WO2001046282A1 - Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer - Google Patents

Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer Download PDF

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Publication number
WO2001046282A1
WO2001046282A1 PCT/KR2000/001483 KR0001483W WO0146282A1 WO 2001046282 A1 WO2001046282 A1 WO 2001046282A1 KR 0001483 W KR0001483 W KR 0001483W WO 0146282 A1 WO0146282 A1 WO 0146282A1
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Prior art keywords
group
ethylene
terpolymer
compound
styrene
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PCT/KR2000/001483
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French (fr)
Inventor
Xuequan Zhang
Jae Gon Lim
Sung Cheol Yoon
Hyun Joon Kim
Young Sub Lee
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Samsung General Chemicals Co., Ltd.
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Priority to JP2001547188A priority Critical patent/JP2003518173A/en
Priority to AT00983570T priority patent/ATE459669T1/en
Priority to AU20308/01A priority patent/AU2030801A/en
Priority to EP00983570A priority patent/EP1268588B1/en
Priority to DE60043945T priority patent/DE60043945D1/en
Publication of WO2001046282A1 publication Critical patent/WO2001046282A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • 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
    • 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 invention relates to an ethylene/aromatic vmyl compound/vmylnorbornene terpolymer. More particularly, the present invention relates to an ethylene/aromatic vmyl compound/vmylnorbornene terpolymer with high activity, a high molecular weight and a high content of aromatic vmyl compound, which can be prepared with a small amount of co-catalyst under mild condition.
  • Copolyme ⁇ zation of ethyl ene and an aromatic vmyl 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 m 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 organoalummum compound.
  • Japanese Patent Laid-Open No 7-53618 discloses a pseudo-random styrene/ethylene copolymer prepared by using a catalyst with a constrained geometrical structure, which does not have head-to-tail bonds.
  • the phenyl groups m the alternating structure of the pseudo-random styrene/ethylene copolymer do not have stereoregula ⁇ ty.
  • the copolymer shows the same properties as an amorphous 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 ethylene/styrene alternating structure in the pseudo random copolymer does not show stereoregularity.
  • Japanese Patent Laid-Open No.3-250007 and Stud. Surf. Sci. Catal. 517 (1990) disclose a styrene/ethylene alternating copolymer prepared by using a Ti complex having a substituted phenol type ligand.
  • 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 ratio of ethylene to styrene is 50 % to 50 % by weight, it is difficult to vary the contents of the composition.
  • the phenyl groups forms 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.
  • Macromol. Chem., 191, 2387 (1990) has reported a styrene/ethylene copolymer prepared by using CpTiCl 3 as a transition metal compound and methyl alumoxane as a cocatalyst.
  • the copolymer includes pseudo random copolymer with no styrene chains.
  • the catalyst shows poor activity.
  • the publication does not mention about stereoregularity of the phenyl groups.
  • 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 discloses polymerization of ethylene/styrene using CpTiC as a catalyst and a boron tytpe 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 molar fraction, wherein the stereoregularity of phenyl groups m the alternating structure of ethylene and styrene is represented by an isotactic diad index of more than o.75.
  • Japanese Patent Laid-Open Nos. 3-163088 and 7-53618 disclose a process of copolymerization of styrene/ethylene using a large amount of an organic aluminum.
  • this process is not practical since it produces not only ethylene/styrene copolymer but also a large amount of syndiotactic polystyrene under mild condition.
  • the present inventors have developed an ethylene/aromatic vmyl compound vmylnorbornene terpolymer with high activity, a high molecular weight and a high content of aromatic vmyl compound, which can be prepared with a small amount of co-catalyst under mild polymerization condition.
  • a feature of the present invention is the provision of a process of preparing ethylene/aromatic vmyl compound copolymer which is designed to improve low activity of catalyst, a low styrene content, an excess amount of homopolymers by-product and uniform composition m the heterogeneous Ziegler-Natta catalyst system.
  • Another feature of the present invention is the provision of a process of preparing a large amount of ethylene/aromatic vmyl compound copolymer using a small amount of a cocatalyst.
  • a further feature of the present invention is the provision of an ethylene/aromatic vmyl compound copolymer having double bonds in which branching and/or cross-linking can be carried out
  • a further feature of the present invention is the provision of an ethylene/aromatic vinyl compound copolymer having double bonds to which long chain branches can be introduced.
  • a further feature of the present invention is the provision of an ethylene/aromatic vinyl compound copolymer having an improved viscosity at melting state and an improved processability by introducing long chain branches thereto.
  • the ethylene/aromatic vinyl compound/vinylnorbornene terpolymer according to the present invention is prepared by copolymerizing 50 ⁇ 90 mol % of ethylene, 1 — 55 mol % of an aromatic vinyl compound and 1 — 55 mol % of a vinylnorbornene under a catalyst system consisting of a transition metal compound represented by the following formula ( I ) and a cocatalyst:
  • M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;
  • Cp' is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a tetrahydroindenyl group; a substituted indenyl group; a fluorenyl group; an octahydrofluorenyl group; or a substituted fluorenyl group; Y is a hydrogen or a silyl group of an alkyl group of C ⁇ - 10 , an aryl group of C]_ ⁇ o, or a combination thereof;
  • A is an alkyl group of C]_ 30 , an alkylamide group of C]- 30 or a derivative of cyclopentadienyl group which is identical to Cp';
  • X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.
  • the transition metal complex may be a racemic mixture of d-form or /-form. Either d-form or /-form can be used in the present invention.
  • Fig. 1 is a 13 C NMR spectrum of the terpolymer obtained in Example 1 ;
  • Fig. 2 shows a micro structure and quantitative analysis of styrene and vinylnorbomene comonomers in the terpolymer by using 13 C-NMR spectrum measurement;
  • Fig. 3 is a comparative diagram showing the styrene content to the ratio of the amount of injected styrene monomer to the copolymer under 60 psi of C 2 ;
  • Fig. 4 is a comparative diagram showing the styrene content to the ratio of the amount of injected styrene monomer to the copolymer under 150 psi of C 2 ;
  • Fig. 5 is a graph of gel permeation chromatography(GPC) of Example 1 and Comparative Example 1.
  • the ethylene/aromatic vinyl compound/vinylnorbornene terpolymer according to the present invention is prepared by copolymerizing 50 ⁇ 90 mol % of ethylene, 1 ⁇ 55 mol % of an aromatic vinyl compound and 1 ⁇ 55 mol % of a vinylnorbomene under a catalyst system.
  • the catalyst system consists of a transition metal compound and a cocatalyst.
  • the polymerization of ethylene/aromatic vinyl compound/vinylnorbornene terpolymer is preferably carried out at 1 ⁇ 1000 bar and 0 ⁇ 200 ° C . Over the self-polymerization temperature of each monomer, free radical polymerization occurs to produce a small amount of homopolymer.
  • the aromatic vmyl compound includes styrene compounds and styrene derivatives such as alkylstyrene, halogenated styrene, halogen-substituted alkylstyrene, alkoxy styrene, vmylbiphenyl, vmylphenylnaphthalene, vmylphenylanthracene, vinylphenylpyrene, trialkylsilylvmylbiphenyl, trialkylstenybiphenyl, alkylsilylstyrene, carboxymethylstyrene, alkylesterstyrene, vmylbenzenesulphomc acid ester, vmylbenzyldialkoxyphosphide, etc.
  • styrene compounds and styrene derivatives such as alkylstyrene, halogenated styrene, halogen-substitute
  • alkylstyrene are styrene, methylstyrene, ethylstyrene, butylstyrene, p-methylstyrene, p-tert-butylstyrene, and dimethylstyrene; those of halogenated styrene are chlorostyrene, bromostyrene, and fluorostyrene; those of halogen-substituted alkylstyrene are chloromethylstyrene, bromomethylstyrene, and fluoromethylstyrene; those of alkoxystyrene are methoxystyrene, ethoxystyrene, and butoxy styrene; those of vmylbiphenyl are 4- vmylbiphenyl, 3-vmylb ⁇ phenyl, and 2 -vmylbiphenyl; those of v
  • those of vmylphenylanthracene are l-(4-vmylphenyl)anthracene, 2-(4-vmylphenyl)anthracene, 9-(4-vmylphenyl)anthracene, 1 -(3 -vmylphenylanthracene, 9-(3 -vmylphenylanthracene, and 1 -(4- vmylphenylanthracene;
  • those of vinylphenylpyrene are 1 -(4-vmylphenyl)pyrene, 2-(4-vmylphenyl)pyrene, 1 -(3-v
  • the content of the aromatic vmyl compound may be at least 0.1 mol %, preferably 0.5 — 55 mol %, more preferably 1.0 — 55 mol %
  • the vinylnorbomene being polymerized by catalyst system of the present invention is a non- conjugated diene which includes dicyclopentadiene, 5-ethyl ⁇ dene-2-norbornene and methyl hexadiene
  • the vinylnorbomene is preferably 0.01 ⁇ 10 mol % in the copolymer.
  • the ethylene/aromatic vmyl compound/vmylnorbornene terpolymer according to the present invention is prepared under a catalyst system which consists of a transition metal compound and a cocatalyst
  • the transition metal compound is represented by the following formula ( I )
  • M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium
  • Cp' is a non-substituted cyclopentadienyl group, a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an mdenyl group, a tetrahydromdenyl group; a substituted mdenyl group, a fluorenyl group, an octahydrofluorenyl group, or a substituted fluorenyl group,
  • Y is a hydrogen or a silyl group of Cj. 10 , an alkyl group of C]- 10 , an aryl group of C ⁇ _ ⁇ o, or a combination thereof,
  • A is an alkyl group of C ⁇ _ 30 , an alkylamide group of C_ 30 or a derivative of cyclopentadienyl group which is identical to Cp', and X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group
  • the transition metal complex may be a racemic mixture of d-form or /-form Either d-form or /-form can be used in the present invention
  • the metallocene catalyst is used with a cocatalyst
  • the cocatalyst is an organometallic compound such as alkylalummoxane and alkylalummum compound, which are known to an ordinary person m the art.
  • the representative examples of alkylalummoxane are methylalummumoxane (MAO) and modified methylalummumoxane (MMAO).
  • the alkylalummoxane includes an alkylalummoxane having a repeating unit of the following formula ( U ), a linear alkylalummoxane represented by the following formula (_H), and a cyclic alkylalummoxane represented by the following formula (IV):
  • R is an hydrogen, an alkyl group of C ⁇ _ 5 or an aryl group of C, 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 alummoxanes, a mixture of alummoxane and alkylalummum such as trimethyl aluminum, tri ethyl aluminum, trnsobutyl aluminum and dimethyl aluminum chloride.
  • the molar ratio of aluminum of organometalhc compound to transition metal of Group IV of metallocene catalyst of the present invention is in the range from 1 1 to 1 x 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-coordmated Lewis acid and alkylalummum.
  • non-coordmated Lewis acid examples include N, N-dimethylamlmium tetrak ⁇ s(pentafluorophenyl)borate, tnphenylcarbenium tetrak ⁇ s(pentafluorophenyl)borate, ferroce ⁇ um tetrakis (pentafluorophenyl)borate, and tr ⁇ s(pentafluorophenyl)borate, and the like
  • alkylalummum examples include trimethylalummum, triethyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, triisobutyl aluminum, dnsobutyl aluminum and dimethyl aluminum chloride, t ⁇ (n-butyl)alummum, t ⁇ (n-propyl)alummum, and triisopropylalummum, and the like.
  • the molar ratio of the non-coordmated 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 alkylalummum 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 withm a range not to adversely affect the effects of the present invention.
  • Preferred additives or adjuvants include, 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 140 °C, preferably from 30 to 100 °C.
  • a polymerization temperature of -78 °C or lower is industrially disadvantageous, and a temperature higher than 200 °C is not suitable, since decomposition of the metal complex will take place.
  • the ethylene/aromatic vmyl compound/vmylnorbornene terpolymer of the present invention has an average molecular weight of more than 5,000, more preferably 10,000 and most preferably 30,000, and the meltmg-mdex(MI; ASTM D-1238; method A and condition E) of 0.001 ⁇ 1000, more preferably 0 01 ⁇ 100 and most preferably 0.1 — 30.
  • the monomers and solvent are purified by vacuum distillation or by contacting with alumina, silica or molecular sieve.
  • a t ⁇ alkylalummum compound, an alkali metal and a metal alloy, especially Na/ may be used to remove the impurities.
  • the terpolymer of the present invention may be blended with a synthetic or natural polymer regardless of modification.
  • the present invention may be preferably blended with polyethylene, ethylene/ ⁇ -olefin copolymer, polypropylene, polyamide, polyisocyanate, polyurethane, polyacrylonitrile, sihcone and polyphenylene oxide, and styrene copolymer such as ethylene-styrene copolymer and polystyrene, which is used in the range from about 0.5 to 50 % by weight.
  • the terpolymer of the present invention preferably ethylene-styrene-vmylnorbornene terpolymer is used as a modifier for a composition of asphalt or bitumen.
  • Bitumen means a hydrocarbon compound of solid, semi-solid, liquid or gas in natural.
  • the present invention uses solid, semisohd or liquid bitumen.
  • the bitumen is generally limited to asphalt, tar and pitch.
  • the amount of the bitumen used herein is preferably 65 ⁇ 99 parts by weight, more preferably 80 — 98 parts by weight.
  • the ethylene-aromatic vmyl compound-vmylnorbornene terpolymer of the 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 Rullet in No.184, a thermoplastic or thermosettmg resm.
  • the terpolymer of the present invention can be easily transformed not only by branching, grafting, hydrogenation, cross-lmkmg but also by introducing functional groups to the double bonds, for example, by sulfonation or chlormation.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 30 mL of vinylnorbomene and terminating the reaction after 15 minutes. Terpolymer of 41 g was obtained.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 10 mL of vinylnorbomene and terminating the reaction after 150 minutes. Terpolymer of 52 g was obtained.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 5 mL of vinylnorbomene and terminating the reaction after 120 minutes. Terpolymer of 39 g was obtained.
  • the polymerization process was conducted m the same manner as in Example 1 except adding 100 mL of styrene and 20 mL of vinylnorbomene and terminating the reaction after 45 minutes. Terpolymer of 27 g was obtained.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbomene and 100 mL of heptane and terminating the reaction after 20 minutes. Terpolymer of 22 g was obtained.
  • the polymerization process was conducted m the same manner as in Example 1 except adding 50 mL of styrene, 5 mL of vinylnorbomene and 150 mL of heptane and terminating the reaction after 31 minutes. Terpolymer of 17 g was obtained.
  • Example 9 The polymerization process was conducted m the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbomene and 300 mL of Isopar E and terminating the reaction after 120 minutes Terpolymer of 18 g was obtained.
  • Example 9 The polymerization process was conducted m the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbomene and 300 mL of Isopar E and terminating the reaction after 120 minutes Terpolymer of 18 g was obtained.
  • Example 9 Example 9
  • the polymerization process was conducted in the same manner as in Example 1 except adding 50 mL of styrene, 5 mL of vinylnorbomene and 150 mL of Isopar E and terminating the reaction after 120 minutes. Terpolymer of 9.1 g was obtained.
  • the polymerization process was conducted in the same manner as in
  • Example 1 except adding 1000 mL of styrene, 2 mL of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 126 g was obtained.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 750 mL of styrene, 2 mL of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 147 g was obtained.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 500 mL of styrene, 2 mL of vinylnorbomene and 500 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 137 g was obtained.
  • Example 13 The polymerization process was conducted in the same manner as m Example 1 except adding 250 mL of styrene, 2 mL of vinylnorbomene and 750 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 132 g was obtained.
  • the polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 2 mL of vinylnorbomene and 900 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 1 1 1 g was obtained.
  • Example 1 except adding 50 mL of styrene, 2 mL of vinylnorbomene and 1000 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 98 g was obtained.
  • the polymerization process was conducted m the same manner as m Example 1 except adding 10 mL of styrene, 2 mL of vinylnorbomene and 1000 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 124 g was obtained.
  • the polymerization process was conducted in the same manner as in Comparative Example 1 except adding 150 mL of styrene and 50 mL of hexane. Copolymer of 35 g was obtained.
  • the polymerization process was conducted in the same manner as in Comparative Example 1 except adding 50 mL of styrene and 150 mL of hexane. Copolymer of 24 g was obtained.
  • the polymerization process was conducted m the same manner as in
  • Comparative Example 5 The polymerization process was conducted in the same manner as in Comparative Example 1 except adding 500 mL of styrene and 500 mL of hexane and reacting under the pressure of 10 bar of ethylene. Copolymer of 61 g was obtained.
  • the polymerization process was conducted in the same manner as in Comparative Example 1 except adding 100 mL of styrene and 900 mL of hexane and reacting under the pressure of 10 bar of ethylene. Copolymer of 68 g was obtained.
  • the polymerization process was conducted in the same manner as in
  • Example 1 except adding 1000 mL of styrene and 10 mL of 1 ,7-octadiene instead of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 14.3 g was obtained.
  • the polymerization process was conducted in the same manner as m Example 1 except adding 1000 mL of styrene and 5 mL of 1 ,7-octadiene instead of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 5.9 g was obtained.
  • styrene 100 50 1000 750 500 solvent (ml) 150 1 ⁇ 300 2) 150 2) - 250 3) 500 3)
  • Isopar E (trademark): a mixture of hydrocarbons by Exxon Co. 3) hexane
  • the structure of terpolymers prepared above was measured by using 13 C-NMR.
  • the 13 C-NMR of the polymers of Example 1 and Comparative Example 1 was shown m Figure 1.
  • the 13 C-NMR measurement was carried out at 100 ° C by using TMS (tetramethylsilane) in the solvent mixture of trichlorobezene and bezene-d-6 mixed solution.
  • the terpolymers are partially soluble in THF or CHC13 at room temperature, and completely soluble in boiling THF.
  • the terpolymer of the present invention showed the distinct peaks of terminal double bond near of 112 and 1 14 ppm, which indicates that most of the vinylnorbomene monomers m the copolymer participate m polymerization using the double bond withm the ring, but not the double bond outside the ring. This indicates that the reaction rate of the double bond withm the ring is faster than that of the terminal double bond, because the former is relatively unstable.
  • the content of the vinylnorbomene was quantitatively analyzed by the peaks from the 13 C-NMR spectrum measurement, and the result are shown m Table 1.
  • terpolymers using 1 ,7-octadiene have a low activity and low content of 1 ,7-octadiene in the terpolymer, which indicates that the double bond withm the vinylnorbomene ring participates in the polymerization.
  • Fig 2 shows a micro structure and quantitative analysis of styrene and vinylnorbomene comonomers in the terpolymer by using ⁇ C-NMR spectrum measurement, wherein S is secondary carbon, Vt is terminal vmyl group; [St], [E] and [VN] are content of styrene, ethylene and vinylnorbomene respectively.
  • Fig.5 shows the result of gel permeation chromatography (GPC) of Example 1 and Comparative Example 1. The peaks are shown in the region of polymer.
  • Example 1 has higher molecular weight distribution due to addition of vinylnorbomene unlike Comparative Example 1.
  • the ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of the present invention has various improved properties such as high activity, a high molecular weight, a wide molecular weight distribution and a high content of styrene.
  • Examples 10-13 concern about terpolymerization by adding a trace of vinylnorbomene, which also indicate that although the vinylnorbomene was not found by 13 C NMR analysis, the activity, molecular weight, molecular weight distribution and content of styrene were increased.

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Abstract

The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer according to the present invention is prepared by copolymerizing 50∩90 mol % of ethylene, 1∩55 mol % of an aromatic vinyl compound and 1∩55 mol % of a vinylnorbornene under a catalyst system consisting of a transition metal compound represented by formula (I) and a cocatalyst, where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium; Cp' is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a substituted indenyl group; a fluorenyl group; or a substituted fluorenyl group; Y is a hydrogen or a silyl group of C1-10, an alkyl group of C1-10, an aryl group of C1-10, or a combination thereof; A is an alkyl group of C1-30, an alkylamide group of C1-30 or a derivative of cyclopentadienyl group which is identical to Cp'; and X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.

Description

Ethylene-Aromatic Vinyl Compound-Vinyl Norbonene Terpolymer
Field of the Invention
The present invention relates to an ethylene/aromatic vmyl compound/vmylnorbornene terpolymer. More particularly, the present invention relates to an ethylene/aromatic vmyl compound/vmylnorbornene terpolymer with high activity, a high molecular weight and a high content of aromatic vmyl compound, which can be prepared with a small amount of co-catalyst under mild condition.
Background of the Invention
Copolymeπzation of ethyl ene and an aromatic vmyl compound such as styrene has been studied for a couple of decades. At the beginning of time, a polymerization method using a heterogeneous Ziegler-Natta catalyst was introduced (Polymer Bulletin 20, 237-241 (1988)). However, the conventional method has shortcomings m that the catalyst has poor activity, the copolymer has a low content of styrene and poor uniformity, and the copolymer is mostly a homopolymer. Further, a copolymer of ethylene and styrene has been prepared using a homogeneous Ziegler-Natta catalyst system comprising a transition metal compound and an organoalummum compound.
Japanese Patent Laid-Open No 7-53618 discloses a pseudo-random styrene/ethylene copolymer prepared by using a catalyst with a constrained geometrical structure, which does not have head-to-tail bonds. The phenyl groups m the alternating structure of the pseudo-random styrene/ethylene copolymer do not have stereoregulaπty. When the pseudo-random styrene/ethylene copolymer has a certain amount of styrene, the copolymer shows the same properties as an amorphous resin with no crystallinity
Japanese Patent Laid-Open No. 6-49132 and Polymer Preprints (Japan 42, 2292 (1993)) 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.
According to the Polymer Preprints, the ethylene/styrene alternating structure in the pseudo random copolymer does not show stereoregularity.
Further, Japanese Patent Laid-Open No.3-250007 and Stud. Surf. Sci. Catal. 517 (1990) disclose a styrene/ethylene alternating copolymer prepared by using a Ti complex having a substituted phenol type ligand. 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. However, as the ratio of ethylene to styrene is 50 % to 50 % by weight, it is difficult to vary the contents of the composition. The phenyl groups forms isotactic streroregularity of which isotactic diad index is 0.92. As 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. Meanwhile, Macromol. Chem., 191, 2387 (1990) has reported a styrene/ethylene copolymer prepared by using CpTiCl3 as a transition metal compound and methyl alumoxane as a cocatalyst. The copolymer includes pseudo random copolymer with no styrene chains. The catalyst shows poor activity. The publication does not mention about stereoregularity of the phenyl groups. Eur. Polym. J., 31, 79(1995) discloses a polymerization of ethylene and styrene using a catalyst of CpTiBz3. 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 CpTiC as a catalyst and a boron tytpe 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 molar fraction, wherein the stereoregularity of phenyl groups m the alternating structure of ethylene and styrene is represented by an isotactic diad index of more than o.75.
Japanese Patent Laid-Open Nos. 3-163088 and 7-53618 disclose a process of copolymerization of styrene/ethylene using a large amount of an organic aluminum. However, this process is not practical since it produces not only ethylene/styrene copolymer but also a large amount of syndiotactic polystyrene under mild condition.
Accordingly, the present inventors have developed an ethylene/aromatic vmyl compound vmylnorbornene terpolymer with high activity, a high molecular weight and a high content of aromatic vmyl compound, which can be prepared with a small amount of co-catalyst under mild polymerization condition.
Objects of the Invention
A feature of the present invention is the provision of a process of preparing ethylene/aromatic vmyl compound copolymer which is designed to improve low activity of catalyst, a low styrene content, an excess amount of homopolymers by-product and uniform composition m the heterogeneous Ziegler-Natta catalyst system. Another feature of the present invention is the provision of a process of preparing a large amount of ethylene/aromatic vmyl compound copolymer using a small amount of a cocatalyst.
A further feature of the present invention is the provision of an ethylene/aromatic vmyl compound copolymer having double bonds in which branching and/or cross-linking can be carried out A further feature of the present invention is the provision of an ethylene/aromatic vinyl compound copolymer having double bonds to which long chain branches can be introduced.
A further feature of the present invention is the provision of an ethylene/aromatic vinyl compound copolymer having an improved viscosity at melting state and an improved processability by introducing long chain branches thereto.
The above and other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
Summary of the Invention
The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer according to the present invention is prepared by copolymerizing 50 ~90 mol % of ethylene, 1 — 55 mol % of an aromatic vinyl compound and 1 — 55 mol % of a vinylnorbornene under a catalyst system consisting of a transition metal compound represented by the following formula ( I ) and a cocatalyst:
X X
A x
where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;
Cp' is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a tetrahydroindenyl group; a substituted indenyl group; a fluorenyl group; an octahydrofluorenyl group; or a substituted fluorenyl group; Y is a hydrogen or a silyl group of
Figure imgf000005_0001
an alkyl group of Cι-10, an aryl group of C]_ιo, or a combination thereof;
A is an alkyl group of C]_30, an alkylamide group of C]-30 or a derivative of cyclopentadienyl group which is identical to Cp'; and
X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.
When A is a derivative of the cyclopentadienyl group, the transition metal complex may be a racemic mixture of d-form or /-form. Either d-form or /-form can be used in the present invention.
Brief Description of the Drawings
Fig. 1 is a 13C NMR spectrum of the terpolymer obtained in Example 1 ;
Fig. 2 shows a micro structure and quantitative analysis of styrene and vinylnorbomene comonomers in the terpolymer by using 13C-NMR spectrum measurement;
Fig. 3 is a comparative diagram showing the styrene content to the ratio of the amount of injected styrene monomer to the copolymer under 60 psi of C2;
Fig. 4 is a comparative diagram showing the styrene content to the ratio of the amount of injected styrene monomer to the copolymer under 150 psi of C2; and
Fig. 5 is a graph of gel permeation chromatography(GPC) of Example 1 and Comparative Example 1.
Detailed Description of the Invention
The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer according to the present invention is prepared by copolymerizing 50 ~90 mol % of ethylene, 1 ~ 55 mol % of an aromatic vinyl compound and 1 ~ 55 mol % of a vinylnorbomene under a catalyst system. The catalyst system consists of a transition metal compound and a cocatalyst.
The polymerization of ethylene/aromatic vinyl compound/vinylnorbornene terpolymer is preferably carried out at 1 ~ 1000 bar and 0 ~ 200 °C . Over the self-polymerization temperature of each monomer, free radical polymerization occurs to produce a small amount of homopolymer.
The aromatic vmyl compound includes styrene compounds and styrene derivatives such as alkylstyrene, halogenated styrene, halogen-substituted alkylstyrene, alkoxy styrene, vmylbiphenyl, vmylphenylnaphthalene, vmylphenylanthracene, vinylphenylpyrene, trialkylsilylvmylbiphenyl, trialkylstenybiphenyl, alkylsilylstyrene, carboxymethylstyrene, alkylesterstyrene, vmylbenzenesulphomc acid ester, vmylbenzyldialkoxyphosphide, etc.
The representative examples of alkylstyrene are styrene, methylstyrene, ethylstyrene, butylstyrene, p-methylstyrene, p-tert-butylstyrene, and dimethylstyrene; those of halogenated styrene are chlorostyrene, bromostyrene, and fluorostyrene; those of halogen-substituted alkylstyrene are chloromethylstyrene, bromomethylstyrene, and fluoromethylstyrene; those of alkoxystyrene are methoxystyrene, ethoxystyrene, and butoxy styrene; those of vmylbiphenyl are 4- vmylbiphenyl, 3-vmylbιphenyl, and 2 -vmylbiphenyl; those of vmylphenylnaphthalene are l-(4-vmylbιphenylnaphthalene),
2-(4-vmylbιphenylnaphthalene), l-(3-vmylbιphenylnaphthalene), 2-(3-vmylbιphenylnaphthalene), and 1 -(2 -vmylbipheny .naphthalene ); those of vmylphenylanthracene are l-(4-vmylphenyl)anthracene, 2-(4-vmylphenyl)anthracene, 9-(4-vmylphenyl)anthracene, 1 -(3 -vmylphenylanthracene, 9-(3 -vmylphenylanthracene, and 1 -(4- vmylphenylanthracene; those of vinylphenylpyrene are 1 -(4-vmylphenyl)pyrene, 2-(4-vmylphenyl)pyrene, 1 -(3-vmylphenyl)pyrene, 2-(3-vmylphenyl)pyrene, l-(2-vmylphenyl)pyrene, and 2-(2 -vinylphenylpyrene, that of trialkylsilylvmylbiphenyl is 4-vmyl-4-trιmethylsιlylbιphenyl, and those of alkylsilylstyrene are p-trimethylsilylstyrene, m-trimethylsilylstyrene, o-trιmethylsιlylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene, and o-trιethylsιlylstyrene.
In the copolymer, the content of the aromatic vmyl compound may be at least 0.1 mol %, preferably 0.5 — 55 mol %, more preferably 1.0 — 55 mol % The vinylnorbomene being polymerized by catalyst system of the present invention is a non- conjugated diene which includes dicyclopentadiene, 5-ethylιdene-2-norbornene and methyl hexadiene The vinylnorbomene is preferably 0.01 ~ 10 mol % in the copolymer.
The ethylene/aromatic vmyl compound/vmylnorbornene terpolymer according to the present invention is prepared under a catalyst system which consists of a transition metal compound and a cocatalyst The transition metal compound is represented by the following formula ( I )
X X
K X
where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium,
Cp' is a non-substituted cyclopentadienyl group, a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an mdenyl group, a tetrahydromdenyl group; a substituted mdenyl group, a fluorenyl group, an octahydrofluorenyl group, or a substituted fluorenyl group,
Y is a hydrogen or a silyl group of Cj.10, an alkyl group of C]-10, an aryl group of Cι_ιo, or a combination thereof,
A is an alkyl group of Cι_30, an alkylamide group of C_ 30 or a derivative of cyclopentadienyl group which is identical to Cp', and X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group
When A is a deπvative of the cyclopentadienyl group, the transition metal complex may be a racemic mixture of d-form or /-form Either d-form or /-form can be used in the present invention
In the present invention, the metallocene catalyst is used with a cocatalyst The cocatalyst is an organometallic compound such as alkylalummoxane and alkylalummum compound, which are known to an ordinary person m the art. The representative examples of alkylalummoxane are methylalummumoxane (MAO) and modified methylalummumoxane (MMAO). The alkylalummoxane includes an alkylalummoxane having a repeating unit of the following formula ( U ), a linear alkylalummoxane represented by the following formula (_H), and a cyclic alkylalummoxane represented by the following formula (IV):
Figure imgf000009_0001
where R is an hydrogen, an alkyl group of Cι_5 or an aryl group of C, 6, being same or different each other, and m and n are an integer of 0 — 100.
Alternatively, the co-catalyst of the present invention may be a mixture of different alummoxanes, a mixture of alummoxane and alkylalummum such as trimethyl aluminum, tri ethyl aluminum, trnsobutyl aluminum and dimethyl aluminum chloride.
The molar ratio of aluminum of organometalhc compound to transition metal of Group IV of metallocene catalyst of the present invention is in the range from 1 1 to 1 x 106 : 1, preferably from 10 : 1 to 1 x 104 : 1. The co-catalyst of the present invention can be a mixture of non-coordmated Lewis acid and alkylalummum. Examples of the non-coordmated Lewis acid include N, N-dimethylamlmium tetrakιs(pentafluorophenyl)borate, tnphenylcarbenium tetrakιs(pentafluorophenyl)borate, ferroceπum tetrakis (pentafluorophenyl)borate, and trιs(pentafluorophenyl)borate, and the like Examples of the alkylalummum include trimethylalummum, triethyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, triisobutyl aluminum, dnsobutyl aluminum and dimethyl aluminum chloride, tπ(n-butyl)alummum, tπ(n-propyl)alummum, and triisopropylalummum, and the like.
The molar ratio of the non-coordmated 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 alkylalummum 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
To the copolymer of the present invention, additives or adjuvants which are commonly used for polymers, may be incorporated withm a range not to adversely affect the effects of the present invention. Preferred additives or adjuvants include, 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 140 °C, preferably from 30 to 100 °C. A polymerization temperature of -78 °C or lower is industrially disadvantageous, and a temperature higher than 200 °C is not suitable, since decomposition of the metal complex will take place.
The ethylene/aromatic vmyl compound/vmylnorbornene terpolymer of the present invention has an average molecular weight of more than 5,000, more preferably 10,000 and most preferably 30,000, and the meltmg-mdex(MI; ASTM D-1238; method A and condition E) of 0.001 ~ 1000, more preferably 0 01 ~ 100 and most preferably 0.1 — 30.
Ethylene/aromatic vmyl compound/vmylnorbornene terpolymer sample of 40 — 50 mg was dissolved m mixed solution of hot trichlorobenzene and benzene-d-6 followed by putting into the 5 mm NMR column, and measured by 100MHz 13C NMR spectrum.
Before polymerization, the monomers and solvent, if any, are purified by vacuum distillation or by contacting with alumina, silica or molecular sieve. Also, a tπalkylalummum compound, an alkali metal and a metal alloy, especially Na/ may be used to remove the impurities.
The terpolymer of the present invention may be blended with a synthetic or natural polymer regardless of modification. Especially, the present invention may be preferably blended with polyethylene, ethylene/α-olefin copolymer, polypropylene, polyamide, polyisocyanate, polyurethane, polyacrylonitrile, sihcone and polyphenylene oxide, and styrene copolymer such as ethylene-styrene copolymer and polystyrene, which is used in the range from about 0.5 to 50 % by weight.
The terpolymer of the present invention, preferably ethylene-styrene-vmylnorbornene terpolymer is used as a modifier for a composition of asphalt or bitumen. "Bitumen" means a hydrocarbon compound of solid, semi-solid, liquid or gas in natural. Preferably, the present invention uses solid, semisohd or liquid bitumen. Commercially speaking, the bitumen is generally limited to asphalt, tar and pitch. The amount of the bitumen used herein is preferably 65 ~ 99 parts by weight, more preferably 80 — 98 parts by weight. The ethylene-aromatic vmyl compound-vmylnorbornene terpolymer of the 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 Rullet in No.184, a thermoplastic or thermosettmg resm. Particularly, the terpolymer of the present invention can be easily transformed not only by branching, grafting, hydrogenation, cross-lmkmg but also by introducing functional groups to the double bonds, for example, by sulfonation or chlormation.
The present invention will be described in more detail by the following Examples. The Examples are given only to illustrate the present invention and not intended in any way to limit the scope of the invention Examples
Example 1
To 2L autoclave was added MAO (lmmol of Al), 200 mL of styrene and 20 mL of vinylnorbomene. The solution was agitated heating up to 70 °C. After adding 20 μmol of dimethylsilyl (t-butylamidotetramethylcyclopentadienyl)-titanium dichloride to the solution, copolymerization was initiated by adding ethylene at 4 bar. The polymerization was carried out until the solution could hardly be agitated, and the amount of ethylene to be used, exothermic calory and agitation state were measured. After 15 minutes, the ethylene gas was released. The reaction was terminated by adding HCl/methanol solution followed by washing and recycling the sticky polymer. Terpolymer of 62 g was obtained after treating with a small amount of anti-oxidant and drying at 130 °C for more than 6 hours under reduced pressure.
Example 2
The polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 30 mL of vinylnorbomene and terminating the reaction after 15 minutes. Terpolymer of 41 g was obtained.
Example 3
The polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 10 mL of vinylnorbomene and terminating the reaction after 150 minutes. Terpolymer of 52 g was obtained.
Example 4
The polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 5 mL of vinylnorbomene and terminating the reaction after 120 minutes. Terpolymer of 39 g was obtained.
Example 5
The polymerization process was conducted m the same manner as in Example 1 except adding 100 mL of styrene and 20 mL of vinylnorbomene and terminating the reaction after 45 minutes. Terpolymer of 27 g was obtained.
Example 6
The polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbomene and 100 mL of heptane and terminating the reaction after 20 minutes. Terpolymer of 22 g was obtained.
Example 7
The polymerization process was conducted m the same manner as in Example 1 except adding 50 mL of styrene, 5 mL of vinylnorbomene and 150 mL of heptane and terminating the reaction after 31 minutes. Terpolymer of 17 g was obtained.
Example 8
The polymerization process was conducted m the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbomene and 300 mL of Isopar E and terminating the reaction after 120 minutes Terpolymer of 18 g was obtained. Example 9
The polymerization process was conducted in the same manner as in Example 1 except adding 50 mL of styrene, 5 mL of vinylnorbomene and 150 mL of Isopar E and terminating the reaction after 120 minutes. Terpolymer of 9.1 g was obtained.
Example 10
The polymerization process was conducted in the same manner as in
Example 1 except adding 1000 mL of styrene, 2 mL of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 126 g was obtained.
Example 11
The polymerization process was conducted in the same manner as in Example 1 except adding 750 mL of styrene, 2 mL of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 147 g was obtained.
Example 12
The polymerization process was conducted in the same manner as in Example 1 except adding 500 mL of styrene, 2 mL of vinylnorbomene and 500 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 137 g was obtained.
Example 13 The polymerization process was conducted in the same manner as m Example 1 except adding 250 mL of styrene, 2 mL of vinylnorbomene and 750 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 132 g was obtained.
Example 14
The polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 2 mL of vinylnorbomene and 900 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 1 1 1 g was obtained.
Example 15
The polymerization process was conducted in the same manner as m
Example 1 except adding 50 mL of styrene, 2 mL of vinylnorbomene and 1000 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 98 g was obtained.
Example 16
The polymerization process was conducted m the same manner as m Example 1 except adding 10 mL of styrene, 2 mL of vinylnorbomene and 1000 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 124 g was obtained.
Comparative Examples
Comparative Example 1 To 1L autoclave was added MAO (1 mmol of Al). 200 mL of styrene. The solution was agitated heating up to 70 °C. After adding 20 μmol of CGC-T, copolymerization was initiated by adding ethylene of 4 bar. The polymerization was carried out until the solution could hardly be agitated any more, and the amount of ethylene to be used, exothermic calory and agitation state were measured. After 60 minutes, the ethylene gas was discharged. The reaction was terminated by adding HCl/methanol solution followed by washing and recycling the sticky polymer. Copolymer of 49 g was obtained after treating with a small amount of anti-oxidant and drying at 130°C for more than 6 hours under reduced pressure.
Comparative Example 2
The polymerization process was conducted in the same manner as in Comparative Example 1 except adding 150 mL of styrene and 50 mL of hexane. Copolymer of 35 g was obtained.
Comparative Example 3
The polymerization process was conducted in the same manner as in Comparative Example 1 except adding 50 mL of styrene and 150 mL of hexane. Copolymer of 24 g was obtained.
Comparative Example 4
The polymerization process was conducted m the same manner as in
Comparative Example 1 except adding 1000 mL of styrene and reacting under the pressure of 10 bar of ethylene. Copolymer of 78 g was obtained
Comparative Example 5 The polymerization process was conducted in the same manner as in Comparative Example 1 except adding 500 mL of styrene and 500 mL of hexane and reacting under the pressure of 10 bar of ethylene. Copolymer of 61 g was obtained.
Comparative Example 6
The polymerization process was conducted in the same manner as in Comparative Example 1 except adding 100 mL of styrene and 900 mL of hexane and reacting under the pressure of 10 bar of ethylene. Copolymer of 68 g was obtained.
Comparative Example 7
The polymerization process was conducted in the same manner as in
Example 1 except adding 1000 mL of styrene and 10 mL of 1 ,7-octadiene instead of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 14.3 g was obtained.
Comparative Example 8
The polymerization process was conducted in the same manner as m Example 1 except adding 1000 mL of styrene and 5 mL of 1 ,7-octadiene instead of vinylnorbomene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 5.9 g was obtained.
The polymerization condition and test results of the Examples and Comparative Examples are shown in Table 1 Table 1
Example 1 2 3 4 5 6
styrene (ml) 200 200 200 200 100 100 solvent (ml) - - - - 100υ 100υ
C2 (psi) 60 60 60 60 60 60 diene (ml) VN4)20 VN30 VN10 VN5 VN20 VN10 polym. time (min) 30 15 50 60 45 20 yield (g) 62 41 52 39 27 22 activity (kg/[Ti]hr) 6,200 8,200 3,120 1,950 1,800 3,300 styrene content (mol%) 34.5 41.8 33.9 31.4 28.4 25.1 diene content (mol%) VN6.4 VN7.6 VN3.8 VN1.4 - -
Mw x lO4 15.5 17.2 12.1 10.8 - -
(MWD) (9.19) (7.83) (5.69) (5.45) - -
Table 1 (continued)
Example 7 8 9 10 11 12
styrene (ml) 50 100 50 1000 750 500 solvent (ml) 1501} 3002) 1502) - 2503) 5003)
C2 (psi) 60 60 60 150 150 150 diene (ml) VN5 VN10 VN5 VN2 VN2 VN2 polym. time (min) 31 120 120 60 60 60 yield (g) 17 18 9.1 126 147 137 activity (kg/[Ti]hr) 1,645 450 228 6,300 7,350 6,850 styrene content (mol%) 19.8 17.0 16.2 27.9 22.3 20.7 diene content (mol%) - - - n.d. n.d. n.d.
Mw x lO4 - - - 21.1 26.3 38.5
(MWD) - - - (4.81) (5.13) (6.21) Table 1 (continued)
Example 13 14 15 16 Com. Ex. 1
styrene (ml) 250 100 50 10 200 150 solvent (ml) 7503) 9003) 10003) 10003) 505 )
C2 (psi) 150 150 150 150 60 60 diene (ml) VN2 VN2 VN2 VN2 polym. time (min) 60 60 60 60 60 60 yield (g) 132 111 98 124 49 35 activity (kg/[Ti]hr) 6,600 5,600 4,900 6,200 2,450 1,750 styrene content (mol%) 13.6 10.5 7.1 1.3 35.2 27.6 diene content (mol%) n.d. VN0.2 VN0.6 VN0.4 Mw x lO4 32.9 10.3 13.6 21.4 10.9 6.26
(MWD) (5.89) (3.97) (3.89) (4.09) (3.28) (3.37)
Table 1 (continued)
Comp . Ex. 3 4 5 6 7 8
styrene (ml) 50 1000 500 100 1000 1000 solvent (ml) 1503) - 5003) 9003) - -
C2 (psi) 60 150 150 150 150 150 diene (ml) - - - - OD 10 OD 5 polym. time (min) 60 60 60 60 60 60 yield (g) 24 78 61 68 14.3 5.9 activity (kg/[Ti]hr) 1,200 3,900 3,050 3,400 715 295 styrene content (mol%) 16.4 26.3 14.4 4.1 16.7 18.1 diene content (mol%) - - - - - -
Mw x 104 9.89 20.8 18.9 19.2 29.3 4.40
(MWD) (2.48) (3.12) (3.35) (3.20) (2.62) (3.24)
Notes: l) hepthane
2) Isopar E (trademark): a mixture of hydrocarbons by Exxon Co. 3) hexane
4) VN: vinylnorbomene 5) OD: 1,7-octadiene
The polymerization of the Examples and Comparative Examples were conducted with metallocene catalyst of 20μ mol and MAO/Ti = 500 at 70 °C .
The structure of terpolymers prepared above was measured by using 13C-NMR. The 13C-NMR of the polymers of Example 1 and Comparative Example 1 was shown m Figure 1. The 13C-NMR measurement was carried out at 100°C by using TMS (tetramethylsilane) in the solvent mixture of trichlorobezene and bezene-d-6 mixed solution. The terpolymers are partially soluble in THF or CHC13 at room temperature, and completely soluble in boiling THF. As a result of 13C-NMR measurement, it is known that the chemical structure of the terpolymer is pseudo-random structure as disclosed m Macromolecules, 1980, 849, because no peak was shown near 42 ppm attributable to head-to-tail bond chain of styrene.
Further, the terpolymer of the present invention showed the distinct peaks of terminal double bond near of 112 and 1 14 ppm, which indicates that most of the vinylnorbomene monomers m the copolymer participate m polymerization using the double bond withm the ring, but not the double bond outside the ring. This indicates that the reaction rate of the double bond withm the ring is faster than that of the terminal double bond, because the former is relatively unstable. The content of the vinylnorbomene was quantitatively analyzed by the peaks from the 13C-NMR spectrum measurement, and the result are shown m Table 1.
As shown m Comparative Examples 7 and 8, the terpolymers using 1 ,7-octadiene have a low activity and low content of 1 ,7-octadiene in the terpolymer, which indicates that the double bond withm the vinylnorbomene ring participates in the polymerization. Fig 2 shows a micro structure and quantitative analysis of styrene and vinylnorbomene comonomers in the terpolymer by using πC-NMR spectrum measurement, wherein S is secondary carbon, Vt is terminal vmyl group; [St], [E] and [VN] are content of styrene, ethylene and vinylnorbomene respectively.
The result of quantitative analysis and integral depending on chemical shift of each carbon in the micro structure m Examples 1 are shown in Table 2
Table 2
vt a T αγ N ^γγ+ ^βγ+ spp Mol%
Peak(ppm) (1 14, (46) (37) (36) (35) (30) (27) (25) [SM] [VN] 112)
Example 1 12.31 103.1 86.62 12.61 48.46 100 0 41 03 23.11 34 5 6 4
The stretching band due to the terminal double bond of C=C and =C-H respectively m the FT-IR measurement indicates that terminal double bonds exist m the terpolymer In the present invention, when vinylnorbomene was used m the polymerization, not only the content of the incorporated styrene but also the activity of the catalyst increased comparing to ethylene-styrene copolymerization at the same condition. The results are shown m Figures 3 and 4 In case of Examples 1 -9, when the molar ratio of the styrene used is the same, the styrene content in the terpolymer was increased more than 50 % as shown in Figure 3, and still more increased, when the molar ratio of the incorporated vinylnorbomene was increased Figure 4 shows the case of Examples 10-16, which is the result of incorporation of a small amount of vinylnorbomene (2ml). Compared Figure 3 with Figure 4, the mol % of the incorporated styrene of the terpolymer in the Example 1-9 was more increased
Further, the molecular weights and the molecular weight distribution of the terpolymer of the present invention were increased altogether compared with the ethylene-styrene copolymer under the same condition. Fig.5 shows the result of gel permeation chromatography (GPC) of Example 1 and Comparative Example 1. The peaks are shown in the region of polymer. Example 1 has higher molecular weight distribution due to addition of vinylnorbomene unlike Comparative Example 1. As compared with a conventional ethylene/styrene copolymer, the ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of the present invention has various improved properties such as high activity, a high molecular weight, a wide molecular weight distribution and a high content of styrene. Especially, Examples 10-13 concern about terpolymerization by adding a trace of vinylnorbomene, which also indicate that although the vinylnorbomene was not found by 13C NMR analysis, the activity, molecular weight, molecular weight distribution and content of styrene were increased.
In the above, the present invention was described based on the preferred embodiment of the present invention, but it should be apparent to those ordinarily skilled in the art that various changes and modifications can be added without departing from the spirit and scope of the present invention. Such changes modifications should come within the scope of the present invention.

Claims

What is claimed is:
1. A method of preparing an ethylene/aromatic vmyl compound/vmylnorbornene terpolymer by copolymerizing 50 — 90 mol % of ethylene, 1 — 55 mol % of an aromatic vmyl compound and 1 — 55 mol % of a vinylnorbomene under a catalyst system consisting of a transition metal compound represented by the following formula ( I ) and a cocatalyst:
Figure imgf000023_0001
where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;
Cp' is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an mdenyl group, a tetrahydromdenyl group; a substituted mdenyl group; a fluorenyl group; a octahydrofluorenyl group; or a substituted fluorenyl group; Y is a hydrogen or a silyl group of C o, an alkyl group of C_ 10, an aryl group of Ci-io, or a combination thereof,
A is an alkyl group of C] 30, an alkylamide group of Cι_30 or a derivative of cyclopentadienyl group which is identical to Cp', and
X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.
2. The method of claim 1 , wherein said cocatalyst is an organometalhc compound or a mixture of a non-coordmated Lewis acid and an alkylalummum compound.
3 The method of claim 2, wherein said organometalhc compound is an alkylalummoxane or an organoalummum compound
?
4. The method of claim 3, wherein said alkylaluminoxane is methylalummumoxane (MAO) or a modified methylalummumoxane (MMAO).
5. The method of claim 3, wherein said organoaluminum compound includes an alkylaluminoxane having a repeating unit of the following formula ( II ), said alkylaluminoxane including a linear alkylaluminoxane represented by the following formula (HI), and a cyclic alkylaluminoxane represented by the following formula (IV):
Figure imgf000024_0001
wherein R is an hydrogen, alkyl group of Cι-5 or aryl group of Cι_6 and may be the same or different from each other, and m and n are an integer of 0 — 100.
6. The method of claim 2, wherein said non-coordinated Lewis acid is selected from the group consisting of N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, ferrocerium tetrakis(pentafluorophenyl)borate, and tris(pentafluorophenyl)borate.
7. An ethylene/aromatic vinyl compound/vinylnorbornene terpolymer consisting essentially of 50 — 90mol% of ethylene, 1 ~ 55mol% of aromatic vinyl compound and 1 ~ 55mol% of vinylnorbomene, which is polymerized under a catalyst system consisting of a transition metal compound represented by the following formula ( I ) and a cocatalyst:
where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;
Cp' is a non-substituted cyclopentadienyl group; a cyclopentadienyl group with 1 to 4 linear alkyl substitutes; an indenyl group; a tetrahydromdenyl group; a substituted indenyl group; a fluorenyl group; a octahydrofluorenyl group; or a substituted fluorenyl group;
Y is a hydrogen or a silyl group of C 0, an alkyl group of C o, an aryl group of CMO, or a combination thereof;
A is an alkyl group of C 30, an alkylamide group of C]_30 or a derivative of cyclopentadienyl group which is identical to Cp'; and
X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.
8. The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of claim 7, in which said vinylnorbomene portion has terminal double bonds.
9. The ethylene/aromatic vinyl compound/vinylnorbornene terpolymer of claim 7, wherein said terpolymer shows distinct peaks nearl 12 and 114 ppm in the
13C-NMR spectrum due to the terminal double bonds.
10. The ethylene/aromatic vinyl compound/vinylnorbomene terpolymer of claim 7, wherein said terpolymer shows stretching bands due to the terminal double bonds of C=C and =C-H near 1636 and 995cm"1, respectively, in the FT-IR spectrum.
11. The ethylene/aromatic vinyl compound/vinylnorbomene terpolymer of claim 7, wherein said terpolymer has a weight average molecular weight of at least 5,000.
PCT/KR2000/001483 1999-12-20 2000-12-18 Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer WO2001046282A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2001547188A JP2003518173A (en) 1999-12-20 2000-12-18 Ethylene-aromatic vinyl compound-vinyl norbornene terpolymer
AT00983570T ATE459669T1 (en) 1999-12-20 2000-12-18 TERPOLYMERS OF ETHYLENE WITH AROMATIC VINYL COMPOUNDS AND VINYLNORBONES
AU20308/01A AU2030801A (en) 1999-12-20 2000-12-18 Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer
EP00983570A EP1268588B1 (en) 1999-12-20 2000-12-18 Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer
DE60043945T DE60043945D1 (en) 1999-12-20 2000-12-18 BINDINGS AND VINYLNORBONS

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KR1999/59308 1999-12-20
KR10-1999-0059308A KR100416470B1 (en) 1999-12-20 1999-12-20 Ethylene-Aromatic Vinyl Compound-Vinyl Norbonene Terpolymer

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WO2019078083A1 (en) * 2017-10-20 2019-04-25 株式会社ブリヂストン Multi-copolymer, rubber composition, cross-linked rubber composition, rubber article, and tire

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US20030130446A1 (en) 2003-07-10
KR20010064893A (en) 2001-07-11
KR100416470B1 (en) 2004-01-31
DE60043945D1 (en) 2010-04-15
JP2003518173A (en) 2003-06-03
EP1268588B1 (en) 2010-03-03
ATE459669T1 (en) 2010-03-15

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