KR20030052016A - Preparation method for norbornene-type copolymer and norbornene-type copolymer using same method - Google Patents

Preparation method for norbornene-type copolymer and norbornene-type copolymer using same method Download PDF

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KR20030052016A
KR20030052016A KR1020010081816A KR20010081816A KR20030052016A KR 20030052016 A KR20030052016 A KR 20030052016A KR 1020010081816 A KR1020010081816 A KR 1020010081816A KR 20010081816 A KR20010081816 A KR 20010081816A KR 20030052016 A KR20030052016 A KR 20030052016A
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norbornene
copolymer
nickel
catalyst
dichloroethane
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KR100476303B1 (en
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임선기
정오용
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한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the 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
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F32/04—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/37—Metal complexes
    • C08G2261/376—Metal complexes of Fe, Co, Ni

Abstract

PURPOSE: Provided are a method for producing norbornene copolymer which can produce norbornene copolymer by copolymerization in the presence of a reaction solvent, a nickel-containing catalyst and a co-catalyst and the norbornene copolymer produced thereby. CONSTITUTION: The method for producing norbornene copolymer includes the steps of copolymerizing 50 mole% to 97 mole% of norbornene and 3 mole% to 50 mole% of a norbornene derivative in the presence of a reaction solvent, a nickel-containing catalyst and a co-catalyst. The norbornene derivative is at least selected from 2-norbornene, 5-vinyl-2-norbornene, 5-butyl-2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene, dicyclopentadiene, 5-norbornene-2-endo-3-exo-dicarboxylic acid and 5-dimethylmethoxy norbornene. The solvent is any one selected from benzene, toluene, chlorobenzene, nitrobenzene, xylene, 1,1-dichloroethane, 1,2-dichloroethane and 1,2-dichloromethane. The nickel-containing catalyst is any one selected from nickel acetylacetonate, nickel-bis-acetylacetonate, nickel-bis cyclo octadiene and nickel-bisallyl. The co-catalyst is any one selected from organic aluminum halides, BF4, PF6, SbF6, B£C6H3(CF3)2|4 and methylaluminoxane(MAO).

Description

노르보넨 공중합체의 제조방법 및 동 방법에 의해 제조한 노르보넨 공중합체{Preparation method for norbornene-type copolymer and norbornene-type copolymer using same method}Preparation method of norbornene copolymer and norbornene copolymer prepared by the same method {preparation method for norbornene-type copolymer and norbornene-type copolymer using same method}

본 발명은 노르보넨 공중합체의 제조방법 및 동 방법에 의해 제조한 노르보넨 공중합체에 관한 것으로 보다 상세하게는 노르보넨과 노르보넨 유도체를 반응용매, 니켈 화합물계 촉매, 공촉매 존재하에서 공중합하여 노르보넨 공중합체를 제조하는 것을 특징으로 한다.The present invention relates to a norbornene copolymer and a norbornene copolymer prepared by the same method, and more particularly, norbornene and norbornene derivatives are copolymerized in the presence of a reaction solvent, a nickel compound catalyst and a cocatalyst. It is characterized by producing a bonene copolymer.

폴리노르보넨 또는 폴리(비씨클로[2.2.1.]-헵트-2-엔)은 두가지 유형의 성질 즉, 부러지기 쉽고 또 하나는 가열성형이 가능한 성질을 포함하고 있다. 부러지기 쉬운 고분자는 저분자량의 불포화 고분자로 밝혀졌으며 가열성형이 가능한 고분자는 개환반응을 통해서 형성되는 것으로 알려졌다.Polynorbornene or poly (bicyclo [2.2.1.]-Hept-2-ene) contains two types of properties: one that is brittle and one that can be thermoformed. The breakable polymers were found to be low molecular weight unsaturated polymers, and heat-forming polymers were known to be formed through ring-opening reactions.

동일한 모노머를 사용함에도 불구하고 부가중합된 폴리노르보넨은 개환중합된 고분자와 뚜렷히 구별되는데 부가중합된 폴리노르보넨은 탄소-탄소의 불포화 이중결합이 없는 반면에 개환중합된 폴리노르보넨은 탄소-탄소의 이중결합을 포함하고 있기 때문이다. 이들의 가장 큰 차이점은 열적 성질에 있는데, 부가중합된 폴리노르보넨은 약 370℃ 이상의 높은 유리전이 온도를 갖는 반면에 불포화 개환중합된 폴리노르보넨은 약 35℃ 정도의 낮은 유리전이 온도를 갖고 있으며 200℃ 이상의 고온에서는 탄소-탄소의 불포화 이중결합으로 인해 열적성질이 약하다.Despite the use of the same monomers, the addition-polymerized polynorbornene is distinctly distinct from the ring-opening polymers, where the addition-polymerized polynorbornene is free of carbon-carbon unsaturated double bonds, while the ring-opening polynorbornene is carbon-carbon This is because it contains a double bond. The main difference between them is the thermal properties: addition-polymerized polynorbornene has a high glass transition temperature of about 370 ° C., while unsaturated ring-opened polynorbornene has a low glass transition temperature of about 35 ° C. At high temperatures of 200 ° C. or higher, thermal properties are weak due to unsaturated double bonds of carbon-carbon.

최근에는 노르보넨의 부가중합을 위해 두가지 유형의 방법이 사용된다. 하나는 약 370℃ 이상의 유리전이 온도를 갖는 무정형 고분자인데, 이것은 하나 또는 그 이상의 노르보넨 유도체의 부가중합에 의해 제조되며, 또 하나는 높은 결정성의 고분자인데 위 고분자는 탄화수소 및 방향족 용매에 거의 녹지 않으며 약 600℃에 이를때 까지는 녹지 않아 가공이 거의 불가능하다(W. Kaminsky et al., J. Mol. Cat., 74 109 (1992)). 이런 고분자는 지르코노센 타입의 촉매에 의해서 중합되며 에틸렌과 노르보넨의 공중합에 유용하다.Recently two types of methods have been used for addition polymerization of norbornene. One is an amorphous polymer having a glass transition temperature of about 370 ° C. or higher, which is prepared by addition polymerization of one or more norbornene derivatives, and another is a highly crystalline polymer, which is hardly soluble in hydrocarbons and aromatic solvents. It does not melt until about 600 ° C, making processing almost impossible (W. Kaminsky et al., J. Mol. Cat., 74 109 (1992)). These polymers are polymerized by a zirconocene type catalyst and are useful for the copolymerization of ethylene and norbornene.

본 발명은 노르보넨 공중합체의 제조에 있어, 노르보넨과 노르보넨 유도체를 단량체로 하고 니켈 화합물계 촉매, 공촉매 존재하에서 공중합 하여 노르보넨 공중합체의 제조방법 제공을 목적으로 한다.An object of the present invention is to provide a method for producing a norbornene copolymer by copolymerizing norbornene and norbornene derivatives as monomers and in the presence of a nickel compound catalyst and a cocatalyst.

도 1은 본 발명에서 모노머로 사용되는 노르보넨 유도체의 구조식이다.1 is a structural formula of a norbornene derivative used as a monomer in the present invention.

도 2는 실시예 1 내지 실시예 6으로부터 노르보넨과 5-비닐-2-노르보넨의 공중합체를 제조하는 공정을 나타낸 것이다.2 shows a process for preparing a copolymer of norbornene and 5-vinyl-2-norbornene from Examples 1 to 6.

도 3은 실시예 7 내지 실시예 12로부터 노르보넨과 5-노르보넨-2-엔도-3-엑소-디카르복실산의 공중합체를 제조하는 공정을 나타낸 것이다.3 shows a process for preparing a copolymer of norbornene and 5-norbornene-2-endo-3-exo-dicarboxylic acid from Examples 7-12.

도 4는 실시예 1에서 제조된 노르보넨과 5-비닐-2-노르보넨의 공중합체의 FT-IR 결과를 나타낸 것이다.Figure 4 shows the FT-IR results of the copolymer of norbornene and 5-vinyl-2-norbornene prepared in Example 1.

본 발명의 노르보넨 공중합체의 제조방법은 노르보넨과 노르보넨 유도체를 반응용매, 촉매, 공촉매 존재하에서 공중합 하는 것을 특징으로 한다.The method for producing a norbornene copolymer of the present invention is characterized by copolymerizing norbornene and norbornene derivatives in the presence of a reaction solvent, a catalyst and a cocatalyst.

본 발명에서 노르보넨 공중합체 제조시 노르보넨은 50몰%∼97몰%를 사용하고, 노르보넨 유도체는 3몰%∼50몰%를 사용하고, 반응용매는 20 밀리리터(㎖)∼60 밀리리터를 사용하고, 촉매는 0.01 밀리몰(mmol)∼0.05 밀리몰을 사용하고, 공촉매는 3 밀리몰∼10 밀리몰을 사용한다.In the present invention, norbornene is used in the production of norbornene copolymer is 50 mol% to 97 mol%, norbornene derivative is used from 3 mol% to 50 mol%, the reaction solvent is 20 milliliters (ml) to 60 milliliters The catalyst is used in the range of 0.01 mmol to 0.05 mmol, and the cocatalyst is 3 mmol to 10 mmol.

만일 본 발명에서 노르보넨, 노르보넨 유도체, 반응용매, 촉매 및 공촉매를 상기에서 언급한 각각의 사용량 미만을 사용하거나 사용량을 초과하면 촉매 활성이 낮아서 공중합체 고분자를 얻기 어려운 문제가 있어 본 발명에서 노르보넨, 노르보넨 유도체, 반응용매, 촉매 및 공촉매의 사용량은 상기에서 언급한 바와 같이 사용하는 것이 좋다.If the norbornene, norbornene derivatives, reaction solvents, catalysts and cocatalysts in the present invention use less than the above-mentioned amounts or exceed the above-mentioned amounts, the catalytic activity is low, making it difficult to obtain a copolymer polymer. Norbornene, norbornene derivatives, reaction solvents, catalysts and cocatalysts may be used as mentioned above.

본 발명에서 사용할 수 있는 노르보넨 유도체는 도 1의 구조식으로 나타낼수 있으며, 도 1의 노르보넨 유도체 구조식에서 R1은 수소, R2는 C1∼C10의 선형 또는 가지 달린 알킬기, R3은 방향족, R4는 포화 또는 불포화 고리형 그룹을 나타낸다.Norbornene derivatives that can be used in the present invention can be represented by the structural formula of Figure 1, in the structural formula of norbornene derivatives of Figure 1 R1 is hydrogen, R2 is a C1-C10 linear or branched alkyl group, R3 is aromatic, R4 is saturated Or unsaturated cyclic groups.

본 발명은 상기에서 설명한 노르보렌 유도체에 있어서, 구제척으로 5-비닐-2-노르보넨, 5-부틸-2-노르보넨, 5-메틸-2-노르보넨, 5-헥실-2-노르보넨, 디싸이클로펜타디엔, 5-노르보넨-2-엔도-3-엑소-디카르복실산, 5-디메틸메톡시 노르보넨 중에서 선택된 어느 하나를 사용할 수 있는데 바람직하게는 빈응활성이 높은 2-노르보넨, 5-비닐-2-노르보넨 또는 5-노르보넨-2-엔도-3-엑소-디카르복실산을 사용하는 것이 좋다.In the above-described norbornene derivative, the present invention relates to 5-vinyl-2-norbornene, 5-butyl-2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene , Dicyclopentadiene, 5-norbornene-2-endo-3-exo-dicarboxylic acid, 5-dimethylmethoxy norbornene can be used, preferably 2-norbornene with high poor activity , 5-vinyl-2-norbornene or 5-norbornene-2-endo-3-exo-dicarboxylic acid is preferred.

본 발명에서 촉매는 노르보넨 중합체 제조시 유용한 니켈계 화합물을 사용하는데 본 발명에서 촉매로 사용하는 니켈계 화합물 촉매로는 니켈 아세틸아세토네이트(nickel(II) acetylacetonate), 니켈-비스아세틸아세토네이트, 니켈-비스시클로옥타디엔, 니켈-비스알릴 중에서 선택된 하나를 사용할 수 있다.In the present invention, the catalyst is a nickel-based compound useful for preparing norbornene polymers. Nickel-based compound catalysts used as catalysts in the present invention include nickel acetylacetonate, nickel-bisacetylacetonate, and nickel. One selected from -biscyclooctadiene and nickel-bisallyl can be used.

한편 본 발명에서는 니켈계 화합물 촉매이외에 루이스 산으로서 양이온성의 촉매에 대해 음이온으로서 작용하여 적절한 전자적 균형을 이루며 반응용매내의 불순물을 제거해 주는 역할을 하는 공촉매를 사용한다. 이러한 공촉매는 너무 강력한 환원제나 산화제로 작용해서는 안되는데 본 발명에서는 이러한 요구를 만족시켜주는 공촉매로 유기알루미늄 할라이드, BF4, PF6, SbF6, B[C6H3(CF3)2]4, 메틸알루미녹산 (methylaluminoxane, MAO) 중에서 선택된 어느 하나를 사용할 수 있는데 보다 바람직하게는 촉매활성이 높은 MAO를 사용하는 것이 좋다.In addition to the nickel-based compound catalyst, the present invention uses a cocatalyst that acts as an anion with respect to the cationic catalyst as a Lewis acid to achieve proper electronic balance and to remove impurities in the reaction solvent. Such cocatalysts should not act as too powerful reducing or oxidizing agents. In the present invention, co-catalysts satisfying these requirements include organoaluminum halides, BF 4 , PF 6 , SbF 6 , B [C 6 H 3 (CF 3 ) 2 ] 4 , methyl aluminoxane (methylaluminoxane, MAO) can be used any one selected, more preferably it is better to use a high catalytic activity MAO.

본 발명에서 반응용매로는 반응열 제거가 용이하고 활성에 유리한 방향족 또는 염소계 지방족 탄화수소를 사용하는 것이 좋다.In the present invention, it is preferable to use an aromatic or chlorine-based aliphatic hydrocarbon which is easy to remove the heat of reaction and advantageous in activity.

상기에서 방향족 용매로는 벤젠, 톨루엔, 클로로벤젠, 니트로벤젠 또는 크실렌을 사용할 수 있으며 염소계 지방족 탄화수소 용매로는 1,1-디클로로에탄, 1,2-디클로로에탄 또는 1,2-디클로로메탄, 1-클로로프로판 등을 사용할 수 있다As the aromatic solvent, benzene, toluene, chlorobenzene, nitrobenzene or xylene may be used, and as the chlorine aliphatic hydrocarbon solvent, 1,1-dichloroethane, 1,2-dichloroethane or 1,2-dichloromethane, 1- Chloropropane can be used.

한편, 본 발명에서 노르보넨과 노르보넨 유도체의 공중합시 압력은 0.5 기압 ∼ 10 기압, 온도는 20∼70℃, 중합시간은 10분∼2시간 실시하는 것이 좋다.On the other hand, in the present invention, the copolymerization pressure of norbornene and norbornene derivative is 0.5 to 10 atm, temperature is 20 to 70 ℃, polymerization time is preferably performed for 10 minutes to 2 hours.

노르보넨 공중합체 제조시 압력이 0.5 기압 미만이면 반응이 시작되는데 오랜 시간이 걸리고 10 기압을 초과하면 안전성의 어려움이 있으며, 온도가 20℃ 미만이면 반응이 더디며 70℃ 초과하면 촉매가 비활성화 되는 문제가 있으며, 중합시간이 10분 미만이면 생성된 공중합체 고분자의 양이 극소량이며 2시간 초과하면 공중합체 고분자의 수율이 거의 일정하기 때문에 발명에서의 공중합 조건은 상기 압력, 온도, 중합시간을 유지하는 것이 좋다.If the pressure is less than 0.5 atm when the norbornene copolymer is produced, it takes a long time to start the reaction, and if it exceeds 10 atm, there is difficulty in safety. If the temperature is less than 20 ° C, the reaction is slow. When the polymerization time is less than 10 minutes, the amount of the copolymer polymer produced is very small, and when the polymerization time is more than 2 hours, the yield of the copolymer polymer is almost constant, so that the copolymerization conditions in the invention maintain the pressure, temperature, and polymerization time. It is good.

이하 본 발명을 다음의 실시예 및 시험예에 의하여 설명하고자 한다. 그러나 이들은 본 발명의 일 실시예에 불과하며 이들이 본 발명의 기술적 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described by the following examples and test examples. However, these are only examples of the present invention and they do not limit the technical scope of the present invention.

<실시예 1 내지 실시예 3><Examples 1 to 3>

도 2는 노르보넨과 5-비닐-2-노르보넨의 공중합체 제조공정을 나타낸 것으로 도 2의 공정에 의한 노르보넨과 5-비닐-2-노르보넨 공중합체의 제조방법은 다음과 같다.FIG. 2 shows a process for preparing a copolymer of norbornene and 5-vinyl-2-norbornene. A method of preparing norbornene and 5-vinyl-2-norbornene copolymer by the process of FIG. 2 is as follows.

50ml의 초자반응기에 1,2-디클로로에탄을 25ml 넣은 다음 니켈 아세틸아세토네이트(nickel(II) acetylacetonate, Ni(acac)2) 0.026mmol과 노르보넨 공중합체의 모노머로서 노르보넨과 공단량체인 5-비닐-2-노르보넨을 하기 표 1에 기재된 사용량과 같이 주사기를 이용하여 반응기에 넣었다.25 ml of 1,2-dichloroethane was added to a 50 ml glass reactor, followed by 0.026 mmol of nickel acetylacetonate (Ni (acac) 2 ) and a norbornene copolymer. Vinyl-2-norbornene was placed in the reactor using a syringe as shown in Table 1 below.

이어서 공촉매인 MMAO-3A(Modified methylaluminoxane, Toso-Akzo company) 7.8mmol을 주입하고 반응온도를 25℃로 유지하는 한편 1시간 동안 반응을 실시한 후 2 밀리리터(㎖)의 염산이 함유된 100 밀리리터의 알콜을 반응기에 주입함으로서 공중합 반응을 종결시킨 다음 세척을 실시한 후 건조하여 하기 구조식 (1)과 같은 공중합체 고분자를 얻을 수 있었다.Subsequently, 7.8 mmol of co-catalyst MMAO-3A (Modified methylaluminoxane, Toso-Akzo company) was injected and the reaction temperature was maintained at 25 ° C, followed by reaction for 1 hour, followed by 100 milliliters of hydrochloric acid containing 2 milliliters (ml). Injecting alcohol into the reactor terminated the copolymerization reaction, followed by washing and drying to obtain a copolymer polymer as shown in Structural Formula (1).

한편 도 4는 실시예 1 로부터 제조된 노르보넨과 5-비닐-2-노르보넨의 공중합체의 FT-IR 결과를 나타낸 것이다.On the other hand, Figure 4 shows the FT-IR results of the copolymer of norbornene and 5-vinyl-2-norbornene prepared in Example 1.

..........구조식 (1) .......... Structure (1)

상기 구조식 (1)에서 m은 0.1 ∼ 10 이고, n은 0.1 ∼6 이다.In Structural Formula (1), m is 0.1-10, n is 0.1-6.

한편 실시예 1 내지 실시예 3의 5-비닐-2-노르보넨 첨가에 대한 중합활성, 고유점도를 측정하여 그 결과를 아래의 표 1에 정리하여 나타내었다.On the other hand, the polymerization activity and intrinsic viscosity with respect to the 5-vinyl-2-norbornene addition of Examples 1 to 3 were measured, and the results are summarized in Table 1 below.

<실시예 4 내지 실시예 6><Examples 4 to 6>

반응용매로 톨루엔을 사용하고, 노르보넨과 5-비닐-2-노르보넨의 사용량을 하기 표 1과 같이 사용하는 것을 제외하고는 상기 실시예 1 내지 실시예 3과 같은 방법으로 노르보넨 공중합체를 제조하고 이의 결과를 측정하였다.A norbornene copolymer was prepared in the same manner as in Examples 1 to 3, except that toluene was used as a reaction solvent, and the amount of norbornene and 5-vinyl-2-norbornene was used as shown in Table 1 below. Was prepared and its results were measured.

표 1. 노르보넨과 5-비닐-2-노르보넨(VNB)의 공중합 결과Table 1. Copolymerization Results of Norbornene and 5-Vinyl-2-norbornene (VNB)

항 목Item VNB 공급량*(mol %)VNB Supply * (mol%) 노르보넨공급량(mol %)Norbornene Supply (mol%) 반응용매Reaction solvent 중합활성**Polymerization activity ** 고유점도Intrinsic viscosity 실시예 1Example 1 28.428.4 71.671.6 1,2-디클로로에탄1,2-dichloroethane 137137 2.42.4 실시예 2Example 2 44.344.3 55.755.7 1,2-디클로로에탄1,2-dichloroethane 118118 1.91.9 실시예 3Example 3 54.454.4 45.645.6 1,2-디클로로에탄1,2-dichloroethane 9191 2.12.1 실시예 4Example 4 28.428.4 71.671.6 톨루엔toluene 116116 1.61.6 실시예 5Example 5 44.344.3 55.755.7 톨루엔toluene 7171 1.71.7 실시예 6Example 6 54.454.4 45.645.6 톨루엔toluene 5959 1.91.9

중합조건 : 촉매/공촉매=Ni(acac)2/MAO, Al/Ni = 300Polymerization conditions: Catalyst / Cocatalyst = Ni (acac) 2 / MAO, Al / Ni = 300

*VNB : 5-비닐-2-노르보넨* VNB: 5-vinyl-2-norbornene

**활성단위 : Kg polymer/mol-Ni hr** Active Unit: Kg polymer / mol-Ni hr

<실시예 7 내지 실시예 9><Example 7 to Example 9>

도 3은 노르보넨과 5-노르보넨-2-엔도-3-엑소-디카르복실산의 공중합체 제조공정을 나타낸 것으로 도 3의 공정에 의한 노르보넨과 5-노르보넨-2-엔도-3-엑소-디카르복실산 공중합체의 제조방법은 다음과 같다.FIG. 3 shows a process for preparing a copolymer of norbornene and 5-norbornene-2-endo-3-exo-dicarboxylic acid, and norbornene and 5-norbornene-2-endo-3 according to the process of FIG. 3. The method for producing the exo-dicarboxylic acid copolymer is as follows.

50ml의 초자반응기에 1,2-디클로로에탄을 25ml 넣은 다음 Ni(acac)20.026mmol과 노르보넨 공중합체의 모노머로서 노르보넨과 공단량체인 5-노르보넨-2-엔도-3-엑소-디카르복실산을 하기 표 2에 기재된 사용량과 같이 주사기를 이용하여 반응기에 넣었다.25 ml of 1,2-dichloroethane was added to a 50 ml super-reactor, followed by 5-norbornene-2-endo-3-exo-dica, which was a monomer of Ni (acac) 2 0.026 mmol and a norbornene copolymer. Leric acid was put into the reactor using a syringe as the amount of use described in Table 2 below.

이어서 공촉매인 MMAO-3A 7.8mmol을 주입하고 반응온도를 25℃로 유지하는 한편 1시간 동안 반응을 실시한 후 2 밀리리터의 염산이 함유된 100 밀리리터의 알콜을 반응기에 주입함으로서 공중합 반응을 종결시킨 다음 세척을 실시한 후 건조하여 하기 구조식 (2)와 같은 고분자를 얻을 수 있었다.Then, 7.8 mmol of the cocatalyst MMAO-3A was injected and the reaction temperature was maintained at 25 ° C., followed by reaction for 1 hour, followed by terminating the copolymerization reaction by injecting 100 milliliters of alcohol containing 2 milliliters of hydrochloric acid into the reactor. After washing, it was dried to obtain a polymer as shown in the following structural formula (2).

.......... 구조식 (2) .......... Structure (2)

상기 구조식 (2)에서 m은 0.1∼10이고, n은 0.1∼6 이다.M is 0.1-10, and n is 0.1-6 in the said Formula (2).

한편 실시예 7 내지 실시예 9의 5-노르보넨-2-엔도-3-엑소-디카르복실산 첨가에 대한 중합활성, 고유점도를 측정하여 그 결과를 아래의 표 2에 정리하여 나타내었다.Meanwhile, the polymerization activity and intrinsic viscosity of the 5-norbornene-2-endo-3-exo-dicarboxylic acid addition of Examples 7 to 9 were measured, and the results are shown in Table 2 below.

<실시예 10 내지 실시예 12><Example 10 to Example 12>

반응용매로 톨루엔을 사용하고, 노르보넨과 5-노르보넨-2-엔도-3-엑소-디카르복실산의 사용량을 하기 표 2와 같이 사용하는 것을 제외하고는 상기 실시예 7 내지 실시예 9와 같은 방법으로 노르보넨 공중합체를 제조하고 이의 결과를 측정하였다.Example 7 to Example 9, except that toluene was used as the reaction solvent, and the amount of norbornene and 5-norbornene-2-endo-exo-dicarboxylic acid was used as in Table 2 below. Norbornene copolymer was prepared in the same manner as described above and the results were measured.

표 2. 니켈 촉매에 의한 노르보넨과 NBDCA의 공중합 결과Table 2. Copolymerization Results of Norbornene and NBDCA by Nickel Catalyst

항 목Item NBDCA 공급량*(mol %)NBDCA Supply * (mol%) 노르보넨공급량(mol %)Norbornene Supply (mol%) 반응용매Reaction solvent 중합활성**Polymerization activity ** 고유점도Intrinsic viscosity 실시예 7Example 7 3.03.0 9797 1,2-디클로로에탄1,2-dichloroethane 315315 2.52.5 실시예 8Example 8 5.95.9 94.194.1 1,2-디클로로에탄1,2-dichloroethane 337337 2.32.3 실시예 9Example 9 8.68.6 91.491.4 1,2-디클로로에탄1,2-dichloroethane 354354 2.42.4 실시예 10Example 10 3.03.0 9797 톨루엔toluene 277277 1.61.6 실시예 11Example 11 5.95.9 94.194.1 톨루엔toluene 342342 2.02.0 실시예 12Example 12 8.68.6 91.491.4 톨루엔toluene 358358 1.91.9

중합조건 : 촉매/공촉매=Ni(acac)2/MAO, Al/Ni = 300Polymerization conditions: Catalyst / Cocatalyst = Ni (acac) 2 / MAO, Al / Ni = 300

*NBDCA : 5-노르보넨-2-엔도-3-엑소-디카르복실산* NBDCA: 5-norbornene-2-endo-3-exo-dicarboxylic acid

**활성단위 : Kg polymer/mol-Ni hr** Active Unit: Kg polymer / mol-Ni hr

본 발명은 상기 실시예 1 내지 실시예 12로부터 니켈계 화합물 촉매 및 공촉매를 이용해서 종래에는 보고되지 않았던 노르보넨과 5-비닐-2-노르보넨 공중합체 및 노르보넨과 5-노르보넨-2-엔도-3-엑소-디카르복실산 공중합체를 우수한 활성으로 얻을 수 있음이 밝혀졌다. 또한 반응용매를 극성이 강한 1,2-디클로로에탄을 사용했을 경우에 톨루엔을 사용한 경우보다 공히 촉매활성이 더 우수하였으며 고유점도 역시 향상됨을 알 수 있었다.In the present invention, a norbornene and 5-vinyl-2-norbornene copolymer, norbornene and 5-norbornene-2, which have not been conventionally reported using a nickel compound catalyst and a cocatalyst from Examples 1 to 12, It has been found that endo-3-exo-dicarboxylic acid copolymers can be obtained with good activity. In addition, it was found that the use of 1,2-dichloroethane with a strong polarity of the reaction solvent resulted in better catalytic activity and higher intrinsic viscosity than toluene.

Claims (8)

노르보넨 공중합체의 제조에 있어서,In the preparation of norbornene copolymers, 노르보넨 50몰%∼97몰%와 노르보넨 유도체 3몰%∼50몰%를 반응용매, 촉매, 공촉매 존재하에서 공중합 하는 것을 특징으로 하는 노르보넨 공중합체의 제조방법A method for producing a norbornene copolymer, characterized in that 50 mol% to 97 mol% of norbornene and 3 to 50 mol% of norbornene derivatives are copolymerized in the presence of a reaction solvent, a catalyst and a cocatalyst. 제 1항에 있어서, 노르보넨 유도체는 2-노르보넨, 5-비닐-2-노르보넨, 5-부틸-2-노르보넨, 5-메틸-2-노르보넨, 5-헥실-2-노르보넨, 디싸이클로펜타디엔, 5-노르보넨-2-엔도-3-엑소-디카르복실산, 5-디메틸메톡시 노르보넨 중에서 선택된 하나 임을 특징으로 하는 노르보넨 공중합체의 제조방법The norbornene derivative of claim 1, wherein the norbornene derivative is 2-norbornene, 5-vinyl-2-norbornene, 5-butyl-2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene , Dicyclopentadiene, 5-norbornene-2-endo-3-exo-dicarboxylic acid, 5-dimethylmethoxy norbornene, characterized in that the manufacturing method of norbornene copolymer 제 1항에 있어서, 용매는 벤젠, 톨루엔, 클로로벤젠, 니트로벤젠, 크실렌, 1,1-디클로로에탄, 1,2-디클로로에탄, 1,2-디클로로메탄 중에서 선택된 어느 하나 임을 특징으로 하는 노르보넨 공중합체의 제조방법The norbornene according to claim 1, wherein the solvent is any one selected from benzene, toluene, chlorobenzene, nitrobenzene, xylene, 1,1-dichloroethane, 1,2-dichloroethane and 1,2-dichloromethane. Method of Preparation of Copolymer 제 1항에 있어서, 촉매는 니켈 아세틸아세토네이트, 니켈-비스아세틸아세토네이트, 니켈-비스시클로옥타디엔, 니켈-비스알릴 중에서 선택된 하나 임을 특징으로 하는 노르보넨 공중합체의 제조방법The method for preparing norbornene copolymer according to claim 1, wherein the catalyst is one selected from nickel acetylacetonate, nickel-bisacetylacetonate, nickel-biscyclooctadiene and nickel-bisallyl. 제 1항에 있어서, 공촉매는 유기알루미늄 할라이드, BF4, PF6, SbF6, B[C6H3(CF3)2]4, 메틸알루미녹산(MAO) 중에서 선택된 하나 임을 특징으로 하는 노르보넨 공중합체의 제조방법The co-catalyst of claim 1, wherein the cocatalyst is one selected from organoaluminum halides, BF 4 , PF 6 , SbF 6 , B [C 6 H 3 (CF 3 ) 2 ] 4 and methylaluminoxane (MAO). Method of preparing a bonene copolymer 제 1항에 있어서, 노르보넨과 노르보넨 유도체의 공중합시 20∼70℃에서 10분∼2시간 동안 공중합 하는 것을 특징으로 하는 노르보넨 공중합체의 제조방법The method for producing a norbornene copolymer according to claim 1, wherein the copolymerization of norbornene and norbornene derivatives is carried out at 20 to 70 ° C for 10 minutes to 2 hours. 특허청구범위 제 1항 내지 제 6항중 선택된 어느 하나의 항을 이용하여 제조한 하기 구조식 (1)의 노르보넨 공중합체Norbornene copolymer of the following structural formula (1) prepared using any one of claims 1 to 6 ..........구조식 (1) .......... Structure (1) 상기 구조식 (1)에서 m은 0.1 ∼ 10 이고, n은 0.1 ∼ 6 이다.In said structural formula (1), m is 0.1-10, n is 0.1-6. 특허청구범위 제 1항 내지 제 6항중 선택된 어느 하나의 항을 이용하여 제조한 하기 구조식 (2)의 노르보넨 공중합체Norbornene copolymer of the following structural formula (2) prepared using any one of claims 1 to 6 .......... 구조식 (2) .......... Structure (2) 상기 구조식 (2)에서 m은 0.1 ∼ 10 이고, n은 0.1 ∼ 6 이다.In said structural formula (2), m is 0.1-10, n is 0.1-6.
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CN114276490A (en) * 2021-12-27 2022-04-05 宁波职业技术学院 Poly (norbornene-co-vinyl norbornene), polar group functionalized norbornene and preparation method thereof
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WO2013118951A1 (en) * 2012-02-08 2013-08-15 주식회사 폴리사이언텍 Highly heat-resistant transparent cyclic olefin copolymers having excellent flexibility, and flexible substrate produced therefrom
CN114276490A (en) * 2021-12-27 2022-04-05 宁波职业技术学院 Poly (norbornene-co-vinyl norbornene), polar group functionalized norbornene and preparation method thereof
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