KR100297589B1 - Polymeric bisphenol-sulfone epoxy resin with improved heat and flame resistance - Google Patents
Polymeric bisphenol-sulfone epoxy resin with improved heat and flame resistance Download PDFInfo
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- KR100297589B1 KR100297589B1 KR1019980023155A KR19980023155A KR100297589B1 KR 100297589 B1 KR100297589 B1 KR 100297589B1 KR 1019980023155 A KR1019980023155 A KR 1019980023155A KR 19980023155 A KR19980023155 A KR 19980023155A KR 100297589 B1 KR100297589 B1 KR 100297589B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
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Abstract
본 발명은 고분자형 비스페놀-술폰 엑폭시 수지에 관한 것으로서, 본 발명에서는 결정성 비스페놀-술폰계 에폭시 수지를 이용하여 중합도가 0.1 내지 10인 고분자형 비스페놀-술폰 에폭시 수지를 제공한다. 본 발명에 의한 고분자형 비스페놀-술폰 에폭시 수지는 내열성이 향상되어 Tg가 높은 특성이 있다. 본 발명에서는 또한 난연성이 부여된 고분자형 비스페놀-술폰 에폭시 수지와 내후성, 흐름성을 보완하기 위하여 변성 반응을 거친 고분자형 비스페놀-술폰 에폭시 수지를 제공한다.The present invention relates to a polymer type bisphenol-sulfone epoxy resin, and the present invention provides a polymer type bisphenol-sulfone epoxy resin having a polymerization degree of 0.1 to 10 using a crystalline bisphenol-sulfone epoxy resin. The polymer type bisphenol-sulfone epoxy resin according to the present invention has improved heat resistance and high Tg. The present invention also provides a polymeric bisphenol-sulfone epoxy resin imparted flame retardancy and a polymerized bisphenol-sulfone epoxy resin subjected to a modification reaction to compensate for weatherability and flowability.
Description
[발명의 명칭][Name of invention]
내열성 및 난연성이 향상된 고분자형 비스페놀-술폰계 에폭시 수지Polymer type bisphenol-sulfone epoxy resin with improved heat resistance and flame resistance
[발명이 속하는 기술분야 및 그 분야의 종래기술][Technical field to which the invention belongs and the prior art in that field]
본 발명은 에폭시 수지에 관한 것으로서, 특히 내열성 및 난연성이 향상된 비스페놀-술폰계 에폭시 수지에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to epoxy resins, and more particularly, to bisphenol-sulfone epoxy resins having improved heat resistance and flame retardancy.
에폭시 수지는 BPF(Bisphenol-F)형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 고무 우레탄 변성 에폭시 수지 등 그 종류가 다양하며, 접착제, 전기, 전자 및 도료, 적층판용, 토목 건축용 등 다양한 용도로 사용되어지고 있다.Epoxy resins come in various varieties such as BPF (Bisphenol-F) type epoxy resins, phenol novolac type epoxy resins, rubber urethane modified epoxy resins, etc., and are used for various purposes such as adhesives, electrical, electronics and paints, laminates, and civil construction It is done.
종래 기술에 의한 비스페놀-A계 에폭시 수지는 비스페놀-A와 에피클로로하이드린(Epichlorohydrin:ECH)을 산 또는 염기촉매 하에서 반응시켜서 얻는다. 필요에 따라서 유기용제를 사용하며, 약 40~100℃에서 개환반응과 에폭시화반응을 거쳐서 얻어진다.Bisphenol-A epoxy resins according to the prior art are obtained by reacting bisphenol-A with epichlorohydrin (ECH) under an acid or base catalyst. If necessary, an organic solvent is used and obtained through a ring-opening reaction and an epoxidation reaction at about 40 to 100 ° C.
다음의 화학식 1은 종래 기술의 의한 비스페놀-A계 에폭시 수지의 제조 공정이다. 특히 화학식 1에서 중간 단계는 개환 반응이며, 최종 단계는 에폭시화 반응이다.Formula 1 is a process for producing a bisphenol-A epoxy resin of the prior art. In particular, the intermediate step in the general formula (1) is the ring-opening reaction, the final step is the epoxidation reaction.
[화학식 1][Formula 1]
상기 화학식 1에서의 X/Y의 몰비를 조정하여 에폭시 당량이 185~187g/eq인 액상 수지로부터 에폭시 당량이 6,000g/eq 이상인 비결정성 고형 수지를 제조할 수 있다.By adjusting the molar ratio of X / Y in Chemical Formula 1, an amorphous solid resin having an epoxy equivalent of 6,000 g / eq or more may be prepared from a liquid resin having an epoxy equivalent of 185 to 187 g / eq.
그러나, 상기의 종래 기술에 의한 비스페놀-A계 에폭시 수지는 내열성이 약하여, 인쇄회로기판(PCB)을 비롯하여 높은 Tg를 요구하는 다양한 분야에 적용하기에 적합하지 않다.However, the bisphenol-A epoxy resin according to the related art is poor in heat resistance, and thus is not suitable for application in various fields requiring high Tg, including a printed circuit board (PCB).
[발명이 이루고자 하는 기술적 과제][Technical problem to be achieved]
본 발명의 목적은 에폭시 수지의 제조 시 술폰을 함유하는 원료를 사용하여 내열성 및 내약품성을 향상시킨 고분자형 비스페놀-술폰계 에폭시 수지를 제공하는데 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer type bisphenol-sulfone epoxy resin having improved heat resistance and chemical resistance by using a raw material containing sulfone when preparing an epoxy resin.
본 발명의 또 다른 목적은, 내열성이 향상된 비스페놀-술폰계 에폭시 수지에 할로겐을 도입하여 난연성을 부여한 고분자형 비스페놀-술폰계 에폭시 수지를 제공하는 데 있다.Still another object of the present invention is to provide a polymer type bisphenol-sulphone epoxy resin in which flame resistance is imparted by introducing halogen into a bisphenol-sulphone epoxy resin having improved heat resistance.
본 발명의 또 다른 목적은, 난연성이 부여된 비스페놀-술폰계 에폭시 수지를 변성 반응하여 내후성 및 흐름성이 개선된 고분자형 비스페놀-술폰계 에폭시 수지를 제공하는데 있다.Still another object of the present invention is to provide a polymer type bisphenol-sulfone epoxy resin having improved weather resistance and flowability by modifying a flame-retardant bisphenol-sulfone epoxy resin.
[발명의 구성 및 작용][Configuration and Function of Invention]
상기한 바와 같은 목적을 달성하기 위하여, 본 발명에 의한 고분자형 비스페놀-술폰계 에폭시 수지는 다음과 같은 공정에 의하여 제조된다.In order to achieve the object as described above, the polymer type bisphenol-sulfone epoxy resin according to the present invention is prepared by the following process.
먼저, 중간 물질로서 결정성 비스페놀-술폰계 에폭시 수지를 다음의 화학식 2와 같은 반응식에 따라서 제조한다.First, a crystalline bisphenol-sulfone epoxy resin is prepared as an intermediate material according to the following reaction formula.
[화학식 2][Formula 2]
상기 화학식 2에서 X는 수소이고, Z는 할로겐(Br, Cl, I, F)을 포함하는 알킬기, 아릴기 또는 페놀기이다. 상기 반응은 예를 들어, 비스페놀-술폰계 에폭시 수지의 -OH를 포함한 화합물과 에피클로로히드린(ECH)의 반응이 된다.In Formula 2, X is hydrogen, and Z is an alkyl group, an aryl group, or a phenol group including halogen (Br, Cl, I, F). The reaction is, for example, a reaction of epichlorohydrin (ECH) with a compound containing -OH of a bisphenol-sulfone epoxy resin.
상기 화학식 2의 반응을 위하여, 비스페놀-술폰계 에폭시 함유 원료를, 케톤류(아세톤, 메틸에틸케톤, 메틸이소부틸케톤), 알코올류(메탄올, 에탄올, 이소프로필알코올, 부틸알코올, 글리콜)와 같은 용제 또는 물, 물과 셀룰로스제용제의 혼합액 또는 물과 케톤류의 혼합액과 같은 용매에 용해시키고, 80~200℃에서 염기촉매 즉, NaOH하에 반응시킨다. 특히 목적 생성물을 재결정으로 회수할 필요가 있을 경우에는 벤젠, 톨루엔, 크실렌, 디클로로벤젠 등과 같은 방향족 용제 또는 수성 용제 및 물을 사용할 수 있다.For the reaction of Chemical Formula 2, bisphenol-sulfone epoxy-containing raw materials, solvents such as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), alcohols (methanol, ethanol, isopropyl alcohol, butyl alcohol, glycol) Or dissolved in a solvent such as a mixture of water, a mixture of water and a cellulose solvent, or a mixture of water and ketones, and reacted at 80 to 200 ° C. under a base catalyst, that is, NaOH. In particular, when it is necessary to recover the desired product by recrystallization, an aromatic solvent such as benzene, toluene, xylene, dichlorobenzene and the like or an aqueous solvent and water can be used.
상기 화학식 2에 의하여 제조된 결정성 비스페놀-술폰계 에폭시 수지는 백색의 입자로서 녹는점이 150~200℃이고, 에폭시당량(E.E.W)이 180~220g/eq일 때, 분자량은 200~1000이다.The crystalline bisphenol-sulfone epoxy resin prepared by Chemical Formula 2 has white melting points of 150 to 200 ° C. and an epoxy equivalent (E.E.W) of 180 to 220 g / eq.
상기 화학식 2에 의하여 제조된 결정성 비스페놀-술폰계 에폭시 수지와 화학식 2에서의 반응물질인 비스페놀-술폰계를 이용하여 다음 화학식 3과 같이 중합화시켜서 본 발명에 의한 비결정성 고분자형 비스페놀-술폰계 에폭시 수지를 제조한다.Using the crystalline bisphenol-sulfone epoxy resin prepared in Chemical Formula 2 and the bisphenol-sulfone system, which is a reactant in Chemical Formula 2, was polymerized as shown in the following Chemical Formula 3 to form an amorphous polymer type bisphenol-sulphone system Prepare an epoxy resin.
[화학식 3][Formula 3]
상기 화학식 3의 반응식은 염기 촉매 즉, NaOH하에 반응시킬 수 있으며, 촉매의 양은 물 또는 알콜류 1ℓ당 0.5~10몰을 사용하는 것이 바람직하다.The reaction formula of Formula 3 may be reacted under a base catalyst, that is, NaOH, and the amount of the catalyst is preferably 0.5 to 10 mol per liter of water or alcohols.
상기 화학식 3의 반응은 결정성 비스페놀-술폰 에폭시 수지의 녹는점으로부터 끓는점까지의 온도에서 진행되며(약 20~200℃), 평균 1 내지 5의 에폭시기와 0.1~10의 중합도(n)를 갖는다. 상기 화학식 3에 의하여 얻어진 고분자형 비스페놀-술폰계 에폭시 수지는 황색을 띠는 분말의 형상이고, Tg가 65~75℃이며, 에폭시당량(E.E.W)이 680~750일 때 분자량은 1000~1600이다.The reaction of Chemical Formula 3 proceeds at a temperature from the melting point to the boiling point of the crystalline bisphenol-sulfone epoxy resin (about 20 to 200 ° C.), and has an average degree of polymerization (n) of 0.1 to 10 with 1 to 5 epoxy groups. The polymer type bisphenol-sulfone epoxy resin obtained by Chemical Formula 3 has a yellowish powder shape, has a Tg of 65 to 75 ° C. and an epoxy equivalent (E.E.W) of 680 to 750, and has a molecular weight of 1000 to 1600.
본 발명에서는 또한, 난연성이 부여된 결정성 비스페놀-술폰계 에폭시 수지와 이를 중합반응시켜 얻어지는 고분자형 비스페놀-술폰계 에폭시 수지를 제공하고자 한다. 난연성이 부여된 고분자형 비스페놀-술폰계 에폭시 수지는 상기한 바와 같은 비스페놀-술폰계 에폭시 수지의 제조 공정과 유사하나, 난연성을 부여하기 위하여 할로겐화 유도체를 사용하는 점이 다르다. 다음의 화학식 4는 난연성을 부여하기 위하여 할로겐화 유도체를 가지는 비스페놀-술폰계를 이용한 결정성 비스페놀-술폰 에폭시 수지의 생성 반응식이다.Another object of the present invention is to provide a crystalline bisphenol-sulfone epoxy resin imparting flame retardancy and a polymer type bisphenol-sulfone epoxy resin obtained by polymerizing the same. The flame-retardant polymer type bisphenol-sulfone epoxy resin is similar to the manufacturing process of the bisphenol-sulfone epoxy resin as described above, except that halogenated derivatives are used to impart flame retardancy. Formula 4 is a reaction scheme for producing a crystalline bisphenol-sulfone epoxy resin using a bisphenol-sulfone system having a halogenated derivative to impart flame retardancy.
[화학식 4][Formula 4]
상기 화학식 4에서 R은 난연성을 부여하기 위한 것으로서, 알킬, 아릴 등의 할로겐화 유도체이다.R in Chemical Formula 4 is to impart flame retardancy, and is a halogenated derivative such as alkyl or aryl.
상기 화학식 4의 반응식에 의하여 평균 1~5개의 에폭시기를 가지고, 중합도(n)가 0~1, 분자량이 300~1000인 결정성 난연성 에폭시 화합물이 얻어진다.By the reaction formula of the formula (4), a crystalline flame retardant epoxy compound having an average of 1 to 5 epoxy groups, having a degree of polymerization (n) of 0 to 1 and a molecular weight of 300 to 1000 is obtained.
다음의 화학식 5는 상기한 화학식 4에 의하여 제조된 난연성 부여 결정성 에폭시 수지를 비스페놀-술폰계와 중합시켜서 본 발명에 의한 난연성 부여 고분자형 비스페놀-술폰 에폭시 수지를 생성하는 반응식이다.The following Chemical Formula 5 is a reaction scheme for producing a flame-retardant imparting polymer type bisphenol-sulfone epoxy resin according to the present invention by polymerizing the flame-retardant imparting crystalline epoxy resin prepared by Chemical Formula 4 with a bisphenol-sulfone system.
[화학식 5][Formula 5]
상기 화학식 5에 의하여 생성되는 난연성 부여 고분자형 비스페놀-술폰계 에폭시 수지는 중합도(n)가 0.1~10이상이고, 분자량은 500~50000이다.The flame-retardant imparting polymer bisphenol-sulfone epoxy resin produced by Chemical Formula 5 has a degree of polymerization (n) of 0.1 to 10 or more and a molecular weight of 500 to 50000.
본 발명에서는 또한, 상기 화학식 5에 의하여 제조된 난연성 부여 고분자형 비스페놀-술폰계 에폭시 수지를 변성 반응시켜서 내후성 및 흐름성의 개선을 제공한다. 고분자형 비스페놀-술폰계 에폭시 수지의 변성 반응은 다음의 화학식 6과 같다.In the present invention, by modifying the flame-retardant imparting polymer type bisphenol- sulfone-based epoxy resin prepared by the formula (5) to provide improved weather resistance and flowability. The modification reaction of the polymer type bisphenol-sulfone epoxy resin is shown in the following Chemical Formula 6.
[화학식 6][Formula 6]
상기 화학식 6에서 변성을 위한 원료로써 사용되는 것은 A 또는 B이며, A는 트리브로모페놀, 테트라브로모페놀, 또는 펜타브로모페놀 중 어느 하나인 할로겐 함유 유도체이며, B는 비할로겐계(산 또는 하이드록시를 함유하는 원료, 인을 함유하는 산 또는 하이드록시 함유 인)로서 에를 들어, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 또는 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide이다. 상기 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide의 화학구조식은 다음과 같다.Used as a raw material for modification in Formula 6 is A or B, A is a halogen-containing derivative of any one of tribromophenol, tetrabromophenol, or pentabromophenol, B is a non-halogen-based (acid Or a raw material containing hydroxy, an acid containing phosphorus or a hydroxy containing phosphorus), for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 3,4,5,6-dibenzo -1,2-oxaphosphane-2-oxide. Chemical structure of the 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide is as follows.
[화학식 7][Formula 7]
상기 화학식 6과 같은 반응은 무용제 조건에서도 가능하나, 용제를 사용하는 경우에는 케톤류(아세톤, 메틸에틸케톤, 메틸이소부틸케톤), 방향족 용제(벤젠, 톨루엔, 오르토, 파라-크실렌, 디클로로벤젠), 또는 셀로솔브(Cellosolve)계 용제를 사용하며, 반응 조건은 대기압 또는 대기압 이하(1/10 내지 8/10 기압), 50~200℃의 온도이며 반응촉매로서 염기 촉매(예를 들어, NaOH)를 사용한다.The reaction as shown in Chemical Formula 6 is possible even in the absence of solvent, but in the case of using a solvent, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), aromatic solvent (benzene, toluene, ortho, para-xylene, dichlorobenzene), Alternatively, a cellosolve solvent is used, and the reaction conditions are atmospheric pressure or subatmospheric pressure (1/10 to 8/10 atm), a temperature of 50 to 200 ° C., and a base catalyst (for example, NaOH) as a reaction catalyst. use.
[발명의 효과][Effects of the Invention]
이상에서 설명한 바와 같이, 본 발명에서는 결정성 비스페놀-술폰계 에폭시 수지를 이용하여 중합도가 0.1 내지 10인 고분자형 비스페놀-술폰 에폭시 수지를 제공한다. 본 발명에 의한 고분자형 비스페놀-술폰 에폭시 수지는 내열성이 향상되어 Tg가 높은 특성이 있다. 본 발명에서는 또한 난연성이 부여된 고분자형 비스페놀-술폰 에폭시 수지와 내후성, 흐름성을 보완하기 위하여 변성 반응을 거친 고분자형 비스페놀-술폰 에폭시 수지를 제공한다.As described above, the present invention provides a polymeric bisphenol-sulfone epoxy resin having a polymerization degree of 0.1 to 10 using a crystalline bisphenol-sulfone epoxy resin. The polymer type bisphenol-sulfone epoxy resin according to the present invention has improved heat resistance and high Tg. The present invention also provides a polymeric bisphenol-sulfone epoxy resin imparted flame retardancy and a polymerized bisphenol-sulfone epoxy resin subjected to a modification reaction to compensate for weatherability and flowability.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980023155A KR100297589B1 (en) | 1998-06-19 | 1998-06-19 | Polymeric bisphenol-sulfone epoxy resin with improved heat and flame resistance |
| JP17411599A JP3193698B2 (en) | 1998-06-19 | 1999-06-21 | Polymeric bisphenolsulfonic acid epoxy resin with improved heat resistance and flame retardancy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980023155A KR100297589B1 (en) | 1998-06-19 | 1998-06-19 | Polymeric bisphenol-sulfone epoxy resin with improved heat and flame resistance |
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| Publication Number | Publication Date |
|---|---|
| KR20000002410A KR20000002410A (en) | 2000-01-15 |
| KR100297589B1 true KR100297589B1 (en) | 2001-10-26 |
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| KR1019980023155A KR100297589B1 (en) | 1998-06-19 | 1998-06-19 | Polymeric bisphenol-sulfone epoxy resin with improved heat and flame resistance |
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| Country | Link |
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| JP (1) | JP3193698B2 (en) |
| KR (1) | KR100297589B1 (en) |
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| KR101742546B1 (en) | 2015-03-20 | 2017-06-02 | 한국과학기술연구원 | Functionalized carbon curing agents and epoxy compounds using the same, and methods of preparing the same |
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Non-Patent Citations (1)
| Title |
|---|
| Angew. Makromol. chemie, 199, 1992, 171-190(1992. 1.2) * |
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| Publication number | Publication date |
|---|---|
| JP2000026576A (en) | 2000-01-25 |
| JP3193698B2 (en) | 2001-07-30 |
| KR20000002410A (en) | 2000-01-15 |
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