KR0164878B1 - Styrenic copolymer and process for producing the same - Google Patents
Styrenic copolymer and process for producing the same Download PDFInfo
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- KR0164878B1 KR0164878B1 KR1019940008723A KR19940008723A KR0164878B1 KR 0164878 B1 KR0164878 B1 KR 0164878B1 KR 1019940008723 A KR1019940008723 A KR 1019940008723A KR 19940008723 A KR19940008723 A KR 19940008723A KR 0164878 B1 KR0164878 B1 KR 0164878B1
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Abstract
본 발명은 입체구조 스티렌계 중합체 또는 공중합체에 올레핀 또는 무정형 스티렌계 공중합체가 그라프트된 공중합체 및 그의 제조방법에 관한 것이다. 더욱 상세하게는, 주쇄의 입체규칙성이 주로 신디오탁틱(syndiotactic) 구조인 스티렌계 중합체 또는 공중합체에 입체규칙성이 주로 어탁틱(atactic)구조인 올레핀이나 축합 중합체 또는 공중합체가 그라프트된 공중합체 및 그의 제조 방법에 관한 것이다.The present invention relates to a copolymer in which an olefin or an amorphous styrene copolymer is grafted to a steric styrenic polymer or copolymer, and a method of preparing the copolymer. More specifically, styrene-based polymers or copolymers in which the stereoregularity of the main chain is mainly syndiotactic is grafted to olefins or condensation polymers or copolymers in which the stereoregularity is mainly atactic. It relates to a copolymer and a method for producing the same.
Description
본 발명은 입체 구조 스티렌계 중합체 또는 공중합체에 올레핀 또는 무정형 스티렌계 공중합체가 그라프트된 공중합체 및 그의 제조방법에 관한 것이다. 더욱 상세하게는 주쇄의 입체 규칙성이 주로 신디오탁틱(syndiotactic) 구조인 스티렌계 중합체 또는 공중합체에 입체규칙성이 주로 어탁틱(atactic) 구조인 올레핀 이나 축합중합체 또는 공중합체가 그라프트된 공중합체 및 그의 제조 방법에 관한 것이다.The present invention relates to a copolymer in which an olefin or an amorphous styrene copolymer is grafted to a three-dimensional styrenic polymer or copolymer, and a method of preparing the copolymer. More specifically, styrene-based polymers or copolymers whose stereoregularity is mainly syndiotactic, are grafted with olefins, condensation polymers or copolymers whose stereoregularity is mainly atactic. It relates to coalescence and a method for producing the same.
한편, 스티렌계 또는 다른 올레핀계 신디오탁틱 중합체에 대한 연구도 많이 수행되었는데 (유럽특허출원 0,120,615 등), 특히 유럽특허 출원 505,972 A2에는 스티렌계 단량체와 극성이 있는 올레핀 단량체와의 공중합체를 제조한 예가 있으며, 일본국 특허 공개 91-205412에는 스티렌계 단량체와 소량의 관능기 등을 포함하는 스티렌계 단량체를 공중합한 후 새로운 단량체를 첨가하여 관능기에서부터 중합이 일어나도록 하여 제조된 그라프트 공중합체에 대한 예도 있다.On the other hand, styrene or studies on other olefin syndiotactic polymers also been a lot carried out (European patent application 0120615 and the like), in particular European Patent Application 505,972 A 2 is prepared a copolymer of the styrene type monomer and an olefin monomer with a polar As an example, Japanese Patent Application Publication No. 91-205412 discloses a graft copolymer prepared by copolymerizing a styrene monomer including a styrene monomer and a small amount of functional group, and then adding a new monomer to cause polymerization from the functional group. There is an example.
그러나, 지금까지의 연구는 입체규칙성이 신디오탁틱인 공중합체의 제조 및 중합된 공중합체의 입체규칙성의 효율과 그에 따른 촉매계만을 언급하고 있다. 이때 제조되는 스티렌계 공중합체는 높은 용융 온도와 열변형 온도를 갖고 있어서 상업적으로 중요한 용도를 갖고 있지만, 스티렌계 수지의 일반적인 단점인 낮은 내충격성 때문에 아직 그 용도가 제한되고 있다. 한편 이때 제조되는 신디오탁틱 공중합체는 높은 결정성때문에 일반적인 충격흡수가 가능한 수지와의 상용성이 적다는 단점이 있다.However, studies to date refer only to the preparation of copolymers whose stereoregularity is syndiotactic and to the efficiency of the stereoregularity of the polymerized copolymer and thus the catalytic system. At this time, the styrenic copolymer prepared has high melting temperature and heat deformation temperature and thus has a commercially important purpose, but its use is still limited due to the low impact resistance, which is a general disadvantage of the styrene resin. Meanwhile, the prepared syndiotactic copolymer has a disadvantage in that it is less compatible with a general shock absorbing resin because of high crystallinity.
따라서, 신디오탁틱 스티렌계 공중합체의 높은 용융 온도와 열병형 온도를 유지하면서 스티렌계 수지의 단점인 낮은 내충격성을 향상시키기 위하여 고분자 사슬에 어탁틱 구조를 정량적으로 포함시켜 일반적인 충격흡수가 가능한 수지와의 상용성을 증진시킬 필요성이 있다.Therefore, in order to improve the low impact resistance, which is a disadvantage of the styrene resin, while maintaining the high melting temperature and the heat-cold temperature of the syndiotactic styrene-based copolymer, a resin capable of general shock absorption by quantitatively including an atactic structure in the polymer chain There is a need to improve compatibility with.
본 발명은 주쇄의 입체규칙성이 주로 신디오탁틱인 스티렌계 공중합체 및 그의 제조방법에 관한 것이다. 더욱 상세하게는, 본 발명은 주쇄의 입체규칙성이 주로 신디오탁틱 구조인 시티렌계 중합체 또는 공중합체에 입체규칙성이 주로 어탁틱 구조인 올레핀이나 축합 중합체 또는 공중합체가 바람직한 길이와 수만큼 그라프트된 스티렌계 공중합체 및 그의 제조방법에 관한 것이다.The present invention relates to a styrene copolymer having a stereoregularity of the main chain mainly syndiotactic and a method for producing the same. More specifically, the present invention relates to a citrate-based polymer or copolymer in which the stereoregularity of the main chain is mainly a syndiotactic structure, and that olefins or condensation polymers or copolymers in which the stereoregularity is mainly an atactic structure are graphed by the desired length and number. To a styrenic copolymer and a method for producing the same.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명은 하기 일반식 (A)로 나타내는 1종류 이상의 반복단위 및 하기 일반식 (B)로 나타내는 1종류 이상이 마크로머로 이루어진 중합체로, 주쇄의 입체규칙성이 주로 신디오탁틱(Syndiotactic)이고, 일반식 (B)로 나타내는 1종류이상의 마크로머가 전체의 5 내지 90중량% 인 공중합체에 관한 것이다.The present invention is a polymer consisting of one or more types of repeating units represented by the following general formula (A) and one or more types represented by the following general formula (B) consisting of macromers, and the stereoregularity of the main chain is mainly syndiotactic. And the copolymer which is 5 to 90 weight% of the whole 1 or more types of macromers represented by general formula (B).
상기식에서,In the above formula,
R1은 -H 또는 -CH3이고,R 1 is -H or -CH 3 ,
R2는 -H, 할로겐원자, 탄소수 1 내지 10 의 알킬, 할로겐치환알킬, 알콕시, 카르복시에스테르, 알킬실릴, 알킬아미노 또는 시아노이거나, 황 또는 인을 포함하는 치환기이고,R 2 is —H, a halogen atom, alkyl having 1 to 10 carbon atoms, halogen substituted alkyl, alkoxy, carboxyester, alkylsilyl, alkylamino or cyano, or a substituent containing sulfur or phosphorus,
h 는 1 내지 3 이며,h is 1 to 3,
h 가 2 또는 3 일때 R2는 서로 동일하거나 상이하다.When h is 2 or 3, R 2 is the same or different from each other.
상기식에서,In the above formula,
R3, R6및 q 는 각각 상기 일반식(A)에서 정의된 R1, R2및 h 와 동일하며, R4및 R5는 각각 -H 또는 -CH3이고,R 3 , R 6 and q are the same as R 1 , R 2 and h defined in general formula (A), respectively, R 4 and R 5 are each -H or -CH 3 ,
X는CH2-, -(CH2)a-(O-(CH2)b)c- 또는 C(O)-(CH2)d-O- 이고,X is CH 2 -,-(CH 2 ) a- (O- (CH 2 ) b ) c -or C (O)-(CH 2 ) d -O-,
여기서,here,
a, b, c 는 1 내지 4의 수이고,a, b, c is a number from 1 to 4,
d 는 0 내지 3의 수이고,d is a number from 0 to 3,
Y는 -COOR7, -CN 또는 -CONR8R9이고,Y is -COOR 7 , -CN or -CONR 8 R 9 ,
여기서,here,
R7은 -H, 탄소수 1 내지 8 개의 알킬, 아릴, 아릴알킬, 2-하이드록시에틸, 디메틸아미노에틸 또는 글리시딜이고,R 7 is —H, alkyl having 1 to 8 carbons, aryl, arylalkyl, 2-hydroxyethyl, dimethylaminoethyl or glycidyl,
R8및 R9는 각각 탄소수 1 내지 8 개의 알킬이고,R 8 and R 9 are each alkyl having 1 to 8 carbons,
i = j = 0 일 때, k 4when i = j = 0, k 4
i = k = 0 일 때, j 4when i = k = 0, j 4
i = k = 0 일 때, i 4i 4 when i = k = 0
k = 0 일 때, i + j 4 이다.When k = 0, it is i + j4.
일반식 (A)에서, 할로겐 원자의 구체적인 예로는 클로라이드, 브로마이트, 아이오다이드가 있다. 탄소수 1 내지 10의 알킬기의 구체적인 예로는 메틸기, 에틸기, 이소프로필기, t-부틸기가 있고, 탄소수 1 내지 10 의 할로겐치환 알킬기의 구체적인 예로는 클로로메틸기, 클로로 에틸기가 있고, 탄소수 1 내지 10의 알콕시기의 구체적인 예로는 메톡시기, 에톡시기, 에폭시기가 있고, 탄소수 1 내지 10의 카르복시에스테르기의 구체적인 예로는 카르복시메틸에스테르기가 있고, 알킬실릴기의 구체적인 예로는 트리에틸실릴기가 있고, 탄소수 1 내지 10의 알킬아미노기의 구체적인 예로는 디메틸아미노기 등이 있다.In general formula (A), specific examples of halogen atoms include chloride, bromite, iodide. Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, isopropyl group, t-butyl group, and specific examples of the halogen substituted alkyl group having 1 to 10 carbon atoms include chloromethyl group and chloroethyl group, and alkoxy having 1 to 10 carbon atoms. Specific examples of the group include a methoxy group, an ethoxy group, an epoxy group, specific examples of the carboxy ester group having 1 to 10 carbon atoms include a carboxymethyl ester group, specific examples of the alkylsilyl group include a triethylsilyl group, and 1 to 10 carbon atoms. Specific examples of the alkylamino group include a dimethylamino group and the like.
또한, 본 발명은In addition, the present invention
1) 티타늄 화합물 또는 티타늄 킬레이트 화합물,1) titanium compound or titanium chelate compound,
2) 트리알킬알루미늄 화합물,2) trialkylaluminum compounds,
3) 트리알킬알루미늄 화합물과 물과의 축합물3) Condensates of Trialkylaluminum Compounds with Water
로 부터 선택된 1종 이상의 촉매 존재하에서, 하기 일반식 (A')로 표시되는 1 종류 이상의 단량체와 하기 일반식(B')료 포시되는 마크로머를 공중합시킴으로써, 하기 일반식 (A)로 나타내는 1종류 이상의 반복단위 및 하기 일반식 (B)로 나타내는 1 종류 이상의 마크로머로 이루어진 중합체로, 주쇄이 입체규칙성이 주로 신디오탁틱이고, 일반식 (B)로 나타내는 1 종류 이상의 마크로머가 전체의 5 내지 90중량% 인 공중합체를 제조하는 방법에 관한 것이다.1 represented by the following general formula (A) by copolymerizing a macromer represented by the following general formula (B ') material with one or more types of monomers represented by the following general formula (A') in the presence of at least one catalyst selected from A polymer composed of one or more types of repeating units and one or more types of macromers represented by the following General Formula (B), wherein the main chain is mainly syndiotactic, and one or more types of macromers represented by General Formula (B) are 5 to 5. A method for producing a 90% by weight phosphorus copolymer.
상기식에서,In the above formula,
R1, R2및 h 는 일반식(A)에서 정의된 것과 동일하다.R 1 , R 2 and h are the same as defined in formula (A).
상기식에서,In the above formula,
R3, R6및 q 는 각각 일반식(A)에서 정의된 R1, R2및 h 와 동일하며, R4, R5, X, Y 는 일반식(B)에서 정의된 것과 동일하며,R 3 , R 6 and q are the same as R 1 , R 2 and h respectively defined in formula (A), and R 4 , R 5 , X, Y are the same as defined in formula (B),
i, j, k 관계 및 범위는 일반식(B)에서 정의된 것과 동일하다.The i, j, k relationships and ranges are the same as defined in formula (B).
일반식(A')로 표시되는 단량체의 구체적인 예로는 스티렌, 메틸스티렌 (p-, o-, m-, α), 디메스티렌, 할로겐치환스티렌(p-클로로, o-클로로, m-클로로, p-브로마이드, o-브로마이드,m-브로마이드, p-플루오로, o-플루오로, m-플루오로), 할로겐치환메틸스티렌(p-클로로메틸, o-클로로메틸, m-클로로메틸), 알콕시스티렌(p-메톡시,o-메톡시, m-메톡시) 등이 있다.Specific examples of the monomer represented by the general formula (A ') include styrene, methyl styrene (p-, o-, m-, α), dimethstyrene, halogen-substituted styrene (p-chloro, o-chloro, m-chloro, p-bromide, o-bromide, m-bromide, p-fluoro, o-fluoro, m-fluoro), halogen-substituted methylstyrene (p-chloromethyl, o-chloromethyl, m-chloromethyl), alkoxy Styrene (p-methoxy, o-methoxy, m-methoxy) and the like.
일반식(B')로 표시되는 마크로머의 구체적인 예로는 스티렌기나 메틸메타크릴레이트기가 말단에 있는 폴리스티렌계 단일 또는 공중합체, 폴리메틸메타크릴레이트 단일 또는 공중합체이거나, 또는 메틸메타크릴레이트기가 말단에 있는 폴리카프로락톤등이 가능하고, 이들과 모노비닐리덴 방향족 단량체, 탄소수 1 내지 8 의 알킬메타크릴레이트, 탄소수 1 내지 8 의 알킬아크릴레이트, 2-하이드록시 에틸메타크릴레이트, 2-알킬이미노 에틸메타크릴레이트, 아크릴로니트릴, 메타크릴로니트릴, 아크릴아미드, 탄소수 1 내지 10 의 알킬비닐에테르, 이소부틸렌 중에서 선택된 1 종 또는 2 종 이상의 단량체와 공중합체를 이루고 있으면서 말단이나 사슬의 일부에 관능기를 가지고 있는 마크로머가 가능하다.Specific examples of the macromer represented by the general formula (B ') include a polystyrene-based single or copolymer in which a styrene group or a methyl methacrylate group is terminated, a polymethyl methacrylate single or copolymer, or a methyl methacrylate group is terminated. Polycaprolactone and the like, and these and monovinylidene aromatic monomer, alkyl methacrylate having 1 to 8 carbon atoms, alkyl acrylate having 1 to 8 carbon atoms, 2-hydroxy ethyl methacrylate, 2-alkyl Part of the terminal or chain while being copolymerized with one or two or more monomers selected from mino ethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, alkyl vinyl ether having 1 to 10 carbon atoms and isobutylene Macromers with functional groups are possible.
이때 사용되는 촉매에서 티타늄 화합물 또는 티타늄킬레이트 화합물은 다음의 일반식(C)로 표시될 수 있다.In this case, the titanium compound or the titanium chelate compound in the catalyst used may be represented by the following general formula (C).
상기식에서,In the above formula,
R10은 -HR 10 is -H
탄소수 1 내지 20 의 알킬,Alkyl having 1 to 20 carbon atoms,
탄소수 1 내지 20의 아릴, 알킬아릴 또는 아랄알킬Aryl, alkylaryl or aralalkyl having 1 to 20 carbon atoms
π-결합된 사이클로펜타디에닐기, π-결합된 일치환 또는 다치환된 사이클로펜타디에닐기, 또는 사이클로펜타디엔의 π-결합된 1 가 올리고머이고, X는 할로겐원자이고,π-bonded cyclopentadienyl group, π-bonded monocyclic or polysubstituted cyclopentadienyl group, or π-bonded monovalent oligomer of cyclopentadiene, X is a halogen atom,
-OR11또는 -NR12 2(여기서 R11및 R12는 각각 탄소수 1 내지 20 의 지방족, 지환족, 방향족 탄화수소 또는 아실기)-OR 11 or -NR 12 2 , wherein R 11 and R 12 are each an aliphatic, alicyclic, aromatic hydrocarbon or acyl group having 1 to 20 carbon atoms
a 는 4 이하의 정수이며,a is an integer of 4 or less,
a가 2 내지 4 일때, R10은 모두 동일하거나 다를 수 있고,when a is 2 to 4, R 10 may be all the same or different,
a가 2 이하 일때, X(4-a)는 모두 동일하거나 다를 수 있다.When a is 2 or less, X (4-a) may be all the same or different.
상기에서, 탄소수 1 내지 20 의 알킬기의 예로는 메틸기, 에틸기, 프로필기, 부틸기, i-부틸기, 옥틸기 등이 있고, 탄소수 1 내지 20 의 아릴기, 알킬아릴기가 있고, 아릴알킬기의 예로는 페닐기, 프로페닐기, 톨릴기, 벤질기 등이 있고, π-결합된 일치환 또는 다치환된 사이클로펜타디에닐기가 있고, 사이클로펜타디엔의 π-결합된 1 가 올리고머의 예로는 메틸사이클로펜타디에닐기, 디메틸사이클로펜타디에닐기, 펜타메틸사이클로펜타디에닐기, 인데닐기 등이 있다.In the above, examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, i-butyl group, octyl group, and the like, and include aryl group and alkylaryl group having 1 to 20 carbon atoms. Is a phenyl group, a propenyl group, a tolyl group, a benzyl group, etc., there is a π-bonded monocyclic or polysubstituted cyclopentadienyl group, and an example of the π-bonded monovalent oligomer of cyclopentadiene is methylcyclopentadiene. And a yl group, a dimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and an indenyl group.
또한 할로겐 원자의 예로는 클로라이드, 브롬 요오드 등이 있고, -OR11과 -NR12 2의 예로는 메톡시기, 에톡시기, 프로폭시기, 아밀록시기, 헵타데실카르보닐옥시 등이 있다.In addition, examples of the halogen atom include chloride and bromine iodine, and examples of -OR 11 and -NR 12 2 include a methoxy group, an ethoxy group, a propoxy group, an amylooxy group, and a heptadecylcarbonyloxy.
일반식(C)의 티타늄 화합물 또는 티타늄킬레이트 화합물의 예로는 사이클로펜타디에닐티타늄트리클로라이드, 비스사이클로펜타디에닐티타늄디클로라이드, 티타늄테트라클로라이드, 티타늄테트라브로마이드, 메틸티타늄트리클로라이드, 에틸티타늄트리클로라이드, 티타늄테트라메톡사이드, 티타늄테트라에톡사이드, 사이클로펜타디에닐티타늄트리부톡사이드, 비스(2,4-펜타디오네이트)티타늄옥사이드, 비스(2,4-펜타디오네이트)티타늄디클로라이드, 비스(2,4-펜타디오네이트)티타늄디프로폭사이드, 사이클로펜타디에닐티타늄트리페녹사이드, 펜타메틸사이클로펜타디에닐티타늄트리페녹사이드, 펜타메틸사이클로펜타디에닐티타늄트리프로폭사이드, 사이클로펜타디에닐티타늄트리(N-디메틸아민), 인데닐티타늄트리(N-디메틸아민) 등이 있다. 이들 화합물 중에서 가장 바람직한 것은 사이클로펜타디에닐티타늄트리클로라이드이다.Examples of the titanium compound or titanium chelate compound of formula (C) include cyclopentadienyl titanium trichloride, biscyclopentadienyl titanium dichloride, titanium tetrachloride, titanium tetrabromide, methyl titanium trichloride, ethyl titanium trichloride, Titanium tetramethoxide, titanium tetraethoxide, cyclopentadienyl titanium tributoxide, bis (2,4-pentadionate) titanium oxide, bis (2,4-pentadionate) titanium dichloride, bis (2 , 4-pentadionate) titanium dipropoxide, cyclopentadienyl titanium triphenoxide, pentamethyl cyclopentadienyl titanium triphenoxide, pentamethyl cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium Tri (N-dimethylamine), indenyl titanium tri (N-dimethylamine), and the like. Most preferred of these compounds are cyclopentadienyl titanium trichloride.
위의 티타늄 화합물 또는 티타늄킬레이트 화합물은 실리카, 알루미나,마그네슘 화합물 등의 담체와 함께 사용될 수 있다.The above titanium compound or titanium chelate compound may be used together with a carrier such as silica, alumina, magnesium compound and the like.
타타늄 화합물과 함께 사용하는 트리알킬알루미늄 화합물은 하기 일반식(D)로 표시될 수 있다.The trialkylaluminum compound used with a titanium compound can be represented by the following general formula (D).
상기식에서,In the above formula,
R13은 탄소수 1 내지 10 의 알킬기이다.R 13 is an alkyl group having 1 to 10 carbon atoms.
일반식(D)의 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄 등이 있으며, 이중 가장 바람직한 것은 트리메틸알루미늄이다.Examples of general formula (D) include trimethylaluminum, triethylaluminum, triisobutylaluminum and the like, of which trimethylaluminum is most preferred.
상기의 트리알킬알루미늄과 축합되는 축합물에는 축합 반응을 일으킬 수 있는 한 특별한 제한이 없으며 가장 대표적인 것은 물이다. 이와 같은 축합반응에 의해서 생성되는 반응 생성물의 대표적인 것은 일반식(E)로 나타낼 수 있는 알킬 알루미녹산이다.The condensate condensed with the trialkylaluminum is not particularly limited as long as it can cause a condensation reaction, and most representative is water. Representative of the reaction product produced by such a condensation reaction is alkyl aluminoxane represented by the general formula (E).
상기 식에서,Where
R14는 탄소수 1 내지 8 의 알킬기이고,R 14 is an alkyl group having 1 to 8 carbon atoms,
e는 2 내지 70 의 정수이다.e is an integer from 2 to 70.
알킬 알루미녹산을 제조하는 방법은 공지의 기술로 수행될 수 있다(일본국 특허 제 89-69305호).The process for producing alkyl aluminoxanes can be carried out by known techniques (Japanese Patent No. 89-69305).
본 발명의 제조에 있어서 사용되는 촉매는The catalyst used in the manufacture of the present invention
a) 1)성분, 2)성분 및 3)성분을 동시에 사용하는 방법.a) A method using simultaneously 1) component, 2) component and 3) component.
b) 1)성분과 3)성분을 동시에 사용하는 방법.b) Method of using 1) component and 3) component simultaneously.
c) 2)성분과 3)성분을 동시에 사용하는 방법, 및c) a method of simultaneously using 2) component and 3) component, and
c) 3)성분을 단독으로 사용하는 방법이 가능하다.c) 3) It is possible to use the components alone.
본 발명의 반응계는 1 종류 이상의 단량체, 1 종류 이상의 마크로머, 및 복잡한 촉매계로 이루어졌기 때문에 반응의 최적 조건에 맞도록 사용되는 촉매의 양은 각각의 경우에 따라 다르지만, 1)성분과 3)상분을 동시에 사용하거나, 1)성분, 2)성분 및 3)성분을 동시에 사용하는 경우에, 일반적으로 알루미늄(Al)과 티타늄원자(Ti)의 비{=[Al]:[Ti]}가 50:1 내지 100,000:1, 바람직하게는 100:1 내지 10,000:1이 되도록 하는 양을 사용한다. 또한, 사용되는 촉매를 희석시켜서 사용할 수도 있는데, 이때의 희석제로는 탄소수 4 내지 20 의 알칸, 사이클로알칸 및 방향족 탄화수소 등이 사용될 수 있는데, 이것의 구체적인 예로는 헥산, 사이클로헥산, 벤젠, 톨루엔, 크실렌 등이 있다.Since the reaction system of the present invention is composed of one or more types of monomers, one or more types of macromers, and a complex catalyst system, the amount of catalyst used to suit the optimum conditions of the reaction varies depending on each case. In the case of simultaneous use, or in the case of using 1) component, 2) component and 3) component simultaneously, the ratio {= [Al]: [Ti]} of aluminum (Al) and titanium atom (Ti) is generally 50: 1. To amounts of from 100,000 to 100,000: 1, preferably from 100: 1 to 10,000: 1. In addition, the catalyst used may be diluted and used, and as the diluent, alkanes, cycloalkanes and aromatic hydrocarbons having 4 to 20 carbon atoms may be used. Specific examples thereof include hexane, cyclohexane, benzene, toluene, and xylene. Etc.
본 발명의 제조방법에서 반응 용매는 촉매의 희석제로 사용 가능한 것을 사용할 수 있다. 또한, 본 발명의 중합제는 벌크중합 또는 용액중합에 의하여 제조될 수 있다. 이때의 중합온도는 0 내지 100℃, 바람직하게는 30 내지 70℃ 이다. 이 중합반응은 사용되는 단량체에 따라 티타늄 촉매의 활성자리 쪽에 결합되어 있는 고분자사슬의 말단에서 β-수소제거 반응에 의해 반응이 종결될 수도 있으므로, 적당한 단량체를 소량 첨가하거나 외부에서 수소기체를 공급함으로써 분자량을 조절할 수도 있다.In the production method of the present invention, the reaction solvent can be used as a diluent of the catalyst. In addition, the polymer of the present invention may be prepared by bulk polymerization or solution polymerization. The polymerization temperature at this time is 0-100 degreeC, Preferably it is 30-70 degreeC. Depending on the monomer used, the reaction may be terminated by β-hydrogenation at the end of the polymer chain bound to the active site of the titanium catalyst. Therefore, by adding a small amount of the appropriate monomer or supplying hydrogen gas from the outside, The molecular weight can also be adjusted.
이때, β-수소제거 반응이 용이한 단량체로는 알파메틸스티렌 및 메틸메타크릴레이트가 있다.At this time, the monomers easily beta-hydrogenation reactions include alpha methyl styrene and methyl methacrylate.
다음의 합성예와 실시예에서 본 발명을 더욱 상세히 설명하고자 한다.In the following synthesis examples and examples will be described the present invention in more detail.
그러나 실시예에 의하여 본 발명이 제한되는 것은 아니다.However, the present invention is not limited by the examples.
합성예 1, 2 는 메타크릴레이트기를 말단에 갖는 폴리스티렌 마크로머의 합성법. 합성예 3 은 폴리스티렌기를 말단에 갖는 폴리스티렌 마크로머의 합성법. 합성예 4 는 폴리메틸메타크릴레이트 마크로머의 합성법, 합성예 5 는 폴리카프로락톤 마크로머의 합성법에 대한 것이다.The synthesis examples 1 and 2 are the synthesis | combining methods of the polystyrene macromer which has a methacrylate group at the terminal. Synthesis Example 3 is a method for synthesizing a polystyrene macromer having a polystyrene group at its terminal. Synthesis Example 4 relates to the synthesis of polymethylmethacrylate macromers, and Synthesis Example 5 relates to the synthesis of polycaprolactone macromers.
[합성예 1]Synthesis Example 1
라디칼 중합법에 의하여 고분자 사슬 말단에 이중결합이 도입된 마크로머를 제조하는 방법은 이토(Ito) 등에 의하여 문헌[Macromolecules 13, 216(1980)]에 보고된 바가 있으며 또한 잭슨(Jackson)에 의하여 미국특허 제 3,689,593 호에 보고된 바가 있다. 합성예 1 에서는 전자의 방법을 변형 응용하였다.A method for producing macromers in which double bonds are introduced at the ends of polymer chains by radical polymerization has been reported by Ito et al. In Macromolecules 13, 216 (1980) and also by Jackson (US). It is reported in patent 3,689,593. In Synthesis Example 1, the former method was modified.
즉, 스티렌단량체 82 중량부, 티오글리코릭산 3.0㎖, 톨루엔 40 중량부, 개시제로 AIBN 1, 2 중량부를 혼합한 다음, 질소가스 하에서 70℃의 온도에서 4 시간 반응시켜 말단에 카르복실산을 갖는 폴리스티렌 42 부를 얻었다. 겔침투르로마토그래피(GPC)에 의한 수평균 분자량 및 분자량 분포는 각각 12000 및 2.24 이었고 말단의 카르복실산을 0.1N 의 포타시움하이드록사이드 용액으로 적정한 결과 99% 이상의 폴리스티렌 말단에 관능기가 도입되었음을 확인하였다.That is, 82 parts by weight of styrene monomer, 3.0 ml of thioglycolic acid, 40 parts by weight of toluene, and 1 part by weight of AIBN as an initiator were mixed, followed by reaction at a temperature of 70 ° C. under nitrogen gas for 4 hours to have carboxylic acid at the terminal. 42 parts of polystyrene were obtained. The number average molecular weight and molecular weight distribution by gel permeation chromatography (GPC) were 12000 and 2.24, respectively, and titration of carboxylic acid at the end with 0.1 N of potassium hydroxide solution showed that functional groups were introduced at 99% or more of polystyrene ends. Confirmed.
이 폴리스티렌과 카르복실산에 대하여 100% 과량의 글리시딜 메타크릴레이트를 코발트 옥토에이트, 니켈 옥토에이트, N,N-디메틸 4-아미노 피리딘 또는 세틸 트리메틸암모니움 브로마이드 등의 촉매 조건하에서 반응시켰으며, 폴리스티렌의 말단에 있는 메타크릴레이트기의 정량은 300MHz FT-NMR 을 사용하였는데 5.5ppm, 6.0ppm 에서 이중결합의 피크를 확인하였고, 겔침투크로마토그래피에 의한 수평균분자량을 기준으로 하여 계산된 이중결합이 함량은 95% 이상이었다.100% excess glycidyl methacrylate was reacted with the polystyrene and carboxylic acid under catalytic conditions such as cobalt octoate, nickel octoate, N, N-dimethyl 4-amino pyridine or cetyl trimethylammonium bromide. The determination of methacrylate groups at the ends of polystyrene was carried out using 300 MHz FT-NMR. The peaks of the double bonds were confirmed at 5.5 ppm and 6.0 ppm, and the double calculated based on the number average molecular weight by gel permeation chromatography. The bond content was at least 95%.
[합성예 2]Synthesis Example 2
고순도 질소 상태의 반응용기에서 스티렌 단량체 60 중량부를 사이클로헥산 용매 600㎖ 에 넣고 고순도의 질소를 20 분간 퍼지시켜 공기를 제거한 후 주사기로 1.3M sec-부틸리튬을 적하하여 반응에 영향을 주는 불순물을 제거하였다. 그리고, 스티릴 음이온의 특정색인 노란색이 사라지지 않는 상태에서 목적한 분자량을 얻기 위하여 4.7㎖ 의 sec-부틸리튬을 적하하여 반응을 개시하였다. 이때의 반응 온도는 45℃이었으며, 발열 반응이 끝난 후 충분한 시간 경과 후에 에틸렌 옥사이드를 가하였다. 적당한 시간 후 메타크릴로일 클로라이드 2㎖ 를 적하한 후 2 시간 동안 반응시켰다(G. O. Shulz et. al., J, Appl. Polym. Sci., 27, 4773(1982) 참조). 반응 후 폴리스티렌을 침전 분리하여 진공 오븐에서 건조시킨 후 겔침투크로마토그래피를 이용하여 폴리스티렌 표준 물질에 대한 상대적인 수평균 분자량 및 분자량 분포를 알아보았는데 그 값은 각각 11500 및 1.02 이었다.In a high-purity nitrogen container, 60 parts by weight of styrene monomer is placed in 600 ml of cyclohexane solvent, purged with high purity nitrogen for 20 minutes to remove air, and then dropping 1.3M sec-butyllithium with a syringe to remove impurities that affect the reaction. It was. Then, 4.7 ml of sec-butyllithium was added dropwise to start the reaction in order to obtain the desired molecular weight in the state that the specific color of the styryl anion did not disappear. At this time, the reaction temperature was 45 ℃, ethylene oxide was added after a sufficient time after the exothermic reaction. After a suitable time, 2 ml of methacryloyl chloride was added dropwise and reacted for 2 hours (see G. O. Shulz et. Al., J, Appl. Polym. Sci., 27, 4773 (1982)). After the reaction, the polystyrene was precipitated, dried, and dried in a vacuum oven, and then gel permeation chromatography was used to determine the relative number average molecular weight and molecular weight distribution of the polystyrene standard. The values were 11500 and 1.02, respectively.
폴리스티렌의 말단에 있는 메타크릴레이트기의 정량은 합성예 1 과 같은 방법으로 하였는데 이중결합의 함량은 94% 이상이었다. 이 결과를 직접 다른 단량체와 중합하여 알아보았다. 에틸아크릴레이트 단량체와 공중합시킨 후 미반응 폴리스티렌의 양을 알기 위하여 겔침투크로마토그래피의 UV 검출기로 폴리스티렌의 방향족 고리를 254㎚ 에서 비교하였을 때 미반응한 폴리스티렌은 7% 로 폴리스티렌의 말단에 이중결합이 있는 메타크릴레이트기가 93% 이상 존재함을 확인하였다.The methacrylate group at the end of polystyrene was quantitatively prepared in the same manner as in Synthesis example 1, but the content of the double bond was 94% or more. This result was examined by direct polymerization with other monomers. In order to know the amount of unreacted polystyrene after copolymerization with ethyl acrylate monomer, when the aromatic ring of polystyrene was compared at 254 nm by UV permeation chromatography of gel permeation chromatography, unreacted polystyrene was doubled at the end of polystyrene at 7%. It was confirmed that more than 93% of the methacrylate groups present.
[합성예 3]Synthesis Example 3
합성예 2 에서와 같은 방법을 사용하되 메타크릴로일 클로라이드 대신 클로로메틸스티렌을 사용하였다. 얻어진 마크로머의 수평균 분자량 및 분자량 분포는 25000, 1.04 이었고, 말단기중 이중결합 함량은 합성예 1 과 동일한 방법으로 실시하였는데 94% 이상이었다.The same method as in Synthesis Example 2 was used, but chloromethylstyrene was used instead of methacryloyl chloride. The number average molecular weight and molecular weight distribution of the obtained macromer were 25000 and 1.04, and the double bond content in the terminal group was carried out in the same manner as in Synthesis example 1, but was 94% or more.
[합성예 4]Synthesis Example 4
합성예 1 에서와 같은 방법을 사용하되 스티렌 대신에 메틸메타크릴레이트를 사용하였다. 얻어진 마크로머의 수평균 분자량 및 분자량 분포는 각각 8000 및 1.95 이었고 말단기중 이중결합 함량은 합성예 1 과 동일한 방법으로 실시하였는데 85% 이상이었다.The same method as in Synthesis Example 1 was used, but methyl methacrylate was used instead of styrene. The number average molecular weight and molecular weight distribution of the obtained macromer were 8000 and 1.95, respectively, and the double bond content in the terminal group was carried out in the same manner as in Synthesis example 1, but was 85% or more.
[합성예 5]Synthesis Example 5
2-하이드록시 에틸메타크릴레이트(HEMA)와 ε-카프로락톤의 혼합물에 촉매량만큼의 틴옥토에이트를 가한 다음 50℃ 로 필요한 시간 동안 반응시켯다.이어서, 이를 과량의 메탄올 중에 침전시키면 폴리카프로락톤 마크로머가 85% 의 수율로 얻어진다. 얻어진 마크로머의 겔침투크로마토그래피(GPC)에 의한 수평균분자량 및 분자량 분포는 각각 12000 및 1.21 이었고, 합성예 1 과 동일한 방법으로 정량한 말단기의 관능기는 91% 이었다.A catalytic amount of tinoctoate was added to a mixture of 2-hydroxy ethyl methacrylate (HEMA) and ε-caprolactone, and then reacted at 50 ° C. for the required time. Then, precipitated in excess methanol to give polycaprolactone Macromers are obtained with a yield of 85%. The number average molecular weight and molecular weight distribution of the obtained macromer by gel permeation chromatography (GPC) were 12000 and 1.21, respectively, and the functional group of the terminal group quantified by the same method as in Synthesis Example 1 was 91%.
[실시예 1]Example 1
140℃ 의 오븐에서 6 시간 건조된 플라스크를 고순도의 질소 분위기 하에서 상온으로 온도를 내린 후, 그 프라스크에 나트륨-벤조페논으로 정제된 톨루엔 용매 200g에 사이클로펜타디에닐티타늄트리클로라이드 0.01mmol, 메틸알루미녹산 2.5mmol 및 트리메틸알루미늄 0.1mmol 을 혼합한 후, 이 용액을 55℃ 로 1 분간 가열하였다.The flask dried for 6 hours in an oven at 140 ° C. was cooled to room temperature under a high-purity nitrogen atmosphere, and then 0.01 g of cyclopentadienyl titanium trichloride was added to 200 g of toluene solvent purified with sodium-benzophenone in the flask, methylaluminum. After mixing 2.5 mmol of noric acid and 0.1 mmol of trimethylaluminum, the solution was heated to 55 ° C. for 1 minute.
그리고 합성예 3 에서 제조된 스티렌 단량체가 말단에 있는 스티렌 마크로머 20g 과 스티렌 단량체 20g 을 정제된 톨루엔 용매 150g 에 용해시켜 용액으로 만들고, 이 용액을 반응 플라스크에 혼합하였다. 100 분 후 메탄올을 가하여 반응을 정지시키고 10% HCI 이 포함된 메탄올 용액에 침전시켰다. 생성된 폴리스티렌 공중합체를 여과하여 10% HCI 의 메탄올 용액으로 4 번 세척한 후 100℃ 의 진공오븐에서 24 시간 건조하였다. 이렇게 생성된 스티렌 공중합체의 수득량은 38.5g 이었다. 이 공중합체를 메틸에틸케톤을 사용하여 미반응 스티렌 마크로머와 가용성 성분을 추출하였는데 이때 불용성 성분은 37.4g 으로 시차주사열분석기(DSC)에 의한 유리전이온도(Tg)는 98.7℃, 용융점(Tm)은 259℃ 로 긴 측쇄에 기인하여 단일 신디오탁틱 스티렌 중합체에 비하여 약 10℃ 정도 낮은 용융점을 갖았다. 이때 그라프트된 폴리스티렌 마크로머의 유리전이온도는 주사슬의 어탁틱 스티렌 부분과 겹쳐 나타났다. 또한, 150℃ 의 트리클로로벤젠 용매를 사용하여 측정된 어탁틴 구조의 폴리스티렌 표준물질에 대한 겔침투크로마토그래피법에서의 중량평균분자량(Mw)은 420,000 이고, 수평균분자량(Mn)은 190,000이었다. 그리고, 그라프트 중합체에서 그라프트된 어탁틱 구조의 폴리스티렌의 함량은1H-NMR 에 의하여 정량하였는데 그 특성 피크인 방향족 고리에 붙어있는 메톡시의 수소 피크가 4.65ppm 에서 나오는데 그 함량은 52 중량% 이었다. 신디오탁틱도는13C-NMR 로 분석하였는데 어탁틱 폴리스티렌에서 방향족고리의 C1피크는 142 내지 147ppm 에 걸쳐 여러가지 피클로 넓게 나오며 주사슬의 신디오탁틱 폴리스티렌에서 방향족고리의 C1피크는 143.7 에서 하나의 피크로 나왔다.The styrene monomer prepared in Synthesis Example 3 was dissolved in 20 g of styrene macromer and 20 g of styrene monomer in 150 g of purified toluene solvent to make a solution, and the solution was mixed in a reaction flask. After 100 minutes, methanol was added to stop the reaction and precipitated in a methanol solution containing 10% HCI. The resulting polystyrene copolymer was filtered, washed four times with 10% HCI methanol solution, and dried in a vacuum oven at 100 ° C. for 24 hours. The yield of the styrene copolymer thus produced was 38.5 g. The unreacted styrene macromer and the soluble component were extracted using methyl ethyl ketone, and the insoluble component was 37.4 g. The glass transition temperature (Tg) by differential scanning thermal analyzer (DSC) was 98.7 ° C. ) Had a melting point of about 10 ° C. lower than single syndiotactic styrene polymer due to the long side chain at 259 ° C. At this time, the glass transition temperature of the grafted polystyrene macromer overlapped with the atactic styrene portion of the main chain. In addition, the weight average molecular weight (Mw) in the gel permeation chromatography method for the polystyrene standard of the attactin structure measured using the trichlorobenzene solvent of 150 degreeC was 420,000, and the number average molecular weight (Mn) was 190,000. The content of polystyrene with grafted atactic structure in the graft polymer was quantified by 1 H-NMR, and the hydrogen peak of methoxy attached to the aromatic ring, the characteristic peak, came out at 4.65 ppm, the content of which was 52% by weight. It was. Syndiotacticity was analyzed by 13 C-NMR. The C 1 peak of the aromatic ring in the atactic polystyrene was wide with various pickles over 142 to 147 ppm, and the C 1 peak of the aromatic ring in the syndiotactic polystyrene of the main chain was found at 143.7. One peak came out.
[실시예 2 내지 15][Examples 2 to 15]
표 1 에서의 단량체와 마크로머를 사용하여 표 1 의 조건에 따라 실시예 1과 동일한 방법으로 공중합 하였다. 공중합물의 분석은 실시예 1 과 동일한 방법으로 실시하였으며, 그 결과는 표 2 와 같다.The monomer and the macromer of Table 1 were used to copolymerize in the same manner as in Example 1 according to the conditions of Table 1. Analysis of the copolymer was carried out in the same manner as in Example 1, the results are shown in Table 2.
공중합물의 조성은1H-NMR 과 원소분석기로 행하였는데 특히1H-NMR 에서 스티렌이 말단에 있는 마크로머의 경우CH2-O-CH2-의 수소 피크는 각각 4.65ppm, 3.75ppm 에서 나왔으며, 메틸메타크릴레이트가 말단에 있는 마크로머의 경우 -C(O)-O-CH2- 의 수소 피크는 3.75ppm, -C-CH3수소 피크는 0.85ppm 에서 나왔다. 또한 스티렌 반복단위에서 방향족 고리의 수소 피크는 6.5 내지 7.5ppm, 메틸스티렌 반복단위에서 -CH3의 수소 피크는 2.75ppm, t-부틸스티렌 반복단위에서 -C(CH3)3의 수소 피크는 1.53ppm 에서 나왔다. 그리고, 할로겐이 치환된 단량체인 경우에는 원소분석을 행하였다.The composition of the copolymer was performed by 1 H-NMR and elemental analyzer, especially for macromers with styrene at the end in 1 H-NMR. The hydrogen peaks of CH 2 -O-CH 2 -are found at 4.65 ppm and 3.75 ppm, respectively, and for the macromers with methyl methacrylate at the end, the hydrogen peak of -C (O) -O-CH 2 -is 3.75 The ppm, -C-CH 3 hydrogen peak was at 0.85 ppm. In addition, the hydrogen peak of the aromatic ring in the styrene repeating unit is 6.5 to 7.5 ppm, the hydrogen peak of -CH 3 in the methylstyrene repeating unit is 2.75 ppm, and the hydrogen peak of -C (CH 3 ) 3 in the t-butylstyrene repeating unit is 1.53. came out in ppm. In the case where the halogen was a substituted monomer, elemental analysis was performed.
공중합물의 신디오탁틱도는13C-NMR 로 분석하였는데 주사슬의 신디오탁틱 폴리스티렌에서 방향족고리의 C1피크는 143.7ppm, C2, C3, C5, C6의 피크는 128.2ppm, C4피크는 125ppm 에서 하나의 피클로 나왔다. m-메틸스티렌인 경우에는 C1피크가 145.1ppm, C4피크가 135.2ppm, p-메틸스티렌의 경우에는 C1피크가 142.2ppm, C4피크가 134.9ppm, p(t-부틸)스티렌인 경우에는 C1피크가 142.2ppm, p-클로로스티렌인 경우에는 C1피크가 143.0ppm, C4피크가 120.1ppm, m-클로로스티렌인 경우에는 C1피크가 142.8ppm, C4피크가 135.0ppm 에서 단일 피크로 나온다.The syndiotacticity of the copolymer was analyzed by 13 C-NMR. The C 1 peak of the aromatic ring in the main chain syndiotactic polystyrene was 143.7 ppm, and the peaks of C 2 , C 3 , C 5 , and C 6 were 128.2 ppm, C Four peaks emerged as one pickle at 125 ppm. In the case of m-methylstyrene, the C 1 peak is 145.1 ppm, the C 4 peak is 135.2 ppm, and in the case of p-methylstyrene, the C 1 peak is 142.2 ppm, the C 4 peak is 134.9 ppm, and p (t-butyl) styrene. C 1 peak is 142.2 ppm, C 1 peak is 143.0 ppm, C 4 peak is 120.1 ppm, and in the case of m-chlorostyrene, C 1 peak is 142.8 ppm and C 4 peak is 135.0 ppm Comes out as a single peak.
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KR100332673B1 (en) * | 1999-08-16 | 2002-04-17 | 윤종용 | Styrene/Macromonomer Random Copolymer Having Excellent Melt Flowability and Method of Preparing The Same |
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KR100375437B1 (en) * | 2000-06-02 | 2003-03-10 | 삼성종합화학주식회사 | Method of Preparing Monomer-Grafted Syndiotactic Polystyrene with Polarity |
KR101984717B1 (en) * | 2015-09-15 | 2019-05-31 | 주식회사 엘지화학 | Polymer, method for preparing the same, and solid electrolyte, electrode, seperator and lithium secondary battery comprising the same |
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KR100332673B1 (en) * | 1999-08-16 | 2002-04-17 | 윤종용 | Styrene/Macromonomer Random Copolymer Having Excellent Melt Flowability and Method of Preparing The Same |
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