KR100583857B1 - Polyimide compounds - Google Patents
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- KR100583857B1 KR100583857B1 KR1019997011249A KR19997011249A KR100583857B1 KR 100583857 B1 KR100583857 B1 KR 100583857B1 KR 1019997011249 A KR1019997011249 A KR 1019997011249A KR 19997011249 A KR19997011249 A KR 19997011249A KR 100583857 B1 KR100583857 B1 KR 100583857B1
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N Cc1ccccc1C Chemical compound Cc1ccccc1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ODGJIXXVIQDADK-UHFFFAOYSA-N CC(N(C)C=O)=O Chemical compound CC(N(C)C=O)=O ODGJIXXVIQDADK-UHFFFAOYSA-N 0.000 description 1
- PDDRRTKJMWZZQU-UHFFFAOYSA-N CN(C)[NH+]([O-])OC Chemical compound CN(C)[NH+]([O-])OC PDDRRTKJMWZZQU-UHFFFAOYSA-N 0.000 description 1
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- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C07C229/44—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton with carboxyl groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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Abstract
본 발명에 따른 신규폴리이미드화합물은, 계피산 혹은 계피유도체골격을 가지고, 계피산골격특유의 광반응성 및 열반응성을 더불어 가지는 신규폴리이미드화합물을 제공한다. 또한, 본 발명의 신규디아민 및 산이무수물은, 주로 상기 계피산골격을 가지는 신규폴리이미드화합물을 제조하는데 사용하는 재료이며, 주쇄 또는 측쇄에 계피산골격 또는 계피산유도체골격을 가지는 디아민 및 산이무수물이다. The novel polyimide compound according to the present invention provides a novel polyimide compound having cinnamic acid or cinnamon derivative skeleton, and having both photoreactivity and thermal reactivity unique to cinnamic acid skeleton. In addition, the novel diamine and acid dianhydride of the present invention is a material mainly used to prepare a novel polyimide compound having the cinnamic acid skeleton, and is a diamine and an acid dianhydride having a cinnamic acid skeleton or a cinnamic acid derivative skeleton in the main chain or side chain.
Description
본 발명은, 신규인 폴리이미드화합물 및 그 제조방법에 관한 것이다. 더욱 상세하게는, 계피산 혹은 계피산 유도체골격을 가지며, 계피산 골격 특유의 광반응성 및 열반응성을 함께 가지는 폴리이미드화합물에 관한 것이다. The present invention relates to a novel polyimide compound and a method for producing the same. More specifically, the present invention relates to a polyimide compound having a cinnamic acid or cinnamic acid derivative skeleton and having both photoreactivity and thermal reactivity unique to the cinnamic acid skeleton.
계피산이 자외선의 조사에 의해, 2량체화하는 것은, 예로부터 알려져 있었다. 따라서, 계피산 골격을 고분자 내에 도입하면 유용한 감광성수지가 될 수 있는 것을 추측할 수 있다. 폴리비닐신나메이트(폴리비닐에 계피산골격이 들어간 것)는, 종래부터, 계피산 골격을 가지는 폴리머로서 잘 알려져 있으며, (Jpn. J. App1. Phys., 31(1992), 2155나 J.Photopolymer Sci. and Tech.8(1995),257)계피산 골격이 빛에 의해 2량화하는 반응에 의해, 용제에 녹지 않는 성질을 이용한 유용한 감광성수지이다(J.App1 Polymer Sci., 2,302(1959)). 이 폴리비닐신나메이트는 네가형 감광수지로서 이용되고 있다. It has long been known that cinnamic acid dimerizes by irradiation of ultraviolet rays. Therefore, it can be inferred that the introduction of cinnamic acid skeleton into the polymer can be a useful photosensitive resin. Polyvinyl cinnamate (which contains cinnamic acid skeleton in polyvinyl) is conventionally well known as a polymer having a cinnamic acid skeleton (Jpn. J. App1. Phys., 31 (1992), 2155 or J. Photopolymer Sci) and Tech. 8 (1995), 257) Cinnamic acid skeleton is a useful photosensitive resin that utilizes a property that does not dissolve in a solvent due to a dimerization reaction by light (J. App1 Polymer Sci., 2,302 (1959)). This polyvinyl cinnamate is used as a negative photosensitive resin.
그러나, 상기 폴리비닐신나메이트는, 내열성이 양호하지 않기 때문에, 내열 용도에는 사용할 수가 없었다. However, since the said polyvinyl cinnamate is not good in heat resistance, it cannot be used for heat resistance use.
또한, 폴리머용의 원료, 즉 반응성 모노머에, 먼저 계피산 골격을 도입하고, 그 후 중합화하는 쪽이 반응공정이 간편하다. 그러나, 현상황에서는 그러한 반응성 모노머는 존재하지 않았다. In addition, the reaction process is simpler when the cinnamic acid skeleton is first introduced into the polymer raw material, that is, the reactive monomer, and then polymerized. However, in the present situation, such a reactive monomer did not exist.
특히, 각종 유기폴리머 중에서도 폴리이미드 혹은 폴리아미드는, 내열성이 우수하기 때문에, 우주, 항공분야에서 전자통신분야까지 폭넓게 사용되고 있는 뛰어난 수지이며, 감광성수지로서의 응용이 기대되고 있다. In particular, among various organic polymers, polyimide or polyamide is an excellent resin widely used in aerospace and aviation fields for electronic communication fields because of its excellent heat resistance, and application as a photosensitive resin is expected.
일반적으로, 방향족폴리이미드의 원료는, 방향족아민과 산이무수물이며, 또한 방향족폴리아미드의 원료는, 방향족아민과 방향족디카르복실산 또는 방향족디카르복실산클로라이드이다. 계피산 골격을 가지는 방향족산이무수물은 알려져 있지 않다. Generally, the raw material of aromatic polyimide is aromatic amine and acid dianhydride, and the raw material of aromatic polyamide is aromatic amine, aromatic dicarboxylic acid or aromatic dicarboxylic acid chloride. Aromatic acid dianhydrides having a cinnamic acid skeleton are not known.
또한, 방향족아민은 통상 방향족 니트로화물을 환원하여 얻어진다. 따라서, 계피산 골격을 가지는 폴리이미드, 폴리아미드를 얻기 위해서는, 계피산 골격을 가지는 니트로화물을 환원함으로써, 계피산골격을 가지는 방향족아민을 얻은 후, 폴리이미드, 폴리아미드에 중합화하는 방법을 생각할 수 있다. 그러나, 현상황에서는, 방향족 니트로화물을 방향족아민에 환원하는 방법은, 하기와 같이 난점이 있고, 감광성수지의 재료인 모노머로서의 계피산 골격을 가지는 아민은 거의 알려져 있지 않으며, 또한, 감광성수지로서 이용할 수 있는 계피산 골격을 가지는 폴리이미드, 폴리아미드는 존재하지 않았다. In addition, aromatic amines are usually obtained by reducing aromatic nitrides. Therefore, in order to obtain the polyimide and polyamide which have a cinnamic acid skeleton, the method of superposing | polymerizing to a polyimide and a polyamide can be considered after reducing the nitrate which has a cinnamic acid skeleton to obtain the aromatic amine which has a cinnamic acid skeleton. However, in the present situation, the method of reducing aromatic nitrides to aromatic amines has difficulties as described below, and amines having a cinnamic acid skeleton as a monomer which is a material of the photosensitive resin are hardly known and can be used as the photosensitive resin. There was no polyimide or polyamide having a cinnamic acid skeleton.
일반적으로, 방향족 니트로화물을 방향족아민에 환원하는 방법으로서, 1) 금 속 혹은 금속염에 의해 환원하는 방법, 2)히드라진에 의한 환원, 3) Pd-활성탄을 촉매로 하는 수소에 의한 환원 등이 있다. In general, methods for reducing aromatic nitrides to aromatic amines include 1) reduction with metals or metal salts, 2) reduction with hydrazines, and 3) reduction with hydrogen using Pd-activated carbon as a catalyst. .
1)의 방법으로서는, 염산용액중염화주석에 의한 환원(주석염산계), 황산철에 의해 환원하여 암모니아에 의해 중화하는 황산철-암모니아계, 용액 속에서 금속철에 의해 직접 환원하는 Bechamp 환원 등이 있다. As the method of 1), reduction with tin chloride in hydrochloric acid solution (tin hydrochloric acid), iron sulfate-ammonia system reduced with iron sulfate and neutralized with ammonia, Bechamp reduction directly with metal iron in solution, etc. There is this.
그러나, 이들 방법은, 반응종료 시에 중화하기 때문에 금속이 염이 되어 석출하고, 방향족아민을 단리(單離)할 때, 매우 번잡한 조작이 필요하게 된다. 또한, 반응조건이 산성 하이기 때문에, 상술의 에스테르결합의 분해나, 알카리성이기 때문에 Michae1부가를 일으킬 가능성이 높다고 하는 문제가 있었다. However, since these methods neutralize at the end of the reaction, when the metal becomes a salt and precipitates and the aromatic amine is isolated, a very complicated operation is required. In addition, since the reaction conditions were acidic high, there was a problem in that the decomposition of the above-mentioned ester bonds and the alkali were highly likely to cause Michae 1 addition.
2)의 방법으로서, Pd-활성탄을 촉매로 하는 히드라진에 의한 환원, 라네니켈(Raney nickel)을 촉매로 하는 히드라진에 의한 환원이 있다. As a method of 2), reduction by hydrazine using Pd-activated carbon and reduction by hydrazine using Raney nickel as a catalyst.
이 중, Pd-활성탄을 촉매로 하는 히드라진에 의한 환원은, Michae1부가 혹은, 니트로화합물분해 등의 부반응이 일어나 바람직하지 않다. 또한, 라네니켈을 촉매로 하는 히드라진에 의한 환원은, Heiv. Chim. Actra., 24,209E(1941)에 라네니켈을 촉매로 하는 히드라진을 사용하여 니트로계피산으로부터 아미노계피산을 합성하는 방법이 기재되어 있다. 그러나, 단체(單體)의 니트로계피산이 아니라 니트로계피산 유도체의 환원에 이 계(系)를 사용하면 Michae1부가 등의 부반응이 진행하여 버린다고 하는 문제가 있었다. Among these, reduction with hydrazine using Pd-activated carbon is not preferable because side reactions such as Michae 1 addition or nitro compound decomposition occur. In addition, the reduction by hydrazine using a raney nickel as a catalyst is Heiv. Chim. Actra., 24,209E (1941), describes a method for synthesizing amino cinnamic acid from nitro cinnamic acid using hydrazine catalyzed by rane nickel. However, when this system is used for the reduction of nitro cinnamic acid derivatives instead of single nitro cinnamic acid, there is a problem that side reactions such as Michae 1 addition proceed.
또한, 3)의 방법으로서는, 일반적으로 유기용매 중, Pd-활성탄을 촉매로 하여 수소분위기 하에서 반응을 행한다. 이것은, 통상의 Pd-활성탄을 사용하면, 계피 산골격의 2중 결합까지 환원하여 버린다고 하는 문제가 있었다. As the method of 3), generally, the reaction is carried out in a hydrogen atmosphere using Pd-activated carbon as a catalyst in an organic solvent. This has a problem that when using ordinary Pd-activated carbon, it reduces to the double bond of cinnamon backbone.
이상 기술한 바와 같이, 니트로화물의 환원조건을 적정화하는 것은 매우 곤란하다고 하는 문제가 있고, 계피산 골격을 가지는 아민은, 단리된 것은 거의 존재하지 않았다. As described above, there is a problem that it is very difficult to optimize the reduction conditions of the nitride, and almost no amine having a cinnamic acid skeleton has been isolated.
본 발명은, 상기 문제를 해결하여, 생성이 불가능하였던 계피산 혹은 계피산 유도체 골격을 가지는 신규의 아민을 얻기 위해서, 니트로화물의 환원조건을 최적으로 하는 제조방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a production method for optimizing the reduction conditions of nitrides in order to solve the above problems and to obtain a novel amine having a cinnamic acid or cinnamic acid derivative skeleton which cannot be produced.
본 발명의 목적은, 계피산 혹은 계피산 유도체를 가지는 신규 폴리이미드화합물을 얻기 위한 신규 디아민 또는 신규 산이무수물을 제공하는 데에 있다. An object of the present invention is to provide a novel diamine or a novel acid dianhydride for obtaining a novel polyimide compound having a cinnamic acid or a cinnamic acid derivative.
본 발명의 다른 목적은, 계피산 혹은, 계피산 유도체를 가지는 신규 디아민 또는 신규산이무수물로부터 신규의 폴리이미드화합물을 제공하는 데에 있다. Another object of the present invention is to provide a novel polyimide compound from cinnamic acid or a novel diamine or a novel acid dianhydride having a cinnamic acid derivative.
본 발명의 다른 목적은, 계피산 혹은, 계피산 유도체를 가지는 신규 디아민의 제조방법을 제공하는 데에 있다. Another object of the present invention is to provide a method for producing a novel diamine having cinnamic acid or a cinnamic acid derivative.
[발명의 개시][Initiation of invention]
그래서, 본 발명자 등은, 광감광성 및 광반응성을 함께 가지는 신규의 계피산 또는 계피산 골격을 가지는 폴리이미드화합물을 얻기 위해 예의 검토를 거듭한 결과, 본 발명에 이르렀다. Therefore, the present inventors have earnestly studied to obtain a novel cinnamic acid or a polyimide compound having a cinnamic acid skeleton having both photosensitive and photoreactive properties.
본 발명의 신규의 폴리이미드화합물은, 주쇄(主鎖) 또는 측쇄에 계피산 골격을 함유한다. The novel polyimide compound of this invention contains a cinnamic acid skeleton in a main chain or a side chain.
본 발명의 신규 폴리이미드화합물은, 일반식(1)The novel polyimide compound of the present invention is represented by the general formula (1)
(단, X1은 4가의 유기기, W1은 식1-a, 1-b, 1-c, 1-d, 1-e, 1-f
(Wherein X 1 is a tetravalent organic group, W 1 is a formula 1-a, 1-b, 1-c, 1-d, 1-e, 1-f)
삭제delete
(식중, R1은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R2는 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R3은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R4, R5는 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R6, R7은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R8은 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타내고, p=1~3, q=1~3을 나타낸다)
(Wherein R 1 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O—)
(Wherein R 2 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 3 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 4 , R 5 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 6 , R 7 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 8 represents a trivalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O— and represents p = 1 to 3 and q = 1 to 3)
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로 나타내는 군으로부터 선택되는 2가의 유기기)를 1중량% 이상 함유한다. Divalent organic group selected from the group represented by 1% or more.
본 발명의 신규 폴리이미드화합물은, 상기 일반식(1)중의 X1이, 방향족환을 1∼3개 가지거나, 지환식인 1종 또는 2종 이상의 4가의 유기기이다. In the novel polyimide compound of the present invention, X 1 in General Formula (1) has one to three aromatic rings, or one or two or more tetravalent organic groups which are alicyclic.
본 발명의 신규 폴리이미드화합물은, 일반식(1-a)의 V는, H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타내고, R1이, In the novel polyimide compound of the present invention, V in general formula (1-a) represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-, and R 1 is
(단, V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다.
(Where, V is, H, CH 3, F, represents a Cl, Br, CH 3 O-. ) Is a divalent organic group selected from.
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본 발명의 신규 폴리이미드화합물은, 일반식(1-b)의 V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타내고, R2는,In the novel polyimide compound of the present invention, V in general formula (1-b) represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-, and R 2 is
(단, w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. Is a divalent organic group selected from (where, w = integer of 1~40, V is H, CH 3, F, Cl , Br, CH 3 shows an O-.).
본 발명의 신규 폴리이미드화합물은, 일반식(1-c)중 V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다. R3은, -CH2-, -(CH2)m-O-, -(CH2)n-OCO-, 단 m=1∼15, n=1∼15에서 선택된다. In the novel polyimide compound of the present invention, V in General Formula (1-c) represents H, CH 3 , F, Cl, Br, CH 3 O-. R 3 is selected from -CH 2 -,-(CH 2 ) m -O-,-(CH 2 ) n -OCO-, provided that m = 1-15 and n = 1-15.
본 발명의 신규 폴리이미드화합물은, 일반식(1-d)중의 R4, R5가, As for the novel polyimide compound of the present invention, R 4 and R 5 in General Formula (1-d) are
(단, R4, R5는 동일하여도 좋고 달라도 좋다. w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. (However, R 4 and R 5 may be the same or different. An integer of w = 1 to 40, and V represents H, CH 3 , F, Cl, Br, CH 3 O—.) It is an organic group.
본 발명의 신규 폴리이미드화합물은, 일반식(1-e)중, V는, CH3, F, Cl, Br, CH3O-를 나타낸다. R6, R7이, In the novel polyimide compound of the present invention, V represents CH 3 , F, Cl, Br, CH 3 O— in General Formula (1-e). R 6 , R 7 is
(단, R6, R7은 동일하여도 좋고 달라도 좋다. w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. (However, R 6 and R 7 may be the same or different. An integer of w = 1 to 40 and V represents H, CH 3 , F, Cl, Br, and CH 3 O—.) It is an organic group.
본 발명의 신규 폴리이미드화합물은, 일반식 (1-f)중, V는 H, CH3, F, Cl, Br, CH3O-, p=1∼3, q=1∼3을 나타낸다.) Y가, In the novel polyimide compound of the present invention, V represents H, CH 3 , F, Cl, Br, CH 3 O−, p = 1 to 3, q = 1 to 3 in General Formula (1-f). ) Y is
(식 중, V는 H, CH3, F, Cl, Br, CH3O-, r=1∼3, n=1∼20, w는 -CH2-, -(CH2)m-O-, -(CH2)k-OCO-, 단 m=1∼15, k=1∼20(k≠2)로부터 선택되는 2가의 유기기를 나타낸다.)로부터 선택되는 3가의 유기기이다. Wherein V is H, CH 3 , F, Cl, Br, CH 3 O-, r = 1 to 3, n = 1 to 20, w is -CH 2 -,-(CH 2 ) m -O- ,-(CH 2 ) k -OCO-, provided that m is 1 to 15 and k is 1 to 20 (which represents a divalent organic group selected from k ≠ 2).
본 발명의 신규폴리이미드화합물은, 일반식(2)The novel polyimide compound of the present invention is represented by the general formula (2)
(식 중, X2가 식 2-a, 2-b(Wherein X 2 is a formula 2-a, 2-b
W2는, 2가의 유기기를 나타낸다. 식 중 R10 및 R11은, 2가의 유기기, R12는 3가의 유기기, V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)를 1중량%이상 함유한다. W 2 represents a divalent organic group. Wherein R 10 and R 11 represent a divalent organic group, R 12 represents a trivalent organic group, and V represents H, CH 3 , F, Cl, Br, and CH 3 O-. do.
본 발명의 신규 폴리이미드화합물은, 상기 식 (2-a)중, R10이 -COO-, -OCO-, -O-, -O-R13-O-, -COO-R13-OCO-, -O-R13-OCO-, -O-R13-COO-, -OOCCH=CH- (단, R13은, -CmH2m-, 벤젠환, 나프탈렌환, 비페닐을, m은 1∼20의 정수를 나타낸다.)중에서 선택되는 2가의 유기기로 나타내어진다. In the novel polyimide compound of the present invention, in formula (2-a), R 10 is -COO-, -OCO-, -O-, -OR 13 -O-, -COO-R 13 -OCO-,- OR 13 -OCO-, -OR 13 -COO-, -OOCCH = CH- ( However, R 13 is, -C m H 2m -, the benzene ring, a naphthalene ring, a biphenyl, m is an integer of 1 to 20 It is represented by the bivalent organic group chosen from.
본 발명의 신규 폴리이미드화합물은, 상기 식 (2-a)중, R11이, -, -R14-OCO-, -R14-O- (단, R14는, -CmH2m-, 벤젠환, 나프탈렌환을, m은 1∼20의 정수를 나타낸다.)중에서 선택되는 2가의 유기기로 나타내어진다. New polyimide compound of the present invention, of the formula (2-a), R 11 a, -, -R 14 -OCO-, -R 14 -O- ( However, R 14 is, -C m H 2m - , Benzene ring and naphthalene ring are represented by a divalent organic group selected from m).
본 발명의 신규 폴리이미드화합물은, 상기 식 (2-b) 중, R12는, 3가의 유기기, V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내어진다. In the novel polyimide compound of the present invention, in formula (2-b), R 12 represents a trivalent organic group, and V represents H, CH 3 , F, Cl, Br, and CH 3 O-. Is represented.
본 발명의 신규 폴리이미드화합물은, 상기 식 (2-b)중, R12가,As for the novel polyimide compound of the present invention, in formula (2-b), R 12 is
(단, R15는, CnH2n-1, 벤젠환, 나프탈렌환, 비페닐을, n은 1∼20의 정수를 나타낸다.)로 나타내어진다.Is represented by (where, R 15 is a benzene ring, naphthalene ring, biphenyl, C n H 2n-1, n is an integer of 1 to 20.).
본 발명의 신규 디아민은, 일반식 (3)The novel diamine of this invention is general formula (3)
으로 나타내는 디아민으로서, V는 H, CH3, F, Cl, Br, CH3O-를 나타내고, R1이, As the diamine represented by: V represents H, CH 3 , F, Cl, Br, CH 3 O-, R 1 is,
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. (However, V represents H, CH 3 , F, Cl, Br, CH 3 O-.) It is a divalent organic group selected from.
본 발명의 신규 디아민은, 일반식 (4)The novel diamine of this invention is general formula (4)
로 나타내는 디아민으로서, V는 H, CH3, F, Cl, Br, CH3O-를 나타내고, R2가, As the diamine represented by: V represents H, CH 3 , F, Cl, Br, CH 3 O-, R 2 is,
(단, w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. (Where, w = integer of 1~40, V is H, CH 3, F, Cl, Br, CH 3 O-.) Is a divalent organic group selected from.
본 발명의 신규 디아민은, 일반식 (5)The novel diamine of this invention is general formula (5)
로 나타내는 디아민으로서, V는, H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타내고, R3은, -CH2-, -(CH2)m-O-, -(CH2)n-OCO-, 단 m=1∼15, n=1∼15로부터 선택되는 2가의 유기기이다. As the diamine represented by V, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-, and R 3 represents -CH 2 -,-(CH 2 ) m -O-, -(CH 2 ) n -OCO-, provided that m = 1 to 15 and n = 1 to 15 are divalent organic groups.
본 발명의 신규 디아민은, 일반식 (6)The novel diamine of this invention is general formula (6)
으로 나타내는 디아민으로서, R4, R5가,As the diamine represented by R 4 , R 5 is
(단, R4와 R5는 동일하여도 좋고 달라도 좋다. w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. (However, R 4 and R 5 may be the same or different. An integer of w = 1 to 40, and V represents H, CH 3 , F, Cl, Br, CH 3 O—.) It is an organic group.
본 발명의 신규 디아민은, 일반식 (7) The novel diamine of this invention is general formula (7)
로 나타내는 디아민으로서, R6, R7이, As the diamine represented by R 6 , R 7 is
(단, R6과 R7은 동일하여도 좋고 달라도 좋다. w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기이다. (However, R 6 and R 7 may be the same or different. An integer of w = 1 to 40, and V represents H, CH 3 , F, Cl, Br, CH 3 O—.) It is an organic group.
본 발명의 신규 디아민은, 일반식 (8) The novel diamine of this invention is general formula (8)
(식 중 V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 디아민으로서, R8이, As a diamine represented by the formula (wherein V is, H, CH 3, F, Cl, Br, CH 3 shows an O-.), A R 8,
삭제delete
(식 중, V는 H, CH3, F, Cl, Br, CH3O-를 나타내고, r=1~3, n=1~20, R9는, -CH2-, -(CH2)m-O-, -(CH2)k-OCO-, (단, m=1∼15, k=1∼20(k≠2))로부터 선택되는 2가의 유기기를 나타낸다.)로부터 선택되는 3가의 유기기이다.(Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—, and r = 1 to 3, n = 1 to 20, and R 9 represents —CH 2 —, — (CH 2 )). trivalent selected from m -O-,-(CH 2 ) k -OCO-, (but divalent organic group selected from m = 1-15, k = 1-20 (k ≠ 2)). It is an organic group.
본 발명의 신규 산이무수물은, 구조가 하기 일반식(9)The novel acid dianhydride of the present invention has a structure represented by the following general formula (9)
로 나타내는 산이무수물로서,As acid dianhydride represented by
(식 중 R10 및 R11은, 2가의 유기기, V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)(R 10 and R 11 in the formula is a divalent organic group, V is, H, CH 3, F, represents a Cl, Br, CH 3 O-.)
로 나타내어진다. It is represented by
본 발명의 신규 산이무수물은, 상기 일반식 (9)중, R10이 -COO-, -OCO-, -O-, -O-R13-O-, -COO-R13-OCO-, -O-R13-OCO-, -O-R13-COO-, -OOCCH=CH- (단, R13은, -CmH2m-, 벤젠환, 나프탈렌환, 비페닐을, m은 1∼20의 정수를 나타낸다.)중에서 선택되는 2가의 유기기로 나타내어진다. In the novel acid dianhydride of the present invention, R 10 is -COO-, -OCO-, -O-, -OR 13 -O-, -COO-R 13 -OCO-, -OR 13 in the general formula (9). -OCO-, -OR 13 -COO-, -OOCCH = CH- ( However, R 13 is, -C m H 2m -, benzene ring, naphthalene ring, biphenyl, m represents an integer of 1 to 20. It is represented by the divalent organic group chosen from.
본 발명의 신규 산이무수물은, 상기 산이무수물의 일반식 (9)중, R11이, -, -R14-OCO-, -R14-O- (단, R14는, -CmH2m-, 벤젠환, 나프탈렌환을, m은 1∼20의 정수를 나타낸다.)중에서 선택되는 2가의 유기기로 나타내어진다. Of these novel acid anhydride of the present invention is represented by the general formula (9) of the acid anhydride, R 11, -, -R 14 -OCO-, -R 14 -O- ( However, R 14 is, -C m H 2m -A benzene ring and a naphthalene ring are represented by the bivalent organic group chosen from m).
본 발명의 신규 산이무수물은, 일반식 (10)The novel acid dianhydride of the present invention is represented by the general formula (10).
으로 나타내는 산이무수물로서, 식 중, R12는 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내어진다. In the formula, R 12 represents a trivalent organic group, and V represents H, CH 3 , F, Cl, Br, and CH 3 O-.
본 발명의 신규 산이무수물은, 일반식 (10)중, R12가The novel acid dianhydride of the present invention, R 12 in General Formula (10)
(단, R15는, CnH2n-1, 벤젠환, 나프탈렌환, 비페닐을, n은 1∼20의 정수를 나타낸다.)로 나타내어진다.Is represented by (where, R 15 is a benzene ring, naphthalene ring, biphenyl, C n H 2n-1, n is an integer of 1 to 20.).
본 발명의 방향족아민의 제조방법은, Pt-카본블랙을 촉매로 하는 수소환원에 의한다. The manufacturing method of the aromatic amine of this invention is based on the hydrogen reduction which uses Pt-carbon black as a catalyst.
또한, 본 발명의 방향족아민의 제조방법은, Fe, Na, Cu, Ni의 어느 하나로부터 선택되는 금속에 의해 니트로기에의 선택적 활성을 높인 Pt-활성탄을 촉매로 하는 수소환원에 의한다.Moreover, the manufacturing method of the aromatic amine of this invention is based on the hydrogen reduction which uses Pt-activated carbon as a catalyst which raised the selective activity to nitro group by the metal chosen from any one of Fe, Na, Cu, and Ni.
[발명을 실시하기 위한 최량의 형태]Best Mode for Carrying Out the Invention
본 발명에 따른 신규의 폴리이미드화합물은, 계피산 혹은 계피유도체골격을 가지며, 계피산 골격 특유의 광반응성 및 열반응성을 함께 가지는 신규 폴리이미드화합물인 것을 특징으로 한다. 또한, 본 발명의 신규 디아민 및 산이무수물은, 주로 상기 계피산골격을 가지는 신규폴리이미드화합물을 제조하는 데 사용하는 재료이며, 주쇄 또는 측쇄에 계피산 골격 또는 계피산 유도체 골격을 가지는 디아민 및 산이무수물이다. The novel polyimide compound according to the present invention is characterized by being a novel polyimide compound having cinnamic acid or cinnamon derivative skeleton and having both photoreactivity and thermal reactivity unique to the cinnamic acid skeleton. In addition, the novel diamine and acid dianhydride of the present invention are materials mainly used to produce a novel polyimide compound having the cinnamic acid skeleton, and are diamines and acid dianhydrides having a cinnamic acid skeleton or a cinnamic acid derivative skeleton in the main chain or side chain.
본 발명에 따른 신규 폴리이미드화합물에 대하여, 구체적인 구조를 들어 실시형태의 일례에 대하여 설명하는데, 계피산 골격을 가지는 폴리이미드화합물이면 특별히 구조는 규정되지 않는다. The novel polyimide compound according to the present invention will be described with reference to a specific structure and an example of the embodiment. However, the structure is not particularly defined as long as it is a polyimide compound having a cinnamic acid skeleton.
본 발명에 따른 폴리이미드화합물은, 주쇄 또는 측쇄에 계피산 골격을 가지는 폴리이미드화합물이면 특히 구조는 규정되지 않지만, 이하에 예를 든다. If the polyimide compound which concerns on this invention is a polyimide compound which has a cinnamic acid skeleton in a principal chain or a side chain in particular, a structure will not be defined, but it gives an example below.
디아민잔기에 계피산골격을 가지는 폴리이미드화합물은, 일반식(1)The polyimide compound having cinnamic acid skeleton in the diamine residue is represented by the general formula (1).
(단, X1은 4가의 유기기, W1은 식1-a, 1-b, 1-c, 1-d, 1-e, 1-f
(식중, R1은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R2는 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R3은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R4, R5는 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R6, R7은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타낸다)
(식중, R8은 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-로부터 선택되는 하나의 기를 나타내고, p=1~3, q=1~3을 나타낸다)
(Wherein X 1 is a tetravalent organic group, W 1 is a formula 1-a, 1-b, 1-c, 1-d, 1-e, 1-f)
(Wherein R 1 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O—)
(Wherein R 2 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 3 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 4 , R 5 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 6 , R 7 represents a divalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O-)
(Wherein R 8 represents a trivalent organic group, V represents one group selected from H, CH 3 , F, Cl, Br, CH 3 O— and represents p = 1 to 3 and q = 1 to 3)
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로 나타내는 군으로부터 선택되는 2가의 유기기)를 1중량% 이상 함유한다. Divalent organic group selected from the group represented by 1% or more.
또한, 산이수물잔기에 계피산골격을 가지는 폴리이미드화합물은, 일반식 (2)
(식 중, X2가 식 2-a, 2-b
(Wherein X 2 is a formula 2-a, 2-b
(R10 및 R11은, 2가의 유기기, R12는 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 표시되는 4가의 유기기이고, W2는 2가의 유기기를 나타낸다.)를 1중량%이상 함유한다.(R 10 and R 11 is a divalent organic group, R 12 is a trivalent organic group, V is H, CH 3, F, Cl, Br, CH 3 shows an O-.) 4-valent organic group represented by a , W 2 represents a divalent organic group.).
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이하, 본 발명의 계피산 골격을 가지는 폴리이미드화합물에 대하여, 제조방법과 함께 설명한다. Hereinafter, the polyimide compound which has the cinnamic acid skeleton of this invention is demonstrated with a manufacturing method.
디아민잔기에 계피산 골격을 가지는 폴리이미드를 제조하는 방법으로서, ① 계피산 골격을 가지는 디아민을 미리 합성하고, 임의의 산이무수물과 반응시켜 폴리아미드산으로 한 후에, 탈수폐환하여 폴리이미드로 하는 방법, ② 디올 말단으로 한 폴리이미드의 올리고머와 계피산 골격을 함유하는 디카르복실산 혹은 디산클로라이드와 반응시켜, 에스테르결합을 생성하여 고분자량화하여 폴리이미드화합물을 얻는 방법 등이 있다. A method for producing a polyimide having a cinnamic acid skeleton in the diamine residue, which comprises: (1) Synthesis of a diamine having a cinnamic acid skeleton in advance, reacting with an acid dianhydride to form a polyamic acid, and then dehydrating and closing the polyimide; And a method of obtaining a polyimide compound by reacting with an oligomer of a polyimide having a diol end and a dicarboxylic acid or diacid chloride containing a cinnamic acid skeleton to form an ester bond to obtain a high molecular weight.
제일 먼저, ① 계피산 골격을 가지는 디아민을 거치는 폴리이미드화합물의 제조방법을 설명한다. First, a method for producing a polyimide compound that passes through a diamine having a cinnamic acid skeleton will be described.
일반식 (1) 중, W1이, 식 (1-a)로 나타내는 신규 폴리이미드화합물In the general formula (1), W 1 represents a novel polyimide compound represented by formula (1-a).
을 예로 들어, 본 발명에 따른 신규 폴리이미드화합물의 구체적인 제조방법에 대하여 설명한다. As an example, a specific method for producing a novel polyimide compound according to the present invention will be described.
일반식 (1) 중, W1가, 식 (1-a)의 신규 폴리이미드화합물의 원료로서 사용되는 디아민은 일반식(3)In general formula (1), diamine used as a raw material of the novel polyimide compound of W <1> Formula (1-a) is General formula (3).
(단, V는 H, CH3, F, Cl, Br, CH3O-를, R1은 2가의 유기기를 나타낸다.)이다. (Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—, and R 1 represents a divalent organic group).
이 디아민은, 계피산 유도체 또는, 계피산클로라이드 유도체와, 수산기를 가지는 니트로화합물을 반응시킨 디니트로화합물을, 환원하여 얻을 수 있다. This diamine can be obtained by reducing a cinnamic acid derivative or a dinitro compound obtained by reacting a cinnamic acid chloride derivative with a nitro compound having a hydroxyl group.
구체적으로는, 계피산 유도체는, 일반식 (1-2)Specifically, the cinnamic acid derivative is a general formula (1-2)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)(V denotes H, CH 3 , F, Cl, Br, CH 3 O-.)
로 나타내어지고, 계피산클로라이드 유도체는, 일반식 (1-3)The cinnamic acid chloride derivative is represented by the general formula (1-3)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타낸다. (Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—).
수산기를 가지는 니트로화합물은, 일반식 (1-4)The nitro compound which has a hydroxyl group is a general formula (1-4)
(단, R1은 2가의 유기기를 나타낸다.)로 나타낸다. (Wherein R 1 represents a divalent organic group).
이들을 반응시켜, 일반식 (1-5) By reacting these, General Formula (1-5)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 디니트로화합물을 얻는다. A dinitro compound represented by (wherein V represents H, CH 3 , F, Cl, Br, and CH 3 O—) is obtained.
일반식 (1-4) 및 일반식 (1-5)중의 R1은, 2가의 유기기이면 특히 한정되지 않지만, Although R <1> in general formula (1-4) and general formula (1-5) is a bivalent organic group, it will not specifically limit,
등을 예시할 수 있다. Etc. can be illustrated.
다음에, 상기 디니트로화합물을 환원하는 조건에 대하여 설명한다. Next, the conditions for reducing the dinitro compound will be described.
일반적으로, 방향족 니트로화물을 방향족아민으로 환원하는 방법으로서, 1) 금속 혹은 금속염에 의해 환원하는 방법, 2) 히드라진에 의한 환원, 3) Pd-활성탄을 촉매로 하는 수소에 의한 환원 등이 있고, 이들 환원방법은, 기본적으로는 본 발명에 따른 방향족아민을 제조하기 위해 사용할 수 있는 환원방법이다. Generally, as a method of reducing aromatic nitrides to aromatic amines, there are 1) a method of reducing by metal or metal salt, 2) reduction by hydrazine, 3) reduction by hydrogen using Pd-activated carbon as a catalyst, These reduction methods are basically reduction methods that can be used for producing the aromatic amine according to the present invention.
그러나, 본 발명에 사용하는 방향족 니트로화합물은, 계피산 골격의 2중 결합을 갖고 있기 때문에, 심한 환원조건을 선택하면, 2중 결합도 환원되어 버린다. 또한, 강한 산성 하에서 행하면 에스테르결합의 분해가 생길 가능성이 있고, 알카리성 하에서는, Michae1부가를 일으킬 가능성이 있다. 이 때문에, 환원조건을 적정화할 필요가 있다. However, since the aromatic nitro compound used in the present invention has a double bond of the cinnamic acid skeleton, the double bond is also reduced when severe reducing conditions are selected. Moreover, if it is performed under strong acidity, there exists a possibility that decomposition | disassembly of an ester bond may occur, and there exists a possibility of generating Michae 1 addition under alkaline property. For this reason, it is necessary to optimize reduction conditions.
본 발명에서는, 이 디니트로화물을 Bechamp환원 혹은, Pt-카본 블랙 촉매 또는, 철 등으로 선택성을 높인 Pt-활성탄 촉매를 사용한 수소환원에 의해, 일반식 (3)In the present invention, the dinitrode is converted to a general formula (3) by a Bechamp reduction or a hydrogen reduction using a Pt-carbon black catalyst or a Pt-activated carbon catalyst having high selectivity with iron or the like.
(단, R1은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)를 고수율로 얻을 수 있다. (However, R 1 is a divalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O-) can be obtained in high yield.
여기서, 본 발명에서 말하는 「Pt-활성탄」이란, 백금을 활성탄에 담지시킨 촉매이고, 「Pt-카본블랙」이란, 백금을 카본블랙에 담지시킨 촉매인 것이다. Here, "Pt-activated carbon" as used in the present invention is a catalyst in which platinum is supported on activated carbon, and "Pt-carbon black" is a catalyst in which platinum is supported on carbon black.
상기 디니트로화합물의 환원에 적합한 환원방법에 있어서, 활성탄, 보다 효과적으로는, 카본블랙을 담지체로서 사용한 Pt를 환원촉매로 하는 것이 특히 적합하다. 발명자들은, Pt-카본블랙 촉매 또는 선택성을 높인 Pt-활성탄 촉매를 사용하고, 계피산 골격을 가지는 니트로화물을 유기용매 중 수소환원하면, 비약적으로 니트로기의 선택성이 높아지는 것을 새로이 발견하였다. 본 발명자들은, 이 환원촉매를 사용하여, 니트로화물로부터 매우 높은 수율로 원하는 신규의 계피산 골격을 가지는 아민을 얻는 데에 성공하였다. In the reduction method suitable for the reduction of the dinitro compound, it is particularly suitable to use activated carbon, more effectively Pt using carbon black as a support catalyst as the reduction catalyst. The inventors have newly discovered that the nitro group selectivity is remarkably increased by hydrogen reduction of a nitride having a cinnamic acid skeleton in an organic solvent using a Pt-carbon black catalyst or a Pt-activated carbon catalyst having high selectivity. The present inventors have succeeded in obtaining an amine having the desired novel cinnamic acid skeleton in a very high yield from the nitride using this reduction catalyst.
Pt-카본블랙계의 촉매는, 본 환원계에 있어서는, 2중 결합을 거의 환원하지 않고, 니트로기를 우선적으로 환원하기 때문에, 고수율로 원하는 디아민을 얻을 수 있기 때문에 바람직하다. Pt-카본블랙 속에, Fe, Na, Cu, Ni 등의 금속을 혼입시킨 촉매에 있어서는, 니트로기에의 선택적인 반응에 있어서도 마찬가지의 양호한 결과를 얻을 수 있다. 특히, Fe가 선택성에서 뛰어나 바람직하다. The Pt-carbon black catalyst is preferable because in the present reduction system, since the nitro group is preferentially reduced without almost reducing the double bond, the desired diamine can be obtained in high yield. In the catalyst in which metals, such as Fe, Na, Cu, and Ni, are mixed in Pt-carbon black, the same favorable result can be obtained also in the selective reaction to nitro group. In particular, Fe is preferred because it is excellent in selectivity.
또한, 담지체는, 카본블랙에 비교하여 선택성은 약간 뒤떨어지지만, 활성탄이어도 좋다. 이 경우, 상기 Fe나 Na 등을 혼입시킨 Pt-활성탄계의 촉매에 있어서는, 니트로기에의 선택적인 반응에 있어서 더욱 양호한 결과를 얻을 수 있으므로 바람직하다. The carrier may be slightly inferior in selectivity to carbon black, but may be activated carbon. In this case, in the Pt-activated carbon-based catalyst in which Fe or Na and the like are mixed, a better result can be obtained in the selective reaction to nitro groups.
또한, 환원방법의 다른 방법에 있어서, Pd-활성탄계의 촉매도 사용할 수 있다. 이 Pd-활성탄계의 환원촉매로는, 반응활성이 강하게 계피산 골격의 탄소-탄소 2중 결합을 환원하여 버리기 때문에, 유황, 이산화황, 일산화탄소 등의 독물질을 함유시킴으로써, 니트로기에의 선택적인 반응선택성을 획득시키면, 본 발명에 따른 신규 디아민을 생성하는 것이 가능하다. 여기서, 「독물질」이란, 촉매의 활성사이트에 불가역 흡착하여 촉매의 기능을 실활(失活)하는 물질을 말한다. In addition, in another method of the reduction method, a catalyst based on Pd-activated carbon may also be used. As the Pd-activated carbon-based reducing catalyst, since the reaction activity is strongly reduced, the carbon-carbon double bond of the cinnamic acid skeleton is reduced, so that it contains a poisonous substance such as sulfur, sulfur dioxide and carbon monoxide, thereby selectively reacting to nitro group. By obtaining it is possible to produce novel diamines according to the invention. Herein, the "toxic material" refers to a substance which irreversibly adsorbs to the active site of the catalyst and deactivates the function of the catalyst.
수소를 첨가하는 방법으로서는, 예를 들면, 유기용매 중에 수소를 직접 흡입시키는 방법, 대기압 하의 수소분위기 하에서 반응시키는 방법, 고압솥(autoclave)등의 내압반응용기 중에 수소를 봉입하고 가압 하에서 반응시키는 방법 등을 생각할 수 있다. As a method of adding hydrogen, for example, a method of directly sucking hydrogen in an organic solvent, a method of reacting under a hydrogen atmosphere at atmospheric pressure, a method of enclosing hydrogen in a pressure-resistant reaction vessel such as an autoclave and reacting under pressure And so on.
반응온도는, 통상 실온에서 120도 정도로 행하는 것이 바람직하다. 180도 이상의 고온에서는, 계피산의 2중 결합이 분해할 우려가 있기 때문에, 180도 미만에서 반응을 행하는 것이 필요하다. 실온이하에서도 반응은 진행하지만, 반응시간이 길어지기 때문에, 공업적으로는 바람직하지 않다. It is preferable to perform reaction temperature at about 120 degreeC normally. Since the double bond of cinnamic acid may decompose at the high temperature of 180 degree or more, it is necessary to react at less than 180 degree | times. Although reaction advances even below room temperature, since reaction time becomes long, it is not industrially preferable.
Pt-카본블랙 또는 활성탄계의 촉매에 있어서, 촉매중의 백금농도는, 중량%로 0.1∼40% 정도이며, 0.1% 이상 함유되어 있으면 촉매의 효과가 발현된다. 백금농도가 높을수록 반응속도가 향상하는 경향이 있는데, 귀금속이기 때문에, 1∼20% 정도의 백금농도의 촉매를 사용하는 것이 바람직하다. Pt-카본블랙 또는 활성탄계 촉매는, 건조한 상태로 사용하여도, 물을 가하여 물을 함유한 상태로 사용하여도 효과는 동일하다. 물을 함유한 상태 쪽이 분진이 날아오르지 않고, 취급성이 좋기 때문에, 공업적으로는 바람직하다. In a Pt-carbon black or activated carbon catalyst, the platinum concentration in the catalyst is about 0.1 to 40% by weight, and when contained in 0.1% or more, the effect of the catalyst is expressed. The higher the platinum concentration, the more the reaction rate tends to be improved. Since it is a noble metal, it is preferable to use a catalyst having a platinum concentration of about 1 to 20%. Pt-carbon black or activated carbon-based catalysts have the same effect even when used in a dry state or in a state in which water is added to water. In the state containing water, since dust does not fly and handling property is good, it is industrially preferable.
환원에 사용되는 용매로서는, 반응을 저해하지 않고, 디아민이나 디니트로화물을 용해하는 것이면 특히 한정되지 않는데, 예를 들어, 알콜류, 디옥산, 톨루엔이나 크실렌등 방향족계 용매, 디메틸술폭시드, 디에틸술폭시드 등의 술폭시드계 용매, N,N-디메틸포름아미드, N,N-디에틸포름아미드등의 포름아미드계 용매, N, N-디메틸아세트아미드, N, N-디에틸아세트아미드 등의 아세트아미드계 용매, N-메틸-2-피롤리돈, N-비닐-2-피롤리돈 등의 피롤리돈계 용매, 페놀, o-, m-, 또는 p-크레졸, 크실렌올, 할로겐화페놀, 카테콜 등의 페놀계 용매, 혹은 헥사메틸포스폴아미드, 
또한, 상기 디니트로화합물의 환원에 적합한 환원방법의 하나로서 Bechamp 환원방법도 사용된다. 이것은, 용매 속에서, 디니트로화물을 Fe분말을 가하고, 130℃ 이하의 온도로 가열함으로써 환원하는 방법이다. 용매로서는, 상기에 나타낸 용매를 사용할 수 있으나, 특히 초산이나 알콜류, 디옥산 등이 바람직하다. In addition, the Bechamp reduction method is also used as one of the reduction methods suitable for the reduction of the dinitro compound. This is a method of reducing dinitrode by adding Fe powder and heating to a temperature of 130 ° C or lower in a solvent. As a solvent, the solvent shown above can be used, but acetic acid, alcohols, dioxane, etc. are especially preferable.
이상 서술한 바와 같은 방법에 의해, 얻어지는 신규의 계피산 골격을 가지는 아민은, 니트로기에의 선택적 활성이 높은 환원촉매를 사용함으로써 매우 높은 수율로 얻을 수 있다. 본 발명에 의한 신규의 아민은 계피산 골격을 가지기 때문에, 아민을 원료로 하는 폴리아미드나 폴리이미드 등의 뛰어난 특성을 가지는 폴리머에, 계피산 골격을 도입하는 것을 가능하게 하고, 이들 폴리머의 열경화성수지, 감광성수지에의 용도를 크게 넓힐 수 있다. 또한, 고수율 고순도를 위해 분리정제의 공정을 생략하는 것도 가능하다. 따라서, 아민 제조공정으로부터 직접 폴리이미드, 폴리아미드제조공정에의 이행을 가능하게 하고, 경제적으로 매우 유용하다. By the method as mentioned above, the amine which has the novel cinnamic-acid skeleton obtained can be obtained by a very high yield by using a reduction catalyst with high selective activity to a nitro group. Since the new amine according to the present invention has a cinnamic acid skeleton, it is possible to introduce the cinnamic acid skeleton into a polymer having excellent properties such as polyamide and polyimide based on amines, and the thermosetting resin and photosensitive properties of these polymers. The use to resin can be greatly extended. It is also possible to omit the step of separation and purification for high yield and high purity. Therefore, it is possible to make the transition from the amine manufacturing process directly to the polyimide and polyamide manufacturing process, and it is very economically useful.
다음으로 상기 얻어진 디아민을 사용하여 일반식 (1)에서 나타내는 폴리이미드를 합성하는 방법을 서술한다. Next, the method of synthesizing the polyimide represented by General formula (1) using the obtained diamine is described.
상기 얻어진 일반식 (3)으로 나타내는 디아민 및 다른 디아민과 산이무수물을 유기극성용매 속에서 반응시켜 폴리아미드산으로 한다. The diamine represented by General formula (3) obtained above, and other diamines and acid dianhydrides are reacted in an organic polar solvent to obtain a polyamic acid.
이 폴리아미드산의 생성반응에 사용되는 유기극성용매로서는, 예를 들어, 디메틸술폭시드, 디에틸술폭시드 등의 술폭시드계 용매, N,N-디메틸포름아미드, N,N-디에틸포름아미드 등의 포름아미드계 용매, N,N-디메틸아세트아미드, N,N-디에틸아세트아미드 등의 아세트아미드계 용매, N-메틸-2-피롤리돈, N-피닐-2-피롤리돈 등의 피롤리돈계 용매, 페놀, o-, m-, 또는 p-크레졸, 크실렌올, 할로겐화페놀, 카테 콜 등의 페놀계 용매, 혹은 헥사메틸포스폴아미드, 
본 발명에 있어서 사용되는 산이무수물은, 산이무수물이라면 특히 한정되지 않지만, 예를 들어 부탄테트라카르복실산이무수물, 1,2,3,4-시클로부탄테트라카르복실산이무수물, 1,3-디메틸-1,2,3,4-시클로부탄테트라카르복실산, 1,2,3,4-시클로펜탄테트라-카르복실산이무수물, 2,3,5-트리카르복시시클로펜틸초산이무수물, 3,5,6-트리카르복시노르보난-2-초산이무수물, 2,3,4,5-테트라히드로프란테트라카르복실산이무수물, 5-(2,5-디옥시테트라히드로프랄)-3-메틸-3-시클로헥센-1,2-디카르복실산이무수물, 비시클로[2,2,2]-옥토-7-엔-2,3,5,6-테트라카르복실산이무수물 등의 지방족 또는 지환식테트라-카르복실산이무수물; 피로멜리트산, 이무수물, 3, 3', 4, 4'-벤조페논테트라카르복실산이무수물, 3, 3', 4, 4'-비페닐술폰테트라카르복실산이무수물, 1,4,5,8-나프탈렌테트라카르복실산이무수물, 2,3,6,7-나프탈렌 테트라카르복실산이무수물, 3,3',4,4'-비페닐에테르테트라카르복실산이무수물, 3,3',4,4'-디메틸디페닐실란테트라카르복실산이무수물, 3,3',4,4'-테트라페닐실란테트라카르복실산이무수물, 1,2,3,4-프란테트라카르복실산이무수물, 4,4'-비스(3, 4-디카르복시페녹시)디페닐술피드이무수물, 4,4'-비스(3,4-디카르복시페녹시)디페닐술폰이무수물, 4,4'-비스(3,4-디카르복시페녹시)디페닐프로판이무수물, 3,3',4, 4'-퍼플루오로이소프로필리덴디프탈산이무수물, 3,3',4,4'-비페닐테트라카르복실산이무수물, 비스(프탈산)페닐포스핀옥사이드이무수물, p-페닐렌-비스(트리페닐프탈 산)이무수물, m-페닐렌-비스(트리페닐프탈산)이무수물, 비스(트리페닐프탈산)-4, 4'-디페닐에테르이무수물, 비스(트리페닐프탈산)-4,4'-디페닐메탄이무수물 등의 방향족테트라카르복실산이무수물; 1,3,3a,4,5,9b-헥사히드로-2,5-디옥소-3-프라닐)-나프트[1,2-c]프란-1,3-디온, 1,3,3a,4,5,9b-헥사히드로-5-메틸-5-(테트라히드로-2,5-디옥소-3-프라닐)-나프트[1,2-c]프란-1,3-디온, 1,3,3a,4,5,9b-헥사히드로-8-메틸-5-(테트라히드로-2,5-디옥소-3-프라닐)-나프트[1,2-c]프란-1,3-디온,The acid dianhydride used in the present invention is not particularly limited as long as it is an acid dianhydride. For example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetra-carboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofrantetracarboxylic dianhydride, 5- (2,5-dioxytetrahydropral) -3-methyl-3- Aliphatic or alicyclic tetra- such as cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride- Carboxylic dianhydrides; Pyromellitic acid, dianhydride, 3, 3 ', 4, 4'-benzophenonetetracarboxylic dianhydride, 3, 3', 4, 4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4, 4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-frantetracarboxylic dianhydride, 4,4 '-Bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3, 4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid Anhydrides, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4, 4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'- diphenylmethane dianhydride Aromatic tetracarboxylic dianhydride; 1,3,3a, 4,5,9b-hexahydro-2,5-dioxo-3-pranil) -naphth [1,2-c] fran-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-pranyl) -naphth [1,2-c] fran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-pranyl) -naphth [1,2-c] fran-1 3-dione,
하기 일반식 (11)General formula (11)
(식 중 R21은 방향환을 가지는 2가의 유기기를 나타내고, R22 및 R23은 각각 수소원자 또는 알킬기를 나타낸다.)(In the formula, R 21 represents a divalent organic group having an aromatic ring, and R 22 and R 23 each represent a hydrogen atom or an alkyl group.)
하기 일반식(12)General formula (12)
(식 중 R24는 방향환을 가지는 2가의 유기기를 나타내고, R25 및 R26은 각각 수소원자 또는 알킬기를 나타낸다.)(R 24 wherein R represents a divalent organic group having an aromatic ring, R 25 and R 26 is a hydrogen atom or an alkyl group.)
로 나타내는 화합물 등의 방향환을 가지는 지방족 테트라카르복실산이무수물 등을 들 수 있다. 이들 테트라카르복실산이무수물은, 단독으로 또는 2종 이상 조합 시켜 사용할 수 있다. Aliphatic tetracarboxylic dianhydride etc. which have aromatic rings, such as a compound, are mentioned. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.
또한, 본 발명의 폴리이미드화합물에 사용되는 디아민은, 상기 얻어진 계피산 골격을 가지는 디아민 외에, 각종 디아민을 사용할 수 있다. 디아민이라면 특히 한정되지 않지만, 예를 들면, p-페닐렌디아민, m-페닐렌디아민, 4,4'-디아미노디페닐메탄, 4,4'-디아미노페닐에탄, 4,4'-디아미노페닐에테르, 4,4'-디디아미노페닐술피드, 4,4'-디디아미노페닐술폰, 1,5-디아미노나프탈렌, 3,3'-디메틸-4,4' -디아미노비페닐, 5-아미노-1-(4-아미노페닐)-1,3,3-트리메틸인단, 6-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 4,4'-디아미노벤즈아닐리드, 3,5-디아미노-3'-트리플루오로메틸벤즈아닐리드, 3,5-디아미노-4'-트리플루오로메틸벤즈아닐리드, 3,4'-디아미노디페닐에테르, 2,7-디아미노플루오렌, 2,2-비스(4-아미노페닐)헥사플루오로프로판, 4,4'-메틸렌-비스(2-클로로아닐린), 2,2',5,5'-테트라클로로-4,4'-디아미노비페닐, 2,2'-디클로로-4,4'-디아미노-5,5'-디메톡시비페닐, 3,3'-디메톡시-4,4'-디아미노비페닐, 4,4'-디아미노-2,2'-비스(트리플루오로메틸)비페닐, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 2,2-비스[4-(4-아미노페녹시)페닐]헥사플루오로프로판, 1,4-비스(4-아미노페녹시)벤젠, 4,4'-비스(4-아미노페녹시)-비페닐, 1,3'-비스 (4-아미노페녹시)벤젠, 9,9-비스(4-아미노페닐)플루오렌, 4,4'-(p-페닐렌이소프로필리덴)비스아닐린, 4,4'-(m-페닐렌이소프로필리덴)비스아닐린, 2,2'-비스[4-(4-아미노-2-트리플루오로메틸페녹시)페닐]헥사플루오로프로판, 4,4'-비스[4-(4-아미노-2-트리플루오로메틸)페녹시]-옥타플루오로비페닐 등의 방향족디아민; Moreover, various diamines can be used for the diamine used for the polyimide compound of this invention other than the diamine which has the obtained cinnamic acid skeleton. The diamine is not particularly limited, but for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylethane, 4,4'-dia Minophenyl ether, 4,4'-didiaminophenylsulfide, 4,4'-didiaminophenylsulfone, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 4,4'- Diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenylether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'- Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4 ' -Diaminobiphenyl, 4,4'-diamino-2,2 ' -Bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3'-bis (4-aminophenoxy) benzene, 9, 9-bis (4-aminophenyl) fluorene, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2 ' -Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy] Aromatic diamines such as octafluorobiphenyl;
디아미노테트라페닐티오페인 등의 방향환에 결합된 2개의 아미노기와 해당 아미노기의 질소원자 이외의 헤테로원자를 가지는 방향족 디아민; Aromatic diamine which has two amino groups couple | bonded with aromatic rings, such as diamino tetraphenyl thiophene, and hetero atoms other than the nitrogen atom of this amino group;
1,1-메타크실렌디아민, 1,3-프로판디아민, 테트라메틸렌디아민, 펜타메틸렌디아민, 옥타메틸렌디아민, 노나메틸렌디아민, 4,4-디아미노헵타메틸렌디아민, 1,4-디아미노시클로헥산, 이소포론디아민, 테트라히드로디시클로펜타디에닐렌디아민, 헥사히드로-4,7-메타노인다닐렌디메틸렌디아민, 트리시클로[6,2,1,02.7]-운데실렌디메틸디아민, 4,4'-메틸렌비스(시클로헥실아민) 등의 지방족 디아민 및 지환식 디아민; 1,1-methaxylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, Isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6,2,1,0 2.7 ] -undecylenedimethyldiamine, 4,4'- Aliphatic diamines and alicyclic diamines such as methylenebis (cyclohexylamine);
하기 일반식(13)General formula (13)
으로 나타내는 모노치환페닐렌디아민류(식 중 R27은, -O-, -COO-, -OCO-, -CONH- 및 -CO-로부터 선택되는 2가의 유기기를 나타내고, R28은 스테로이드골격을 가지는 1가의 유기기를 나타낸다); Mono-substituted phenylenediamines represented by the formula (In formula, R 27 represents a divalent organic group selected from -O-, -COO-, -OCO-, -CONH- and -CO-, R 28 has a steroid skeleton Monovalent organic group);
하기 일반식(14)General formula (14)
(R29는 탄소수1∼12의 탄화수소기를 나타내고, y는 1∼3의 정수이며, z는 1∼20의 정수이다.)로 나타내지는 화합물 등을 들 수 있다. 계피산 골격을 가지는 디아민을 1% 이상을 함유하는 외에, 이들 디아민화합물을, 단독으로 또는 2종 이상 조합시켜 사용할 수 있다. And the like can be mentioned a compound represented by (R 29 represents a hydrocarbon group of a carbon number of 1~12, y is an integer of 1~3, z is an integer. Of 1 to 20). In addition to containing 1% or more of the diamine having a cinnamic acid skeleton, these diamine compounds can be used alone or in combination of two or more thereof.
상기 얻어진 폴리이미드의 전구체로서의 폴리아미드산을, 열적으로 혹은 화학적으로 이미드화함으로써, 계피산 골격을 가지는 폴리이미드화합물을 얻을 수 있다. 여기서 말하는, 열적으로 이미드화하는 방법이란, 이미 서술한 폴리아미드산 공중합체에, 3급 아민과 공비(共沸)용매를 가하여 탈수이미드화하는 방법이다. 또한, 화학적으로 이미드화하는 방법이란, 폴리아미드산중합체 또는 그 용액에 화학량론 이상의 탈수제와 촉매량의 제3급 아민을 가하고, 가열함으로써 이미드화하는 방법이다. The polyimide compound which has a cinnamic acid skeleton can be obtained by imidating polyamic acid as a precursor of the obtained polyimide thermally or chemically. The method of thermally imidating here is the method of adding a tertiary amine and an azeotropic solvent to the polyamic-acid copolymer mentioned above, and dehydrating it. In addition, the method of chemically imidizing is a method of imidizing by adding a stoichiometric or more dehydrating agent and a catalytic amount of tertiary amine to a polyamic acid polymer or its solution, and heating.
여기서 말하는 탈수제로서는, 예를 들면 무수초산 등의 지방족 산무수물, 방향족 산무수물 등을 들 수 있다. 또한 촉매로서는, 예를 들면 트리에틸아민 등의 지방족 제3급 아민류, 디메틸아닐린 등의 방향족 제3급 아민류, 피리딘, 피콜린, 이소퀴놀린 등의 복소환식 제3급 아민류 등을 들 수 있다. As a dehydrating agent here, aliphatic acid anhydrides, such as acetic anhydride, an aromatic acid anhydride, etc. are mentioned, for example. Moreover, as a catalyst, aliphatic tertiary amines, such as triethylamine, aromatic tertiary amines, such as dimethylaniline, heterocyclic tertiary amines, such as pyridine, picoline, and isoquinoline, etc. are mentioned, for example.
탈수제로서는, 예를 들면 무수초산 등의 지방족 산무수물, 방향족 산무수물 등을 들 수 있다. 또한 촉매로서는, 예를 들면 트리에틸아민 등의 지방족 제3급 아민류, 디메틸아닐린 등의 방향족 제3급 아민류, 피리딘, 피콜린, 이소퀴놀린 등의 복소환식 제3급 아민류 등을 들 수 있다. As a dehydrating agent, aliphatic acid anhydrides, such as acetic anhydride, an aromatic acid anhydride, etc. are mentioned, for example. Moreover, as a catalyst, aliphatic tertiary amines, such as triethylamine, aromatic tertiary amines, such as dimethylaniline, heterocyclic tertiary amines, such as pyridine, picoline, and isoquinoline, etc. are mentioned, for example.
일반적으로, 열적으로 이미드화하는 방법은, 150℃ 이상으로 가열함으로써 행하여진다. 그러나, 계피산 혹은 계피산 유도체에 함유되는 탄소-탄소 2중 결합이, 180℃ 이상의 온도에서는 다른 탄소 2중 결합끼리, 혹은 산소와 결합하여, 2중 결합이 절단되는 반응을 일으키는 경우가 있다. 따라서, 본 발명에 있어서는, 계피산 골격을 가지는 폴리이미드를 얻기 위해서는, 150℃∼180℃의 온도조건으로, 상술의 3급아민을 가하는 열적으로 이미드화하는 것이 바람직하다. 또한, 산무수물을 가한 화학적 이미드화 및 열적 이미드화의 병용이면, 더욱 저온에서 반응할 수 있다. Generally, the method of thermally imidizing is performed by heating at 150 degreeC or more. However, carbon-carbon double bonds contained in cinnamic acid or cinnamic acid derivatives may combine with other carbon double bonds or oxygen at a temperature of 180 ° C. or higher to cause a reaction in which the double bond is cleaved. Therefore, in this invention, in order to obtain the polyimide which has a cinnamic acid skeleton, it is preferable to thermally imidize the above-mentioned tertiary amine on 150 degreeC-180 degreeC temperature conditions. Moreover, if it uses together the chemical imidation and thermal imidation which added the acid anhydride, it can react at low temperature further.
폴리아미드산의 평균분자량은 5000∼1000000인 것이 바람직하다. 평균분자량이 5000미만에서는, 제조된 폴리이미드화합물의 분자량도 낮아지고, 그 폴리이미드화합물을 이대로 광반응성수지로서 사용하여도 수지가 무르게 되어 바람직하지 못하고, 한편, 1000000을 넘으면 폴리아미드산 와니스의 점도가 지나치게 높아져서 취급이 어려워져 바람직하지 못하다. It is preferable that the average molecular weight of polyamic acid is 5000-1 million. If the average molecular weight is less than 5000, the molecular weight of the produced polyimide compound is also lowered, and even if the polyimide compound is used as the photoreactive resin as it is, the resin becomes soft, which is not preferable. Is too high, making handling difficult, which is undesirable.
상기한 바와 같이 하여, 본 발명의 신규의 폴리이미드화합물을 얻을 수 있다. As described above, the novel polyimide compound of the present invention can be obtained.
또한, 이 폴리이미드화합물에 각종의 유기첨가제, 혹은 무기 필러류, 혹은 각종의 강화재를 복합하는 것도 가능하다. Moreover, it is also possible to combine various organic additives, inorganic fillers, or various reinforcing materials with this polyimide compound.
다음으로, 일반식 (1)중 W가 (1-b)∼(1-e)의 폴리이미드화합물의 계피산 골격을 가지는 디아민을 거치는 폴리이미드화합물의 제조방법을 설명한다. 디니트로화물의 환원방법, 환원조건 및 폴리이미드의 제조방법에 있어서는 일반식 (1)의 폴리이미드화합물의 경우와 같은 조건이다. Next, the manufacturing method of the polyimide compound which W passes through the diamine which has the cinnamic acid skeleton of the polyimide compound of (1-b)-(1-e) in General formula (1) is demonstrated. In the dinitrode reduction method, the reduction conditions and the polyimide production method, the same conditions as in the case of the polyimide compound of the general formula (1).
일반식 (1)중 W1이 (1-b)의 신규폴리이미드화합물Novel polyimide compound of formula (1), wherein W 1 is (1-b)
의 원료로서 사용되는 디아민은 일반식(4)Diamines used as raw materials for the general formula (4)
로 표시된다.
이 디아민은, 니트로계피산유도체 또는, 니트로계피산클로라이드유도체와 디올을 반응시킨 디니트로화합물을 환원하여 얻을 수 있다. Is displayed.
This diamine can be obtained by reducing a nitro cinnamic acid derivative or a dinitro compound obtained by reacting a nitro cinnamic acid chloride derivative with a diol.
구체적으로는, 니트로계피산 유도체는, 일반식(2-2)Specifically, the nitro cinnamic acid derivative is a general formula (2-2)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타낸다. (Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—).
또한, 니트로계피산클로라이드 유도체는, 일반식(2-3)In addition, nitro cinnamic acid chloride derivative is a general formula (2-3)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타낸다. (Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—).
디올은, 일반식(2-4)Diol is a general formula (2-4)
(단, R2는 2가의 유기기를 나타낸다.)로 나타내는 수산기를 2개 가지는 화합물이다. (However, R 2 represents a divalent organic group.) Is a compound having two hydroxyl groups.
이들을 반응시켜, 일반식 (2-5)By reacting these, General Formula (2-5)
(단, R2는 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 디니트로화합물을 환원함으로써 얻어진다. Is obtained by reducing a dinitro compound represented by the formula (where, R 2 is a divalent organic group, V is H, CH 3, F, Cl , Br, CH 3 shows an O-.).
일반식 (2-4) 및 일반식 (2-5)중의 R2는, 2가의 유기기이면 특히 한정되지 않지만, R 2 in General Formula (2-4) and General Formula (2-5) is not particularly limited as long as it is a divalent organic group.
(V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)(V represents H, CH 3 , F, Cl, Br, CH 3 O-.)
등을 예시할 수 있다. Etc. can be illustrated.
일반식 (1)중 W1이 (1-c)의 신규 폴리이미드화합물New polyimide compound of formula (1) wherein W 1 is (1-c)
의 원료로서 사용되는 디아민은 일반식 (5)Diamines used as raw materials for the general formula (5)
(단, R3은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다. V는 동일하여도 달라도 좋다.)이다. (However, R 3 is a divalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O-. V may be the same or different.).
디아민은, 일반식(3-2)Diamine is a general formula (3-2)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 계피산유도체 또는, 일반식 (3-3)(Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—) or a cinnamic acid derivative represented by General Formula (3-3)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 계피산클로라이드 유도체와, 일반식 (3-4)(V represents H, CH 3 , F, Cl, Br, CH 3 O-.) Cinnamic acid chloride derivative represented by General Formula (3-4)
(단, V는 H, CH3, F, Cl, Br, CH3O-를, R3은 2가의 유기기를 나타낸다.)로 나타내는 수산기를 가지는 니트로화합물과 반응시키고, 일반식 (3-5)(However, V is reacted with a nitro compound having a hydroxyl group represented by H, CH 3 , F, Cl, Br, CH 3 O-, and R 3 represents a divalent organic group.).
(단, R3은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 디니트로화합물을 얻을 수 있다. A dinitro compound represented by (wherein, R 3 represents a divalent organic group, V represents H, CH 3 , F, Cl, Br, and CH 3 O—).
상기 얻어진 일반식 (3-5)로 나타내는 디니트로화합물을 환원하여, 일반식 (5)로 나타내는 디아민을 얻을 수 있다. The dinitro compound represented by General formula (3-5) obtained above can be reduced, and the diamine represented by General formula (5) can be obtained.
일반식 (3-4) 및 일반식 (3-5)중의 R3은, 2가의 유기기이면 특히 한정되지 않지만, -CH2-, -(CH2)m-O-, -(CH2)n-OCO-, 단 m= 1∼15, n=1∼15로부터 선택되는 2가의 유기기 등을 예시할 수 있다. R 3 in General Formula (3-4) and (3-5) is not particularly limited as long as it is a divalent organic group, but is —CH 2 —, — (CH 2 ) m —O—, — (CH 2 ) and divalent organic groups selected from n -OCO-, provided that m = 1 to 15 and n = 1 to 15.
일반식 (1)중 W1이 (1-d)의 신규 폴리이미드화합물New polyimide compound of formula (1), wherein W 1 is (1-d)
의 원료로서 사용되는 디아민은 일반식 (6)Diamines used as raw materials for the general formula (6)
이다. to be.
일반식 (4-2)General formula (4-2)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)(V denotes H, CH 3 , F, Cl, Br, CH 3 O-.)
로 나타내는 계피산유도체 또는, 일반식 (4-3)Cinnamic acid derivative represented by the general formula (4-3) or
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 계피산디클로라이드 유도체와, 일반식 (4-4)(V represents H, CH 3 , F, Cl, Br, CH 3 O-.) Cinnamic acid dichloride derivative represented by General formula (4-4)
(단, R4, R5는 2가의 유기기를 나타낸다.)로 나타내는 수산기를 가지는 니트로화합물과 반응시키고, 일반식 (4-5)(However, R 4 , R 5 represents a divalent organic group.) And reacts with a nitro compound having a hydroxyl group represented by the general formula (4-5)
(단, R4, R5는 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 디니트로화합물을 얻고, 그 디니트로화합물을 환원함으로써 얻어진다. By obtaining a dinitro compound represented by (wherein R 4 , R 5 is a divalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O-), and the dinitro compound is reduced. Obtained.
일반식 (4-4) 및 일반식 (4-5) 중의 R4, R5는, 2가의 유기기이면 특히 한정되지 않지만, Although R <4> , R <5> in general formula (4-4) and general formula (4-5) is a bivalent organic group, it will not specifically limit,
(단, w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기 등을 예시할 수 있다. And the like can be given (where, w = integer of 1~40, V is H, CH 3, F, Cl , Br, CH 3 O- represents a.) 2-valent organic group selected from.
일반식 (1)중 W1이 (1-e)의 신규 폴리이미드화합물 New polyimide compound of formula (1) wherein W 1 is (1-e)
의 원료로서 사용되는 디아민은 일반식 (7) Diamines used as raw materials for the general formula (7)
이다. 이 디아민은 일반식 (5-2)to be. This diamine is of the general formula (5-2)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 페닐렌디아크릴산 유도체 또는, 일반식 (5-3)(Wherein V represents H, CH 3 , F, Cl, Br, CH 3 O—) or a phenylenediacrylic acid derivative represented by General Formula (5-3)
(단, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 페닐렌디아크릴디클로라이드 유도체와, 일반식 (5-4) (V represents H, CH 3 , F, Cl, Br, CH 3 O-.), And a phenylenediacryldichloride derivative represented by General Formula (5-4)
(단, R6, R7은 2가의 유기기를 나타낸다.)로 나타내는 수산기를 가지는 니트로화합물과 반응시키고, 일반식 (5-5) (However, R 6 , R 7 represent a divalent organic group.) And react with a nitro compound having a hydroxyl group represented by the general formula (5-5)
(단, R6, R7은 2가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로 나타내는 디니트로화합물을 얻을 수 있다. A dinitro compound represented by (However, R 6 , R 7 represents a divalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O—).
상기 얻어진 디니트로화합물을 환원함으로써 얻어진다. It is obtained by reducing the obtained dinitro compound.
일반식 (5-4) 또는 일반식 (5-5) 중의 R6, R7은, 2가의 유기기이면 특히 한정되지 않지만, Although R <6> , R <7> in general formula (5-4) or general formula (5-5) is a bivalent organic group, it will not specifically limit,
(단, w=1∼40의 정수, V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)로부터 선택되는 2가의 유기기 등을 예시할 수 있다.And the like can be given (where, w = integer of 1~40, V is H, CH 3, F, Cl , Br, CH 3 O- represents a.) 2-valent organic group selected from.
일반식 (1)중 W1이 (1-f)의 신규 폴리이미드화합물New polyimide compound of formula (1) wherein W 1 is (1-f)
의 원료로서 사용되는 디아민은 일반식 (8) Diamines used as raw materials for the general formula (8)
이다. (단, R8은 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-, p=1∼3, q= 1∼3을 나타낸다.)to be. (Wherein R 8 is a trivalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O—, p = 1 to 3, q = 1 to 3).
이 디아민은 일반식 (6-1)This diamine is of the general formula (6-1)
(단, V는 H, CH3, F, Cl, Br, CH3O-, p= 1∼3을 나타낸다.)(V denotes H, CH 3 , F, Cl, Br, CH 3 O−, p = 1 to 3).
로 나타내는 계피산 유도체가, 일반식 (6-2)Cinnamic acid derivative represented by general formula (6-2)
(단, V는 H, CH3, F, Cl, Br, CH3O-, p=1∼3을 나타낸다.)(V represents H, CH 3 , F, Cl, Br, CH 3 O-, p = 1 to 3)
로 나타내는 계피산클로라이드 유도체와, 일반식 (6-3)Cinnamic acid chloride derivative represented by general formula (6-3)
(단, R8은 3가의 유기기, q=1∼3을 나타낸다)(However, R 8 represents a trivalent organic group, q = 1 to 3)
으로 나타내는 수산기를 가지는 니트로화합물과 반응시키고, 일반식 (6-4)Reacted with a nitro compound having a hydroxyl group represented by formula (6-4)
(단, R8은 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-, p=1∼3, q=1∼3을 나타낸다.)(Wherein R 8 is a trivalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O—, p = 1 to 3, q = 1 to 3).
로 나타내는 디니트로화합물을 환원함으로써 얻어진다. 일반식 (6-4) 중의 Y는, 3가의 유기기이면 특별히 한정되지 않지만, It is obtained by reducing the dinitro compound shown by. Y in General Formula (6-4) is not particularly limited as long as it is a trivalent organic group.
(식 중, V는 H, CH3, F, Cl, Br, CH3O-, r=1∼3, n=1∼20, w는 -CH2-, -(CH2)m-O-, -(CH2)k-OCO-, 단 m=1∼15, k=1∼20(k≠2)로부터 선택되는 2가의 유기기를 나타낸다.)Wherein V is H, CH 3 , F, Cl, Br, CH 3 O-, r = 1 to 3, n = 1 to 20, w is -CH 2 -,-(CH 2 ) m -O- ,-(CH 2 ) k -OCO-, provided a divalent organic group selected from m = 1-15, k = 1-20 (k ≠ 2).)
등을 예시할 수 있다. Etc. can be illustrated.
이 디니트로화물을 상기 환원조건의 수소화에 의해, 일반식(8)The dinitrodide was hydrogenated under the above reducing conditions to give general formula (8).
(단, R8은 3가의 유기기, V는 H, CH3, F, Cl, Br, CH3O-, p=1∼3, q=1∼3을 나타낸다.)이 얻어진다.
다음에, ②디올 말단으로 한 폴리이미드의 올리고머와 계피산 골격을 가지는 디카르복실산 혹은 디산클로라이드와 반응시키고, 에스테르결합을 생성하고 고분자량화하여 폴리이미드화합물을 얻는 방법에 대하여 설명한다. (However, R 8 is a trivalent organic group, V represents H, CH 3 , F, Cl, Br, CH 3 O −, p = 1 to 3, q = 1 to 3).
Next, a method of obtaining a polyimide compound by reacting with an oligomer of a polyimide having a diol end and a dicarboxylic acid or diacid chloride having a cinnamic acid skeleton, generating an ester bond and high molecular weight is described.
예컨대, 일반식(1)중 W1이 (1-a)에 상당하는 폴리이미드화합물은, For example, the polyimide compound corresponding to W 1 is (1-a) of the general formula (1),
로 나타내는 디카르복실산 혹은 산클로라이드와Dicarboxylic acid or acid chloride represented by
로 나타내는 디올과 반응시켜 에스테르결합을 형성함으로써 얻어진다. It is obtained by reacting with diol represented by this to form ester bond.
또한, 일반식 (1)중 W1이 (1-b)에 상당하는 폴리이미드화합물은, In addition, in the general formula (1), a polyimide compound in which W 1 corresponds to (1-b),
로 나타내는 디카르복실산 혹은 그 산클로라이드와 Dicarboxylic acid or its acid chloride represented by
로 나타내는 디올과 반응시키고 에스테르결합을 형성함으로써 얻어진다. It is obtained by reacting with diol represented by this and forming ester bond.
일반식 (1)중 W가 (1-c)에 상당하는 폴리이미드화합물은, In the general formula (1), the polyimide compound in which W corresponds to (1-c) is
(단, V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)(However, V represents H, CH 3 , F, Cl, Br, CH 3 O-.)
로 나타내는 디카르복실산 혹은 그 산클로라이드와Dicarboxylic acid or its acid chloride represented by
(단 V는 H, CH3, F, Cl, Br, CH3O-를 나타낸다.)(V denotes H, CH 3 , F, Cl, Br, CH 3 O-.)
로 나타내는 디올과 반응시켜 에스테르결합을 형성함으로써 얻어진다. It is obtained by reacting with diol represented by this to form ester bond.
일반식 (1)중 W1이 (1-d)에 상당하는 폴리이미드화합물은, In the general formula (1), the polyimide compound in which W 1 corresponds to (1-d) is
로 나타내는 디카르복실산 혹은 그 산클로라이드와Dicarboxylic acid or its acid chloride represented by
로 나타내는 디올과 반응시키고 에스테르결합을 형성함으로써 얻어진다. It is obtained by reacting with diol represented by this and forming ester bond.
일반식 (1)중 W1이 (1-e)에 상당하는 폴리이미드화합물은, In the general formula (1), the polyimide compound in which W 1 corresponds to (1-e) is
로 나타내는 디카르복실산 혹은 그 산클로라이드와 Dicarboxylic acid or its acid chloride represented by
로 나타내는 디올과 반응시키고 에스테르결합을 형성함으로써 얻어진다. It is obtained by reacting with diol represented by this and forming ester bond.
이들 디올말단으로 한 폴리이미드의 올리고머와 계피산골격을 함유하는 디카르복실산 혹은 디산클로라이드와 반응시키고, 에스테르결합을 생성하는 폴리이미드화합물의 합성방법은, 디올이 페놀성수산기의 경우보다 알콜성 수산기의 경우 쪽이, 고분자량물을 얻을 수 있는 경향에 있다. The synthesis method of the polyimide compound which reacts with the oligomer of the polyimide which made these diol terminal, and dicarboxylic acid or diacid chloride containing cinnamic acid skeleton, and produces | generates ester bond is more alcoholic hydroxyl group than the case where a diol is phenolic hydroxyl group. In the case of, the tendency to obtain a high molecular weight material.
다음에 산이무수물잔기로 계피산 골격을 가지는 폴리이미드를 제조하는 방법으로서는, 첫째로 계피산골격을 가지는 산이무수물과 디아민을 반응시키는 방법이 있다. Next, as a method for producing a polyimide having a cinnamic acid skeleton as an acid dianhydride residue, first, there is a method of reacting an acid dianhydride having a cinnamic acid skeleton with a diamine.
신규 산이무수물의 구체적인 제조방법에 대하여 설명한다. The concrete manufacturing method of new acid dianhydride is demonstrated.
예를 들면, 상기 일반식 (9)For example, the general formula (9)
로 나타내는 계피산골격을 가지는 신규 산이무수물의 제조방법을 설명한다. It describes a novel acid dianhydride manufacturing method having a cinnamic acid skeleton represented by.
일반식 (9)중의 R10의 -COO-결합을 만드는 데에는, 무수트리멜리트산 클로라이드와 HO-C6H4(V)CH=CHCOO-를 반응시킴으로써 합성된다.(이하 V는, H, CH3, F, Cl, Br, CH3O-를 나타낸다.)To form a -COO-bond of R 10 in the general formula (9), it is synthesized by reacting trimellitic anhydride chloride with HO-C 6 H 4 (V) CH = CHCOO- (hereinafter, V is H, CH 3 , F, Cl, Br, CH 3 O-.)
또한, 일반식 (9)중의 R10의 -OCO-결합을 만드는 데에는, 히드록시무수프탈산과 In addition, in order to form the -OCO-bond of R <10> in General formula (9), it is hydroxy phthalic anhydride,
ClCO-C6H4(V)CH=CHCOO-ClCO-C 6 H 4 (V) CH = CHCOO-
를 반응시킴으로써 합성된다. It is synthesized by reacting.
마찬가지로, 일반식(9)중의 R10의 -O-결합을 만드는 데에는, 클로로무수프탈산과 Similarly, in order to form -O-bond of R <10> in General formula (9), chlorophthalic anhydride and
HO-C6H4(V)CH=CHCOO-HO-C 6 H 4 (V) CH = CHCOO-
를 반응시킴으로써 합성된다. It is synthesized by reacting.
일반식(9)중 R10의 -OR13O-결합을 만드는 데에는, 모노할로겐화무수프탈산과 In the general formula (9), to form an -OR 13 O-bond of R 10 , a monohalogenated phthalic anhydride and
Cl-C6H4(V)CH=CHCOO-Cl-C 6 H 4 (V) CH = CHCOO-
등의 할로겐화물과With halides such as
HO-R13-OH 로 나타내는 디올Diol represented by HO-R 13 -OH
(식 중, R13은, 벤젠환, 나프탈렌환, 비페닐, -CmH2m-, m은 1∼20의 정수를 나타낸다. 이하, R13에 대하여 동일.)을 반응시킴으로써 합성된다. Is synthesized by reacting a - (wherein, R 13 is a benzene ring, naphthalene ring, biphenyl, -C m H 2m., M is an integer of 1 to 20. Hereinafter, the same for R 13.).
일반식 (9)중 R10의 -COOR13OCO-결합을 만드는 데에는, 무수트리멜리트산 클로라이드와, To make a -COOR 13 OCO-bond of R 10 in formula (9), trimellitic anhydride chloride,
ClCO-C6H4(V)CH=CHCOO-와, ClCO-C 6 H 4 (V) CH = CHCOO-,
HO-R13-OH 로 나타내는 디올Diol represented by HO-R 13 -OH
을 반응시킴으로써 합성된다. It is synthesized by reacting.
일반식 (9)중 R10의 -OOCCH=CH-결합을 만드는 데에는, 페닐렌아크릴산혹은 페닐렌아크릴산의 산클로라이드와 무수히드록시프탈산과 반응시킴으로써 합성된다. In order to make -OOCCH = CH-bond of R <10> in General formula (9), it is synthesize | combined by making it react with the acid chloride of phenylene acrylic acid or phenylene acrylic acid, and hydroxyphthalic anhydride.
마찬가지로, 일반식 (9)중 R10의 -O-R13OCO- 나 -O-R13-COO- 결합을 만드는 데에는, 에테르결합은 할로겐화물과 HO-의 반응, 에스테르결합은, 카르복실산 혹은 산클로라이드와 HO-의 반응에 의해 형성된다. Similarly, in the formula (9), in order to form an -OR 13 OCO- or -OR 13 -COO- bond of R 10 , an ether bond is a reaction of a halide with HO-, and an ester bond is a carboxylic acid or an acid chloride. It is formed by the reaction of HO-.
또한, 일반식(9)중 R11의 -의 결합을 만드는 데에는, 히드록시무수프탈산과 In addition, in order to form the bond of-of R <11> in General formula (9), it is hydroxy phthalic anhydride,
ClCO-CH=CHC6H4(V)-ClCO-CH = CHC 6 H 4 (V)-
를 반응시킴으로써 합성된다. It is synthesized by reacting.
일반식 (9)중의 R11의 -R14-OCO-결합을 만드는 데에는, 무수트리멜리트산 클로라이드와 In order to form -R 14 -OCO-bond of R 11 in formula (9), trimellitic anhydride chloride and
-C6H4(V)CH=CHCOCl--C 6 H 4 (V) CH = CHCOCl-
를 HO-R14-OH 로 나타내는 디올Diols represented by HO-R 14 -OH
(이하, 식 중 R14는, 벤젠환, 나프탈렌환, 비페닐, -CmH2m-를 나타낸다. 단 m=1∼20의 정수를 나타낸다.)로 나타내는 디올로 연결시킴으로써 합성된다. (Hereinafter, R 14 represents a benzene ring, a naphthalene ring, biphenyl, and -C m H 2m- . However, an integer of m = 1 to 20 is represented.).
또한, 일반식 (9)중 R11의 -R14-O-의 결합을 만들기 위해서는, In addition, in order to make the bond of -R <14> -O- of R <11> in General formula (9),
ClCO-CH=CH-C6H4(V)-와 ClCO-CH = CH-C 6 H 4 (V)-and
HO-R14-Cl과 반응시키고, React with HO-R 14 -Cl,
Cl-R14-OCO-CH=CHC6H4(V)- 를 얻고, 그것에 히드록시무수프탈산을 반응시킴으로써 합성된다. Cl-R 14 -OCO-CH = CHC 6 H 4 (V) - gained, is synthesized by reacting a hydroxy-phthalic anhydride to it.
다음에 일반식(10)General formula (10)
으로 나타내는 계피산 골격, 또는 계피산 유도체를 측쇄에 가지는 신규의 산이무수물의 제조방법을 설명한다. The manufacturing method of the novel acid dianhydride which has a cinnamic acid skeleton or a cinnamic acid derivative shown in the side chain is demonstrated.
예컨대, for example,
Cl-R12(OH)-Cl
과 계피산클로라이드 혹은 계피산의 산클로라이드의 벤젠환에 H, CH3, F, Cl, Br, CH3O-등이 도입된 계피산 유도체의 산클로라이드를 반응시키고, 일반식 (10-1)Cl-R 12 (OH) -Cl
And acid chlorides of cinnamic acid derivatives in which H, CH 3 , F, Cl, Br, CH 3 O- and the like are introduced into a benzene ring of cinnamic acid chloride or cinnamic acid chloride, and the general formula (10-1)
(식 중, V는, H, CH3, F, Cl, Br, CH3O- 등을 나타낸다.)(In the formula, V represents an H, CH 3, F, Cl, Br, CH 3 O- and the like.)
의 디클로라이드를 얻는다. Dichloride is obtained.
이 일반식 (10-1)의 디클로라이드와 히드록시무수프탈산과 반응시키고, 일반식(10)-AThe dichloride of this general formula (10-1) is reacted with hydroxyphthalic anhydride, and general formula (10) -A
(식 중, V는, H, CH3, F, Cl, Br, CH3O- 등을 나타낸다.)(In the formula, V represents an H, CH 3, F, Cl, Br, CH 3 O- and the like.)
로 나타내는 산이무수물을 얻는다. Obtain the acid dianhydride represented by
또한, 상기 일반식 (10)-A에서 나타내는 산이무수물은, 이하의 방법으로도 얻을 수 있다. In addition, the acid dianhydride shown by the said General formula (10) -A can also be obtained with the following method.
HO-R12(OH)-OHHO-R 12 (OH) -OH
로 나타내는 트리올과, 계피산클로라이드 혹은 계피산클로라이드의 벤젠환에 H, CH3, F, Cl, Br, CH3O-등이 도입된 계피산유도체의 산클로라이드를 반응시키고, 일반식 (10-2)An acid chloride of a cinnamic acid derivative having H, CH 3 , F, Cl, Br, or CH 3 O- is introduced into a triol and a benzene ring of cinnamic acid chloride or cinnamic acid chloride, and is represented by General Formula (10-2).
(식 중, V는, H, CH3, F, Cl, Br, CH3O- 등을 나타낸다.)(In the formula, V represents an H, CH 3, F, Cl, Br, CH 3 O- and the like.)
의 디올을 얻는다. Gets Dior.
이 디올과 모노할로겐화무수프탈산과 반응시키고, 일반식(10)-A로 나타내는 신규의 산이무수물을 얻는다. This diol is reacted with monohalogenated phthalic anhydride to obtain a novel acid dianhydride represented by the general formula (10) -A.
또한, 무수트리멜리트산클로라이드와, 일반식 (10-2)의 디올을 반응시키면, 일반식(10-B)In addition, when trimellitic anhydride chloride and the diol of General formula (10-2) are made to react, General formula (10-B)
로 나타내는 신규인 산이무수물을 얻는다. New acid dianhydride shown by is obtained.
또한, CH3OCO-R12(OH)COOCH3와 계피산클로라이드 혹은 계피산클로라이드의 벤젠환에 H, CH3, F, Cl, Br, CH3O- 등이 도입된 계피산 유도체의 산클로라이드를 반응시키고, 일반식 (10-3) In addition, an acid chloride of a cinnamic acid derivative having H, CH 3 , F, Cl, Br, CH 3 O- or the like is reacted with a benzene ring of CH 3 OCO-R 12 (OH) COOCH 3 and cinnamic acid chloride or cinnamic acid chloride. , Formula (10-3)
을 얻는다.Get
여기에 히드록시무수프탈산과 에스테르교환반응시키고, 일반식(10-C)It is transesterified with hydroxyphthalic anhydride thereto and formula (10-C)
로 나타내는 신규인 산이무수물을 얻는다. New acid dianhydride shown by is obtained.
상기 반응으로 얻어지는 일반식(9)로 나타내는 신규산이무수물은, 계피산 혹은 계피산 유도체 골격을 주쇄에 가지는 신규산이무수물이며, 일반식 (1O)로 나타내는 신규산이무수물은, 계피산 혹은 계피산유도체 골격을 측쇄에 가지는 신규산이무수물이며, 계피산 특유의 광반응성 및 열반응성을 함께 가지는 신규인 폴리이미드화합물의 모노머로서 유용한 것이다. The novel acid dianhydride represented by the general formula (9) obtained by the above reaction is a novel acid dianhydride having a cinnamic acid or cinnamic acid derivative skeleton in the main chain, and the novel acid dianhydride represented by the general formula (10) represents a cinnamic acid or cinnamic acid derivative skeleton in the side chain. The branch is a novel acid dianhydride and is useful as a monomer of a novel polyimide compound having both photoreactivity and thermal reactivity unique to cinnamic acid.
다음으로 폴리이미드화합물을 합성하는 방법을 기술한다. Next, a method for synthesizing a polyimide compound is described.
본 발명에 따른 계피산골격 혹은 계피산이무수물 유도체를 골격을 가지는 폴리이미드화합물에는, 본 발명에 이러한 일반식 (9) 또는 일반식 (10)으로 나타내는 산이무수물 외에, 다른 산이무수물을 사용할 수 있다. 본 발명에 따른 일반식 (9) 또는 일반식 (10)으로 나타내는 산이무수물이, 전체 산이무수물량의 1%이상 함유되면, 본 발명에 따른 폴리이미드화합물은 계피산골격 특유의 특성을 발휘할 수 있다. In addition to the acid dianhydride represented by General Formula (9) or General Formula (10), other acid dianhydrides may be used for the polyimide compound having a skeleton of the cinnamic acid skeleton or the cinnamic dianhydride derivative according to the present invention. When the acid dianhydride represented by the general formula (9) or the general formula (10) according to the present invention contains 1% or more of the total amount of the acid dianhydride, the polyimide compound according to the present invention can exhibit the peculiar characteristic of cinnamic acid skeleton.
상기 얻어진 일반식 (9) 또는 일반식 (10)으로 나타내는 신규의 계피산 혹은 계피산 유도체 골격을 주쇄 또는 측쇄에 가지는 산이무수물과, 디아민을 유기극성용매속에서 반응시키고, 폴리아미드산으로 하고, 열적으로 혹은 화학적으로 이미드화함으로써, 계피산 골격을 가지는 폴리이미드화합물을 얻을 수 있다. 폴리이미드의 제조방법은, 상기와 마찬가지이다. 사용되는 계피산골격을 갖지 않은 디아민 및 다른 산이무수물은 상기와 마찬가지이다. The acid dianhydride having the novel cinnamic acid or cinnamic acid derivative skeleton represented by the general formula (9) or the general formula (10) obtained in the main chain or side chain and the diamine are reacted in an organic polar solvent to form a polyamic acid. Alternatively, by chemically imidizing, a polyimide compound having a cinnamic acid skeleton can be obtained. The manufacturing method of a polyimide is similar to the above. Diamines and other acid dianhydrides which do not have a cinnamic acid skeleton used are the same as above.
상술한 바와 같이, 본 발명에 따른 신규의 폴리이미드화합물은, 계피산 골격을 가지는 디아민 또는 산이무수물을 사용하여 얻을 수 있지만, 이하는, 상기 방법의 다른 방법으로서, 본 발명에 따른 계피산골격을 가지는 폴리이미드화합물의 제조방법에 대하여 설명한다. As described above, the novel polyimide compound according to the present invention can be obtained by using a diamine or an acid dianhydride having a cinnamic acid skeleton. However, as a different method of the above method, the polyimide having a cinnamic acid skeleton according to the present invention can be obtained. The manufacturing method of a mid compound is demonstrated.
수산기를 가지는 산이무수물과 임의의 디아민과 반응시켜 아미드산으로 한 후에, 탈수폐환하여 수산기말단의 이미드의 올리고머로 하고, 그 이미드와 계피산 유도체의 디카르복실산 혹은 그 산디클로라이드를 반응시켜 에스테르결합을 형성하고, 예컨대, 일반식 (2)중 X2가, 식 (2-a)인 주쇄에 계피산 골격 또는 계피산유도체 골격을 가지는 폴리이미드화합물 After reacting an acid dianhydride having a hydroxyl group with an optional diamine to form amic acid, it is dehydrated and closed to form an oligomer of an imide at the terminal of a hydroxyl group, and the imide and dicarboxylic acid or cinnamic acid derivative of cinnamic acid derivative are reacted to produce an ester. A polyimide compound which forms a bond and has, for example, a cinnamic acid skeleton or a cinnamic acid derivative skeleton in a main chain wherein X 2 in General Formula (2) is Formula (2-a)
을 얻는다.Get
또한, 수산기말단의 이미드올리고머와 일반식In addition, the imide oligomer and the general formula of the hydroxyl terminal end
으로 나타내는 화합물을 반응시키면, 일반식 (2)중 X2가 식(2-b)로 나타내는 측쇄에 계피산 골격 또는 계피산 유도체 골격을 가지는 폴리이미드화합물When the compound represented by the above reaction is reacted, a polyimide compound having a cinnamic acid skeleton or a cinnamic acid derivative skeleton in the side chain represented by the formula (2-b) where X 2 in General Formula (2)
을 얻을 수 있다. Can be obtained.
또한, 본 발명에 따른 폴리이미드화합물의 다른 제조방법으로서는, 트리멜리트산무수물과 임의의 디아민과 반응시켜 아미드산으로 한 후에, 탈수폐환하여 카르복실산말단의 이미드의 올리고머로 하고, 그 이미드와 계피산유도체의 디올을 반응시켜 에스테르결합을 형성하고 계피산 골격을 가지는 폴리이미드화합물을 얻는 방법이 있다. In addition, as another method for producing a polyimide compound according to the present invention, it is made to react with trimellitic anhydride and an optional diamine to form amic acid, followed by dehydration ring to form an oligomer of an imide at the terminal of carboxylic acid. And a diol of a cinnamic acid derivative is reacted to form an ester bond to obtain a polyimide compound having a cinnamic acid skeleton.
구체적으로는, 카르복실산말단의 이미드올리고머와Specifically, the imide oligomer of the carboxylic acid terminal
(단, 식 중, E는, 벤젠환, 나프탈렌환, 비페닐, -CmH2m-, m은 1∼20의 정수를 나타낸다. F는, -CmH2m-, 벤젠환, 나프탈렌환을, m은 1∼20의 정수를 나타낸다.)로 나타내는 화합물을 반응시키고, 일반식 (1)로 나타내는 주쇄에 계피산 골격 또는 계피산유도체 골격을 가지는 폴리이미드화합물을 얻는다. (Wherein E represents a benzene ring, naphthalene ring, biphenyl, -C m H 2m- , and m represents an integer of 1 to 20. F represents -C m H 2m- , benzene ring, naphthalene ring M represents an integer of 1 to 20.), and a polyimide compound having a cinnamic acid skeleton or a cinnamic acid derivative skeleton in the main chain represented by the general formula (1) is obtained.
또한, 카르복실산말단의 이미드올리고머와 일반식 (10-2)Moreover, the imide oligomer of the carboxylic acid terminal and general formula (10-2)
로 나타내는 디올을 반응시키고 일반식 (2)로 나타내는 측쇄에 계피산 골격 또는 계피산유도체 골격을 가지는 폴리이미드화합물을 얻을 수 있다. A polyimide compound having a cinnamic acid skeleton or a cinnamic acid derivative skeleton in the side chain represented by the general formula (2) can be obtained by reacting a diol represented by the formula (2).
상기한 바와 같이 하여 얻어지는 본 발명에 따른 폴리이미드화합물에 각종의 유기첨가제, 혹은 무기 필러류, 혹은 각종 강화제를 복합하는 것도 가능하다. It is also possible to combine various organic additives, inorganic fillers, or various reinforcing agents with the polyimide compound according to the present invention obtained as described above.
이상 서술한 바와 같이 제조되는 본 발명에 따른 신규 폴리이미드화합물은, 계피산 골격을 가지기 때문에, 종래의 폴리이미드의 여러가지 뛰어 난 특성에 더하여, 열 또는 빛에 반응하고, 가교반응을 일으키는 계피산골격의 성질을 가진다. 따라서, 특정한 온도, 및/또는 특정한 파장에 의해 반응하는 뛰어난 열경화성수지, 열반응성수지로서의 새로운 용도를 제공한다. Since the novel polyimide compound according to the present invention produced as described above has a cinnamic acid skeleton, in addition to the various excellent properties of the conventional polyimide, the properties of cinnamic acid skeleton that react to heat or light and cause crosslinking reactions. Has Thus, it provides a novel use as an excellent thermosetting resin, a thermoreactive resin that reacts at a specific temperature and / or a specific wavelength.
이하, 실시예에 의해 본 발명을 구체적으로 설명하는데, 본 발명은 이들 실시예에만 한정되는 것이 아니다. Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
실시예중, ESDA는, 2,2-비스(4-히드록시페닐)프로판디벤조에이트-3,3',4,4'-테트라카르복실산이무수물, 6FDA는, 2,2'-헥사플루오로프로필리덴디프탈산이무수물, DMAc은, N,N-디메틸아세트아미드, DMF는, N,N-디메틸 포름아미드를 나타낸다. In Examples, ESDA is 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'- tetracarboxylic dianhydride, 6FDA is 2,2'-hexafluoro Propylidenediphthalic anhydride, DMAc, N, N-dimethylacetamide, DMF represents N, N-dimethyl formamide.
「발열 피크온도」는, 시마즈제작소 DSC CELL SCC-41(시차주사열량계)에 의해, 질소기류 하에서 승온속도 1O℃/분에서 실온으로부터 40O℃까지의 온도범위를 측정하였을 때의 피크온도인 것이다. 탄소-탄소 2중결합이, 이량화한 경우의, 발열 피크 온도는 230℃ 전후이다. An "exothermic peak temperature" is a peak temperature when the temperature range from room temperature to 40 ° C is measured by a Shimadzu Corporation DSC CELL SCC-41 (differential scanning calorimeter) at a temperature increase rate of 10 ° C / min under a nitrogen stream. The exothermic peak temperature when the carbon-carbon double bond is dimerized is around 230 ° C.
「중량평균분자량」은, Waters제 GPC을 사용하여 이하의 조건으로 측정하였다.[칼럼: Shodex제 KD-806M 2개, 온도 60℃, 검출기:RI, 유량:1ml/분, 전개액:DMF(브롬화리튬 0.03M, 인산 0.03M), 시료농도: 0.2wt%, 주입량: 20㎕, 기준물질:폴리에틸렌옥사이드] The "weight average molecular weight" was measured under the following conditions using GPC manufactured by Waters. [Column: Two Shodex KD-806M, temperature 60 ° C, detector: RI, flow rate: 1 ml / min, developing solution: DMF ( Lithium bromide 0.03M, phosphoric acid 0.03M), sample concentration: 0.2wt%, injection amount: 20µl, reference material: polyethylene oxide]
이하 실시예1∼9에 있어서는, 계피산골격을 가지는 신규인 디아민을 제조하고, 폴리이미드화합물을 합성하였다. In Examples 1 to 9 below, a novel diamine having a cinnamic acid skeleton was produced, and a polyimide compound was synthesized.
(실시예 1)(Example 1)
① 3,5-디니트로벤질 신나메이트의 합성① Synthesis of 3,5-dinitrobenzyl cinnamate
3,5-디니트로벤질알콜 59.44g(0.3몰), 계피산클로라이드 66.64g(0.4몰), o-디클로로벤젠 700ml을 반응용기에 취하고, 질소기류 하에서, 120∼130℃에서 2시간 교반을 행하였다. 반응종료 후, 반응용액을 헥산에 투입하고, 침전을 얻었다. 침전을 재결정에 의해 정제하고, 85g의 3,5-디니트로벤질 신나메이트를 얻었다. 59.44 g (0.3 mol) of 3,5-dinitrobenzyl alcohol, 66.64 g (0.4 mol) of cinnamic acid chloride, and 700 ml of o-dichlorobenzene were taken into a reaction vessel, and the mixture was stirred at 120 to 130 ° C. for 2 hours under a nitrogen stream. . After the reaction was completed, the reaction solution was poured into hexane to obtain a precipitate. The precipitate was purified by recrystallization to give 85 g of 3,5-dinitrobenzyl cinnamate.
② 3,5-디아미노벤질 신나메이트의 합성② Synthesis of 3,5-diaminobenzyl cinnamate
3,5-디니트로벤질 신나메이트 65.6g(200 밀리몰), 5% Pt함유 카본블랙 10g(약 50% 함수품(含水品)), 1,4-디옥산 500ml을 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약 2시간에 14.5리터의 수소를 흡수하고, 수소의 흡수가 정지하였으므로, 반응을 멈추고, 반응용액을 여별하여, Pt함유카본을 제거하고 나서, 농축하여 3,5-디아미노벤질 신나메이트 53.6g을 얻었다. 발열피크는 230℃ 이었다. 65.6 g (200 mmol) of 3,5-dinitrobenzyl cinnamate, 10 g of carbon black containing 5% Pt (about 50% water-containing product) and 500 ml of 1,4-dioxane were added to the reaction vessel. The mixture was stirred at 60 DEG C under a hydrogen atmosphere. After absorbing 14.5 liters of hydrogen in about 2 hours and the absorption of hydrogen stopped, the reaction was stopped, the reaction solution was filtered off, the Pt-containing carbon was removed and concentrated to give 53.6 g of 3,5-diaminobenzyl cinnamate. Got. The exothermic peak was 230 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 2000ml의 분리플라스크에 3,5-디아미노벤질 신나메이트 26.8g(0.1몰), DMAc 300g을 취하고, ESDA 57.65g(0.1몰)을 단숨에 격렬하게 교반하면서 첨가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약 150 ℃로 가열하고, 이미드화하 였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 73g의 황색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은 8만이었다. 26.8 g (0.1 mol) of 3,5-diaminobenzyl cinnamate and 300 g of DMAc were added to a 2000 ml separatory flask equipped with a stirrer, and 57.65 g (0.1 mol) of ESDA was added at once with vigorous stirring, followed by stirring for 30 minutes. Continued. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride and 100 g of DMAc were added to the reaction solution, and heated to about 150 ° C. and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 73 g of a powder of yellow polyimide. The weight average molecular weight of the powder of this polyimide was 80,000.
(실시예 2)(Example 2)
① 2,4-디니트로페닐 신나메이트의 합성① Synthesis of 2,4-dinitrophenyl cinnamate
계피산클로라이드 66.64g(0.4몰), 메틸에틸케톤(이하 MEK라 한다) 300g를 반응용기에 취하고 질소기류 하에서 60℃로 가열교반한다.66.64 g (0.4 mol) of cinnamic acid chloride and 300 g of methyl ethyl ketone (hereinafter referred to as MEK) are taken into a reaction vessel and heated and stirred at 60 ° C. under a stream of nitrogen.
상기 반응용기에 2,4-디니트로페닐 73.64g(0.4몰), 피리딘 50g, MEK 500g을 적하로트로 적하하고, 적하종료 후, 질소기류 하에서 2시간 환류교반을 행하였다. 반응종료 후, 침전을 여별하고, 여과액을 결정이 석출할 때까지 농축하고, 메탄올에 투입하여, 담황색의 바늘형상결정(2, 4-디니트로로페닐 신나메이트 90g을 얻었다. 2,4-dinitrophenyl 73.64 g (0.4 mol), pyridine 50g, and MEK 500g were dripped at the said reaction container by the dropping lot, and after completion | finish of dripping, reflux stirring was performed for 2 hours under nitrogen stream. After completion of the reaction, the precipitate was filtered off, the filtrate was concentrated until crystals were precipitated, and poured into methanol to obtain 90 g of a pale yellow needle-like crystal (2,4-dinitrolophenyl cinnamate).
② 2,4-디디아미노페닐 신나메이트의 합성② Synthesis of 2,4-diaminoamino cinnamate
2,4-디니트로페닐 신나메이트 62.8g(200 밀리몰), 5% Pt 및 2% 철함유 카본블랙 15g (약 50% 함수품), 1,4-디옥산 500ml을 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약 2시간에 14.5리터의 수소를 흡수하고, 수소의 흡수가 정지되었으므로, 반응을 멈추고, 반응용액을 여별하여, 촉매를 제거하고 나서, 농축하여 2,4-디아미노페닐 신나메이트 50.8g을 얻었다. 발열 피크 온도는, 230℃ 이었다. 62.8g (200mmol) of 2,4-dinitrophenyl cinnamate, 5g of Pt and 2% of iron black carbon black 15g (about 50% water), 500ml of 1,4-dioxane The mixture was stirred at 60 DEG C under a hydrogen atmosphere. After absorbing 14.5 liters of hydrogen in about 2 hours and the absorption of hydrogen was stopped, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed and concentrated to give 50.8 g of 2,4-diaminophenyl cinnamate. . The exothermic peak temperature was 230 ° C.
③ 폴리이미드의 합성 ③ Synthesis of Polyimide
교반기를 설치한 2000ml의 분리플라스크에 2,4-디아미노페닐 신나메이트 25.4g(0.1몰), DMAc 300g을 취하고, ESDA 57.65g(0.1몰)을 단숨에 격렬하게 교반하면서 첨가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약 150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별 건조하여, 79g의 황색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은 10만이었다. 25.4 g (0.1 mole) of 2,4-diaminophenyl cinnamate and 300 g of DMAc were added to a 2000 ml separating flask equipped with a stirrer, and 57.65 g (0.1 mole) of ESDA was added with vigorous stirring at once, followed by stirring for 30 minutes. Continued. 9.3 g (0.2 mol) of β picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the resultant was poured into methanol, dried by filtration to obtain 79 g of a yellow polyimide powder. The weight average molecular weight of the powder of this polyimide was 100,000.
(실시예 3)(Example 3)
① 2-(2,4-디니트로페녹시)에틸-1-신나메이트의 합성① Synthesis of 2- (2,4-dinitrophenoxy) ethyl-1-cinnamate
2,4-디니트로클로로벤젠 20.25g(0.1몰), 에틸렌글리콜 124g(2몰), 탄산칼륨 82.93g(0.6몰), 크실렌 600 ml을 반응용기에 취하고, 12시간 가열교반을 행하였다. 반응용액을 여별하고, 여액을 농축, 컬럼정제하고, 2-(2,4-디니트로페녹시)에탄올 17.0g 얻었다. 20.25 g (0.1 mol) of 2,4-dinitrochlorobenzene, 124 g (2 mol) of ethylene glycol, 82.93 g (0.6 mol) of potassium carbonate, and 600 ml of xylene were taken into a reaction vessel and heat stirring was carried out for 12 hours. The reaction solution was filtered, the filtrate was concentrated and purified by column to obtain 17.0 g of 2- (2,4-dinitrophenoxy) ethanol.
2-(2,4-디니트로페녹시)에탄올 10.65g(0.05몰), 계피산클로라이드 8.33g (0.05몰), o-디클로로벤젠 100 ml을 질소기류 하, 120∼130℃에서 2시간 교반을 행하였다. 반응종료 후, 반응용액을 헥산에 투입하고, 침전을 얻었다. 침전을 재결정에 의해 정제하고, 15.4g의 2-(2,4-디니트로페녹시)에틸-1-신나메이트를 얻었다. 10.65 g (0.05 mol) of 2- (2,4-dinitrophenoxy) ethanol, 8.33 g (0.05 mol) of cinnamic acid chloride, and 100 ml of o-dichlorobenzene were stirred at 120-130 degreeC for 2 hours under nitrogen stream. It was. After the reaction was completed, the reaction solution was poured into hexane to obtain a precipitate. The precipitate was purified by recrystallization to give 15.4 g of 2- (2,4-dinitrophenoxy) ethyl-1-cinnamate.
② 2-(2,4-디아미노페녹시)에틸-1-신나메이트의 합성② Synthesis of 2- (2,4-diaminophenoxy) ethyl-1-cinnamate
실시예2와 같은 방법으로, 환원하여 2-(2,4-디아미노페녹시)에틸-1-신나메이트를 얻었다. 발열 피크온도는 232℃ 이었다. In the same manner as in Example 2, reduction was carried out to obtain 2- (2,4-diaminophenoxy) ethyl-1-cinnamate. The exothermic peak temperature was 232 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 1000 ml의 분리플라스크에 2-(2,4-디아미노페녹시)에틸-1-신나메이트 14.4g(0.1몰), DMAc 150g을 취하고, 6FDA 22.2g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 34g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 11만이었다. 14.4 g (0.1 mol) of 2- (2,4-diaminophenoxy) ethyl-1-cinnamate and 150 g of DMAc were taken in a 1000 ml separating flask equipped with a stirrer, and 22.2 g (0.1 mol) of 6FDA were heated at once. It was added with stirring, and stirring was continued for 30 minutes as it was. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 34 g of a powder of white polyimide. The weight average molecular weight of the powder of this polyimide was 110,000.
(실시예4)Example 4
① 2-(3,5-디니트로벤조산)프로필-1-신나메이트의 합성① Synthesis of 2- (3,5-dinitrobenzoic acid) propyl-1-cinnamate
과잉인 프로필렌글리콜(계피산클로라이드에 대하여 10배몰 정도)을 용기에 취하고, 얼음으로 냉각한다. 이것에 계피산클로라이드를 가하고, 약120∼130℃에서 2시간정도, N2기류 하에서 교반한다. 반응혼합용액을 디클로로메탄으로 추출, 농축한다. 이 농축물을 컬럼으로 정제하고, 2-(2,4-디니트로벤조산)프로필-1-신나메이트를 수율70%로 얻었다. Excess propylene glycol (about 10 times molar relative to cinnamic acid chloride) is taken into a container and cooled with ice. Cinnamic acid chloride is added to this, and it stirs for about 2 hours at about 120-130 degreeC under N2 stream. The reaction mixture solution is extracted with dichloromethane and concentrated. This concentrate was purified by column to give 2- (2,4-dinitrobenzoic acid) propyl-1-cinnamate in 70% yield.
② 3,5-디니트로벤조산 클로라이드의 합성② Synthesis of 3,5-dinitrobenzoic acid chloride
3,5디니트로벤조산, 초산에틸을 반응용기에 취하고, 몇 방울의 DMF를 가한 염화티오닐(디니트로벤조산에 대하여 2배몰 정도)을 적하하고 염화수소가스가 발생하지 않게 될 때까지 환류교반한다. 반응용액을 고체가 석출하기 시작할 때까지 농축하고, 헥산에 투입하여 침전을 여별건조하고, 3,5-디니트로벤조산 클로라이드를 수율90%로 얻었다. 3,5 dinitrobenzoic acid and ethyl acetate are taken into a reaction vessel, and thionyl chloride (about 2 times molar relative to dinitrobenzoic acid) to which a few drops of DMF is added is added dropwise and stirred under reflux until no hydrogen chloride gas is generated. The reaction solution was concentrated until solids started to precipitate, and the resultant was added to hexane to separate the precipitates, and 3,5-dinitrobenzoic acid chloride was obtained in a yield of 90%.
③ 2-(3,5-디아미노벤조산)프로필-1-신나메이트의 합성③ Synthesis of 2- (3,5-diaminobenzoic acid) propyl-1-cinnamate
실시예2와 같은 방법으로, 환원하여 2-(3,5-디아미노벤조산)프로필-1-신나메이트를 얻었다. 발열 피크온도는 233℃ 이었다. In the same manner as in Example 2, reduction was performed to obtain 2- (3,5-diaminobenzoic acid) propyl-1-cinnamate. The exothermic peak temperature was 233 ° C.
④ 폴리이미드의 합성④ Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 2-(3,5-디아미노벤조산)프로필-1-신나메이트 34.0g(0.1몰), DMAc 300g을 취하고, 6FDA 44.4g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. 34.0 g (0.1 mol) of 2- (3,5-diaminobenzoic acid) propyl-1-cinnamate and 300 g of DMAc were added to a 2000 ml separating flask equipped with a stirrer, and 44.4 g (0.1 mol) of 6FDA was violently vigorously. It added while stirring, and continued stirring for 30 minutes as it is.
β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 74.5g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 10만이었다. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 74.5 g of a white polyimide powder. The weight average molecular weight of the powder of this polyimide was 100,000.
(실시예5)Example 5
① (4'-니트로페닐)-4-니트로신나메이트의 합성① Synthesis of (4'-nitrophenyl) -4-nitrocinnamate
4-니트로계피산 193.2g(1몰), 초산에틸 650g을 반응용기에 취하고, 몇 방울의 DMF를 가한 염화티오닐 200g를 적하하여 염화수소가스가 발생하지 않을 때까지 환류교반한다. 반응용액을 고체가 석출하기 시작할 때까지 농축하고, 헥산에 투입하여 침전을 여별건조하고, 4-니트로계피산클로라이드를 210g 얻었다. 193.2 g (1 mol) of 4-nitro cinnamic acid and 650 g of ethyl acetate are taken into a reaction vessel, 200 g of thionyl chloride added with a few drops of DMF is added dropwise, and the mixture is stirred under reflux until no hydrogen chloride gas is generated. The reaction solution was concentrated until solids started to precipitate, and the resultant was added to hexane to separate the precipitates, and 210 g of 4-nitro cinnamic acid chloride was obtained.
4-니트로계피산클로라이드 64.5g(0.3몰), 아세톤 300g을 반응용기에 취하고 질소기류 하에서 50℃로 가열교반한다. 상기 반응용기에 4-니트로페놀 41.73g(0.3 몰), 피리딘 60g, 아세톤 300g을 적하로트로 적하하고, 적하종료 후, 질소기류 하에서 2시간 환류교반을 하였다. 반응종료 후, 침전을 여별하고, 여별한 개체를 수세하고, 건조하여, 담황색의 바늘형상결정((4-니트로로페닐)-4-신나메이트) 90g를 얻었다. 64.5 g (0.3 mol) of 4-nitro cinnamic acid chloride and 300 g of acetone are taken into a reaction vessel, and the mixture is stirred by heating to 50 ° C. under a stream of nitrogen. 41.73 g (0.3 mol) of 4-nitrophenol, 60 g of pyridine, and 300 g of acetone were added dropwise to the reaction vessel, followed by stirring under reflux for 2 hours under nitrogen flow. After completion of the reaction, the precipitate was filtered and the filtered individual was washed with water and dried to obtain 90 g of a pale yellow needle-like crystal ((4-nitrolophenyl) -4-cinnamate).
② (4'-아미노페닐)-4-아미노신나메이트의 합성② Synthesis of (4'-aminophenyl) -4-aminocinnamate
(4-니트로로페닐)-4-신나메이트 6.91g(22 밀리몰), 5% Pt 및 2% 나트륨함유 카본블랙 0.6g(약50% 함수품), 1,4-디옥산 100 ml을 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약4시간에 3.17 리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여별하여, Pt함유 카본을 제거하고 나서, 농축, 재결정하여 (4'-아미노페닐)-4-아미노신나메이트 4.9g를 얻었다. 발열 피크온도는 233℃이었다. 6.91 g (22 mmol) of (4-nitrolophenyl) -4-cinnamate, 0.6 g (about 50% water) of 5% Pt and 2% sodium, and 100 ml of 1,4-dioxane The mixture was taken up in a water addition device, and heated and stirred at 60 ° C. under a hydrogen atmosphere. 3.17 liters of hydrogen was absorbed in about 4 hours, and the absorption of hydrogen was stopped. Therefore, the reaction was stopped, the reaction solution was filtered off, the Pt-containing carbon was removed, concentrated and recrystallized from (4'-aminophenyl)- 4.9 g of 4-aminocinnamate were obtained. The exothermic peak temperature was 233 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에(4'-아미노페닐)-4-아미노신나메이트 25.4g(0.1몰), DMAc 300g을 취하고, 6FDA 44.4g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 66g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 12만이었다. (4'-aminophenyl) -4-aminocinnamate 25.4g (0.1 mol) and DMAc 300g were taken into a 2000 ml separatory flask equipped with the stirrer, and 64.4 F (44.4 g) (0.1 mol) was added at once, vigorously stirring, Stirring was continued for 30 minutes as it was. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 66 g of a powder of white polyimide. The weight average molecular weight of the powder of this polyimide was 120,000.
(실시예6) Example 6
① (3'-니트로페닐)-3-니트로신나메이트의 합성① Synthesis of (3'-nitrophenyl) -3-nitrocinnamate
3-니트로계피산 193.2g(1몰), 초산에틸 650g을 반응용기에 취하고, 몇 방울의 DMF를 가한 염화티오닐 200g을 적하하여 염화수소가스가 발생하지 않게 될 때까지 환류교반한다. 반응용액을 고체가 석출하기 시작할 때까지 농축하고, 헥산에 투입하여 침전을 여별건조하고, 3-니트로계피산클로라이드를 205g 얻었다. 193.2 g (1 mol) of 3-nitro cinnamic acid and 650 g of ethyl acetate are taken into a reaction vessel, and 200 g of thionyl chloride added with a few drops of DMF is added dropwise and stirred under reflux until no hydrogen chloride gas is generated. The reaction solution was concentrated until solids started to precipitate, and the resultant was added to hexane to separate the precipitates, and 205 g of 3-nitro cinnamic acid chloride was obtained.
3-니트로계피산클로라이드 64.5g(0.3몰), 아세톤 300g을 반응용기에 취하고 질소기류 하에서 50℃로 가열교반한다. 상기 반응용기에 3-니트로페놀 41.73g(0.3몰), 피리딘 60g, 아세톤 300g을 적하로트로 적하하고, 적하종료 후, 질소기류 하에서 2시간 환류교반을 핼하였다. 반응종료 후, 용액을 농축하여 얻은 개체를 수세하고, 건조하여, 담황색의 바늘형상결정(3-니트로페닐)-3-신나메이트 85g를 얻었다.64.5 g (0.3 mol) of 3-nitro cinnamic acid chloride and 300 g of acetone are taken in a reaction vessel and stirred by heating to 50 ° C. under a stream of nitrogen. 41.73 g (0.3 mole) of 3-nitrophenol, 60 g of pyridine, and 300 g of acetone were added dropwise to the reaction vessel, and the mixture was refluxed under reflux for 2 hours under a nitrogen stream. After completion of the reaction, the individual obtained by concentrating the solution was washed with water and dried to obtain 85 g of pale yellow needle-like crystals (3-nitrophenyl) -3-cinnamate.
② (3'-아미노페닐)-3-아미노신나메이트의 합성② Synthesis of (3'-aminophenyl) -3-aminocinnamate
(3-니트로페닐)-3-신나메이트 6.91g(22 밀리몰), 5% Pt함유 카본블랙 0.5g(약50% 함수품), 1,4-디옥산 100ml을 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약4시간에 3.15 리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여별하여, Pt함유 카본을 제거하고 나서, 농축, 재결정하고 (3'-아미노페닐)-3-아미노신나메이트 4.0g를 얻었다. 발열 피크온도는 233℃ 이었다.6.91 g (22 mmol) of (3-nitrophenyl) -3-cinnamate, 0.5 g of carbon black containing 5% Pt (about 50% water-containing product), and 100 ml of 1,4-dioxane were added to the reaction vessel (water addition device). The mixture was heated and stirred at 60 ° C. under a hydrogen atmosphere. After absorbing 3.15 liters of hydrogen in about 4 hours and the absorption of hydrogen stopped, the reaction was stopped, the reaction solution was filtered off, the Pt-containing carbon was removed, concentrated and recrystallized (3'-aminophenyl)- 4.0 g of 3-aminocinnamate was obtained. The exothermic peak temperature was 233 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 (3'-아미노페닐)-3-아미노신나메 이트 25.4g(0.1몰), DMAc 300g을 취하고, 6FDA 44.4g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β 피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하여, 여별건조하여, 65g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 10만이었다. 25.4 g (0.1 mol) of (3'-aminophenyl) -3-aminocinnamate and 300 g of DMAc were added to a 2000 ml separatory flask equipped with a stirrer, and 44.4 g (0.1 mol) of 6FDA was added to the flask with vigorous stirring. Stirring was continued for 30 minutes as it was. 9.3 g (0.2 mol) of β picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 65 g of a powder of white polyimide. The weight average molecular weight of the powder of this polyimide was 100,000.
(실시예7)Example 7
① 1'-니트로-2'-나프틸-(3-니트로신나메이트)의 합성① Synthesis of 1'-nitro-2'-naphthyl- (3-nitrocinnamate)
실시예2에서 얻은 3-니트로계피산클로라이드 21.5g(0.1몰), 아세톤200g을 반응용기에 취하고 질소기류 하에서 50℃에 가열교반한다. 상기 반응용기에 1-니트로-2-나프톨 18.9g(0.1몰), 피리딘 20g, 아세톤 300g을 적하로트로 적하하고, 적하종료 후, 질소기류 하에서 2시간 환류교반을 행하였다. 반응종료 후, 용액을 농축하여 얻은 개체를 수세하고, 건조하여, 담황색의 바늘형상결정 1'-니트로-2'-나프틸-(3-니트로신나메이트) 35g를 얻었다. 21.5 g (0.1 mol) of 3-nitro cinnamic acid chloride and 200 g of acetone obtained in Example 2 were taken into a reaction vessel and stirred by heating at 50 ° C. under a stream of nitrogen. 18.9 g (0.1 mol) of 1-nitro-2-naphthol, 20 g of pyridine, and 300 g of acetone were added dropwise to the reaction vessel, and the mixture was refluxed under a stream of nitrogen for 2 hours after completion of the dropwise addition. After completion of the reaction, the individual obtained by concentrating the solution was washed with water and dried to obtain 35 g of a pale yellow needle-like crystal 1'-nitro-2'-naphthyl- (3-nitrocinnamate).
② 1'-아미노-2'-나프틸-(3-아미노신나메이트)의 합성② Synthesis of 1'-amino-2'-naphthyl- (3-aminocinnamate)
1'-니트로-2'나프틸-(3-니트로신나메이트) 7.28g(20 밀리몰), 5% Pt 함유 카본블랙 0.5g(약50% 함수품), 1,4-디옥산 100 ml를 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 하였다. 약4시간에 2.9 리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여별하여, Pt함유 카본을 제거하고 나서, 농축, 재결정하여 1'-아미노-2'-나프틸-(3-아미노신나메 이트) 4.5g를 얻었다. 발열 피크온도는 231℃ 이었다. 7.28 g (20 mmol) of 1'-nitro-2 'naphthyl- (3-nitrocinnamate), 0.5 g of carbon black containing 5% Pt (about 50% water), 100 ml of 1,4-dioxane It was taken in a container (water addition device) and heated and stirred at 60 ° C under a hydrogen atmosphere. After absorbing 2.9 liters of hydrogen in about 4 hours and the absorption of hydrogen stopped, the reaction was stopped, the reaction solution was filtered off, the Pt-containing carbon was removed, concentrated and recrystallized to obtain 1'-amino-2'-. 4.5 g of naphthyl- (3-aminocinnamate) were obtained. The exothermic peak temperature was 231 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 1'-아미노-2'-나프틸-(3-아미노신나메이트) 30.4g(0.1몰), DMAc 300g을 취하고, 6FDA 44.4g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 70g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 13만이었다. 30.4 g (0.1 mol) of 1'-amino-2'-naphthyl- (3-aminocinnamate) and 300 g of DMAc were taken in a 2000 ml separating flask equipped with a stirrer, and 44.4 g (0.1 mol) of 6FDA were vigorously heated. It was added with stirring, and stirring was continued for 30 minutes as it was. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 70 g of a powder of white polyimide. The weight average molecular weight of the powder of this polyimide was 130,000.
(실시예8)Example 8
① 1,3-비스(4-니트로계피산) 벤젠의 합성① Synthesis of 1,3-bis (4-nitro cinnamic acid) benzene
4-니트로계피산 193.2g(1몰), 초산에틸 650g을 반응용기에 취하고, 몇 방울의 DMF를 가한 염화티오닐 200g를 적하하여 염화수소가스가 발생하지 않게 될 때까지 환류교반한다. 반응용액을 고체가 석출하기 시작할 때까지 농축하고, 헥산에 투입하여 침전을 여별건조하고, 4-니트로계피산클로라이드를 210g 얻었다. 193.2 g (1 mol) of 4-nitro cinnamic acid and 650 g of ethyl acetate are taken into a reaction vessel, and 200 g of thionyl chloride added with a few drops of DMF is added dropwise and stirred under reflux until no hydrogen chloride gas is generated. The reaction solution was concentrated until solids started to precipitate, and the resultant was added to hexane to separate the precipitates, and 210 g of 4-nitro cinnamic acid chloride was obtained.
4-니트로계피산클로라이드 63.5g(0.3몰), 메틸에틸케톤 400g을 반응용기에 취하고 질소기류 하에서 50℃로 가열교반한다. 상기 반응용기에 레졸시놀 15.42g(0.14몰), 피리딘 32g, 메틸에틸케톤 100g를 적하로트로 적하하고, 적하종료 후, 질소기류 하에서 2시간 환류교반을 행하였다. 반응종료 후, 침전을 여별하고, 여별한 개체를 수세하고, 건조하여, 백색결정(1,3-비스(4-니트로계피산)벤젠) 64g 를 얻었다. 63.5 g (0.3 mol) of 4-nitro cinnamic acid chloride and 400 g of methyl ethyl ketone are taken into a reaction vessel and stirred by heating to 50 ° C. under a stream of nitrogen. 15.42 g (0.14 mol) of resorcinol, 32 g of pyridine, and 100 g of methyl ethyl ketone were added dropwise to the reaction vessel, and the mixture was refluxed under a stream of nitrogen for 2 hours after completion of the dropwise addition. After completion of the reaction, the precipitate was filtered off, the filtered individual was washed with water and dried to obtain 64 g of white crystals (1,3-bis (4-nitro cinnamic acid) benzene).
② 1,3-비스(4-아미노계피산) 벤젠의 합성 ② Synthesis of 1,3-bis (4-amino Cinnamic Acid) Benzene
1,3-비스(4-니트로계피산) 벤젠 10.13g(22 밀리몰), 5% Pt함유 카본블랙 0.5g(약50% 함수품), 1,4-디옥산 100 ml를 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약4시간에 3.14리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여별하여, Pt함유 카본을 제거하고 나서, 농축, 재결정하여 1,3-비스(4-아미노계피산) 벤젠 8.0g을 얻었다. 발열 피크온도는 231℃ 이었다. 1,3-bis (4-nitro cinnamic acid) Benzene 10.13 g (22 mmol), 5% Pt-containing carbon black 0.5g (about 50% water), 100 ml of 1,4-dioxane reaction vessel (water addition device) ), And stirring was carried out at 60 DEG C under a hydrogen atmosphere. 3.14 liters of hydrogen was absorbed in about 4 hours, and the absorption of hydrogen was stopped. Therefore, the reaction was stopped, the reaction solution was filtered off, the Pt-containing carbon was removed, concentrated and recrystallized to obtain 1,3-bis (4- Amino cinnamic acid) 8.0g of benzene was obtained. The exothermic peak temperature was 231 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 1,3-비스(4-아미노계피산) 벤젠 40.0g(0.1몰), DMAc 300g을 취하고, 6FDA 44.4g(0.1몰)를 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃에 가열하여, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하여, 여별건조하여, 79g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 10만이었다. 40.0 g (0.1 mol) of 1,3-bis (4-amino cinnamic acid) benzene and 300 g of DMAc were added to a 2000 ml separatory flask equipped with a stirrer, and 44.4 g (0.1 mol) of 6FDA was added at once with vigorous stirring. Stirring was continued for 30 minutes. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, and heated to about 150 ° C to imide. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 79 g of a white polyimide powder. The weight average molecular weight of the powder of this polyimide was 100,000.
(실시예9)Example 9
① 1,2-비스(4-니트로계피산)에틸의 합성① Synthesis of 1,2-bis (4-nitro cinnamic acid) ethyl
실시예2의 4-니트로계피산클로라이드 11.64g(55 밀리몰), o-디클로로벤젠 100 ml, 에틸렌글리콜 1.55g(25 밀리몰)을 반응용기에 취하여 질소기류 하에서 120 ∼130℃로 가열교반한다. 약2시간 후 반응용액을 메탄올에 투입하여 석출한 침전을 여별건조하여 백색의 고체 6.83g(1,2-비스(4-니트로계피산)에틸)을 얻었다. 11.64 g (55 mmol) of 4-nitro cinnamic acid chloride of Example 2, 100 ml of o-dichlorobenzene, and 1.55 g (25 mmol) of ethylene glycol are taken into a reaction vessel and heated and stirred at 120 to 130 ° C. under a nitrogen stream. After about 2 hours, the reaction solution was poured into methanol, and the precipitated precipitate was filtered and dried to yield 6.83 g (1,2-bis (4-nitro cinnamic acid) ethyl) as a white solid.
② 1,2-비스(4-아미노계피산)에틸의 합성② Synthesis of 1,2-bis (4-amino Cinnamic Acid) ethyl
3-비스(4-아미노계피산)에틸 9.07g(22밀리몰), 5% Pt함유 카본블랙 0.5g(약50% 함수품), 1,4-디옥산 100 ml를 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃에 가열교반을 하였다. 약4시간으로 3.18리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여별하여, Pt함유 카본을 제거하고 나서, 농축, 재결정하여 1,3-비스(4-아미노계피산)에틸 7.0g을 얻었다. 발열 피크온도는 231℃ 이었다. 9.07 g (22 mmol) of 3-bis (4-amino cinnamic acid) ethyl, 0.5 g (about 50% water-containing product) containing 5% Pt, and 100 ml of 1,4-dioxane were added to a reaction vessel (water addition device). The mixture was heated and stirred at 60 ° C. under a hydrogen atmosphere. 3.18 liters of hydrogen was absorbed in about 4 hours and the absorption of hydrogen was stopped. Therefore, the reaction was stopped, the reaction solution was filtered off, the Pt-containing carbon was removed, concentrated and recrystallized, and then 1,3-bis (4- 7.0 g of amino cinnamic acid) was obtained. The exothermic peak temperature was 231 ° C.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 1,3-비스(4-아미노계피산)에틸 35.2g(0.1몰), DMAc 300g을 취하고, 6FDA 44.4g (0.1몰)를 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약150℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 74g의 백색의 폴리이미드의 분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 10만이었다. 35.2 g (0.1 mol) of 1,3-bis (4-amino cinnamic acid) ethyl and 300 g of DMAc were added to a 2000 ml separatory flask equipped with a stirrer, and 44.4 g (0.1 mol) of 6FDA was added to the flask with vigorous stirring. Stirring was continued for 30 minutes. 9.3 g (0.2 mol) of β-picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, heated to about 150 ° C, and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 74 g of a powder of white polyimide. The weight average molecular weight of the powder of this polyimide was 100,000.
실시예10은, 디올말단의 이미드올리고머와 계피산유도체의 클로라이드와의 반응에 의해 폴리이미드를 얻었다. Example 10 obtained polyimide by reaction of the diol terminal imide oligomer and the chloride of a cinnamic acid derivative.
(실시예10) Example 10
① 디올말단의 이미드올리고머와 2-카르복시계피산의 디산클로라이드의 합성 ① Synthesis of diol terminal imide oligomer and dicarboxylic acid salt of 2-carboxylactic acid
교반기 및 딘스타크관이 있는 1000 ml의 둥근바닥 플라스크에 ESDA 115.3g(0.2몰)을 취하고, 2-아미노에탄올 30.7g(0.48몰)과 DMAc 200g을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 41.9g(0.45몰), 톨루엔 50g을 상기 반응용액에 가하고, 물을 딘스타크관에 의해 제외하면서 가열환류하고, 이미드화하였다.(약4시간) 반응종료 후, 용매를 증류 제거하고, 디올말단의 이미드올리고머를 138g 얻었다. 이것을 컬럼정제(실리카겔/용매아세톤)하여 약80g의 디올말단의 이미드올리고머를 얻었다. Take 115.3 g (0.2 mol) of ESDA into a 1000 ml round bottom flask with a stirrer and a Dean Stark tube, add 30.7 g (0.48 mol) of 2-aminoethanol and 200 g of DMAc with vigorous stirring at once, and stir for 30 minutes. Continued. 41.9 g (0.45 mole) of β-picoline and 50 g of toluene were added to the reaction solution, and the mixture was heated to reflux and imidized while removing water through a Dean Stark tube. (about 4 hours) After completion of the reaction, the solvent was distilled off. And 138g of imol oligomers of the diol terminal were obtained. This was purified by column (silica gel / solvent acetone) to obtain an imide oligomer of about 80 g of diol terminal.
2-카르복시계피산 28.8g(0.15몰), 초산에틸 300g을 반응용기에 취하고, 몇 방울의 DMF를 가한 염화티오닐 90g를 적하하여 염화수소가스가 발생하지 않게 될 때까지 환류교반한다. 반응용액을 고체가 석출하기 시작할 때까지 농축하고, 헥산에 투입하여 침전을 여별건조하고, 2-카르복시계피산의 디산클로라이드를 25.9g 얻었다. 28.8 g (0.15 mole) of 2-carboxylic acid and 300 g of ethyl acetate are taken into a reaction vessel, and 90 g of thionyl chloride to which a few drops of DMF is added is added dropwise and stirred under reflux until no hydrogen chloride gas is generated. The reaction solution was concentrated until solids started to precipitate, and the resultant was added to hexane, and the precipitate was filtered and dried to obtain 25.9 g of diacid chloride of 2-carboxylic acid.
② 폴리이미드의 합성② Synthesis of Polyimide
2-카르복시계피산의 디산클로라이드 11.4g(50 밀리몰), 니트로벤젠200 ml, 디올말단의 이미드올리고머 33.1g(50 밀리몰)을 반응용기에 취하고 질소기류 하에서 120∼130℃로 가열교반한다. 약2시간 후 반응용액을 메탄올에 투입하여 석출한 침전을 여별건조하여 백색의 고체 33.6g를 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 8만이었다. 11.4 g (50 mmol) of diacid chloride of 2-carboxypic acid, 200 ml of nitrobenzene, and 33.1 g (50 mmol) of imide oligomer of the diol terminal are taken into a reaction vessel and stirred by heating at 120 to 130 ° C. under a nitrogen stream. After about 2 hours, the reaction solution was poured into methanol, and the precipitated precipitate was filtered and dried to yield 33.6 g of a white solid. The weight average molecular weight of the powder of this polyimide was 80,000.
이하 실시예11∼13에 있어서는, 본 발명에 이러한 계피산골격을 가지는 신규인 산이무수물을 제조하고, 폴리이미드화합물을 합성하였다. In Examples 11 to 13 below, novel acid dianhydrides having such cinnamic acid skeletons were prepared in the present invention, and polyimide compounds were synthesized.
(실시예11)Example 11
① 2-카르복시계피산의 디산클로라이드의 합성① Synthesis of diacid chloride of 2-carboxypic acid
2-카르복시계피산 28.8g(0.15몰), 초산에틸 300g을 반응용기에 취하고, 몇 방울의 DMF를 가한 염화티오닐 90g를 적하하여 염화수소가스가 발생하지 않을 때까지 환류교반한다. 반응용액을 고체가 석출하기 시작할 때까지 농축하고, 헥산에 투입하여 침전을 여별건조하고, 2-카르복시계피산의 디산클로라이드를 25.9g 얻었다. 28.8 g (0.15 mol) of 2-carboxypic acid and 300 g of ethyl acetate are taken into a reaction vessel, and 90 g of thionyl chloride added with a few drops of DMF is added dropwise, and the mixture is stirred under reflux until no hydrogen chloride gas is generated. The reaction solution was concentrated until solids started to precipitate, and the resultant was added to hexane, and the precipitate was filtered and dried to obtain 25.9 g of diacid chloride of 2-carboxylic acid.
② 2-카르복시계피산의 디산클로라이드와 3-히드록시무수프탈산에 의한 산이무수물의 합성② Synthesis of acid dianhydride by diacid chloride and 3-hydroxyphthalic anhydride of 2-carboxypic acid
3-히드록시무수프탈산 4.92g(30 밀리몰), 메틸에틸케톤 50g, 피리딘3g을 반응용기에 취하고, 질소기류 하 60℃에서 교반한다. 이 용액에 2-카르복시계피산의 디산클로라이드 3.44g(15 밀리몰)을 메틸에틸케톤 30g에 용해하여 천천히 적하한다. 적하종료 후 약2시간 교반을 계속하였다. 냉각후, 석출한 고체를 여별하고, 물로 세정 후, 무수초산으로 재결정하여, 5.5g의 산이무수물을 얻었다. 발열 피크온도는 233도이었다. 4.92 g (30 mmol) of 3-hydroxyphthalic anhydride, 50 g of methyl ethyl ketone, and 3 g of pyridine are taken into a reaction vessel and stirred at 60 ° C. under a nitrogen stream. To this solution, 3.44 g (15 mmol) of dicarboxylic acid chloride of 2-carboxypic acid is dissolved in 30 g of methyl ethyl ketone and slowly added dropwise thereto. After the dropwise addition, stirring was continued for about 2 hours. After cooling, the precipitated solid was filtered off, washed with water and recrystallized with acetic anhydride to obtain 5.5 g of acid dianhydride. The exothermic peak temperature was 233 degrees.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 300 ml의 분리플라스크에 옥시디아닐리온 200g (0.01몰), DMAc 30g을 취하고, 실시예1의 산이무수물 4.84g(0.01몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. 200 g (0.01 mol) of oxydianilion and 30 g of DMAc were added to a 300 ml separatory flask equipped with a stirrer, and 4.84 g (0.01 mol) of the acid dianhydride of Example 1 was added thereto under vigorous stirring, followed by stirring for 30 minutes. Continued.
β피콜린 0.93g(0.02몰), 무수초산 5g, DMAc 10g을 상기 반응용액에 가하고, 약120℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 메탄올에 투입하고, 여별건조하여, 6.2g의 황색의 폴리이미드화합물의 분말을 얻었다. 이 폴리이미드화합물의 분말의 중량평균분자량은, 8만이었다. 0.93 g (0.02 mol) of β-picoline, 5 g of acetic anhydride, and 10 g of DMAc were added to the reaction solution, heated to about 120 ° C., and imidized. These reactions were performed under nitrogen stream. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 6.2 g of a powder of yellow polyimide compound. The weight average molecular weight of the powder of this polyimide compound was 80,000.
(실시예12)Example 12
① 에틸렌글리콜과 2-카르복시계피산의 디산클로라이드에 의한 디올의 합성① Synthesis of Diol by Diacid Chloride of Ethylene Glycol and 2-Carboxypic Acid
에틸렌글리콜 186.2g(3몰), 2-카르복시계피산의 디산클로라이드 22.9g (0.1몰)을 반응용기에 취하고, 질소기류 하 약120℃에서 염화수소의 발생이 멈출 때까지 약2시간 교반을 행하였다. 186.2 g (3 mol) of ethylene glycol and 22.9 g (0.1 mol) of diacid chloride of 2-carboxynic acid were taken into a reaction vessel, and the mixture was stirred for about 2 hours until the generation of hydrogen chloride stopped at about 120 ° C under a nitrogen stream.
반응종료 후, 반응용액을 물에 투입하고, 이 물층을 염화메틸렌에 의해 추출하고, 염화메틸렌을 농축건조함에 의해, 25g의 디올을 얻었다. After completion of the reaction, the reaction solution was poured into water, the water layer was extracted with methylene chloride, and methylene chloride was concentrated to dryness to obtain 25 g of diol.
② 상기 디올과 트리멜리트산 클로라이드에 의한 산이무수물의 합성② Synthesis of acid dianhydride by the diol and trimellitic acid chloride
상기 디올 16.3g(58 밀리몰), 트리멜리트산 클로라이드 25.3g(l20 밀리몰), 니트로벤젠 450 ml를 반응용기에 취하고, 질소기류 하 약120℃에서 염화수소의 발생이 멈출 때까지 약2시간 교반을 행하였다. 냉각 후, 헥산에 투입하고, 분리한 액체를 나눠, 감압건조하고, 컬럼정제하여, 원하는 산이무수물 19g을 얻었다. 발열 피크온도는 232도이었다. 16.3 g (58 mmol) of diol, 25.3 g (l20 mmol) of trimellitic acid chloride, and 450 ml of nitrobenzene were taken into a reaction vessel and stirred for about 2 hours until the generation of hydrogen chloride stopped at about 120 ° C. under a nitrogen stream. It was. After cooling, the mixture was poured into hexane, the separated liquid was divided, dried under reduced pressure, and the column was purified to obtain 19 g of the desired acid dianhydride. The exothermic peak temperature was 232 degrees.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 300ml의 분리플라스크에 옥시디아닐리온 200g (0.01몰), DMAc 30g를 취하고, 실시예2의 산이무수물 6.29g(0.01몰)를 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. 200 g (0.01 mol) of oxydianilion and 30 g of DMAc were added to a 300 ml separatory flask equipped with a stirrer, and 6.29 g (0.01 mol) of the acid dianhydride of Example 2 was added thereto under vigorous stirring, and stirring was continued for 30 minutes. It was.
β피콜린 0.93g(0.02몰), 무수초산 5g, DMAc 10g을 상기 반응용액에 가하고, 약120℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 0.93 g (0.02 mol) of β-picoline, 5 g of acetic anhydride, and 10 g of DMAc were added to the reaction solution, heated to about 120 ° C., and imidized. These reactions were performed under nitrogen stream.
반응종료 후, 메탄올에 투입하고, 여별건조하여, 7.7g의 황색의 폴리이미드화합물의 분말을 얻었다. 이 폴리이미드화합물의 분말의 중량평균분자량은, 9만이었다. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 7.7 g of a yellow polyimide compound powder. The weight average molecular weight of the powder of this polyimide compound was 90,000.
(실시예13)Example 13
① 글리세롤과 계피산클로라이드에 의한 디올의 합성① Synthesis of diol by glycerol and cinnamon chloride
글리세롤 46.04g(0.5몰), 계피산클로라이드 8.33g(0.05몰)을 반응용기에 취하고, 질소기류 하에서 약120도로 HCl의 발생이 멈출 때까지 약2시간 가열교반을 행하였다. 46.04 g (0.5 mol) of glycerol and 8.33 g (0.05 mol) of cinnamic acid chloride were taken into a reaction vessel, and heating and stirring were performed for about 2 hours until the generation of HCl stopped at about 120 degrees under a nitrogen stream.
반응종료 후, 물에 반응용액을 투입하고, 디클로로메탄으로 추출건조 후, 컬럼정제하고, 9.9g의 2-(1,3-프로필렌글리콜)신나메이트와 3-(1,2-프로필렌글리콜)신나메이트의 혼합물(약3:1의 비율의 혼합물)을 얻었다. 이것은, 중아세톤용매이고, H-NMR에 의해 동정(同定)하였다. After completion of the reaction, the reaction solution was added to water, extracted and dried with dichloromethane, and then purified by column, and 9.9 g of 2- (1,3-propylene glycol) cinnamate and 3- (1,2-propylene glycol) cinna A mixture of mate (a mixture of about 3: 1 ratio) was obtained. This was a heavy acetone solvent and was identified by H-NMR.
② 상기 디올의 혼합물과 트리멜리트산 클로라이드에 의한 산이무수물의 합성② Synthesis of acid dianhydride by mixture of diol and trimellitic acid chloride
상기 디올 8.89g(40 밀리몰), 무수트리멜리트산 클로라이드 17.9g(85 밀리몰), o-디클로로벤젠 150 ml를 반응용기에 취하고, 질소기류 하에서 약120도로 HCl의 발생이 멈출 때까지 가열교반을 행하였다(약3시간). 냉각 후, 헥산에 투입하고, 감압건조하고, 컬럼정제하여, 원하는 산이무수물 8.3g을 얻었다. 발열 피크온도는 235도이었다. 8.89 g (40 mmol) of diol, 17.9 g (85 mmol) of trimellitic anhydride chloride, and 150 ml of o-dichlorobenzene were taken into a reaction vessel, and heated and stirred until the generation of HCl stopped at about 120 ° C under a nitrogen stream. (About 3 hours). After cooling, the mixture was poured into hexane, dried under reduced pressure, and purified by column to obtain 8.3 g of the desired acid dianhydride. The exothermic peak temperature was 235 degrees.
③ 폴리이미드의 합성③ Synthesis of Polyimide
교반기를 설치한 300 ml의 분리플라스크에 옥시디아닐리온 200g (0.01몰), DMAc 30g를 취하고, 실시예3의 산이무수물 5.70g(0.01몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. 200 g (0.01 mol) of oxydianione and 30 g of DMAc were added to a 300 ml separatory flask equipped with a stirrer, and 5.70 g (0.01 mol) of the acid dianhydride of Example 3 was added with vigorous stirring at once, and stirring was continued for 30 minutes. Continued.
β피콜린 0.93g(0.02몰), 무수초산 5g, DMAc 10g을 상기 반응용액에 가하고, 약120℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 0.93 g (0.02 mol) of β-picoline, 5 g of acetic anhydride, and 10 g of DMAc were added to the reaction solution, heated to about 120 ° C., and imidized. These reactions were performed under nitrogen stream.
반응종료 후, 메탄올에 투입하고, 여별건조하여, 7.2g의 황색의 폴리이미드화합물의 분말을 얻었다. 이 폴리이미드화합물의 분말의 중량평균분자량은, 8만이었다. After completion of the reaction, the mixture was poured into methanol, and dried separately to obtain 7.2 g of a yellow polyimide compound powder. The weight average molecular weight of the powder of this polyimide compound was 80,000.
(실시예14)Example 14
교반기와 딘스타크관을 설치한 1000 ml의 분리플라스크에 1,3-디아미노-프로판-2-올 9.01g(0.1몰), DMAc 100g을 취하고, 6FDA 44.4g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. β피콜린 18.6g, 톨루엔 50g을 상기 반응용액에 가하고, 물을 적극적으로 제거하면서 약3시간 환류교반하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 반응용액을 메탄올에 투입하고, 여별건조하여 48g의 백색폴리이미드분말을 얻었다. 9.01 g (0.1 mole) of 1,3-diamino-propan-2-ol and 100 g of DMAc were added to a 1000 ml separation flask equipped with a stirrer and a Dean Stark tube, and 44.4 g (0.1 mole) of 6FDA was stirred vigorously at once. Was added while stirring was continued for 30 minutes. 18.6 g of β picoline and 50 g of toluene were added to the reaction solution, and the mixture was stirred under reflux for about 3 hours while actively removing water, followed by imidization. These reactions were performed under nitrogen stream. After completion of the reaction, the reaction solution was poured into methanol, and dried by filtration to obtain 48 g of white polyimide powder.
이 백색폴리이미드분말 25g, 니트로벤젠 200 ml, 계피산클로라이드 16.6g(0.1몰)를 반응용기에 취하고, 약120℃로 2시간 가열교반하였다. 반응용액을 메탄올에 투입하고, 여별건조하여 31g의 계피산골격이 측쇄에 도입된 백색폴리이미 드분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 7만이었다. 25 g of this white polyimide powder, 200 ml of nitrobenzene and 16.6 g (0.1 mol) of cinnamic acid chloride were taken into a reaction vessel, and the mixture was heated and stirred at about 120 ° C. for 2 hours. The reaction solution was poured into methanol, and dried by filtration to obtain a white polyimide powder having 31 g of cinnamic acid skeleton introduced into the side chain. The weight average molecular weight of the powder of this polyimide was 70,000.
(실시예15) Example 15
1,3-비스(4-니트로페녹시)-2-프로필알콜의 합성Synthesis of 1,3-bis (4-nitrophenoxy) -2-propyl alcohol
p-니트로페놀 76.5g(0.55몰), 글리세롤-αα'-디클로로히드린 32.3g (0.25몰) 크실렌 500 ml를 반응용액에 가하고, 질소기류 하에서 가열교반을 행하였다. 고형물이 용해하면, 무수탄산칼륨 345g(2.5몰)을 가하고, 12시간 환류교반하였다. 반응용액이 뜨거운 동안에 여별하고, 냉각 후 헥산을 여액에 보태고, 황색의 점조(粘調)한 액체를 얻었다. 이 액체를 건조하여, 컬럼정제하여 55g의 황색의 점조한 액체(1,3-비스(4-니트로페녹시-2-프로필알콜)을 얻었다. 76.5 g (0.55 mol) of p-nitrophenols and 500 ml of 32.3 g (0.25 mol) xylenes of glycerol-alpha-'dichlorohydrin were added to the reaction solution, and heat stirring was carried out under nitrogen stream. When the solid dissolved, 345 g (2.5 mol) of anhydrous potassium carbonate was added, and the mixture was stirred under reflux for 12 hours. The reaction solution was filtered while hot, and after cooling, hexane was added to the filtrate to obtain a yellow viscous liquid. This liquid was dried and column purified to obtain 55 g of a yellow viscous liquid (1,3-bis (4-nitrophenoxy-2-propyl alcohol).
1,3-비스(4-니트로페녹시)-2-프로필신나메이트의 합성Synthesis of 1,3-bis (4-nitrophenoxy) -2-propylcinnamate
상기 점조한 액체 33.4g(0.1몰)로 계피산클로라이드 25g(0.15몰) o-디클로로벤젠 300 ml를 반응용기에 취하고, 약120℃에서 2시간 가열교반하였다. 반응용액에 헥산을 보태고, 황색의 점조한 액체를 얻었다. 이 액체를 건조하고 컬럼정제하여 35g의 황색의 점조한 액체 「1,3-비스(4-니트로페녹시)-2-프로필신나메이트」를 얻었다. 300 g of cinnamic acid chloride 25 g (0.15 mole) o-dichlorobenzene was taken into a reaction vessel with 33.4 g (0.1 mole) of the viscous liquid, and the mixture was heated and stirred at about 120 ° C. for 2 hours. Hexane was added to the reaction solution to obtain a yellow viscous liquid. This liquid was dried and column purified to obtain 35 g of a yellow viscous liquid, "1,3-bis (4-nitrophenoxy) -2-propyl cinnamate".
1,3-비스(4-아미노페녹시)-2-프로필신나메이트의 합성 Synthesis of 1,3-bis (4-aminophenoxy) -2-propylcinnamate
1,3-비스(4-니트로페녹시)-2-프로필신나메이트 34.8g(0.075몰), 5% Pt 및 2% 철함유카본분말 15g(약50% 함수품), 1,4-디옥산 300 ml를 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약8시간으로 10.8 리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여 별하여, 촉매를 제거하고 나서, 농축하여 1,3-비스(4-아미노페녹시)-2-프로필신나메이트 30.3g를 얻었다. 발열 피크온도는, 230℃이었다. 34.8 g (0.075 mol) of 1,3-bis (4-nitrophenoxy) -2-propyl cinnamate, 5 g of Pt and 2% of iron-containing carbon powder (about 50% of water), 1,4-dioxane 300 ml was taken in a reaction vessel (water addition device), and the heating was stirred at 60 ° C. under a hydrogen atmosphere. After absorbing 10.8 liters of hydrogen in about 8 hours and the absorption of hydrogen stopped, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed and concentrated to give 1,3-bis (4-aminophenoxy. 30.3 g of) -2-propyl cinnamate was obtained. The exothermic peak temperature was 230 ° C.
폴리이미드의 합성Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 30.3g(0.075몰), DMAc 250g을 취하고, 6FDA 33.3g(0.075몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반을 계속하였다. 30.3 g (0.075 mol) and DMAc 250 g were taken into a 2000 ml separatory flask equipped with a stirrer, and 33.3 g (0.075 mol) of 6FDA was added with vigorous stirring at once, and stirring was continued for 30 minutes.
β피콜린 9.3g(0.2몰), 무수초산 50g, DMAc 100g을 상기 반응용액에 가하고, 약120℃로 가열하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 반응용액을 메탄올에 투입하고, 여별건조하여 60g의 백색폴리이미드분말을 얻었다. 이 폴리이미드의 분말의 중량평균분자량은, 12만이었다. 9.3 g (0.2 mol) of β picoline, 50 g of acetic anhydride, and 100 g of DMAc were added to the reaction solution, and heated to about 120 ° C. and imidized. These reactions were performed under nitrogen stream. After the reaction was completed, the reaction solution was poured into methanol, and dried separately to obtain 60 g of a white polyimide powder. The weight average molecular weight of the powder of this polyimide was 120,000.
(실시예16) Example 16
1,3-비스(4-아미노페녹시)-2-프로필알콜의 합성Synthesis of 1,3-bis (4-aminophenoxy) -2-propyl alcohol
실시예6의 점조한 액체 1,3-비스(4-니트로페녹시)-2-프로필알콜 33.4g(0.1몰), 5% Pd함유 활성탄분말 3g, 1,4-디옥산 250 ml를 반응용기(물첨가장치)에 취하고, 수소분위기 하에서 60℃로 가열교반을 행하였다. 약8시간에 14.4 리터의 수소를 흡수하고, 수소의 흡수가 멈추었기 때문에, 반응을 멈추고, 반응용액을 여별하여, 촉매를 제거하고 나서, 농축하여 27.4g을 얻었다. 33.4 g (0.1 mol) of viscous liquid 1,3-bis (4-nitrophenoxy) -2-propyl alcohol of Example 6, 3 g of activated carbon powder containing 5% Pd, and 250 ml of 1,4-dioxane were added to the reaction vessel. The mixture was taken up in a water addition device, and heated and stirred at 60 ° C. under a hydrogen atmosphere. Since 14.4 liters of hydrogen were absorbed in about 8 hours and the absorption of hydrogen was stopped, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed and concentrated to obtain 27.4 g.
폴리이미드의 합성Synthesis of Polyimide
교반기를 설치한 2000 ml의 분리플라스크에 27.4g(0.1몰), DMAc 250g을 취하고, 6FDA 44.4g(0.1몰)을 단숨에 격렬하게 교반하면서 가하고, 이대로 30분간 교반 을 계속하였다. 27.4 g (0.1 mol) and DMAc 250 g were taken into a 2000 ml separatory flask equipped with a stirrer, and 44.4 g (0.1 mol) of 6FDA was added with vigorous stirring at once, and stirring was continued for 30 minutes.
β피콜린 18.6g, 톨루엔 50g을 상기 반응용액에 가하고, 물을 적극적으로 제거하면서 약3시간 환류교반하고, 이미드화하였다. 이들 반응은, 질소기류 하에서 행하였다. 반응종료 후, 반응용액을 메탄올에 투입하고, 여별건조하여 67g의 백색폴리이미드분말을 얻었다. 18.6 g of β picoline and 50 g of toluene were added to the reaction solution, and the mixture was stirred under reflux for about 3 hours while actively removing water, followed by imidization. These reactions were performed under nitrogen stream. After the reaction was completed, the reaction solution was poured into methanol, and dried separately to obtain 67 g of white polyimide powder.
측쇄에의 계피산의 도입Introduction of cinnamon to side chain
상기 실시예14-실시예16에서 얻어진 폴리이미드의 백색폴리이미드분말 34.1g, 니트로벤젠 350 ml, 계피산클로라이드 16.6g(0.1몰)을 반응용기에 취하고, 약120℃로 4시간 가열교반하였다. 반응용액을 메탄올에 투입하고, 여별건조하여 40g의 실시예14-실시예16에서 얻어진 폴리이미드에 대응하는 계피산골격이 측쇄에 도입된 백색폴리이미드분말을 얻었다. 이들 폴리이미드의 분말의 중량평균분자량은, 6.5만이었다. 34.1 g of a white polyimide powder of the polyimide obtained in Example 14 to Example 16, 350 ml of nitrobenzene, and 16.6 g (0.1 mol) of cinnamic acid chloride were taken in a reaction vessel, and the mixture was heated and stirred at about 120 ° C. for 4 hours. The reaction solution was poured into methanol, and dried separately to obtain a white polyimide powder having 40 g of cinnamon backbone corresponding to the polyimide obtained in Example 14-Example 16 introduced into the side chain. The weight average molecular weight of the powder of these polyimide was 6.50,000.
본 발명은, 폴리이미드에 계피산골격을 가지는 신규폴리이미드화합물을 제공할 수가 있고, 본 발명에 따른 신규폴리이미드화합물은, 우수한 감광성수지로서 에칭가공, 수지철판 등의 인쇄분야, 또한 반도체디바이스의 미세가공, 프린트배선판의 레지스트막의 형성이나, 반도체디바이스의 다층배선의 층간 절연막등 전자부품용도, 기타, 광디스크기판형성용재료 등 여러 가지의 용도를 확대하는 것에 공헌한다. The present invention can provide a novel polyimide compound having a cinnamic acid skeleton in a polyimide, and the novel polyimide compound according to the present invention is an excellent photosensitive resin in the printing field such as etching processing, resin sheet, and fine semiconductor devices. It contributes to the expansion of various applications such as processing, forming a resist film of a printed wiring board, an electronic component such as an interlayer insulating film of a multilayer wiring of a semiconductor device, and other materials for forming an optical disk substrate.
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