KR940005978B1 - Phosphorus-containing polyallylate and producing method thereof - Google Patents
Phosphorus-containing polyallylate and producing method thereof Download PDFInfo
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Description
본 발명은 인을 함유한 폴리아릴레이트와 그의 제조방법에 관한 것으로서 더욱 상세하게는 각종 수지조성물과의 복합성이 우수하며 그 복합된 수지조성물에 우수한 가공성 및 내열성을 부여해 줄 수 있는 다음 구조식(I)로 표시되는 함인 폴리아릴레이트와 그의 제조방법에 관한 것이다.The present invention relates to a polyarylate containing phosphorus and a method for preparing the same, and more particularly, to the polyarylate containing phosphorus, which is excellent in complexity with various resin compositions and which can impart excellent processability and heat resistance to the composite resin composition. The present invention relates to a polyarylate containing phosphorus and a method for preparing the same.
상기식에서, R1과 R2는 서로 같거나 다른것으로서 각각 할로겐원자, 수소원자, 탄소수 1∼8개의 알킬기, 사이클로알킬기, 아릴기 또는 아릴알킬기를 나타내며, R3는 메틸기, 에틸기, 페닐기,또는 탄소수 1∼10개의 아릴기를 나타내며, R4는 수소원자, 할로겐원자 또는 탄소수 1∼6개의 알킬기를 나타내며, A는 탄소수 1∼6개의 알킬렌기, 산소원자 또는 케톤기를 나타내며, m은 0∼4의 정수이고, n은 0 또는 1이며, Y는 80∼150의 정수이다.Wherein R 1 and R 2 are the same as or different from each other, and represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an aryl group or an arylalkyl group, and R 3 is a methyl group, an ethyl group, a phenyl group, Or an aryl group having 1 to 10 carbon atoms, R 4 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, A represents an alkylene group, an oxygen atom or a ketone group having 1 to 6 carbon atoms, and m is 0 to 4 N is 0 or 1, and Y is an integer of 80-150.
일반적으로 폴리아릴레이트는 "유니티카"가 맨처음 개발하여 시장에 내놓은 U-폴리머로 고기능성을 지닌 전방향족 폴리에스테르계의 엔지니어링 폴라스틱으로서 전기, 전자부품, 정밀기계부품과 자동차분야를 중심으로 사용되는 바, 종래의 범용 엔지니어링 플라스틱에서는 해결하기 어려운 보다 고기능성이 요구되는 분야나 용도에 쓰여지고 있다.In general, polyarylate is a U-polymer developed and marketed by "UNITICA" for the first time, and is a highly functional, all-aromatic polyester-based engineering plastic used mainly in the fields of electric, electronic parts, precision machine parts, and automobiles. As a result, it is used in fields and applications that require higher functionality, which is difficult to solve in conventional general-purpose engineering plastics.
이러한 폴리아릴레이트 합성에 대한 종래의 방법으로 미국특허 제4,612,350호에서는 비스페놀 에이 대신 다음 구조식(A)의 비스(하이드록시 페닐)플루오렌을 사용하여 폴리머의 기계적 성질을 향상시키는 방법이 개시되어 있고,As a conventional method for the synthesis of such polyarylate, US Patent No. 4,612, 350 discloses a method of improving the mechanical properties of a polymer by using bis (hydroxy phenyl) fluorene of the following structural formula (A) instead of bisphenol A,
상기식에서 R은 수소원자, 알킬기, 할로겐원자이다.In the formula, R is a hydrogen atom, an alkyl group, a halogen atom.
미국특허 제4,447,647호에서는 비스페놀 에이와 다음 구조식(B)의 티오디페놀을 적당한 비율로 첨가하여 난연성을 향상시키는 방법이 개시되어 있으며U.S. Patent No. 4,447,647 discloses a method for improving flame retardancy by adding bisphenol A and thiodiphenol of the following structural formula (B) in an appropriate ratio.
상기식에서 R은 수소원자, 알킬기, 할로겐원자이다.In the formula, R is a hydrogen atom, an alkyl group, a halogen atom.
미국특허 제4,330,662호에서는 기존의 폴리아릴레이트와 폴리카보네이트를 혼합하므로써 다음 구조식(C)로 표시되는 폴리아릴레이트를 제조하는 방법에 관해 기술하고 있다.US Patent No. 4,330,662 describes a method for preparing a polyarylate represented by the following structural formula (C) by mixing the existing polyarylate and polycarbonate.
그러나, 이러한 종래의 방법에 의해 제조된 폴리아릴레이트는 개질에 따른 원가 상승과 높은 성형온도로 인해 가공성이 용이하지 못한 단점이 있다.However, the polyarylate produced by such a conventional method has a disadvantage in that processability is not easy due to the cost increase and the high molding temperature due to the modification.
이에 본 발명에서는 폴리아릴레이트를 제조함에 있어서, 비스페놀 유도체와 디클로라이드 유도체를 등몰반응시켜 폴리아릴레이트를 합성하므로써 그 합성이 용이하며, 경제성과 가공성이 우수한 상기 구조식(I)의 폴리아릴레이트와 그를 제조하는 방법을 제공하는데에 그 목적이 있다.Accordingly, in the present invention, in preparing the polyarylate, the polyarylate of the structural formula (I) and the same are easily synthesized by synthesizing the polyarylate by equimolar reaction between the bisphenol derivative and the dichloride derivative. Its purpose is to provide a method of manufacture.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 상기 구조식(I)로 표시되는 함인 폴리아릴레이트에 관한 것으로서, 이러한 본 발명에 따른 폴리아릴레이트를 제조하기 위해서는, 다음 구조식(II)의 비스페놀 유도체를 알카리수용액에 용해시키고, 이를 다음 구조식(III)과 (IV)의 디클로라이드 유도체를 유기용매에 녹인 용액과 혼합시키되 상기 비스페놀 유도체와 디클로라이드 유도체 혼합물을 같은 몰비로 혼합하여 계면 중합 반응시키므로써 제조할 수 있다.The present invention relates to a polyarylate containing a phosphorus represented by the above formula (I), in order to prepare a polyarylate according to the present invention, the bisphenol derivative of the following formula (II) is dissolved in an aqueous alkali solution, and the following formula The dichloride derivatives of (III) and (IV) may be mixed with a solution dissolved in an organic solvent, but the bisphenol derivative and the dichloride derivative mixture may be mixed in the same molar ratio to prepare an interfacial polymerization reaction.
상기식들 중에서, R1, R2, R3, R4, A,m,n 및 Y는 상기한 바와같고, X는 할로겐원자이다.In the formulas above, R 1 , R 2 , R 3 , R 4 , A, m, n and Y are as described above, and X is a halogen atom.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에서는 상기 구조식(II)의 비스페놀 유도체를 알칼리 수용액에 용해시키고, 이를 상기구조식(III)과 (IV)의 디클로라이드 유도체를 혼합물을 유기용매에 녹인 용액과 혼합시키는데, 이와같은 본 반응은 수용액층과 유기층의 계면에서 반응이 일어나는 계면 중합이므로 두 계면이 잘 섞어지도록 계면을 분산시켜야 한다. 이때, 계면 중합은 보통 대기압에서 반응이 진행되며 약 1∼4시간후 종결된다. 이때 반응온도는 5∼30℃ 정도가 좋다.In the present invention, the bisphenol derivative of the formula (II) is dissolved in an aqueous alkali solution, and the dichloride derivatives of the formula (III) and (IV) are mixed with a solution in which the mixture is dissolved in an organic solvent. Since the interface polymerization occurs at the interface between the layer and the organic layer, the interface must be dispersed to mix well. At this time, the interfacial polymerization usually proceeds at atmospheric pressure and terminates after about 1 to 4 hours. At this time, the reaction temperature is preferably about 5 to 30 ℃.
본 발명에서는 디클로라이드 유도체의 혼합물과 비스페놀 유도체의 양은 등몰이어야 하는데, 만일 디클로라이드 유도체의 혼합물이 과다하거나 과소하면 고분자량의 폴리아릴레이트를 얻기 어려운 문제점이 있다.In the present invention, the amount of the mixture of dichloride derivatives and bisphenol derivatives should be equimolar. If the mixture of dichloride derivatives is excessive or too low, it is difficult to obtain a high molecular weight polyarylate.
또한 본 발명에서 상기 구조식(II)의 비스페놀 유도체로는 2,2-비스(4-히드록시 페닐) 프로판, 2,4-디히드록시 디페닐 메탄, 비스(2-히드록시 페닐) 메탄, 비스(4-히드록시 페닐) 메탄,In the present invention, as the bisphenol derivative of the formula (II), 2,2-bis (4-hydroxy phenyl) propane, 2,4-dihydroxy diphenyl methane, bis (2-hydroxy phenyl) methane, bis (4-hydroxy phenyl) methane,
1,1-비스(4-히드록시 페닐) 에탄,1,1-bis (4-hydroxy phenyl) ethane,
1,3-비스(3-메틸-4-히드록시 페닐) 프로판1,3-bis (3-methyl-4-hydroxy phenyl) propane
2,2-비스(3,5-디브로모-4-히드록시 페닐) 프로판,2,2-bis (3,5-dibromo-4-hydroxy phenyl) propane,
2,2-비스(3-이소프로필-4-히드록시 페닐) 사이클로 헥산,2,2-bis (3-isopropyl-4-hydroxy phenyl) cyclohexane,
1,1-비스(4-히드록시 페닐) 사이클로 헥산,1,1-bis (4-hydroxy phenyl) cyclohexane,
1,1-비스(3,5-디메틸-4-히드록시 페닐) 사이클로 헥산,1,1-bis (3,5-dimethyl-4-hydroxy phenyl) cyclohexane,
비스(3-에틸-4-히드록시 페닐) 에테르,Bis (3-ethyl-4-hydroxy phenyl) ether,
비스(4-히드록시 페닐) 에테르 등이 사용되는데, 특히 비스페놀에이로 알려진 2,2-비스(4-히드록시 페닐) 프로판을 사용했을때 더욱 효과적이다.Bis (4-hydroxy phenyl) ether and the like are used, particularly when 2,2-bis (4-hydroxy phenyl) propane known as bisphenolA is used.
그리고, 알카리 수용액으로는 수산화나트륨 또는 수산화칼륨 용액을 사용하며 알카리 농도는 0.1∼8중량% 범위가 되도록 한다.As the alkaline aqueous solution, sodium hydroxide or potassium hydroxide solution is used, and the alkali concentration is in the range of 0.1 to 8% by weight.
또한, 알카리 수용액에 비스페놀 유도체를 녹인 농도는 2∼30중량%가 되게 하는데, 바람직하기는 4∼13중량%이다.In addition, the concentration of the bisphenol derivative dissolved in the aqueous alkali solution is 2 to 30% by weight, preferably 4 to 13% by weight.
이때 알카리와 비스페놀중 히드록시기의 몰비는 1 : 1∼1.1 : 1의 범위가 좋은데, 만일 알카리양이 사용된 비스페놀의 히드록시기 보다 과다하거나 과소하면 고분자량의 폴리아릴레이트를 얻기가 어려운 문제점이 있다.At this time, the molar ratio of the hydroxy group in the alkali and bisphenol is in the range of 1: 1 to 1.1: 1, if the alkali amount is excessively or less than the hydroxyl group of the bisphenol used, there is a problem that it is difficult to obtain a high molecular weight polyarylate.
본 발명에서 사용되는 상기 구조식(III)의 화합물로는 페닐포스포닉 디클로라이드가 유용하며, 상기 구조식(IV)의 화합물로는 테레프탈로일 클로라이드와 이소프탈로일 클로라이드가 유용하고, 상기 구조식(III)과 (IV)의 혼합물을 용해시킬때 사용할 수 있는 용매로는 메틸렌 디클로라이드, 클로로포름, 테트라클로로 메탄, 1,2-디클로로 에탄, 1,1,2-트리클로로 에탄, 테트라클로로 에탄, 벤젠, 메틸 벤젠등의 탄화수소 또는 할로겐화된 탄화수소 용매가 사용된다. 이때 디클로라이드 유도체의 혼합물을 유기용매에 용해시킨 농도는 2∼30중량%, 바람직하기는 4∼13중량%이다.Phenylphosphonic dichloride is useful as the compound of formula (III) used in the present invention, terephthaloyl chloride and isophthaloyl chloride are useful as the compound of formula (IV), and the above formula (III) Solvents that can be used to dissolve the mixture of (IV) and (IV) include methylene dichloride, chloroform, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethane, benzene, methyl Hydrocarbons or halogenated hydrocarbon solvents such as benzene are used. At this time, the concentration of the mixture of dichloride derivatives in the organic solvent is 2 to 30% by weight, preferably 4 to 13% by weight.
한편, 본 발명에서는 촉매, 점도 안정화제, 산화 방지제, 분산제 등을 알카리 수용액이나 반응 혼합물에 첨가하는데, 이때 촉매로는 트리메틸벤질 암모니움 히드로옥사이드, 트리메틸벤질 암모니움 클로라이드 또는 트리에틸 벤질 암모니움 클로라이드중에서 선택된 제4급 암모니움염, 트리에틸아민, 트리메틸아민 또는 벤질디메틸 아민중에서 선택된 제3급 암모니움 화합물, 또는 디메틸-2-히드록시페닐 슬포니움 클로라이드의 제4급 술포니움염중에서 선택된 어느 하나를 사용한다.Meanwhile, in the present invention, a catalyst, a viscosity stabilizer, an antioxidant, a dispersant, and the like are added to an aqueous alkali solution or a reaction mixture, wherein the catalyst is trimethylbenzyl ammonium hydroxide, trimethylbenzyl ammonium chloride or triethyl benzyl ammonium chloride. Any one selected from tertiary ammonium compounds selected from quaternary ammonium salts, triethylamine, trimethylamine or benzyldimethyl amine, or quaternary sulfonium salts of dimethyl-2-hydroxyphenyl sulfonium chloride use.
점도 안정화제로서는 p-큐밀페놀, o-페닐페놀, m-크레졸, β-나프톨과 같은 일가의 페놀화합물이 사용되어진다.As the viscosity stabilizer, monovalent phenol compounds such as p-cumylphenol, o-phenylphenol, m-cresol and β-naphthol are used.
분산제로는 라울 설파이드 나트륨과 같은 음이온 표면활성제나 세틸트리메틸 암모니움 클로라이드와 같은 양이온 표면활성제가 사용되어진다.As the dispersant, anionic surfactants such as Raul sulfide sodium or cationic surfactants such as cetyltrimethyl ammonium chloride are used.
이와같이 본 발명에 따라 제조된 함인 폴리아릴레이트는 일반적으로 그 분자량이 7,000에서 180,000범위이나 바람직하기는 15,000에서 100,000이다. 또한, 본 발명에서의 함인 폴리아릴레이트에 포함된 인의 함량은 0.01중량%에서 10중량%, 바람직하기는 0.05중량%∼3중량%가 되도록 하는 것이 좋은데, 인의 함량이 0.01중량% 이하가 되면 폴리머의 열안정성이 현격하게 떨어지는 단점이 발생하고 10중량% 이상의 되면 폴리머의 녹는점이 198℃ 이하로 떨어져 가공성이 나빠지는 단점이 발생한다.As such, the containing polyarylates prepared according to the present invention generally have a molecular weight in the range of 7,000 to 180,000 but preferably 15,000 to 100,000. In addition, the content of phosphorus in the polyarylate containing in the present invention is preferably from 0.01% by weight to 10% by weight, preferably from 0.05% to 3% by weight, if the content of phosphorus is less than 0.01% by weight The disadvantage is that the thermal stability of the markedly falling, if more than 10% by weight of the melting point of the polymer falls below 198 ℃ disadvantages in the processability worsens.
본 발명에 따르면 가공성이 가장 양호한 상태의 중합체의 녹는점은 200℃∼230℃ 정도이다.According to the present invention, the melting point of the polymer having the best processability is about 200 ° C to 230 ° C.
이와같이 하여 제조된 본 발명에 따른 폴리아릴레이트는 자동차, 기계분야에서의 경량화, 고급화 및 난연화 추세에 따른 고기능성 플라스틱 소재의 요구증대와 식품등의 포장에서의 내열성소재의 요구증가에 따른 내열성 플라스틱의 수요분야로 급속히 확대될 것이며 또한 내열성, 내후성 뿐만아니라 내마모성, 충격강도등의 기계적 성능이 우수하며 다른수지와 알로이(alloy) 및 혼합에 의해 다른수지의 결점을 보완하면서 자체의 성능을 개선한 개질 폴리아릴레이트의 용도 전개가 가능하며 일반적인 사출성형, 압출성형이나 브-로성형등의 열용융 성형법을 적용할 수 있는 장점이 있다.The polyarylate according to the present invention prepared in this way is heat-resistant plastic according to the increase in the demand of high-performance plastic material according to the trend of light weight, advanced and flame retardant in the automobile, machinery field and the demand of heat-resistant material in packaging such as food It will be expanded rapidly to the demand field, and also has excellent mechanical performance such as heat resistance and weather resistance as well as wear resistance and impact strength, and it is a modified polya polymer that has improved its performance while compensating for the defects of other resins by alloying with other resins and alloys. It is possible to develop the use of the relation, and there is an advantage that the hot melt molding method such as injection molding, extrusion molding or blow molding can be applied.
이하 본 발명을 실시예에 따라 더욱 상세히 설명하겠는 바, 실시예에 의해 본 발명이 한정되는 것이 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
본 실시에서의 물성측정은 다음과 같은 방법으로 하였다.The physical property measurement in this Example was carried out as follows.
* 고유점도 :* Intrinsic Viscosity:
30℃에서 페놀 및 1,1,2,2-테트라클로로 에탄 혼합용 매{중량비(50 : 50)}중에서 측정된 값으로부터 구한것이다.It was calculated | required from the value measured in the solvent {weight ratio (50:50)} for mixing a phenol and 1,1,2,2- tetrachloroethane at 30 degreeC.
* TGA(열 중량분석) :* TGA (thermogravimetric analysis):
페르킨-엘머 시차주사 열량계-4에 의해 승온속도 20℃/ 분으로 측정하였다.The temperature was raised at a rate of 20 ° C./min by Perkin-Elmer differential scanning calorimeter-4.
[실시예 1]Example 1
1,000ml 삼구의 플라스크에 교반기, 온도계 및 질소유입기를 장치한후 물 250 ml, 수산화나트륨 4.35g, 비스페놀 에이 11.25g과 촉매로서 트리에틸벤질 암모니움 클로라이드 0.15g을 가하고서 이반응 혼합물을 상온질소 기류하에서 1,000rpm의 교반속도로 저어주면서 100ml의 메틸렌클로라이드에 녹인 테레프탈로일 클로라이드 5.0g, 이소프탈로일 클로라이드 4.0g과 페닐포스포닉 디클로라이드 0.9g을 20분에 걸쳐 첨가한 후에 4시간 더 반응시킨 다음 유기층을 분리하여 물로 두번 씻어주고 유기층을 메탄올에 침전시켜 이것을 여과한후 물과 메탄올로 두번더 씻어준 다음 100℃ 진공 오븐에서 15시간 건조시킨 후 측정한 고유점도는 1.50이었으며, 열 중량 분석기에 의해 측정한 열분해 개시온도는 555℃이었고 녹는 점은 230℃였다.The reaction mixture was placed in a 1000 ml three-necked flask equipped with a stirrer, thermometer, and nitrogen inlet, followed by adding 250 ml of water, 4.35 g of sodium hydroxide, 11.25 g of bisphenol A, and 0.15 g of triethylbenzyl ammonium chloride as a catalyst. After stirring at 1,000 rpm under stirring at 100 rpm, 5.0 g of terephthaloyl chloride dissolved in 100 ml of methylene chloride, 4.0 g of isophthaloyl chloride and 0.9 g of phenylphosphonic dichloride were added over 20 minutes, followed by further 4 hours of reaction. The organic layer was separated, washed twice with water, the organic layer was precipitated in methanol, filtered, washed twice with water and methanol, dried in a vacuum oven at 100 ° C. for 15 hours, and the inherent viscosity measured was 1.50. The measured pyrolysis start temperature was 555 ° C and the melting point was 230 ° C.
[실시예 2]Example 2
이소프탈로일 클로라이드를 3.0g, 페닐포스포닉 디클로라이드를 1.95g 첨가한 것을 제외하고는 실시예 1과 동일하게 실시하였다. 제조된 화합물의 고유점도는 1.30이었고 열분해 개시온도는 545℃이었으며 녹는점은 200℃였다.The same procedure as in Example 1 was carried out except that 3.0 g of isophthaloyl chloride and 1.95 g of phenylphosphonic dichloride were added. The intrinsic viscosity of the prepared compound was 1.30, the onset temperature of pyrolysis was 545 ° C, and the melting point was 200 ° C.
[실시예 3]Example 3
테레프탈로일 클로라이드를 4.0g, 페닐포스포닉 디클로라이드를 1.95g 첨가한 것을 제외하고는 실시예 1과 동일하게 실시하였다. 제조된 화합물의 고유점도는 1.45이었고 열분해 개시온도는 550℃이었으며 녹는점은 225℃였다.The procedure was the same as in Example 1 except that 4.0 g of terephthaloyl chloride and 1.95 g of phenylphosphonic dichloride were added. The inherent viscosity of the prepared compound was 1.45, pyrolysis initiation temperature was 550 ℃ and melting point was 225 ℃.
[비교예][Comparative Example]
페닐포스포닉 디클로라이드를 첨가하지 않은 것을 제외하고는 실시예 1과 동일하게 실시하였다. 제조된 화합물의 고유점도는 1.30이었고 열분해 개시온도는 530℃이었으며 녹는 점은 250℃였다.The same procedure as in Example 1 was conducted except that no phenylphosphonic dichloride was added. The intrinsic viscosity of the prepared compound was 1.30, the thermal decomposition initiation temperature was 530 ℃ and melting point was 250 ℃.
Claims (7)
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| KR1019900016194A KR940005978B1 (en) | 1990-10-12 | 1990-10-12 | Phosphorus-containing polyallylate and producing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006080613A1 (en) * | 2004-09-15 | 2006-08-03 | Lg Chem, Ltd. | Process for preparing polyarylate having high thermo-resistance and high transparency |
| KR100833037B1 (en) * | 2006-02-17 | 2008-05-27 | 주식회사 엘지화학 | Preparing method of polyarylate |
| CN102675616A (en) * | 2012-05-18 | 2012-09-19 | 东华大学 | Phosphorus-containing flame retardant polyarylester and preparation method of phosphorus-containing flame retardant polyarylester |
-
1990
- 1990-10-12 KR KR1019900016194A patent/KR940005978B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006080613A1 (en) * | 2004-09-15 | 2006-08-03 | Lg Chem, Ltd. | Process for preparing polyarylate having high thermo-resistance and high transparency |
| KR100833037B1 (en) * | 2006-02-17 | 2008-05-27 | 주식회사 엘지화학 | Preparing method of polyarylate |
| CN102675616A (en) * | 2012-05-18 | 2012-09-19 | 东华大学 | Phosphorus-containing flame retardant polyarylester and preparation method of phosphorus-containing flame retardant polyarylester |
| CN102675616B (en) * | 2012-05-18 | 2013-10-30 | 东华大学 | Phosphorus-containing flame retardant polyarylester and preparation method of phosphorus-containing flame retardant polyarylester |
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| KR920008085A (en) | 1992-05-27 |
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