KR20100091624A - Cycloolefin copolymers and their preparation - Google Patents

Abstract

The present invention provides a cyclic olefin copolymer using a dihydrotricyclopentadiene compound obtained through hydrogenation after chemically bonding three molecules of cyclopentadiene, which is a C5- fraction of naphtha cracking, through a Diels-Alder reaction, and a method of preparing the same. The new copolymer shows a high glass transition temperature and can be used for various purposes as an amorphous transparent resin.

Description

 Cycloolefin-based high molecular compound and its manufacturing method {Cycloolefin Copolymers and Their Preparation}

The present invention relates to a cyclic olefin polymer compound and a method for preparing the same, and more particularly, three molecules of cyclopentadiene, which occupy a large portion of the C5 fraction of naphtha cracking, are chemically bonded through Diels-Alder reaction and then obtained by hydrogenation. The present invention relates to a dihydrotricyclopentadiene compound and a cyclic olefin copolymer prepared using the same as a monomer.

Among the products of naphtha cracking, the carbon number of 4 or less is separated and refined to be useful for the petrochemical industry, but most of the C5 oil having 5 carbon atoms is burned and used as fuel, and only some of them are separated and refined and used industrially. Therefore, efforts have been made to produce high value-added chemicals by separating and refining C5-oil.

It is the cyclopentadiene that makes up a large part of the C5-oil. Cyclopentadiene spontaneously undergoes a Diels-Alder reaction at room temperature to be converted to dicyclopentadiene. In order to prepare plastics from dicyclopentadiene, a lot of studies have been conducted on the copolymerization of ethylene, alpha olefins or styrene (see Scheme 1). Of the two olefin groups of dicyclopentadiene, it is known that the 5-6 carbon olefin group is more reactive than the 2-3 carbon olefin group. When the copolymerization reaction with the vinyl monomer is carried out using a polymerization catalyst, an olefin group of carbon 5-6 is first reacted to obtain a polymer having an intermediate structure of Scheme 1, but in general, the reaction does not stop at this stage. The crosslinked polymer was obtained by additionally participating in the polymerization reaction of the olefin group (Naga, N. J. Polym. Sci., Part A: Polym. Chem. 2005 , 43 , 1285-1291). By the way, cross-linked polymer is difficult to process, there is a limit to the development of the application.

In the case of the Group 4 metallocene catalyst, it was reported that when the content of the dicyclopentadiene of the copolymer is adjusted to less than 10%, a polymer of an intermediate stage of the uncrosslinked Scheme 1 can be obtained (Simanke, AG; Mauler, RS; Galland, GB J. Polym. Sci., Part A: Polym. Chem. 2002 , 40 , 471-485; Suzuki, J .; Kino, Y .; Uozumi, T .; Sano, T .; Teranishi, T .; Jin, J .; Soga, K .; Shiono, T. J. Appl. Polym. Sci. 1999 , 72 , 103-108). In the case of a catalyst prepared based on Group 3 metals recently, only olefin groups of 5-6 carbons show reactivity and olefin groups of 2-3 carbons show no reactivity, thereby preparing a copolymer having a high content of dicyclopentadiene. (Journal of Organometallic Chemistry 691 (2006) 3114-3121; Xiaofang Li and Zhaomin Hou, Macromolecules 2005 , 38, 6767-6769; Xiaofang Li, Masayoshi Nishiura, Kyouichi Mori, Tomohiro Mashiko and Zhaomin Hou, Chem. Commun. , 2007 , 4137-4139). However, this polymer contains olefin groups that do not react with its molecular structure, which is problematic for direct commercial use. Olefin groups are highly reactive and may result in deformation of the resin during melt processing and are also less durable. For this reason, it is not uncommon to use resins containing olefin groups in the polymer chain in industrial sites.

Zeon, Japan, produced a linear polymer through ring-opening metathesis polymerization (ROMP) reaction of 5-6 carbon olefin groups of dicyclopentadiene and hydrogenated it as shown in [Scheme 2]. (Masahiro Yamazaki, Journal of Molecular Catalysis A: Chemical 213 ( 2004 ) 81-87). In this case as well, it is essential to completely remove the double bond in the resin through a hydrogenation reaction. It is not easy to transform all double bonds into single bonds by hydrogenation of a polymer compound including an olefin group.

Meanwhile, dicyclopentadiene may be converted to cyclopentadiene at high temperature, and then subjected to Diels-Alder reaction with ethylene or alpha olefin to prepare norbornene-based cyclic olefin and copolymerize it with ethylene (Cho, ES; Joung, UG; Lee, BY; Lee, H .; Park, Y.-W .; Lee, CH; Shin, DM Organometallics 2004 , 23 , 4693-4699; Lee Si-keun, Park Young-hwan, Hong Sung-don, Song Kwang-ho, Jung Bung-gun, Nam Dae-woo, Lee 10-0458600 (Nov. 16, 2004); Incoronata Tritto, Laura Boggioni, Dino R. Ferro, Coordination Chemistry Reviews 250 (2006) 212-241). The copolymer thus prepared is called a cycloolefin copolymer (COC) (see Scheme 3). Norbornene-based monomers can also be prepared by hydrogenation after ROMP reaction as shown at the bottom of Scheme 3 (Masahiro Yamazaki, Journal of Molecular Catalysis A: Chemical 213 ( 2004 ) 81-87). The polymer thus obtained is called a cycloolefin polymer (COP). As mentioned above, the hydrogenation of high molecular compounds is not easy for the cyclic olefin copolymer (COC) compared to the cyclic olefin polymer (COP) is more attractive in terms of manufacturing method. COC can control the Tg of the resin by adjusting the ratio of ethylene and norbornene, which makes it possible to manufacture various grades, and also has the advantages of high transparency in terms of physical properties, a low pear citrus ratio, and a low density of resin. First, applications are being developed for DVD materials and optical films for displays.

However, in the case of COC resin manufactured using norbornene, since it contains a lot of norbornene units, a grade having a high Tg may be brittle and insufficient for use in applications such as optical films. In order to make up for the shortcomings of the physical properties of COC resins produced using norbornene, including these problems, 1,4,5,8- obtained by diels-alder reaction of cyclopentadiene once more with norbornene Efforts have been made to use large cyclic olefin compounds such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphtalene (hereinafter abbreviated as 'DMON') as COC monomers. (Scheme 4; W. Kaminsky, Catalysis Today 62 (2000) 23-34). In order to supplement the physical properties of COP, efforts to prepare resins by ROMP and hydrogenation of DMON as shown at the bottom of Scheme 4 are considerable (Masahiro Yamazaki, Journal of Molecular Catalysis A: Chemical 213 ( 2004 ). -87) By using a large cyclic olefin as a monomer in COC synthesis, a resin having a high Tg can be produced even with a polymer containing a relatively large amount of ethylene as compared with the production of COC with norbornene. The inclusion of more flexible ethylene units than cyclic olefin units in the polymer chain can provide a way to overcome the above-mentioned brittle problem, however, as shown in Scheme 4, It is manufactured in two steps from cyclopentadiene and the manufacturing process is not easy, so it is quite expensive to use as a polymer monomer. Therefore, economically, manufacturing DMON is an important issue for commercialization of resins based on DMON.

In other words, the bottom polymer material of Scheme 4 was commercialized by Zeon.

The present invention is to provide a cyclic olefin polymer compound that can implement the physical properties equivalent to the cyclic olefin polymer compound obtained from the conventional DMON while using a monomer that can be obtained by a simple method.

The present invention also provides a method for producing a cyclic olefin polymer compound through vinyl polymerization using a monomer that can be obtained by a simple method.

In particular, one embodiment of the present invention is to provide a cyclic olefin polymer compound having a high glass transition temperature.

In one embodiment of the present invention provides a cyclic olefin polymer compound comprising a repeating unit represented by the following formula (1).

Wherein the molar ratio of x: y is 99: 1 to 1:99 and z has an average value of 10 to 20,000.

In a preferred embodiment of the present invention, the molar ratio of x: y is 90:10 to 50:50, and z provides a cyclic olefin polymer compound comprising a repeating unit represented by Formula 1 having an average value of 500 to 3000.

An embodiment of the present invention provides a method for preparing a cyclic olefin polymer compound including a repeating unit represented by Chemical Formula 1 by vinyl polymerization of a compound represented by Chemical Formula 2 with ethylene in the presence of a catalyst.

In a process according to one embodiment of the invention, the catalyst is methylaluminoxane, Al (R ³ ) ₃ , wherein the catalyst is a compound obtained by partial hydrolysis of trimethylaluminum alone or a mixture with triisobutylaluminum (wherein R ³ is the same as or different from each other and is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, B (Ar _f ) ₃ (wherein Ar _f is an aryl group substituted with a fluorine atom), and [L] ⁺ [B (Ar _f ) ₄ ] ^- (wherein Ar _f is as defined above and [L] ⁺ is selected from carbocation or tertiary ammonium) It may be activated by using a single or a mixture as a promoter.

Wherein M is Ti, Zr, Hf; X is halogen or an alkyl group having 1-20 carbon atoms; R ¹ is the same or different from each other and is a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, an alkenyl group or an alkynyl group; R ² is the same or different and is a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group.

According to a preferred embodiment of the present invention, in the compound represented by the formula (3), M is Ti, X is a methyl group or a chlorine radical, R ¹ and R ² are both methyl groups; Al (R ³⁾ ₃ in R ³ is a methyl group, an ethyl group or an isobutyl group; In B (Ar _{f) 3} Ar _f is a penta-fluorophenyl (C ₆ F ₅₎ group; ^{[L] + [B (Ar} f) 4] - Ar f may be a penta-fluorophenyl (C ₆ F ₅₎ group and [L] ⁺ is [Ph ₃ C] ⁺ or [PhNMe ₂ H] ⁺ at .

According to the present invention, by introducing dihydrotricyclopentadiene as a new cyclic olefin monomer to implement copolymerization with ethylene, a relatively small amount of dihydrotricyclo as compared to the norbornene-ethylene copolymer which is a typical cyclic olefin copolymer Even if the polymer chain contains pentadiene units (or relatively high amounts of ethylene units), the glass transition temperature can be achieved at the same level, and the polymer chains showing high glass transition temperatures contain relatively high amounts of ethylene units. Accordingly, the polymer chain may be more flexible to compensate for the disadvantages of the existing norbornene-ethylene copolymer.

Hereinafter, the present invention will be described in detail.

The present invention relates to a cyclic olefin polymer compound comprising a repeating unit represented by the following formula (1).

Formula 1

Wherein the molar ratio of x: y is 99: 1 to 1:99 and z has an average value of 10-20,000.

The cyclic olefin polymer compound including the repeating unit represented by the formula (1) is obtained by vinyl polymerization of the dihydrotricyclopentadiene vinyl group-containing monomer represented by the following formula (2) and ethylene together. Here, dihydrotricyclopentadiene can be manufactured through the hydrogenation reaction of tricyclopentadiene, as shown in following Reaction Formula 5.

Formula 2

Tricyclopentadiene can be prepared by Diels-Alder reaction of dicyclopentadiene and cyclopentadiene. Studies on the yield of tricyclopentadiene depending on the reaction conditions have been reported (Zhongqiang Xiong, Zhentao Mi and Xiangwen Zhang, React. Kinet. Catal. Lett. Vol. 85, 89-97 (2005)), No pure separation of the major isomers of cyclopentadiene has been reported.

Preferably, in the present invention, in order to purely separate only the main isomers of tricyclopentadiene from the by-products, a recrystallization method may be introduced in which the by-products are dissolved in ethanol and separated by a difference in solubility according to temperature.

Meanwhile, various methods may be considered as a method of selectively hydrogenating only norbornene-type olefins among the two olefins of tricyclopentadiene thus obtained.

As an example, a paper reported by Athelstan LJ Beckwith and Martin L. Gilpin in JCS Perkin I, 1977 , pp19-27, shows that one equivalent of hydrogen is used as a catalyst using a nickel compound obtained by reducing nickel acetate from ethanol to NaBH ₄ . Was added to implement a selective hydrogenation reaction. In the case of dicyclopentadiene, examples of the hydrogenation reaction of the norbornene-type olefin group having a high reactivity are added to the catalyst and 1 equivalent of hydrogen to selectively perform the hydrogenation reaction (Brunel, JM Tetrahedron 2007 , 63 , 3899 .; Alonso, F .; Osante, I .; Yus, M. Tetrahedron 2007 , 63 , 93; Bartlett, PD; Banavali, R. J. Org. Chem. 1991 , 56 , 6043.) However, in this case all 1 equivalent Implementing the selectivity by the introduction of hydrogen, if the amount of hydrogen is not controlled during the reaction, the compound is reduced in both the olefin group and the compound in which both of the two olefin group is not reduced as impurities may cause problems. In addition, in order to achieve high selectivity, the state of the catalyst and the reaction conditions must be sensitively controlled.

In this regard, it may be desirable to use a catalyst that selectively hydrogenates only norbornene-type olefin groups of tricyclopentadiene. Specific examples include palladium compounds coordinated by N-heterocyclic carbine, More specifically, a compound selected from the compounds represented by the following formula (4) can be used as a hydrogenation catalyst.

Formula 4

Wherein R ¹ and R ⁴ are independently selected from an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, unsubstituted or substituted with a hetero atom such as N, O, or S; R ² and R ³ are independently selected from an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms or a hydrogen atom unsubstituted or substituted with a hetero atom such as N, O, or S; X ¹ and X ² can be independently selected from halogen ligands, substituted or unsubstituted allyl ligands, or carboxylate ligands, or can be selected from olefin ligands or solvent ligands; Two compounds may exist in dimer form.

More preferably, in the compound represented by the formula (4), R ¹ and R ⁴ are both 2,6-diaisopropylphenyl (2,6-iPr ₂ C ₆ H ₃ −); R ² and R ³ are both hydrogen atoms; X ¹ and X ² may both be chlorine or both acetate, in which case two compounds may be present in the dimer form, or one may be a compound that is one chlorine and one allyl.

In the present invention, dihydrotricyclopentadiene obtained by the above method is copolymerized with ethylene to prepare a cyclic olefin copolymer. Since dihydrotricyclopentadiene has a large monomer size, a small amount of Even if only the cyclic olefin contains the polymer chain, the glass transition temperature is high, thereby providing flexibility of the polymer chain.

The compound represented by Formula 2 may have four isomers due to endo and exo aromaticity. The starting dicyclopentadiene compound is usually a mixture of endo-isomers and exo-isomers of at least 9: 1, and also when the norbornene-type olefin group and cyclopentadiene are subjected to the Diels-Alder reaction. Compounds can be formed with endo and exo. Zhongqiang Xiong, Zhentao Mi, Xiangwen Zhang, React. Kinet. Catal. Lett. Vol. 85, 89-97 (2005) reported that only two compounds were formed at a ratio of about 5: 1. The monomer used in the present invention is a pure dihydrotricyclopentadiene compound prepared by removing a small amount of the compound out of this mixture by recrystallization, obtaining only one pure isomer and hydrogenating it. This is to closely analyze the newly prepared high molecular compound, it is also possible to prepare a high molecular weight using a mixture without separating the isomers.

The cyclic olefin polymer compound including the repeating unit represented by Formula 1 according to the present invention may be a cyclic olefin copolymer obtained by vinyl-copolymerization of the compound of Formula 2 with ethylene. The molar ratio can be from 99: 1 to 1:99. In terms of preparing a transparent amorphous resin, preferably the molar ratio of x: y is 90:10 to 10:90 and more preferably 90:10 to 50:50. The molar ratio of x: y in the polymer chain can be controlled by adjusting the molar ratio of two monomers introduced into the reactor. The average value of z indicating the degree of polymerization is preferably 10-20,000 and is preferably 500-3000 in view of having a suitable mechanical strength.

In the present invention, the compound represented by the following formula (3) was used as a catalyst precursor to induce olefin polymerization of the compound of formula (2) and the vinyl monomer. Specifically, the catalyst in the preparation method of the present invention is methyl _{^{aluminoxane, Al (R 3) 3,}} B (Ar f) 3, and ^{[L] + [B (Ar} f) 4] - to activate using a single or a mixture selected from the group consisting of a co-catalyst, by using this, the solvent The cyclic olefin polymer compound according to the present invention can be obtained by performing olefin polymerization of the compound of Formula 2 and the vinyl monomer in the presence or without solvent.

Formula 3

Wherein M is Ti, Zr, Hf; X is halogen or an alkyl group having 1-20 carbon atoms; R ¹ is the same as or different from each other and is a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group; R ² is the same or different hydrogen radicals, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group. Preferably M is Ti; X is a methyl group or a chlorine radical; R ¹ and R ² are both methyl groups.

The compound represented by the formula (3) may be prepared by a method known by the present inventors (Wu, CJ; Lee, SH; Yun, H .; Lee, BY Organometallics 2007 , 26 , 6685-6687) .

Methylaluminoxane is commercially available as a compound obtained by partial hydrolysis of trimethylaluminum alone or mixed with triisobutylaluminum. The structure is expected to be a linear, circular or reticulated-[Al (Me or i Bu) -O] _a -structure.

Al (R ³⁾ R ³ eseo ₃ is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms and each R ³ may be the same or different. Preferably methyl, ethyl, isobutyl.

In B (Ar _{f) 3} Ar _f is an aryl group substituted with a fluorine atom. Preferably a penta fluoro phenyl group (C ₆ F _5).

^{[L] + [B (Ar} f) 4] - Ar f is as defined above, [L] ⁺ is a carbonyl kaeteu AION or tertiary ammonium. Preferred form of Ar _f is pentafluorophenyl (C ₆ F ₅ ) and preferred form of [L] ⁺ is [Ph ₃ C] ⁺ or [PhNMe ₂ H] ⁺ .

In carrying out the olefin polymerization in the presence of such a catalyst, it may be carried out in the presence of a solvent or in the absence of a solvent, wherein the solvent may be toluene, hexane, cyclohexane, methylene chloride, chlorobenzene and the like. It is preferable to use.

For reference, a patent was filed for a copolymer of 5,6-dihydrodicyclopentadiene and ethylene as shown in the following Scheme 6 (Korean Patent Application 10-2008-0012749 (2008.02.12)).

In the case of the cyclic olefin copolymer represented by Formula 1 according to the present invention, the glass transition temperature is higher than that of the copolymer of 5,6-dihydrodicyclopentadiene and ethylene obtained from Scheme 6, and 5,6 Copolymers containing a high content (up to 45%) of dihydrotricyclopentadiene can be prepared. Therefore, the cyclic olefin type copolymer which extended the use range further can be provided.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example: Synthesis and Purification of Dihydrotricyclopentadiene Compound

Dicyclopentadiene is distilled off while heating to 170 ° C. to obtain cyclopentadiene. 160 g of the obtained cyclopentadiene and 320 g of dicyclopentadiene were put in a high pressure reactor, and stirred at 300 rpm for 12 hours while applying a nitrogen pressure of 20 bar at 150 ° C. After the reaction, unreacted cyclopentadiene and dicyclopentadiene were first removed through vacuum distillation at 70 ° C. (380 g). 900 ml of ethanol was added thereto, followed by heating at reflux at 80 ° C. to dissolve the remaining solid material, and then recrystallized and stored in a refrigerator to obtain 67 g of pure tricyclopentadiene through a filter.

Tricyclopentadiene (63 g, 0.318 mol) obtained in the formula (4) and R ¹ , R ⁴ = 2,6-diaisopropylphenyl; R ² , R ³ = H; X ¹ = allyl; Compound (18 mg, 0.0318 mmol) and methylene chloride (204 mL) with X ² = Cl are added together in a high pressure reactor and hydrogen pressure at 20 ° C. is added 20 bar and stirred at 300 rpm for 12 hours. The catalyst was removed by passing through silica gel, and then the solvent was removed under reduced pressure to obtain 63 g of a pure compound (yield 99%).

Example 1-9. Dihydrotricyclopentadiene-ethylene copolymerization

Dihydrotricyclopentadiene (8.01 g, 40 mmol) obtained from the above synthesis example was added to a polymerization reactor under a nitrogen atmosphere, and toluene was added so that the total amount was 28 mL. After immersing the polymerization reactor in a 70 ° C. thermostatic bath to reach thermal equilibrium, the compound represented by the formula (3) (1.4 mg, 4 μmol) and [Ph ₃ C] ⁺ [B (C ₆ F ₅ ) ₄ ] ⁻ (14.7 mg, 16.0 μmol) and triisobutylaluminum (160 mg, 800 μmol) were dissolved in 2.0 mL of toluene and the activated catalyst was introduced into the reactor using a syringe. Ethylene gas was injected at a pressure of 60 psig and stirred for 8 minutes. The ethylene pressure was removed, the reactor was opened, and the reactant was added to a vessel containing 30 mL of methanol to precipitate the produced polymer. Filtration gave a precipitate, which was vacuum reduced at 100 ° C. to remove residual solvent contained in the precipitate, thereby obtaining 2.2 g of a polymer material.

As shown in the following Table 1, in the above method, the dihydrotricyclopentadiene amount was fixed at 8.01 g (concentration 1.4 mmol / mL) and the ethylene pressure was 60 psig, 40 psig, 30 psig, 20 psig, 10 psig. The polymerization was carried out with varying viscous solutions (8.0 min, 5.0 min, 6.0 min, 6.0 min, 9.0 min, respectively) from which point 2.2 g, 1.8 g, 1.2 g, 1.6 g and 0.6 g of polymer material were obtained. Got.

In addition, the ethylene pressure was fixed at 20 psig, and the dihydrotricyclopentadiene monomer concentration was changed to 1.4, 1.8, 2.1, 2.8, 3.2 mmol / mL, until the time when a viscous solution was obtained (6.0 min, 8.0 min, 6.0 min, 7.0 min, 7.0 min) polymerization was carried out to obtain 1.6 g, 2.3 g, 1.3 g, 1.4 g and 2.2 g polymer material, respectively.

The polymer material thus obtained was subjected to structural analysis through ¹ H NMR spectrum to determine the content of dihydrotricyclopentadiene in the polymer.

As an example, FIG. 1 shows the ¹ H NMR spectrum of a dihydrotricyclopentadiene / ethylene copolymer (Example 9) obtained at an ethylene pressure of 20 psig, dihydrotricyclopentadiene at a concentration of 3.2 mmol / mL. The content of dihydrotricyclopentadiene (HTCPD) was determined by the following relationship through the integral value of ¹ H NMR spectrum.

Integral of A = 2.45-1.75 ppm

Integral value of B = 1.65-0.75 ppm

HTCPD content = (A / 10) / [(A / 10) + (B-10) / 4]

Glass transition temperature (Tg) was measured by scanning twice while raising the temperature at a rate of 15 ℃ / min through DSC of model-Q10 manufactured by Thermal Analysis. Molecular weight and molecular weight distribution were measured using polystyrene as standard in THF solvent at 30 ° C. through GPC of Model 150-C + manufactured by Waters.

Table 1 shows the synthesis results.

Example Ethylene pressure
(psig) Ethylene Concentration (M) HTCPD
Concentration (m) reaction
time
(minute) Yield activation
(kg / Ti-molh) HTCPD
content
(mol%)
T _g (℃)
(Mw)
Mw / Mn One 60 1.90 1.4 8.0 2.2 4.110 ³ 20 64 11,226 1.18 2 40 1.30 1.4 5.0 1.8 5.310 ³ 21 76 13,871 1.24 3 30 0.95 1.4 6.0 1.2 2.810 ³ 26 101 12,248 1.19 4 20 0.63 1.4 6.0 1.6 3.910 ³ 31 126 10,604 1.13 5 10 0.32 1.4 9.0 0.6 1.810 ³ 41 165 9,401 1.10 6 20 0.63 1.8 8.0 2.3 4.310 ³ 33 135 11,135 1.15 7 20 0.63 2.1 6.0 1.3 3.310 ³ 40 156 9,455 1.10 8 20 0.63 2.8 7.0 1.4 3.010 ³ 44 174 9,624 1.09 9 20 0.63 3.2 7.0 2.2 4.710 ³ 45 177 10,367 1.09

From the results of Table 1, it can be seen that the cyclic olefin copolymer using the dihydrotricyclopentadiene compound shows a high glass transition temperature. Accordingly, the dihydrotricyclopentadiene compound-ethylene copolymer according to one embodiment of the present invention is expected to be used in a wide range of fields due to its excellent thermal stability.

Meanwhile, in order to more easily show that the dihydrotricyclopentadiene compound (HTCPD) -ethylene copolymer is improved in glass transition temperature as compared to other cyclic olefin copolymers, as in one embodiment of the present invention, it is referred to another cycle. The cyclic olefin copolymer obtained from the pentadienes (dihydrodicyclopentadiene compound (HDCPD) and norbornene compound) and the glass transition temperature is shown in FIG.

Figure 2 shows the glass transition temperature of the three cyclic olefin copolymers (HTCPD / ethylene copolymer, Norbonene / ethylene copolymer, HDCPD / ethylene copolymer obtained by varying the molar ratio of the cyclic olefin, HTCPD in terms of thermal stability It can be seen that the / ethylene copolymer is excellent.

1 is a ¹ H NMR spectrum of a dihydrotricyclopentadiene / ethylene copolymer obtained from Example 9. FIG.

Figure 2 is a graph showing the glass transition temperature trend for the three copolymers according to the cyclic olefin molar ratio.

Claims (4)

A cyclic olefin polymer compound comprising a repeating unit represented by the following formula (1). Formula 1

Wherein the molar ratio of x: y is 99: 1 to 1:99 and z has an average value of 10 to 20,000. The cyclic olefin polymer compound of claim 1, wherein the molar ratio of x: y is 90:10 to 50:50, and z has an average value of 500 to 3000. Methyl aluminoxane, Al (R ³ ) ₃ , wherein the compound represented by the following formula (3) is a compound obtained by partially hydrolyzing trimethylaluminum alone or a mixture with triisobutylaluminum, wherein R ³ is the same as or different from each other and is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, B (Ar _f ) ₃ (wherein Ar _f is an aryl group substituted with a fluorine atom), and [L] ⁺ [B (Ar _f ) ₄ ] ^- (wherein Ar _f is as defined above and [L] ⁺ is selected from carbocation or tertiary ammonium) In the presence of a catalyst activated either alone or using a mixture as a promoter, A method for producing a cyclic olefin polymer compound comprising a repeating unit represented by the following formula (1) by vinyl polymerization of the compound represented by the following formula (2) with ethylene. Formula 1

Wherein the molar ratio of x: y is 99: 1 to 1:99 and z has an average value of 10-20,000. Formula 2

Formula 3

Wherein M is Ti, Zr, Hf; X is halogen or an alkyl group having 1-20 carbon atoms; R ¹ is the same or different from each other and is a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, an alkenyl group or an alkynyl group; R ² is the same as or different from each other and is a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group. 4. The compound of claim 3, wherein in the compound represented by the formula (3), M is Ti, X is a methyl group or a chlorine radical, and R ¹ and R ² are both methyl groups; Al (R ³⁾ ₃ in R ³ is a methyl group, an ethyl group or an isobutyl group; In B (Ar _{f) 3} Ar _f is a penta-fluorophenyl (C ₆ F ₅₎ group; ^{[L] + [B (Ar} f) 4] - in the Ar _f is wherein penta-fluorophenyl (C ₆ F ₅₎ group and [L] ⁺ is a [Ph ₃ C] ⁺ or [PhNMe ₂ H] ⁺ How to.

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