KR20030091463A - Method to produce aromatic sulfide organic compound and aromatic sulfide organic compound prepared by the said method - Google Patents

Method to produce aromatic sulfide organic compound and aromatic sulfide organic compound prepared by the said method Download PDF

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KR20030091463A
KR20030091463A KR1020020029520A KR20020029520A KR20030091463A KR 20030091463 A KR20030091463 A KR 20030091463A KR 1020020029520 A KR1020020029520 A KR 1020020029520A KR 20020029520 A KR20020029520 A KR 20020029520A KR 20030091463 A KR20030091463 A KR 20030091463A
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aromatic
sulfur compound
sulfur
producing
aromatic sulfur
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Korean (ko)
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이종두
허금욱
김진환
이상훈
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주식회사 엠엔비그린어스
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE: A method for preparing an aromatic sulfur compound and an aromatic sulfur compound prepared by the method are provided, to improve the compatibility with a synthetic resin and the adhesive strength with a synthetic resin in blending. CONSTITUTION: The aromatic sulfur compound is represented by the formula 1, wherein R1 is H, OH or an alkyl group of C1-C10; R2 is H, OH or an alkyl group of C1-C5; and n is an integer of 0-5. The method comprises the step of reacting at least one aromatic sulfur compound selected from the group consisting of phenol, methylhydroxybenzene, butylhydroxybenzene, octylhydroxybenzene, nonylhydroxybenzene, dimethylhydroxybenzene, resorcinol and bisphenol with sulfur chloride. Preferably the reaction is carried out in the presence of a reaction catalyst selected from the group consisting of sulfuric acid, nitric acid, acetic acid, hydrohalogen acid and oxalic acid.

Description

방향족황화합물의 제조방법 및 그 방법에 의하여 제조되는 방향족황화합물{Method to produce aromatic sulfide organic compound and aromatic sulfide organic compound prepared by the said method}Method for produce aromatic sulfide organic compound and aromatic sulfide organic compound prepared by the said method}

본 발명은 방향족황화합물을 제조하는 방법에 관한 것으로, 더욱 상세하게는, 페놀, 메칠히드록실벤젠, 부틸히드록실벤젠, 옥틸히드록실벤젠, 노닐히드록실벤젠, 디메칠히드록실벤젠, 레졸시놀, 비스페놀로 이루어지는 군으로부터 1이상 선택된 방향족화합물과 염화유황을 반응시켜 제조됨으로써, 합성수지와 상용성이 우수하고, 배합시 합성수지와 점착력이 양호한 방향족황화합물의 제조방법에 관한 것이다. 또한, 본 발명은 상기 방법에 의하여 제조되는 하기 화학식 1의 구조를 가지는 방향족황화합물에 관한 것이다.The present invention relates to a method for preparing an aromatic sulfur compound, and more particularly, to phenol, methylhydroxybenzene, butylhydroxybenzene, octylhydroxybenzene, nonylhydroxybenzene, dimethylhydroxybenzene, resorcinol, The present invention relates to a method for producing an aromatic sulfur compound having excellent compatibility with synthetic resins and good adhesion with synthetic resins by being prepared by reacting sulfur chloride with at least one aromatic compound selected from the group consisting of bisphenols. In addition, the present invention relates to an aromatic sulfur compound having a structure represented by the following Chemical Formula 1 prepared by the above method.

( 상기 식 중에서(In the above formula

R1= 수소, 수산기, 또는 탄소수 1~10의 알킬기R 1 = hydrogen, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms

R2= 수소, 수산기, 또는 탄소수 1~5의 알킬기R 2 = hydrogen, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms

n = 0 또는 1~5의 정수)n = 0 or an integer from 1 to 5)

종래 황화합물은 주로 무기황화합물로써, 예컨대 천연산의 황을 승화 또는 용융정제한 분말황, 결정성인 입자구조로 이황산탄소(CS2) 불용분이 함유된 불용성황, 오황화칼슘등이 다황화물을 분해시켜 만든 침강황, 황을 콜로이드 밀에서 갈아서 만들거나, 콜로이드 불용액으로부터 침강시켜 만든 콜로이드황 등이 주로 사용되어 왔으나, 이러한 무기황화합물은 합성수지에 첨가제로 사용시 상용성이 저하되고, 투입량에 따라 점착력이 저하되는 문제점이 있었다.Conventional sulfur compounds are mainly inorganic sulfur compounds, for example, powdered sulfur obtained by sublimation or melt purification of natural acid, insoluble sulfur containing calcium disulfide (CS 2 ) insoluble in a crystalline particle structure, calcium pentasulphide, and the like. Precipitated sulfur and colloidal sulfur made by grinding in colloid mill, or colloidal sulfur made by sedimentation from colloidal insoluble solution, etc. have been mainly used. There was a problem.

따라서, 합성수지에 적용시, 스코오치 현상, 축열현상 등의 발생을 최소화하면서, 합성수지에 필요한 물성을 최대화시킬 수 있는 새로운 황화합물의 개발이 필요하다.Therefore, when applied to a synthetic resin, it is necessary to develop a new sulfur compound that can maximize the properties required for the synthetic resin while minimizing the occurrence of scorch phenomenon, heat storage phenomenon, and the like.

본 발명은 상기한 바와 같은 종래 기술의 문제점을 해결하기 위한 것으로서, 본 발명의 목적은, 페놀, 메칠히드록실벤젠, 부틸히드록실벤젠, 옥틸히드록실벤젠, 노닐히드록실벤젠, 디메칠히드록실벤젠, 레졸시놀, 비스페놀로 이루어지는 군으로부터 1이상 선택된 방향족화합물과 염화유황을 반응시켜 제조함으로써, 합성수지와 상용성이 우수하고, 배합시 합성수지와 점착력이 양호한 방향족황화합물의 제조방법 및 그 방법에 의하여 제조되는 방향족황화합물을 제공하는 것이다.The present invention is to solve the problems of the prior art as described above, the object of the present invention is phenol, methyl hydroxyl benzene, butyl hydroxyl benzene, octyl hydroxyl benzene, nonyl hydroxyl benzene, dimethyl hydroxyl benzene Prepared by reacting sulfur chloride with at least one aromatic compound selected from the group consisting of resorcinol and bisphenol, and having excellent compatibility with synthetic resins and good synthetic resins and good adhesion when formulated and prepared by the method It is to provide an aromatic sulfur compound.

상기한 바와 같은 목적을 달성하기 위하여, 본 발명에 의한 방향족황화합물의 제조방법은, 페놀, 메칠히드록실벤젠, 부틸히드록실벤젠, 옥틸히드록실벤젠, 노닐히드록실벤젠, 디메칠히드록실벤젠, 레조시놀, 비스페놀로 이루어지는 군으로부터 1이상 선택된 방향족화합물과 염화유황을 반응시켜 합성되는 것을 특징으로 한다.In order to achieve the above object, the method for producing an aromatic sulfur compound according to the present invention is phenol, methyl hydroxyl benzene, butyl hydroxyl benzene, octyl hydroxyl benzene, nonyl hydroxyl benzene, dimethyl hydroxyl benzene, reso Synthesized by reacting sulfur chloride with at least one aromatic compound selected from the group consisting of synols and bisphenols.

본 발명에 의한 방향족황화합물의 제조방법에 있어서, 염화유황은 일염화유황과 이염화유황을 포함하는 것을 특징으로 한다.In the method for producing an aromatic sulfur compound according to the present invention, sulfur chloride includes sulfur monochloride and sulfur dichloride.

본 발명에 의한 방향족황화합물의 제조방법에 있어서, 방향족화합물과 염화유황은 0.2몰비 내지 2.0몰비로 반응시키는 것을 특징으로 한다.In the method for producing an aromatic sulfur compound according to the present invention, the aromatic compound and sulfur chloride are characterized in that the reaction in a 0.2 to 2.0 molar ratio.

본 발명에 의한 방향족황화합물의 제조방법에 있어서, 방향족황화합물 합성시 반응온도는 30℃ 내지 300℃인 것을 특징으로 한다.In the method for producing an aromatic sulfur compound according to the present invention, the reaction temperature during the synthesis of the aromatic sulfur compound is characterized in that 30 ℃ to 300 ℃.

본 발명에 의한 방향족황화합물의 제조방법에 있어서, 방향족황화합물 합성시 황산, 질산, 초산, 할로겐화 수소산 또는 옥살산을 반응촉매로 사용하는 것을 특징한다.In the method for producing an aromatic sulfur compound according to the present invention, sulfuric acid, nitric acid, acetic acid, hydrogen halide or oxalic acid is used as a reaction catalyst when synthesizing the aromatic sulfur compound.

본 발명에 의한 방향족황화합물의 제조방법에 있어서, 반응촉매는 투입되는 방향족화합물의 중량 대비 5.0wt% 이하로 첨가시키는 것을 특징으로 한다.In the method for producing an aromatic sulfur compound according to the present invention, the reaction catalyst is characterized in that the addition of 5.0wt% or less relative to the weight of the aromatic compound to be added.

본 발명에 의한 방향족황화합물은, 상기의 방법에 의하여 제조되고, 하기 화학식 1로 표시되는 것을 특징으로 한다.The aromatic sulfur compound according to the present invention is produced by the above method, and is characterized by the following formula (1).

[화학식 1][Formula 1]

( 상기 식 중에서(In the above formula

R1= 수소, 수산기, 또는 탄소수 1~10의 알킬기R 1 = hydrogen, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms

R2= 수소, 수산기, 또는 탄소수 1~5의 알킬기R 2 = hydrogen, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms

n = 0 또는 1~5의 정수)n = 0 or an integer from 1 to 5)

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

다음 실시예는 본 발명을 상세하게 예증하여 줄 것이나, 이는 본 발명의 예시에 불과하고 본 발명의 범주가 이에 한정되는 것은 아니다.The following examples will illustrate the invention in detail, but this is merely illustrative of the invention and the scope of the invention is not limited thereto.

<실시예 1 : 방향족황화합물의 제조>Example 1 Preparation of Aromatic Sulfur Compounds

본 실시예에 의한 방향족황화합물의 제조방법은 다음과 같다.Method for producing an aromatic sulfur compound according to the present embodiment is as follows.

1) 환류 반응기 내에 부틸히드록실벤젠 500g을 투입한다.1) 500 g of butylhydroxybenzene are added to the reflux reactor.

2) 120℃까지 승온하여 용융 교반한다.2) It heats up to 120 degreeC and it stirs and melts.

3) 황산 10g을 발열에 주의하면서 서서히 투입한다.3) Slowly add 10 g of sulfuric acid while paying attention to heat generation.

4) 반응기내의 내용물을 교반시키면서, 일염화유황 275g을 천천히 투입한다.4) Slowly add 275 g of sulfur monochloride while stirring the contents in the reactor.

5) 반응기내 진공탈기를 실시한다.5) Vacuum degassing in the reactor.

6) 진공탈기 후 취출/냉각한다.6) Take out / cool down after vacuum degassing.

상기의 실시예에 의하여 방향족황화합물의 제조에 적합한 반응물질의 조성비율과 제조방법이 확립되었음을 알 수 있다.According to the above embodiment, it can be seen that a composition ratio and a preparation method of a reactant suitable for preparing an aromatic sulfur compound have been established.

위와 같이 본 발명의 실시예에 대해 기술하였지만, 본 발명이 속하는 기술 분야에 있어서 통상의 지식을 가진 사람이라면, 본 발명을 여러 가지로 변형 또는 변경하여 실시할 수 있음을 알 수 있을 것이다. 따라서 본 발명의 실시예의 변경은 본 발명의 기술적 범위를 벗어날 수 없을 것이다.Although the embodiments of the present invention have been described as described above, it will be understood by those skilled in the art that the present invention may be modified or modified in various ways. Therefore, changes of the embodiments of the present invention will not be able to escape the technical scope of the present invention.

상술한 바와 같이, 본 발명에 따른 방향족황화합물은, 페놀, 메칠히드록실벤젠, 부틸히드록실벤젠, 옥틸히드록실벤젠, 노닐히드록실벤젠, 디메칠히드록실벤젠, 레졸시놀, 비스페놀로 이루어지는 군으로부터 1이상 선택된 방향족화합물과 염화유황을 반응시켜 제조함으로써, 합성수지와 상용성이 우수하고, 배합시 합성수지와 점착력이 양호하여 합성수지에 적용시 물성을 향상시킬 수 있으며, 나아가 제조 공정의 경제성도 향상시킬 수 있게 된다.As described above, the aromatic sulfur compound according to the present invention is selected from the group consisting of phenol, methyl hydroxyl benzene, butyl hydroxyl benzene, octyl hydroxyl benzene, nonyl hydroxyl benzene, dimethyl hydroxyl benzene, resorcinol and bisphenol. By producing at least one selected aromatic compound by reacting with sulfur chloride, it has excellent compatibility with synthetic resins and good adhesion with synthetic resins when blended, which can improve physical properties when applied to synthetic resins and further improve the economics of the manufacturing process. Will be.

Claims (7)

페놀, 메칠히드록실벤젠, 부틸히드록실벤젠, 옥틸히드록실벤젠, 노닐히드록실벤젠, 디메칠히드록실벤젠, 레졸시놀, 비스페놀로 이루어지는 군으로부터 1이상 선택된 방향족화합물과 염화유황을 반응시켜 합성하는 것을 특징으로 하는 방향족황화합물의 제조방법.Synthesized by reacting sulfur chloride with at least one aromatic compound selected from the group consisting of phenol, methylhydroxybenzene, butylhydroxybenzene, octylhydroxybenzene, nonylhydroxybenzene, dimethylhydroxybenzene, resorcinol and bisphenol Method for producing an aromatic sulfur compound, characterized in that. 제1항에 있어서,The method of claim 1, 염화유황은 일염화유황과 이염화유황을 포함하는 것을 특징으로 하는 방향족황화합물의 제조방법.Sulfur chloride is a method for producing an aromatic sulfur compound, characterized in that it comprises sulfur monochloride and sulfur dichloride. 제1항에 있어서,The method of claim 1, 방향족화합물과 염화유황은 0.2몰비 내지 2.0몰비로 반응시키는 것을 특징으로 하는 방향족황화합물의 제조방법.Aromatic compounds and sulfur chloride is a method for producing an aromatic sulfur compound, characterized in that the reaction in a 0.2 to 2.0 molar ratio. 제1항에 있어서,The method of claim 1, 방향족황화합물 합성시 반응온도는 30℃ 내지 300℃인 것을 특징으로 하는 방향족황화합물의 제조방법.The reaction temperature for the synthesis of aromatic sulfur compounds is a method for producing an aromatic sulfur compound, characterized in that 30 ℃ to 300 ℃. 제1항 내지 제4항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 4, 방향족황화합물 합성시 황산, 질산, 초산, 할로겐화 수소산 또는 옥살산을 반응촉매로 사용하는 것을 특징으로 하는 방향족황화합물의 제조방법.A method for producing an aromatic sulfur compound, characterized in that sulfuric acid, nitric acid, acetic acid, hydrogen halide or oxalic acid is used as a reaction catalyst when synthesizing the aromatic sulfur compound. 제5항에 있어서,The method of claim 5, 반응촉매는 투입되는 방향족화합물의 중량 대비 5.0wt% 이하로 첨가시키는 것을 특징으로 하는 방향족황화합물의 제조방법.The reaction catalyst is a method for producing an aromatic sulfur compound, characterized in that the addition of less than 5.0wt% relative to the weight of the aromatic compound. 상기 제1항의 방법에 의하여 제조되고, 하기 화학식 1로 표시되는 것을 특징으로 하는 방향족황화합물.An aromatic sulfur compound, prepared by the method of claim 1, represented by the following Chemical Formula 1. [화학식 1][Formula 1] ( 상기 식 중에서(In the above formula R1= 수소, 수산기, 또는 탄소수 1~10의 알킬기R 1 = hydrogen, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms R2= 수소, 수산기, 또는 탄소수 1~5의 알킬기R 2 = hydrogen, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms n = 0 또는 1~5의 정수)n = 0 or an integer from 1 to 5)
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63255260A (en) * 1987-04-13 1988-10-21 Idemitsu Petrochem Co Ltd Production of bis(hydroxyphenyl)sulfide
KR20000006649A (en) * 1999-09-15 2000-02-07 심경섭 A Novel Aromatic Polysulfide and Asphalt Paving Composition Containing the Same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63255260A (en) * 1987-04-13 1988-10-21 Idemitsu Petrochem Co Ltd Production of bis(hydroxyphenyl)sulfide
KR20000006649A (en) * 1999-09-15 2000-02-07 심경섭 A Novel Aromatic Polysulfide and Asphalt Paving Composition Containing the Same

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