KR100562462B1 - A manufacturing method of flame retardant polyester resin - Google Patents
A manufacturing method of flame retardant polyester resin Download PDFInfo
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- KR100562462B1 KR100562462B1 KR1019990028860A KR19990028860A KR100562462B1 KR 100562462 B1 KR100562462 B1 KR 100562462B1 KR 1019990028860 A KR1019990028860 A KR 1019990028860A KR 19990028860 A KR19990028860 A KR 19990028860A KR 100562462 B1 KR100562462 B1 KR 100562462B1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2467/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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Abstract
본 발명은 난연성 폴리에스테르 수지의 제조방법에 관한 것으로서, 더욱 상세하게는 다음 화학식 1로 표시되는 인계 난연제와 폴리에스테르 수지를 공중합시킨 난연성 폴리에틸렌테레프탈레이트 수지의 일정량을 폴리부틸렌테레프탈레이트 수지와 용융블렌드함으로써 연소시 다이옥신 등의 유해성 물질을 발생하지 않으며 결정성 및 내열성을 저하시키지 않으면서 성형성이 우수한 난연성 폴리에스테르 수지의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a flame retardant polyester resin, and more particularly, a predetermined amount of a flame retardant polyethylene terephthalate resin copolymerized with a phosphorus flame retardant represented by the following formula (1) and a polyester resin is melt blended with a polybutylene terephthalate resin. The present invention relates to a method for producing a flame retardant polyester resin having excellent moldability without causing harmful substances such as dioxins during combustion and deteriorating crystallinity and heat resistance.
상기 화학식 1에서 R1은 탄소수 1 ∼ 18인 알킬기이고, R2 및 R3는 탄소수 1 ∼ 18인 알킬기, 아릴기, 모노히드록시알킬기 또는 수소원자이고, A는 탄소수 1 ∼ 18인 2가의 탄화수소를 나타낸다.In Formula 1, R 1 is an alkyl group having 1 to 18 carbon atoms, R 2 and R 3 are an alkyl group having 1 to 18 carbon atoms, an aryl group, a monohydroxyalkyl group or a hydrogen atom, and A is a divalent hydrocarbon having 1 to 18 carbon atoms. Indicates.
Description
본 발명은 난연성 폴리에스테르 수지의 제조방법에 관한 것으로서, 더욱 상세하게는 다음 화학식 1로 표시되는 인계 난연제와 폴리에스테르 수지를 공중합시킨 난연성 폴리에틸렌테레프탈레이트 수지의 일정량을 폴리부틸렌테레프탈레이트 수지와 용융블렌드함으로써 연소시 다이옥신 등의 유해성 물질을 발생하지 않으며 결정성 및 내열성을 저하시키지 않으면서 성형성이 우수한 난연성 폴리에스테르 수지의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a flame retardant polyester resin, and more particularly, a predetermined amount of a flame retardant polyethylene terephthalate resin copolymerized with a phosphorus flame retardant represented by the following formula (1) and a polyester resin is melt blended with a polybutylene terephthalate resin. The present invention relates to a method for producing a flame retardant polyester resin having excellent moldability without causing harmful substances such as dioxins during combustion and deteriorating crystallinity and heat resistance.
화학식 1Formula 1
상기 화학식 1에서 R1은 탄소수 1 ∼ 18인 알킬기이고, R2 및 R3는 탄소수 1 ∼ 18인 알킬기, 아릴기, 모노히드록시알킬기 또는 수소원자이고, A는 탄소수 1 ∼ 18인 2가의 탄화수소를 나타낸다.In Formula 1, R 1 is an alkyl group having 1 to 18 carbon atoms, R 2 and R 3 are an alkyl group having 1 to 18 carbon atoms, an aryl group, a monohydroxyalkyl group or a hydrogen atom, and A is a divalent hydrocarbon having 1 to 18 carbon atoms. Indicates.
폴리에틸렌테레프탈레이트(이하 "PET"라 함)와 폴리부틸렌테레프탈레이트(이하 "PBT"라 함)로 대표되는 포화 지방족 폴리에스테르는 내열성 및 기계적 강도, 내약품성, 내광성, 전기절연성이 우수하여 필름, 쉬트, 보틀, 의류용사, 산업용사 또는 기타 성형품에 널리 사용되고 있다. 이렇게 여러 종류의 제품으로 만들어지는 폴리에스테르는 사용할 때에 화재예방 등의 관점에서 난연성을 부여할 필요가 있다. 이중 PBT는 결정화속도가 빠르고 전기적 특성이 우수하기 때문에 주로 자동차 용품, 전기-전자재료 용도로 널리 사용되는데 이들 용도분야는 특히 난연성을 필요로 한다.Saturated aliphatic polyesters represented by polyethylene terephthalate (hereinafter referred to as "PET") and polybutylene terephthalate (hereinafter referred to as "PBT") are excellent in heat and mechanical strength, chemical resistance, light resistance and electrical insulation, It is widely used in sheets, bottles, garment sprayers, industrial yarns and other molded articles. Such polyesters made of various kinds of products need to impart flame retardancy from the viewpoint of fire prevention and the like when used. Among them, PBT is widely used for automotive products and electric-electronic materials because of its fast crystallization rate and excellent electrical properties. These fields of application require flame retardancy.
이러한 폴리에스테르에 난연성을 부여하는 방법으로는 (1) 난연제를 폴리에스테르 제조시 또는 성형시에 혼련하는 방법(블렌드법), (2) 난연제를 폴리에스테르 제조시에 첨가해서 공중합시키는 방법(공중합법)이 알려져 있다. 이들 방법중 블렌드법은 제품 사용중 난연제가 배어나와 난연성이 저하될 뿐만 아니라 연소시에 다이옥신 등의 유해성 물질을 생성하는 등의 문제가 되어 왔다.As a method of imparting flame retardancy to such polyesters, (1) a method of kneading a flame retardant at the time of polyester production or molding (blend method), and (2) a method of adding and copolymerizing a flame retardant at the time of polyester production (copolymerization method) Is known. Among these methods, the blending method has become a problem such as not only the flame retardant bleeds out during the use of the product, but also the flame retardancy is lowered, and harmful substances such as dioxins are generated during combustion.
한편, 공중합에 사용되는 난연제로는 에스테르 형성성 관능기를 갖는 할로겐 화합물과 인화합물이 알려져 있지만 착색이 적고, 내광성이 우수하며 연소시에 유해성 물질을 생성하지 않는다는 점에서 인화합물이 할로겐 화합물보다 우수하다. 이러한 인화합물을 난연제로 첨가하여 난연성 폴리에스테르 수지를 제조할 때 PET 수지의 경우는 중합반응성이 다소 저하되거나, 난연제와 촉매 화합물의 반응에 의해 겔이 형성되는 경우가 있기는 하지만, 난연제의 선택 및 중합조건을 알맞게 조 절하면 이들 문제를 해결할 수 있다. 그러나, PBT 수지를 공중합법으로 제조시에는 인화합물이 촉매와의 반응에 의해 촉매의 활성을 떨어뜨리고, 또한 원료중 디올성분인 1,4-부탄디올을 분해시켜 테트라하이드로퓨란과 물을 생성시켜 중합속도를 극히 떨어뜨릴 뿐만 아니라 중합반응자체가 진행되지 않는 문제점이 있었다.On the other hand, as flame retardants used for copolymerization, halogen compounds and phosphorus compounds having ester-forming functional groups are known, but phosphorus compounds are superior to halogen compounds in that they are less colored, have excellent light resistance, and do not produce harmful substances upon combustion. . When producing a flame retardant polyester resin by adding such a phosphorus compound as a flame retardant, in the case of PET resin, the polymerization reactivity is slightly lowered, or a gel may be formed by the reaction of the flame retardant and the catalyst compound. By properly adjusting the polymerization conditions, these problems can be solved. However, when the PBT resin is prepared by the copolymerization method, the phosphorus compound deteriorates the activity of the catalyst by the reaction with the catalyst, and also decomposes 1,4-butanediol, a diol component, in the raw material to produce tetrahydrofuran and water to polymerize. In addition to the extremely slow speed, there was a problem that the polymerization reaction itself did not proceed.
이에 본 발명자들은 상기와 같은 문제점을 개선하기 위해 예의 검토한 결과, 인체에 유해하지 않고 독성물질을 발생하지 않는 상기 화학식 1로 표시되는 인계 난연제와 폴리에스테르 수지를 공중합시킨 난연성 PET 수지의 일정량을 PBT 수지와 용융블렌드함으로써 PBT 수지의 결정성을 저해시키지 않고 효과적으로 난연성을 부여해 줄 수 있음을 알게되어 본 발명을 완성하게 되었다.Therefore, the present inventors have diligently studied to improve the above problems, and as a result, a certain amount of flame retardant PET resin copolymerized with a polyester resin and a phosphorous flame retardant represented by Chemical Formula 1, which is not harmful to the human body and does not generate toxic substances, is PBT. The present invention has been completed by melting and blending the resin to effectively impart flame retardancy without inhibiting the crystallinity of the PBT resin.
따라서, 본 발명에서는 결정화속도가 빨라 성형용 재료로 널리 사용되는 PBT 수지의 성형성, 결정성 및 내열성을 저해하지 않으면서 난연성을 부여할 수 있는 난연성 폴리에스테르 수지의 제조방법을 제공하는데 그 목적이 있다.
Accordingly, the present invention provides a method for producing a flame retardant polyester resin that can impart flame retardance without impairing the moldability, crystallinity and heat resistance of PBT resin widely used as a molding material due to its high crystallization rate. have.
상기와 같은 목적을 달성하기 위한 본 발명은 디카르본산 또는 그 에스테르 유도체와 디올 또는 그 에스테르 유도체를 에스테르 교환반응시킨 후, 다음 화학식 1로 표시되는 인계 난연제를 디카르본산 또는 그 에스테르 유도체에 대하여 5 ∼ 50 몰%를 투입하여 10 ∼ 60분동안 반응시키고, 탄소수 2 ∼ 6의 알킬기로 치환된 테트라알킬티타네이트를 첨가한 후, 중축합반응시켜 난연성 폴리에스테르를 제조한 다음,In order to achieve the above object, the present invention provides a phosphorus-based flame retardant represented by the following Chemical Formula 1 with respect to dicarboxylic acid or its ester derivative after transesterification of dicarboxylic acid or its ester derivative with diol or its ester derivative. To 50 mol% was added for reaction for 10 to 60 minutes, tetraalkyl titanate substituted with an alkyl group having 2 to 6 carbon atoms was added, followed by polycondensation to prepare a flame retardant polyester.
상기 난연성 폴리에스테르 5 ∼ 50 중량%와 주 반복단위가 부틸렌테레프탈레이트이며 고유점도 0.70 ∼ 2.0인 수지 50 ∼ 95 중량%를 혼합하여 용융블렌드하는 난연성 폴리에스테르 수지의 제조방법을 그 특징으로 한다.Characterized by the method for producing a flame-retardant polyester resin of 5 to 50% by weight of the flame-retardant polyester and 50 to 95% by weight of the main repeating unit is butylene terephthalate and 50 to 95% by weight of resin having an intrinsic viscosity of 0.70 to 2.0.
화학식 1Formula 1
상기 화학식 1에서 R1은 탄소수 1 ∼ 18인 알킬기이고, R2 및 R3는 탄소수 1 ∼ 18인 알킬기, 아릴기, 모노히드록시알킬기 또는 수소원자이고, A는 탄소수 1 ∼ 18인 2가의 탄화수소를 나타낸다.In Formula 1, R 1 is an alkyl group having 1 to 18 carbon atoms, R 2 and R 3 are an alkyl group having 1 to 18 carbon atoms, an aryl group, a monohydroxyalkyl group or a hydrogen atom, and A is a divalent hydrocarbon having 1 to 18 carbon atoms. Indicates.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명에 따른 난연성 폴리에스테르 수지는 디카르본산 또는 그 에스테르 유도체와 디올 또는 그 에스테르 유도체를 주요 출발원료로 하여 제조된 저분자 물질에 상기 화학식 1로 표시되는 인계 난연제를 함유시켜 반응시키고, 여기에 중축합촉매를 첨가하여 난연성 폴리에스테르를 제조하고, 이를 PBT와 용융블렌드함으로써 제조된다. 종래에는 폴리에스테르에 인계 난연 효과를 부여하기 위하여 적인 등의 화합물을 블렌드에 의해서 다량 함유시키는 방법이 사용되었으나, 이 방법은 난연제가 폴리머계내에 단순 분산됨으로써 난연효과가 비교적 떨어졌다. 그러나, 폴 리머 체인내에 인화합물이 결합되도록 하면 혼련에 의한 것에 비하여 10% 정도만 첨가해도 더 우수한 난연효과를 부여하는 것이 가능하므로 본 발명에서는 난연성 폴리에스테르 수지의 제조시 반응성 인계 난연제를 용융중합중에 함유시켜 폴리머 체인내에 난연제가 결합되도록 하는 것이다. 한편, 상기와 같이 인계 난연제를 PBT 중합중에 첨가하여 공중합시킬 경우에는 인계 난연제에 의한 촉매활성의 저하 및 테트라하이드로퓨란 등의 부산물에 의해서 중합반응이 거의 진행되지 않는 문제점이 있는 반면 본 발명에서는 난연제를 출발원료성분과 함께 공중합시키고, 제조된 수지와 PBT 수지를 용융블렌드함으로써 상기와 같은 문제점을 해결할 수 있다.The flame retardant polyester resin according to the present invention contains a phosphorus flame retardant represented by the formula (1) in a low molecular weight material prepared by using dicarboxylic acid or its ester derivatives and diol or its ester derivatives as a main starting material, and reacts therewith. A flame-retardant polyester is prepared by adding a cocatalyst, which is prepared by melt blending with PBT. Conventionally, in order to impart phosphorus-based flame retardant effect to polyester, a method in which a compound such as red is contained in a large amount by a blend has been used, but this method has a relatively low flame retardant effect by simply dispersing the flame retardant in the polymer system. However, when the phosphorus compound is bound in the polymer chain, it is possible to give a better flame retardant effect by adding only about 10% as compared to that by kneading, so in the present invention, a reactive phosphorus flame retardant is included in the melt polymerization during the production of the flame retardant polyester resin. This allows the flame retardant to bond within the polymer chain. On the other hand, when the phosphorus-based flame retardant is added to the copolymerization during the PBT polymerization, there is a problem in that the polymerization reaction is hardly progressed due to the decrease in catalytic activity by the phosphorus-based flame retardant and by-products such as tetrahydrofuran, etc. The above problems can be solved by copolymerizing with the starting material components and melt blending the produced resin with the PBT resin.
본 발명에 따른 난연성 폴리에스테르 수지의 주요 출발원료인 디카르본산 또는 그 에스테르 유도체로는 테레프탈산, 2,6-나프탈렌디카르본산, 이소프탈산, 프탈산 및 5-나트륨술폰이소프탈산 중에서 선택된 방향족 디카르본산 및 그의 에스테르 유도체와 1,4-시클로헥산디카르본산, 1,3-시클로헥산디카르본산 등의 지환족 디카르본산 및 그의 에스테르 유도체 중에서 선택된 2종 이상을 혼합사용할 수 있고, 바람직하기로는 테레프탈산 또는 그 에스테르 유도체를 90 몰% 이상으로 사용하는 것이 PBT와의 혼련성면에서 좋다.Dicarboxylic acids or ester derivatives thereof, which are the main starting materials of the flame retardant polyester resin according to the present invention, are aromatic dicarboxylic acids selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, phthalic acid, and 5-sodium sulfonic isophthalic acid. And ester esters thereof and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, and two or more kinds selected from ester derivatives thereof, may be used in combination. Preferably, terephthalic acid is used. Alternatively, the use of the ester derivative in an amount of 90 mol% or more is good in terms of kneading with PBT.
그리고, 디올 또는 그 에스테르 유도체로는 에틸렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥산디올, 1,4-시클로헥산디메탄올, 비스페놀A 및 비스페놀S 중에서 선택된 2종 이상을 혼합사용할 수 있고, 바람직하기로는 에틸렌글리콜 또는 그 에스테르 유도체를 90 몰% 이상으로 사용하는 것이 PBT와의 혼련성면에서 유리하다.Diols or ester derivatives thereof include two selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, bisphenol A, and bisphenol S The above can be mixed and used, Preferably, it is advantageous to use ethylene glycol or its ester derivative in 90 mol% or more from the point of kneading | mixing with PBT.
상기와 같은 디카르본산 또는 그 에스테르 유도체와 디올 화합물을 출발원료로 하여 에스테르화 또는 에스테르 교환반응에 의해 저분자 물질을 제조한 후, 상기 화학식 1로 표시되는 인계 난연제를 첨가하여 반응시키고 고온고진공하에서 중축합촉매하에서 중합반응을 진행하여 난연성 폴리에스테르를 제조한다.Using a dicarboxylic acid or its ester derivative and a diol compound as a starting material to prepare a low molecular weight material by esterification or transesterification reaction, and then by adding a phosphorous flame retardant represented by the formula (1) and polycondensation under high temperature and high vacuum The polymerization reaction is carried out under a polymerization catalyst to prepare a flame retardant polyester.
일반적으로 난연제를 원료인 디카르본산 또는 그 에스테르 유도체에 대하여 10 몰% 이상 첨가하여 중합할 경우에는 중합속도가 극히 느려질 뿐만 아니라 제조되는 폴리에스테르의 고유점도도 극히 낮은 값을 갖게 되는 반면 본 발명에서는 촉매의 종류 및 투입시점, 상기 화학식 1로 표시되는 인계 난연제의 투입시점 등을 조절함으로써 중합반응성을 저하시키지 않고, 고점도의 난연성 폴리에스테르 수지를 제조할 수 있다.In general, when the flame retardant is added at least 10 mol% based on the dicarboxylic acid or its ester derivative, the polymerization rate is extremely slow and the intrinsic viscosity of the polyester produced is extremely low. By adjusting the type of catalyst, the timing of the input, and the timing of the input of the phosphorus-based flame retardant represented by Chemical Formula 1, it is possible to produce a flame-retardant polyester resin having a high viscosity without reducing the polymerization reactivity.
상기 화학식 1로 표시되는 인계 난연제는 1 ∼ 30 중량%의 인 원자를 함유하는 것으로서, 메틸(2-카르복시에틸)포스핀산, 메틸(4-카르복시부틸)포스핀산, 페닐(2-카르복시에틸)포스핀산 및 페닐(2-(메톡시카르보닐)에틸)포스핀산 중에서 선택한 2종 이상을 혼합사용할 수 있고, 바람직하기로는 페닐(2-카르복시에틸)포스핀산을 사용하는 것이 좋다. 이러한 상기 화학식 1로 표시되는 인계 난연제는 디카르본산 또는 그 에스테르 유도체에 대하여 5 ∼ 50 몰%로 함유하는 것이 좋다.Phosphorus flame retardant represented by the formula (1) contains 1 to 30% by weight of phosphorus atoms, methyl (2-carboxyethyl) phosphinic acid, methyl (4-carboxybutyl) phosphinic acid, phenyl (2-carboxyethyl) Two or more types selected from pinic acid and phenyl (2- (methoxycarbonyl) ethyl) phosphinic acid can be mixed and used, and preferably phenyl (2-carboxyethyl) phosphinic acid is used. Phosphorus-based flame retardant represented by the formula (1) is preferably contained in 5 to 50 mol% based on dicarboxylic acid or ester derivatives thereof.
디카르본산 또는 그 에스테르 유도체와 디올 화합물을 출발원료로 하는 에스테르 교환반응을 완결한 후, 상기와 같은 인계 난연제를 투입하여 10 ∼ 60분 동안 반응시킨 다음, 중축합촉매를 투입하여 중합반응을 수행하여 고유점도 0.60 이상을 갖는 난연성 폴리에스테르를 제조한다.After completion of the transesterification reaction using dicarboxylic acid or its ester derivative and diol compound as starting materials, the reaction was carried out for 10 to 60 minutes by adding the phosphorus-based flame retardant as described above, and then a polycondensation catalyst was added to carry out the polymerization reaction. To produce a flame-retardant polyester having an intrinsic viscosity of 0.60 or more.
이때, 에스테르 교환반응 촉매로는 망간아세테이트, 징크아세테이트, 코발트아세테이트, 칼슘아세테이트, 마그네슘아세테이트, 소듐아세테이트 및 리튬아세테이트 중에서 선택된 금속아세테이트염과 수산화망간, 수산화아연, 수산화코발트, 수산화칼슘, 수산화마그네슘 및 수산화나트륨 중에서 선택된 금속수산화물과 소듐메톡사이드, 소듐에톡사이드, 칼륨메톡사이드 및 칼륨에톡사이드 중에서 선택된 알칼리 금속의 알콕시화합물 중에서 선택된 2종 이상을 혼합하여 사용할 수 있고, 바람직하기로는 망간아세테이트와 징크아세테이트를 함께 사용하는 것이 좋다.At this time, as the transesterification catalyst, metal acetate salt and manganese hydroxide, zinc hydroxide, cobalt hydroxide, calcium hydroxide, magnesium hydroxide and sodium hydroxide selected from manganese acetate, zinc acetate, cobalt acetate, calcium acetate, magnesium acetate, sodium acetate and lithium acetate. Among the metal hydroxide selected from sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide selected from alkoxy compounds of the alkali metal selected from among two or more may be used in combination, preferably manganese acetate and zinc acetate It is good to use together.
그리고, 중축합반응 촉매로는 안티모니옥사이드, 틴옥사이드 및 게르마늄디옥사이드 중에서 선택된 금속산화물과 테트라부틸티타네이트, 테트라이소프로필티타네이트, 테트라하이드록실티타네이트 등의 탄소수 2 ∼ 6의 알킬기로 치환된 테트라알킬티타네이트를 사용할 수 있다. 이들을 2종 이상 혼합하여 사용할 수 있고, 바람직하기로는 안티모니옥사이드와 테트라부틸티타네이트를 사용하는 것이 좋다.As the polycondensation reaction catalyst, tetrametal substituted with an alkyl group having 2 to 6 carbon atoms, such as a metal oxide selected from antimony oxide, tin oxide and germanium dioxide, and tetrabutyl titanate, tetraisopropyl titanate and tetrahydroxytitanate Alkyl titanates can be used. These can be used in mixture of 2 or more types, It is preferable to use antimony oxide and tetrabutyl titanate preferably.
그런다음 상기에서 제조된 난연성 폴리에스테르와 PBT 수지를 용융블렌드하여 본 발명에 따른 난연성 및 성형성이 우수한 성형용 폴리에스테르 수지를 제조한다. 이때, 난연성 폴리에스테르는 5 ∼ 50 중량%로 사용하고, PBT 수지는 50 ∼ 95 중량%로 사용하는 것이 좋다. 이때, 난연성 폴리에스테르의 함량이 5 중량% 미만이면 난연성이 부족하여 바람직하지 않고, 50 중량%를 초과하면 PBT의 결정성이 저하되어 성형성이 극히 불량해지므로 좋지 않다. 여기서 사용하는 PBT 수지로는 산성분으로 테레프탈산 또는 디메틸테레프탈레이트, 디올성분으로 1,4-부탄디올을 주요 출발원료로 하여 통상의 중합법으로 제조되는 고유점도 0.70 ∼ 2.0을 갖는 수지를 사용하면 된다.Then, melt blending the flame-retardant polyester and PBT resin prepared above to produce a polyester resin for molding excellent in flame retardancy and moldability according to the present invention. At this time, it is good to use flame retardant polyester at 5 to 50 weight%, and to use PBT resin at 50 to 95 weight%. At this time, if the content of the flame retardant polyester is less than 5% by weight, it is not preferable because the flame retardancy is insufficient, and if it exceeds 50% by weight, the crystallinity of the PBT is lowered and the moldability becomes extremely poor. As the PBT resin used here, a resin having an intrinsic viscosity of 0.70 to 2.0 produced by a conventional polymerization method using terephthalic acid or dimethyl terephthalate as an acid component and 1,4-butanediol as a main starting material as a diol component may be used.
이러한 본 발명에 따른 난연성 폴리에스테르 수지는 난연제 첨가에 의해 중합성능 저하가 비교적 적은 PET 수지를 주요 구성성분으로 하는 난연성 폴리에스테르를 제조한 후, 이를 PBT 수지와 용융블렌드하여 폴리머내에 0.04 ∼ 5 중량%의 인 원자가 함유됨으로써 PBT 수지의 결정성 및 성형성을 저해시키지 않으면서 수지에 난연성을 부여할 수 있다.The flame-retardant polyester resin according to the present invention is prepared by flame-retardant polyester mainly composed of PET resin having a relatively low degradation of polymerization performance by the addition of a flame retardant, and then melt blended with PBT resin to 0.04 to 5% by weight in the polymer By containing phosphorus atom, flame retardance can be provided to resin, without impairing the crystallinity and moldability of PBT resin.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예로 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
실시예 1Example 1
디메틸테레프탈레이트 100 중량부와 에틸렌글리콜 60 중량부에 마그네슘아세테이트 0.045 중량부, 코발트아세테이트 0.004 중량부, 삼산화안티몬 0.03 중량부를 첨가하여 3시간에 걸쳐 온도를 140℃에서 230℃까지 승온하면서 에스테르 교환반응을 수행하고, 이어서 얻어진 저분자물질에 페닐(2-카르복시에틸)포스핀산을 디메틸테레프탈레이트에 대하여 15 몰% 첨가하여 30분간 반응시킨 후, 테트라부틸티타네이트 0.03 중량부를 첨가하여 285℃, 0.5 torr 미만에서 4시간동안 중축합반응을 행하여 고유점도 0.655인 난연성 폴리에스테르를 수득하였다.To 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.045 parts by weight of magnesium acetate, 0.004 parts by weight of cobalt acetate and 0.03 parts by weight of antimony trioxide were added and the ester exchange reaction was carried out while raising the temperature from 140 ° C to 230 ° C over 3 hours. Then, 15 mol% of phenyl (2-carboxyethyl) phosphinic acid was added to the obtained low molecular weight to dimethyl terephthalate and reacted for 30 minutes, and then 0.03 parts by weight of tetrabutyl titanate was added at 285 ° C and less than 0.5 torr. The polycondensation reaction was carried out for 4 hours to obtain a flame retardant polyester having an intrinsic viscosity of 0.655.
상기 난연성 폴리에스테르 30 중량%와 고유점도 1.20인 PBT 수지 70 중량%를 혼합하여 브라벤더믹서를 이용하여 270℃에서 블렌드시켜 난연성 PBT 수지를 제조하였다. 이렇게 제조된 난연성 폴리에스테르 수지의 고유점도는 0.98 이었으며, UL법에 의해 난연시편을 제조한 결과, 통상의 PBT 성형조건에서 성형수축율이 0.02% 미만인 시편을 제조할 수 있고, 이의 난연성을 평가한 결과, UL94-V2 등급으로 평가되었다.A flame retardant PBT resin was prepared by mixing 30 wt% of the flame retardant polyester and 70 wt% of the PBT resin having an intrinsic viscosity of 1.20 by using a Brabender mixer. The intrinsic viscosity of the flame retardant polyester resin thus prepared was 0.98, and the flame retardant specimens were manufactured by the UL method. As a result, specimens having a molding shrinkage of less than 0.02% under ordinary PBT molding conditions could be manufactured, and the results of evaluating the flame retardance thereof were as follows. , Rated as UL94-V2.
실시예 2Example 2
상기 실시예 1과 동일한 방법으로 하되, 난연성 폴리에스테르 40 중량%와 PBT 수지 60 중량%를 혼합하여 난연성 폴리에스테르 수지를 제조하였다. 제조된 난연성 폴리에스테르 수지의 고유점도는 0.95 이었으며, 난연성을 평가한 결과 UL94-V0 등급으로 평가되었고, 성형성도 양호하였다.In the same manner as in Example 1, a flame-retardant polyester resin was prepared by mixing 40% by weight of flame-retardant polyester and 60% by weight of PBT resin. The intrinsic viscosity of the prepared flame retardant polyester resin was 0.95, the flame retardancy was evaluated as a UL94-V0 grade, the moldability was also good.
실시예 3Example 3
상기 실시예 1과 동일한 방법으로 하되, 난연성 폴리에스테르 20 중량%와 PBT 수지 80 중량%를 혼합하여 난연성 폴리에스테르 수지를 제조하였다. 제조된 난연성 폴리에스테르 수지의 고유점도는 0.103 이었으며, 난연성을 평가한 결과 UL94-V2 등급으로 평가되었고, PBT와 동일 조건으로 성형이 가능하였다.In the same manner as in Example 1, 20% by weight of flame-retardant polyester and 80% by weight of PBT resin was mixed to prepare a flame-retardant polyester resin. The intrinsic viscosity of the prepared flame-retardant polyester resin was 0.103, the flame retardancy was evaluated as a UL94-V2 grade, it was possible to mold under the same conditions as PBT.
비교예 1Comparative Example 1
디메틸테레프탈레이트 100 중량부와 에틸렌글리콜 60 중량부에 마그네슘아세테이트 0.045 중량부, 코발트아세테이트 0.004 중량부, 삼산화안티몬 0.03 중량부를 첨가하여 4시간에 걸쳐 온도를 140℃에서 230℃까지 승온하면서 에스테르 교환반응을 수행하고, 이어서 얻어진 저분자물질에 페닐(2-카르복시에틸)포스핀산을 디메틸테레프탈레이트에 대하여 15 몰%와 테트라부틸티타네이트 0.03 중량%를 첨가한 후, 일정 시간동안 반응시키지 않고 바로 285℃, 0.5 torr 미만에서 중축합반응을 행하였으나, 중축합반응성이 극히 저하되어 반응시간 45시간 경과 후에 반응을 종 료한 후, 토출 칩화하여 물성을 평가한 결과 고유점도가 0.462로 극히 낮은 값을 얻었다.To 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.045 parts by weight of magnesium acetate, 0.004 parts by weight of cobalt acetate, and 0.03 parts by weight of antimony trioxide were added and the ester exchange reaction was carried out while raising the temperature from 140 ° C to 230 ° C over 4 hours. Subsequently, 15 mol% of phenyl (2-carboxyethyl) phosphinic acid and 0.03 wt% of tetrabutyl titanate were added to the dimethyl terephthalate to the obtained low molecular weight material, and then immediately reacted at a constant temperature of 285 ° C., 0.5. Although the polycondensation reaction was carried out below torr, the polycondensation reactivity was extremely reduced, and after 45 hours of reaction time, the reaction was terminated.
상기 폴리에스테르 30 중량%와 고유점도 1.20인 PBT 수지 70 중량%를 혼합하여 브라벤더 믹서를 이용하여 270℃에서 블렌드시켜 난연성 폴리에스테르 수지를 제조하였다. 이렇게 제조된 난연성 폴리에스테르 수지의 고유점도는 0.88 이었으며, UL법에 의해 난연시편을 제조한 결과, 난연성은 UL94-V2 등급으로 판정되었으나, 고유점도의 저하로 인해 기계적 물성이 극히 떨어지는 문제점이 있다.30 wt% of the polyester and 70 wt% of the PBT resin having an intrinsic viscosity of 1.20 were mixed and blended at 270 ° C. using a Brabender mixer to prepare a flame retardant polyester resin. The intrinsic viscosity of the flame-retardant polyester resin thus prepared was 0.88, as a result of manufacturing the flame-retardant specimen by the UL method, the flame retardancy was determined to be UL94-V2 grade, there is a problem that the mechanical properties are extremely deteriorated due to the decrease in intrinsic viscosity.
비교예 2Comparative Example 2
상기 실시예 1과 동일한 방법으로 하되, 에스테르 교환반응 종료 후, 테트라부틸티타네이트를 첨가하지 않았다. 제조된 난연성 폴리에스테르 수지의 고유점도가 0.41로 낮아져 PBT와의 블렌드 성능이 극히 불량하여 난연시편 제조에 실패하였다.In the same manner as in Example 1, but after the completion of the transesterification reaction, tetrabutyl titanate was not added. The intrinsic viscosity of the prepared flame retardant polyester resin was lowered to 0.41, so that the blend performance with the PBT was extremely poor, and thus the production of the flame retardant specimen failed.
상술한 바와 같이, 본 발명에 따른 난연성 폴리에스테르 수지는 난연성이 좋아 연소시 다이옥신 등의 유해성 물질을 발생하지 않으며 결정성 및 내열성을 저하시키지 않으면서 성형성이 우수하다.As described above, the flame retardant polyester resin according to the present invention has good flame retardancy and does not generate harmful substances such as dioxins during combustion, and has excellent moldability without lowering crystallinity and heat resistance.
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| WO2010077009A3 (en) * | 2008-12-31 | 2010-10-21 | 에스케이케미칼 주식회사 | Method for preparing a polyester resin |
| US9279033B2 (en) | 2012-06-05 | 2016-03-08 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
| US9284405B2 (en) | 2012-05-25 | 2016-03-15 | Sk Chemicals Co., Ltd. | Preparation method of polyester resin |
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| KR100452798B1 (en) * | 2001-07-02 | 2004-10-14 | 주식회사 코오롱 | Polybutyleneterephthalate resin |
| KR100616185B1 (en) * | 2004-04-27 | 2006-08-25 | 주식회사 코오롱 | Fire retardant Polyester resin composite for wig-hair |
| KR101717985B1 (en) * | 2014-12-31 | 2017-03-20 | 도레이케미칼 주식회사 | Flame-retardant polyester resin for Flame-retardant fiber having good dyeing property, Preparing method thereof and Flame-retardant fiber of good color depth containing the same |
| CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
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| KR910011972A (en) * | 1989-12-28 | 1991-08-07 | 이승동 | Process for preparing flame retardant polyester polymer |
| KR0175691B1 (en) * | 1996-02-23 | 1999-05-15 | 박홍기 | Process for preparing flame retardant polyester |
| KR100295014B1 (en) * | 1994-06-17 | 2001-10-24 | 조민호 | Manufacturing method of antistatic polyester fiber |
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| KR910011972A (en) * | 1989-12-28 | 1991-08-07 | 이승동 | Process for preparing flame retardant polyester polymer |
| KR100295014B1 (en) * | 1994-06-17 | 2001-10-24 | 조민호 | Manufacturing method of antistatic polyester fiber |
| KR0175691B1 (en) * | 1996-02-23 | 1999-05-15 | 박홍기 | Process for preparing flame retardant polyester |
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| WO2010077009A3 (en) * | 2008-12-31 | 2010-10-21 | 에스케이케미칼 주식회사 | Method for preparing a polyester resin |
| US9328195B2 (en) | 2008-12-31 | 2016-05-03 | Sk Chemicals Co., Ltd. | Method for preparing a polyester resin |
| US9284405B2 (en) | 2012-05-25 | 2016-03-15 | Sk Chemicals Co., Ltd. | Preparation method of polyester resin |
| US9279033B2 (en) | 2012-06-05 | 2016-03-08 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
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