.
  • the cocatalyst is an organometallic compound such as alkyl aluminoxane and alkyl aluminum compound, which are known to an ordinary person in the art.
  • alkyl aluminoxane are methyl aluminoxane (MAO) and modified methyl aluminoxane (MMAO).
  • the alkyl aluminoxane includes an alkyl aluminoxane having a repeating unit ofthe following formula (5), a linear alkyl aluminoxane represented by the following formula (6), and a cyclic alkyl aluminoxane represented by the following formula (7):
  • R is a hydrogen atom, an alkyl group of C ⁇ or an aryl group of . 6 , being same or different each other, and m and n are an integer of 0 — 100.
  • the co-catalyst of the present invention may be a mixture of different aluminoxanes, a mixture of aluminoxane and alkyl aluminum such as trimethyl aluminum, triethylaluminum, triisobutylaluminum and dimethyl aluminum chloride.
  • the molar ratio of aluminum of organometallic compound to transition metal of Group IV of metaUocene catalyst of the present invention is in the range from 1 : 1 to 1 10 6 : 1, preferably from 10 : 1 to 1 x 10 4 : 1.
  • the co-catalyst of the present invention can be a mixture of non-coordinated Lewis acid and alkyl aluminum.
  • the non-coordinated Lewis acid include N, N-dimethyl anilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, ferrocerium tetrakis (pentafluorophenyl)borate, and tris(pentafluorophenyl)borate, and the like.
  • the alkyl aluminum examples include trimethylaluminum, triethylaluminum, diethylaluminum chloride, dimethyl aluminum chloride, triisobutylaluminum, diisobutylaluminum and dimethylaluminum chloride, tri(n-butyl)aluminum, tri(n-propyl)aluminum, and triisopropylaluminum, and the like.
  • the molar ratio of the non-coordinated Lewis acid to the transition metal in the catalyst system according to the present invention is preferably in the range from about 0.1 : 1 to about 20 : 1 and more preferably in the range of about 1 : 1. If the molar ratio of the alkyl aluminum to transition metal in the catalyst system is less than 0.01 : 1, it tends to be difficult to effectively activate the metal complex, and if it exceeds 100 : 1, such is economically disadvantageous.
  • additives or adjuvants which are commonly used for polymers, may be incorporated within a range not to adversely affect the effects of the present invention.
  • Preferred additives or adjuvants mclude, for example, an antioxidant, a lubricant, a plasticizer, an ultraviolet ray absorber, a stabilizer, a pigment, a colorant, a filler and/or a blowing agent.
  • the polymerization temperature is usually from 0 to 200 °C, preferably from 30 to 150 °C.
  • a polymerization temperature of -78 °C or lower is practically disadvantageous, and a temperature higher than 200 °C is not suitable, since decomposition of the metal complex will take place.
  • the ethylene monomer polymerized by using the catalyst system of the present invention is an ethylene, an unsaturated ethylene having a substituted group, or an ⁇ , ⁇ -diene.
  • the ethylene monomer is copolymerized with a vinyl aromatic compound.
  • the representative examples of the vinyl aromatic compound include alkylstyrene, halogenated styrene, halogen-substituted alkyl styrene, alkoxy styrene, vinylbiphenyl, vinylphenylnaphthalene, vinylphenylanthracene, vinylphenylpyrene, trialkylsilylvinylbiphenyl, trialkylstanylvinylbiphenyl, alkylsilyl styrene, carboxymethyl styrene, alkyl ester styrene, vinyl benzene sulphonic acid ester, and vinylbenzyl dialkoxyphosphide.
  • alkyl styrene are styrene, methyl styrene, ethyl styrene, butyl styrene, p-methyl styrene, p-tert-butyl styrene, and dimethyl styrene; those of halogenated styrene are chlorostyrene, bromostyrene, and fluorostyrene; those of halogen-substituted alkyl styrene are chloromethyl styrene, bromomethyl styrene, and fluoromethyl styrene; those of alkoxy styrene are methoxy styrene, ethoxy styrene, and butoxy styrene; those of vinyl biphenyl(?) are 4- vinyl biphenyl, 3-vinyl biphenyl, and 2-vinyl biphenyl;
  • olefin In the ethylenically unsaturated monomer, the representative examples of olefin are ethylene, propylene, 1-butene, 1-hexene and 1-octene; and those of cyclic olefin are cyclobutene, cyclopentene cyclohexene, 3 -methyl cyclopentene, 3 -methyl cyclohexene, and norbornene.
  • ⁇ , ⁇ -diene means non-conjugated diene, and the examples are 1 ,4-pentadiene, 1 ,5-hexadiene, 1 ,6-heptadiene, 1 ,7-octadiene, 1 ,8-nonadiene, 1 ,9-decadiene, 1 ,4-hexadiene, dicyclopentadiene, 5-ethylene-2-norbornen, 5-vinyl norbornene, and methyl hexadiene.
  • the content of the ethylenically unsaturated monomer in the copolymer is about 0 to 25 % by weight.
  • the weight average molecular weight (M w ) of ethylene/vinyl aromatic compound copolymer according to the present invention preferably exceeds 13,000, more preferably exceeds 20,000, and most preferably exceeds 30,000.
  • the melt index (ATSM D-1238 procedure A, condition of E) is in the range from 0.001 to 1000, preferably in the range from 0.01 to 100, most preferably in the range from 0.1 to 30.
  • monomers and solvent may be refined by vacuum distillation or by contacting alumna, silica, or Molecular Sieve before polymerization.
  • impurities may be eliminated by using a trialkyl aluminum compound, an alkali metal, or an alloy such as Na/K, etc.
  • the polymer of styrene/ethylene prefferably has a styrene content of at least 0.1 mol%, more preferable 0.1 to 55 mol%.
  • the polymer can be obtained at the pressure of 1 to 1 ,000 bar and at room temperature to 200 °C.
  • the polymer obtained at higher temperature than the automatic polymerization temperature of each monomer contains a small amount of homopolymer prepared by free radical polymerization.
  • the copolymer of the present invention shows various physical properties depending upon the styrene content in the copolymer.
  • the melting point decreases at the lower range of styrene content from about 0 to about 20 mol%, however, increases at the higher range of styrene content from about 20 to about 30 mol%.
  • the melting point is constant when the styrene content reaches to a certain amount. In case that the styrene content is over 50 mol% and the alternative index is 0.85, the melting point (Tm) is 124 °C, which is much higher by about 30 °C comparing with the melting point of 90 °C disclosed in US Patent No. 5,883,213.
  • the polymer ofthe present invention is especially suitable for the thermoplastic elastomer used as a reinforcing material of thermoplastic or thermosetting copolymer.
  • a synthetic and/or natural polymers may be blended thereto.
  • an additional polymer such as polyethylene, ethylene/ ⁇ -olefm copolymer, polypropylene, polyamide, aromatic polyester, polyisocyanate, polyurethane, polyacrylonitrile, silicon, and polyphenylene oxide may be blended with the copolymer ofthe present invention.
  • the additional polymer is preferably employed in the amount of 0.5 to 50% by weight.
  • the ethylene/vinyl aromatic compound copolymer ofthe present invention is a material which retracts its original length after drawing to the length of 2 times at room temperature and exhibits physical properties of as an elastomer by ASTM Special Technical Bulletin No.184, a thermoplastic or thermosetting resin.
  • the copolymer of the present invention can be easily transformed not only by branching, grafting, hydrogenation, cross-linking but also by introducing functional groups to the double bonds, for example, by sulfonation or chlorination.
  • the dilithium salt was dissolved in THF (100 ml) and reacted with 12.9 g (60 mmol) of chloro-2,3,4,5-tetramethyl cyclopentadienyl methyl silane at -78 ° C . After overnight reaction at room temperature, the temperature was raised to 70 ° C .Then the solvent and unreacted material were removed under vacuum, and washed with pentane to obtain light yellow Me 4 CpSi(Me) 2 NH-C 6 H 4 -C(Me) 2 -C 6 H 4 -C(Me) 2 -C 6 H 4 -NHSi(Me) 2 CpMe 4 with the yield of 76 %.
  • Example 2 was carried out in the same manner as m Example 1 except that
  • Example 3 was carried out m the same manner as m Example 1 except that tetramagnesium salt was used instead of tetralithium salt and the reaction time is over 10 hours.
  • Example 4 was carried out in the same manner as in Example 1 except that AgCl was used instead of CH 2 C1 2
  • Polymerization was carried out in an electro-heating glass autoclave having a capacity of 1 liter or a metal autoclave having a capacity of 2 liters, which was equipped with a magnetic stirrer and completely substituted by nitrogen by repeating evacuation and nitrogen substitution. Cooling water flew through the cooling coil equipped in the reactor. A solvent such as hexane or toluene, to which Na was added and distilled, was used. The solution was contacted with Molecular Sieve, alumina, or silica under nitrogen gas.
  • Comparative Example was conducted in the same manner as Example 1 except that [C ⁇ (Me) 4 -Si(Me) 2 -N-t-Bu]TiCl 2 (CGC) was used instead of the catalyst of Example 1.
  • Copolymer of 8.5 g was obtained after being dried at 130 ° C for 6 hours under reduced pressure. 13 C NMR analysis showed that it was a pseudo-random copolymer containing 35.3 mol% of styrene. The alternating index was 41 %.
  • Comparative Example was conducted in the same manner as Example 1 except that rac- [C 2 H 4 (Ind) 2 ]ZrCl 2 was used instead ofthe catalyst of Example 1.
  • Copolymer of 62 g was obtained after being dried at 130 ° C for 6 hours under reduced pressure. 13 C NMR analysis showed that it was a pseudo-random copolymer containing 7.9 mol% of styrene.
  • the isotacticity (diad) was 71 % and the alternating index was 21 %.
  • the ethylene/styrene copolymers by using the catalyst ofthe present invention have a higher styrene content as compared with conventional copolymers by using CGC or EBIZ (rac-ethylenebisindenylzirconium chloride, a common catalyst for iPP copolymerization), especially, as compared with Comparative Example 2 by using a zirconium catalyst.
  • the alternating index is very high compared with those of Comparative Examples 1 and 2.
  • the higher isotacticities of Examples 7 and 8 over 60 % show that the copolymer of the present mvention is a semi-crystalline copolymer having the melting point of 125 ° C even at a high styrene content.
  • microstructure of ethylene/styrene copolymer identified by 13 C NMR is shown in Fig. 1., and the analysis of 13 C NMR chemical shift is shown in Table 2.
  • S is a secondary carbon and T is a methine bonded to a phenyl group of styrene as a tertiary carbon
  • ⁇ , ⁇ and y mean that a phenyl- substituted secondary carbon is located at 2, 3, and 4 position of itself respectively.
  • S ⁇ ⁇ is a secondary carbon having a phenyl substituted secondary carbon at its 2 position on one side and a secondary carbon at its 4 position on the other side.
  • "+" means that a secondary carbon exists over 5 position of itself.
  • Comparative Examples 1 ⁇ 2 were analyzed by means of 13 C NMR, and the comparison result of Example 7 and Comparative Example 1 is shown m Fig. 2.
  • 13 C NMR analyst was carried out by using a mixed solvent of trichlorobenzene and benzene at 100 ° C and TMS(t ⁇ methyl silane). Such copolymer was substantially soluble in THF or CHC1 3 by more than 91% by weight at room temperature, and completely soluble in boiling THF.
  • the integral near 25 ppm attributable to the alternating structure was high compared with that of pseudo-random copolymer. Further, the peak attributable to the ethylene cham was nearly not observed m the vicinity of 30 ppm. It indicates that the polymer has an alternating structure. Also, S ⁇ ⁇ peak attributable to a head-to-tail structure of styrene was nearly not observed m the vicinity of 42 ppm. It indicates that there is no styrene chain having a styrene-styrene structure.
  • the diad (mm) integral at 45.2 ppm is measured by the peak attributable to a secondary carbon observed m the range of 45.2 to 46.6 ppm, and the isotacticity was measured by the ratio to integral of the total secondary carbon
  • the isotacticities were 63 % and 65 % respectively, as shown in Table 1 , which are different from those ofthe conventional pseudo-random copolymers
  • the multi-nuclear constrained geometry catalyst ofthe present invention improves the styrene content and is especially useful to prepare isotactic alternating ethylene/styrene copolymer, compared with the conventional constrained geometry catalysts.
  • the copolymer has high activity of polymerization and exceedingly improves styrene content, as compared with a traditional ethylene/styrene copolymer, at the same polymerization condition New copolymer having a higher alternating index over 80 % and a stereoregularity of about 60 % can be obtained. Further, a new semi-crystalline copolymer with a high styrene content, which has the melting point of about 125 ° C , can be prepared.

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Abstract

Cette invention concerne un catalyseur métallocène renfermant dans une seule molécule 2 à 4 métaux de transition reliés par des ligands. Ce catalyseur métallocène sert à préparer un coploymère de composé aromatique éthylène/vinyle. Il s'utilise avec un co-catalyseur tel qu'un composé organométallique ou un mélange d'acide de Lewis non coordonné et d'alkyl aluminium. Le copolymère de composé aromatique éthylène/vinyle obtenu au moyen du catalyseur métallocène présente une isostaticité d'au moins 60 % et, plus particulièrement un indice d'alternance de 80 % mesuré par l'analyse RMN magnétique de C13.
PCT/KR2000/001486 1999-12-20 2000-12-18 Catalyseurs metallocenes a geometrie contrainte mutli-nucleaire et copolymeres de compose aromatique ethylene/vinyle ainsi obtenus WO2001046276A1 (fr)

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US20180265607A1 (en) * 2017-03-15 2018-09-20 Florida State University Research Foundation, Inc. Polystyrene Sulfonate Analogs and Methods
CN109575211A (zh) * 2018-11-23 2019-04-05 广州优润合成材料有限公司 低聚配位杂合有机金属催化剂及其制备方法与应用
CN111171205A (zh) * 2020-03-02 2020-05-19 石家庄联合石化有限公司 一种聚丙烯的生产方法
WO2022242045A1 (fr) * 2021-05-19 2022-11-24 青岛科技大学 Préparation d'un catalyseur bimétallique à base de squelette anthracène, et son application dans la polymérisation en solution d'oléfine à température élevée
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CN111171205A (zh) * 2020-03-02 2020-05-19 石家庄联合石化有限公司 一种聚丙烯的生产方法
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WO2022242045A1 (fr) * 2021-05-19 2022-11-24 青岛科技大学 Préparation d'un catalyseur bimétallique à base de squelette anthracène, et son application dans la polymérisation en solution d'oléfine à température élevée
CN115710327A (zh) * 2022-11-28 2023-02-24 中山大学 一种支化乙烯-极性苯乙烯共聚物及其制备方法和应用
CN115710327B (zh) * 2022-11-28 2023-11-14 中山大学 一种支化乙烯-极性苯乙烯共聚物及其制备方法和应用

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