KR100393334B1 - Curing accelerator combined with electron-donating group - Google Patents

Curing accelerator combined with electron-donating group Download PDF

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Publication number
KR100393334B1
KR100393334B1 KR1019950036282A KR19950036282A KR100393334B1 KR 100393334 B1 KR100393334 B1 KR 100393334B1 KR 1019950036282 A KR1019950036282 A KR 1019950036282A KR 19950036282 A KR19950036282 A KR 19950036282A KR 100393334 B1 KR100393334 B1 KR 100393334B1
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vulcanization
electron
donating group
curing accelerator
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KR1019950036282A
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Korean (ko)
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KR970021165A (en
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안은경
최윤희
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금호산업주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms

Abstract

PURPOSE: A curing accelerator combined with an electron-donating group is provided, to reduce the activation energy in curing transition state and to increase a curing reaction velocity coefficient, thereby reducing curing time. CONSTITUTION: The curing accelerator is combined with an electron donating group at the p-position of a benzene ring in 2-mercaptobenzothiazole and its derivatives represented by the formula I, wherein R is H, -SBT or -NHR. Preferably the electron donating group is selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group and a methyl group.

Description

전자주는기가 결합된 가류촉진제Vulcanization accelerator combined with electron giver

본 발명은 전자주는기(electron-donating group)를 결합시킴으로써 가류시간을 단축시키는 효과를 갖도록 하는 가류촉진제에 관한 것으로써, 더욱 상세하게는 하기 일반식(1)로 표시되는 가류촉진제인 2-머캅토벤조티아졸(MBT) 및 그 유도체에서 벤젠고리의 파라(para) 위치에 전자주는기를 결합시켜 가류 전이상태의 활성화에너지를 감소시켜 가류 반응속도상수를 증가시켜 가류시간을 단축시키는 효과를 갖도록 한 가류촉진제에 관한 것이다.The present invention relates to a vulcanization accelerator which has an effect of shortening the vulcanization time by combining an electron-donating group, and more particularly, a 2-mer as a vulcanization accelerator represented by the following general formula (1): In the captobenzothiazole (MBT) and its derivatives, electron donating groups are bonded to the para position of the benzene ring to reduce the activation energy of the vulcanization transition state, thereby increasing the vulcanization reaction rate constant to shorten the vulcanization time. It relates to a vulcanization accelerator.

여기서 R은 H, SBT, NHR 중에서 선택된다.Where R is selected from H, SBT and NHR.

현재 널리 사용되고 있는 가류공정은 하기와 같다.Currently used vulcanization processes are as follows.

즉, 가류 초기단계에서 활성화된 가류촉진제는 가류제와 반응하여 황화복합물을 형성하고, 이 복합물은 고무와 반응하여 가교결합을 하게 함으로써 고무는 탄성을 갖는다. 그러나 이경우 가류속도가 늦어 가류시간이 길어지는 문제점이 있다.That is, the vulcanization accelerator activated at the initial stage of vulcanization reacts with the vulcanizing agent to form a sulfide complex, and the composite reacts with the rubber to crosslink to make the rubber elastic. However, in this case, there is a problem that the vulcanization speed is slow and the vulcanization time is long.

본 발명자는 상기와 같은 문제점을 해결하기 위하여 예의 검토한 결과, 통상의 가류촉진제인 2-머캅토벤조티아졸 및 그 유도체에서 벤젠고리의 파라위치에 전자주는기는 결합시킨 가류촉진제가 가류시간을 단축시킬 수 있다는 것을 발견하여 본 발명을 완성하게 되었다.The present inventors have diligently studied to solve the above problems, and as a result, the vulcanization accelerator combined with the electron giving group at the para position of the benzene ring in the conventional vulcanization accelerator 2-mercaptobenzothiazole and its derivatives has shortened the vulcanization time. The present invention has been completed by discovering that it can be done.

이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

현재 널리 사용되고 있는 가류촉진제인 2-머캅토벤조티아졸 및 그 유도체의가류전이상태의 구조는 하기와 같다.The structure of the vulcanization transition state of 2-mercaptobenzothiazole and its derivatives, which are currently widely used vulcanization accelerators, are as follows.

하기 아레니우스 식(Arrhenenius equation) :The Arrhenenius equation:

k = Aexp(-Ea/RT)k = A exp (-Ea / RT)

여기서, k는 반응속도상수,Where k is the rate constant,

A는 프리-지수인자(pre-exponential factor),A is the pre-exponential factor,

Ea는 활성화에너지,Ea is the activation energy,

R은 기체상수,R is the gas constant,

T는 절대온도,T is the absolute temperature,

그리고 하기 가류속도 반응식 :And the following vulcanization rate scheme:

V = k[A]nV = k [A] n

여기서, V는 가류속도,Where V is the vulcanization rate,

[A]는 촉진제의 농도,[A] is the concentration of accelerator,

n은 반응차수,n is the reaction order,

으로부터, 활성화에너지(Ea)를 감소시키면 반응속도상수(k)가 커지므로 가류속도(V)가 빨라진다. 즉, 가류전이상태의 활성화에너지를 감소시키기 위하여 벤젠 고리의 파라(para) 또는 오르토(ortho) 위치에 전자주는기를 결합시키면 공명효과에 의해 N(질소)의 염기도를 증가시켜 전이상태가 안정화된다.From the above, if the activation energy Ea is reduced, the reaction rate constant k becomes large, and thus the vulcanization rate V becomes faster. That is, in order to reduce the activation energy of the vulcanization transition state, when the electron donor is bound to the para or ortho position of the benzene ring, the transition state is stabilized by increasing the basicity of N (nitrogen) by a resonance effect.

여기서, R은 -H, -STB, -NHR 중에서 선택되고,Wherein R is selected from -H, -STB, and -NHR,

R'는 메틸기(CH3-), 메톡시기(CH3O-), 에톡시기(CH3CH2O-), 페녹시기() 중에서 선택된다.R 'is a methyl group (CH 3- ), methoxy group (CH 3 O-), ethoxy group (CH 3 CH 2 O-), phenoxy group ( ) Is selected from.

그러나, 오르토 위치에 치환기를 결합시키면 공명효과보다는 입체적 장애효과가 더 크기 때문에 전이상태는 오히려 불안정해지므로 가류속도를 감소시켜 가류시간이 증가되게 된다.However, when the substituent is bonded to the ortho position, the steric hindrance is greater than the resonance effect, so the transition state becomes unstable, thereby decreasing the vulcanization rate and increasing the vulcanization time.

따라서, 안정화된 전이상태는 가류속도상수를 증가시켜 가류시간을 단축시킬 수 있다.Therefore, the stabilized transition state can increase the vulcanization rate constant and shorten the vulcanization time.

그리고 하기 가류속도 반응식 :And the following vulcanization rate scheme:

V = k[A]nV = k [A] n

여기서, V는 가류속도,Where V is the vulcanization rate,

[A]는 촉진제의 농도,[A] is the concentration of accelerator,

n은 반응차수,n is the reaction order,

으로부터, 활성화에너지(Ea)를 감소시키면 반응속도상수(k)가 커지므로 가류속도(V)가 빨라친다. 즉, 가류전이상태의 활성화에너지를 감소시키기 위하여 벤젠고리의 파라(para) 또는 오르토(ortho) 위치에 전자주는기를 결합시키면 공명효과에 의해 N(질소)의 염기도를 증가시켜 전이상태가 안정화된다.From the above, if the activation energy Ea is decreased, the reaction rate constant k becomes large, and thus the vulcanization rate V becomes faster. That is, in order to reduce the activation energy of the vulcanization transition state, when the electron donor is bonded to the para or ortho position of the benzene ring, the transition state is stabilized by increasing the basicity of N (nitrogen) by the resonance effect.

여기서, R은 -H, -STB, -NHR 중에서 선택되고,Wherein R is selected from -H, -STB, and -NHR,

R'는 메틸기(CH3-), 메톡시기(CH3O-), 에톡시기(CH3CH2O-), 페녹시기() 중에서 선택된다.R 'is a methyl group (CH 3- ), methoxy group (CH 3 O-), ethoxy group (CH 3 CH 2 O-), phenoxy group ( ) Is selected from.

그러나, 오르토 위치에 치환기를 결합시키던 공명효과보다는 입체적 장애효과가 더 크기 때문에 전이상태는 오히려 불안정해지므로 가류속도를 감소시켜 가류시간이 증가되게 된다.However, since the steric hindrance is greater than the resonance effect of binding the substituent to the ortho position, the transition state becomes rather unstable, so that the vulcanization rate is increased to increase the vulcanization time.

따라서, 안정화된 전이상태는 가류속도상수를 증가시켜 가류시간을 단축시킬 수 있다.Therefore, the stabilized transition state can increase the vulcanization rate constant and shorten the vulcanization time.

실시예Example

표1의 조성으로 배합후 160℃에서 핫 프레스(Hot press)로 가류시킨 결과 비교예는 가류시간이 18분 소요되었고, 실시예 1은 0.3분 소요(비교예에 비해 60배빠름), 실시예 2는 4분 소요(비교예에 비해 4.5배 빠름) 되었다.After mixing with the composition shown in Table 1 and vulcanized by hot press at 160 ° C., the comparative example took 18 minutes of vulcanization time, and Example 1 required 0.3 minutes (60 times faster than the comparative example). 2 took 4 minutes (4.5 times faster than the comparative example).

* 촉진제 : 사용된 촉진제로 비교예는 2-머캅토벤조티아졸, 실시예 1은 4-메톡시-2-머캅토벤조티아졸, 실시예 2는 4-메틸-2-머캅토벤조티아졸 임.* Accelerator: The accelerator used was Comparative Example 2-mercaptobenzothiazole, Example 1 4-methoxy-2-mercaptobenzothiazole, Example 2 4-methyl-2-mercaptobenzothiazole being.

Claims (2)

하기 일반식(1)로 표시되는 2-머캅토벤조티아졸 및 그 유도체에서 벤젠고리의 파라위치에 전자주는기가 결합된 가류촉진제 :In the 2-mercaptobenzothiazole and its derivatives represented by the following general formula (1), a vulcanization accelerator having an electron donor group bonded to the para position of the benzene ring: 여기서, R은 H, SBT, NHR 중에서 선택된다.Here, R is selected from H, SBT and NHR. 제 1 항에 있어서, 전자주는기는 메톡시기(CH3O-), 에톡시기(CH3CH2O-), 페녹시기(), 메틸기 (CH3-)중에서 선택되는 것을 특징으로 하는 가류촉진제.The electron donating group according to claim 1, wherein the electron donating group is a methoxy group (CH 3 O-), an ethoxy group (CH 3 CH 2 O-), a phenoxy group ( ), Methyl group (CH 3- ), a vulcanization accelerator, characterized in that selected from.
KR1019950036282A 1995-10-19 1995-10-19 Curing accelerator combined with electron-donating group KR100393334B1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629208A (en) * 1969-06-18 1971-12-21 Monsanto Co N-aminoalkyl thiazolesulfenamides as vulcanization accelerators
US3919179A (en) * 1972-04-18 1975-11-11 Goodyear Tire & Rubber Three-component accelerator system
JPS51149336A (en) * 1975-06-18 1976-12-22 Nippon Soda Co Ltd A method for accelerating the vulcanization of rubber
JPS56161378A (en) * 1980-05-16 1981-12-11 Sanshin Kagaku Kogyo Kk N-substituted benzothiazole-2-sulfonamide compound and its preparation
JPS6254739A (en) * 1985-09-04 1987-03-10 Sumitomo Chem Co Ltd Vulcanization accelerator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629208A (en) * 1969-06-18 1971-12-21 Monsanto Co N-aminoalkyl thiazolesulfenamides as vulcanization accelerators
US3919179A (en) * 1972-04-18 1975-11-11 Goodyear Tire & Rubber Three-component accelerator system
JPS51149336A (en) * 1975-06-18 1976-12-22 Nippon Soda Co Ltd A method for accelerating the vulcanization of rubber
JPS56161378A (en) * 1980-05-16 1981-12-11 Sanshin Kagaku Kogyo Kk N-substituted benzothiazole-2-sulfonamide compound and its preparation
JPS6254739A (en) * 1985-09-04 1987-03-10 Sumitomo Chem Co Ltd Vulcanization accelerator

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