Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer

FIELD OF THE INVENTION

[0001] The present invention relates to an ethylene/aromatic vinyl compound/vinylnorbornene terpolymer. More particularly, the present invention relates to an ethylene/aromatic vinyl compound/vinylnorbornene terpolymer with high activity, a high molecular weight and a high content of aromatic vinyl compound, which can be prepared with a small amount of co-catalyst under mild condition.

BACKGROUND OF THE INVENTION

[0002] Copolymerization of ethylene and an aromatic vinyl 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 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. Further, 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.

[0003] 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 in the alternating structure of the pseudo-random styrene/ethylene copolymer do not have stereoregularity. 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

[0004] 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.

[0005] 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.

[0006] 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.

[0007] 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.

[0008] Macromolecules, 29, 1158 (1996) discloses polymerization of ethylene/styrene using CpTiCl3 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.

[0009] U.S. Pat. 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 in the alternating structure of ethylene and styrene is represented by an isotactic diad index of more than o.75.

[0010] 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.

[0011] Accordingly, the present inventors have developed an ethylene/aromatic vinyl compound/vinylnorbornene terpolymer with high activity, a high molecular weight and a high content of aromatic vinyl compound, which can be prepared with a small amount of co-catalyst under mild polymerization condition.

OBJECTS OF THE INVENTION

[0012] A feature of the present invention is the provision of a process of preparing ethylene/aromatic vinyl 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 in the heterogeneous Ziegler-Natta catalyst system.

[0013] Another feature of the present invention is the provision of a process of preparing a large amount of ethylene/aromatic vinyl compound copolymer using a small amount of a cocatalyst.

[0014] A further feature of the present invention is the provision of an ethylene/aromatic vinyl compound copolymer having double bonds in which branching and/or cross-linking can be carried out.

[0015] 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.

[0016] 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.

[0017] The above and other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

[0018] 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:

[0019] where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;

[0020] 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;

[0021] 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;

[0022] 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

[0023] X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.

[0024] When A is a derivative of the cyclopentadienyl group, the transition metal complex may be a racemic mixture of d-form or l-form. Either d-form or l-form can be used in the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025]
FIG. 1 is a 13C NMR spectrum of the terpolymer obtained in Example 1;

[0026]
FIG. 2 shows a micro structure and quantitative analysis of styrene and vinylnorbornene comonomers in the terpolymer by using 13C-NMR spectrum measurement;

[0027]
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;

[0028]
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

[0029]
FIG. 5 is a graph of gel permeation chromatography(GPC) of Example 1 and Comparative Example 1.

DETAILED DESCRIPTION OF THE INVENTION

[0030] 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. The catalyst system consists of a transition metal compound and a cocatalyst.

[0031] 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.

[0032] The aromatic vinyl compound includes styrene compounds and styrene derivatives such as alkylstyrene, halogenated styrene, halogen-substituted alkylstyrene, alkoxystyrene, vinylbiphenyl, vinylphenylnaphthalene, vinylphenylanthracene, vinylphenylpyrene, trialkylsilylvinylbiphenyl, trialkylstenybiphenyl, alkylsilylstyrene, carboxymethylstyrene, alkylesterstyrene, vinylbenzenesulphonic acid ester, vinylbenzyldialkoxyphosphide, etc.

[0033] 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 butoxystyrene; those of vinylbiphenyl are 4-vinylbiphenyl, 3-vinylbiphenyl, and 2-vinylbiphenyl; those of vinylphenylnaphthalene are 1-(4-vinylbiphenylnaphthalene), 2-(4-vinylbiphenylnaphthalene), 1-(3-vinylbiphenylnaphthalene), 2-(3-vinylbiphenylnaphthalene), and 1-(2-vinylbiphenylnaphthalene); those of vinylphenylanthracene are 1-(4-vinylphenyl)anthracene, 2-(4-vinylphenyl)anthracene, 9-(4-vinylphenyl)anthracene, 1-(3-vinylphenyl)anthracene, 9-(3-vinylphenyl)anthracene, and 1-(4-vinylphenyl)anthracene; those of vinylphenylpyrene are 1-(4-vinylphenyl)pyrene, 2-(4-vinylphenyl)pyrene, 1-(3-vinylphenyl)pyrene, 2-(3-vinylphenyl)pyrene, 1-(2-vinylphenyl)pyrene, and 2-(2-vinylphenyl)pyrene; that of trialkylsilylvinylbiphenyl is 4-vinyl-4-trimethylsilylbiphenyl; and those of alkylsilylstyrene are p-trimethylsilylstyrene, m-trimethylsilylstyrene, o-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene, and o-triethylsilylstyrene.

[0034] In the copolymer, the content of the aromatic vinyl compound may be at least 0.1 mol %, preferably 0.5˜55 mol %, more preferably 1.0˜55 mol %.

[0035] The vinylnorbornene being polymerized by catalyst system of the present invention is a non-conjugated diene which includes dicyclopentadiene, 5-ethylidene-2-norbornene and methyl hexadiene. The vinylnorbornene is preferably 0.01˜10 mol % in the copolymer.

[0036] The ethylene/aromatic vinyl compound/vinylnorbornene 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):

[0037] where M represents a transition metal of Group IV of the Periodic Table such as titanium, zirconium or hafnium;

[0038] 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;

[0039] 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;

[0040] 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

[0041] X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a diene group.

[0042] When A is a derivative of the cyclopentadienyl group, the transition metal complex may be a racemic mixture of d-form or l-form. Either d-form or l-form can be used in the present invention.

[0043] In the present invention, the metallocene catalyst is used with a cocatalyst. The cocatalyst is an organometallic compound such as alkylaluminoxane and alkylaluminum compound, which are known to an ordinary person in the art. The representative examples of alkylaluminoxane are methylaluminumoxane (MAO) and modified methylaluminumoxane (MMAO). The alkylaluminoxane includes an alkylaluminoxane having a repeating unit of the following formula (II), a linear alkylaluminoxane represented by the following formula (III), and a cyclic alkylaluminoxane represented by the following formula (IV):

[0044] where R is an hydrogen, an alkyl group of C1-5 or an aryl group of C1-6, being same or different each other, and m and n are an integer of 0˜100.

[0045] Alternatively, the co-catalyst of the present invention may be a mixture of different aluminoxanes, a mixture of aluminoxane and alkylaluminum such as trimethyl aluminum, triethyl aluminum. triisobutyl aluminum and dimethyl aluminum chloride.

[0046] The molar ratio of aluminum of organometallic compound to transition metal of Group IV of metallocene catalyst of the present invention is in the range from 1:1 to 1×106:1, preferably from 10:1 to 1×104:1.

[0047] The co-catalyst of the present invention can be a mixture of non-coordinated Lewis acid and alkylaluminum. Examples of the non-coordinated Lewis acid include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, ferrocerium tetrakis (pentafluorophenyl)borate, and tris(pentafluorophenyl)borate, and the like. Examples of the alkylaluminum include trimethylaluminum, triethyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, triisobutyl aluminum, diisobutyl aluminum and dimethyl aluminum chloride, tri(n-butyl)aluminum, tri(n-propyl)aluminum, and triisopropylaluminum, and the like.

[0048] 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 alkylaluminum 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.

[0049] To the copolymer of the present invention, 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 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.

[0050] 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.

[0051] The ethylene/aromatic vinyl compound/vinylnorbornene 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 melting-index(MI; ASTM D-1238; method A and condition E) of 0.001˜1000, more preferably 0.01˜100 and most preferably 0.1˜30.

[0052] Ethylene/aromatic vinyl compound/vinylnorbornene terpolymer sample of 40˜50 mg was dissolved in mixed solution of hot trichlorobenzene and benzene-d-6 followed by putting into the 5 mm NMR column, and measured by 100 MHz 13C NMR spectrum.

[0053] Before polymerization, the monomers and solvent, if any, are purified by vacuum distillation or by contacting with alumina, silica or molecular sieve. Also, a trialkylaluminum compound, an alkali metal and a metal alloy, especially Na/K may be used to remove the impurities.

[0054] 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, silicone 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.

[0055] The terpolymer of the present invention, preferably ethylene-styrene-vinylnorbornene 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, semisolid 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.

[0056] The ethylene-aromatic vinyl compound-vinylnorbornene 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 thermosetting resin. Particularly, the terpolymer 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.

[0057] 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

[0058] To 2L autoclave was added MAO (1 mmol of Al), 200 mL of styrene and 20 mL of vinylnorbornene. 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

[0059] The polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 30 mL of vinylnorbornene and terminating the reaction after 15 minutes. Terpolymer of 41 g was obtained.

Example 3

[0060] The polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 10 mL of vinylnorbornene and terminating the reaction after 150 minutes. Terpolymer of 52 g was obtained.

Example 4

[0061] The polymerization process was conducted in the same manner as in Example 1 except adding 200 mL of styrene and 5 mL of vinylnorbornene and terminating the reaction after 120 minutes. Terpolymer of 39 g was obtained.

Example 5

[0062] The polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene and 20 mL of vinylnorbornene and terminating the reaction after 45 minutes. Terpolymer of 27 g was obtained.

Example 6

[0063] The polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbornene and 100 mL of heptane and terminating the reaction after 20 minutes. Terpolymer of 22 g was obtained.

Example 7

[0064] The polymerization process was conducted in the same manner as in Example 1 except adding 50 mL of styrene, 5 mL of vinylnorbornene and 150 mL of heptane and terminating the reaction after 31 minutes. Terpolymer of 17 g was obtained.

Example 8

[0065] The polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 10 mL of vinylnorbornene and 300 mL of Isopar E and terminating the reaction after 120 minutes. Terpolymer of 18 g was obtained.

Example 9

[0066] The polymerization process was conducted in the same manner as in Example I except adding 50 mL of styrene, 5 mL of vinylnorbornene and 150 mL of Isopar E and terminating the reaction after 120 minutes. Terpolymer of 9.1 g was obtained.

Example 10

[0067] The polymerization process was conducted in the same manner as in Example 1 except adding 1000 mL of styrene, 2 mL of vinylnorbornene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 126 g was obtained.

Example 11

[0068] The polymerization process was conducted in the same manner as in Example 1 except adding 750 mL of styrene, 2 mL of vinylnorbornene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 147 g was obtained.

Example 12

[0069] The polymerization process was conducted in the same manner as in Example 1 except adding 500 mL of styrene, 2 mL of vinylnorbornene 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

[0070] The polymerization process was conducted in the same manner as in Example 1 except adding 250 mL of styrene, 2 mL of vinylnorbornene 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

[0071] The polymerization process was conducted in the same manner as in Example 1 except adding 100 mL of styrene, 2 mL of vinylnorbornene and 900 mL of hexane and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 111 g was obtained.

Example 15

[0072] The polymerization process was conducted in the same manner as in Example 1 except adding 50 mL of styrene, 2 mL of vinylnorbornene 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

[0073] The polymerization process was conducted in the same manner as in Example 1 except adding 10 mL of styrene, 2 mL of vinylnorbornene 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

[0074] 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

[0075] 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

[0076] 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

[0077] The polymerization process was conducted in 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

[0078] 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

[0079] 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

[0080] 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 vinylnorbornene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 14.3 g was obtained.

Comparative Example 8

[0081] The polymerization process was conducted in the same manner as in Example 1 except adding 1000 mL of styrene and 5 mL of 1,7-octadiene instead of vinylnorbornene and reacting for 60 minutes under the pressure of 10 bar of ethylene. Terpolymer of 5.9 g was obtained.

[0082] The polymerization condition and test results of the Examples and Comparative Examples are shown in Table 1.

1TABLE 1Example123456styrene (ml)200200200200100100solvent (ml)————1001)1001)C2 (psi)606060606060diene (ml)VN1)20VN30VN10VN5VN20VN10polym. time (min)301550604520yield (g)624152392722activity (kg/[Ti]hr)6,2008,2003,1201,9501,8003,300styrene content (mol %)34.541.833.931.428.425.1diene content (mol %)VN6.4VN7.6VN3.8VN1.4——Mw × 10415.517.212.110.8——(MWD)(9.19)(7.83)(5.69)(5.45)——Example789101112styrene (ml)50100501000750500solvent (ml)1501)3002)1502)—2503)5003)C2 (psi)606060150150150diene (ml)VN5VN10VN5VN2VN2VN2polym. time (min)31120120606060yield (g)17189.1126147137activity (kg/[Ti]hr)1,6454502286,3007,3506,850styrene content (mol %)19.817.016.227.922.320.7diene content (mol %)———n.d.n.d.n.d.Mw × 104———21.126.338.5(MWD)———(4.81)(5.13)(6.21)Com.Example13141516Ex. 12styrene (ml)2501005010200150solvent (ml)7503) 9003)10003)10003)—501)C2 (psi)1501501501506060diene (ml)VN2VN2VN2VN2——polym. time (min)606060606060yield (g)132111981244935activity (kg/[Ti]hr)6,6005,6004,9006,2002,4501,750styrene content (mol %)13.610.57.11.335.227.6diene content (mol %)n.d.VN0.2VN0.6VN0.4——Mw × 10432.910.313.621.410.96.26(MWD)(5.89)(3.97)(3.89)(4.09)(3.28)(3.37)Comp. Ex.345678styrene (ml)50100050010010001000solvent (ml)1503)—5003)9003)——C2 (psi)60150150150150150diene (ml)————OD 10OD 5polym. time (min)606060606060yield (g)2478616814.35.9activity (kg/[Ti]hr)1,2003,9003,0503,400715295styrene content (mol %)16.426.314.44.116.718.1diene content (mol %)——————Mw × 1049.8920.818.919.229.34.40(MWD)(2.48)(3.12)(3.35)(3.20)(2.62)(3.24)Notes: 1)hepthane 2)Isopar E (trademark): a mixture of hydrocarbons by Exxon Co. 3)hexane 4)VN: vinylnorbornene 5)OD: 1,7-octadiene

[0083] The polymerization of the Examples and Comparative Examples were conducted with metallocene catalyst of 20 μmol and MAO/Ti=500 at 70° C.

[0084] 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 in FIG. 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 CHCl3 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 in Macromolecules, 1980, 849, because no peak was shown near 42 ppm attributable to head-to-tail bond chain of styrene.

[0085] Further, the terpolymer of the present invention showed the distinct peaks of terminal double bond near of 112 and 114 ppm, which indicates that most of the vinylnorbornene monomers in the copolymer participate in polymerization using the double bond within the ring, but not the double bond outside the ring. This indicates that the reaction rate of the double bond within the ring is faster than that of the terminal double bond, because the former is relatively unstable. The content of the vinylnorbornene was quantitatively analyzed by the peaks from the 13C-NMR spectrum measurement, and the result are shown in Table 1.

[0086] As shown in 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 within the vinylnorbornene ring participates in the polymerization.

[0087]
FIG. 2 shows a micro structure and quantitative analysis of styrene and vinylnorbornene comonomers in the terpolymer by using 13C-NMR spectrum measurement, wherein S is secondary carbon; Vt is terminal vinyl group; [St], [E] and [VN] are content of styrene, ethylene and vinylnorbornene respectively.

[0088] The result of quantitative analysis and integral depending on chemical shift of each carbon in the micro structure in Examples 1 are shown in Table 2.

2TABLE 2Vta(114,TSαγNSαγ−Sγγ−Sβγ+SββMol %Peak(ppm)112)(46)(37)(36)(35)(30)(27)(25)[SM][VN]Example 112.31103.186.6212.6148.46100.041.0323.1134.56.4

[0089] The stretching band due to the terminal double bond of C═C and ═C—H respectively in the FT-IR measurement indicates that terminal double bonds exist in the terpolymer.

[0090] In the present invention, when vinylnorbornene was used in 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 in FIGS. 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 FIG. 3, and still more increased, when the molar ratio of the incorporated vinylnorbornene was increased. FIG. 4 shows the case of Examples 10-16, which is the result of incorporation of a small amount of vinylnorbornene (2 ml). Compared FIG. 3 with FIG. 4, the mol % of the incorporated styrene of the terpolymer in the Example 1-9 was more increased.

[0091] 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 vinylnorbornene unlike Comparative Example 1.

[0092] 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 vinylnorbornene, which also indicate that although the vinylnorbornene was not found by 13C NMR analysis, the activity, molecular weight, molecular weight distribution and content of styrene were increased.

[0093] 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.

Ethylene-aromatic vinyl compound-vinyl norbonene terpolymer

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