KR100197947B1 - Process for preparing flame-retardant polyester - Google Patents
Process for preparing flame-retardant polyester Download PDFInfo
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- KR100197947B1 KR100197947B1 KR1019960026903A KR19960026903A KR100197947B1 KR 100197947 B1 KR100197947 B1 KR 100197947B1 KR 1019960026903 A KR1019960026903 A KR 1019960026903A KR 19960026903 A KR19960026903 A KR 19960026903A KR 100197947 B1 KR100197947 B1 KR 100197947B1
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
본 발명은 인계화합물과 중축합 촉매를 미리 반응시켜서 제조한 반응물을 사용하여 난연성이 향상된 폴리에스테르를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a polyester having improved flame retardancy by using a reactant prepared by reacting a phosphorus compound and a polycondensation catalyst in advance.
본 발명은 폴리에스테르 중축합 전에 일반식(I)에 표시되는 아릴포스피닐카르본산 또는 그 유도체를 안티몬 또는 안티몬 산화물의 중축합 촉매와 미리 반응시켜 반응물을 제조하고, 제조된 반응물을 폴리에스테르 중축합시에 첨가한다. 여기서 인계 난연제인 아릴포스피닐카르본산 또는 그 유도체와 중축합 촉매 중의 안티몬 원자의 비율이 몰비로 2:1∼3:1이 되도록 한다.The present invention is prepared by reacting the arylphosphinylcarboxylic acid or its derivative represented by the general formula (I) with a polycondensation catalyst of antimony or antimony oxide before the polyester polycondensation, and preparing the reactant in polyester polycondensation. Add to Here, the ratio of the aryl phosphinyl carboxylic acid or its derivative which is a phosphorus flame retardant, and antimony atom in a polycondensation catalyst shall be 2: 1-3: 1 in molar ratio.
(구조식 중에서 R1은 수소, 하이디록시에틸 또는 하이드록시프로필기이며, R2은 알킬렌기이고 n=1∼10의 정수이다.)(In the structural formula, R 1 is hydrogen, hydroxyethyl or hydroxypropyl group, R 2 is an alkylene group and is an integer of n = 1 to 10.)
이와 같이 제조된 난연성 폴리에스테르는 인함량이 500∼5000ppm이고, 색상, 난연성, 투명성 및 내광성이 우수하다.The flame retardant polyester thus prepared has a phosphorus content of 500 to 5000 ppm and is excellent in color, flame retardancy, transparency and light resistance.
Description
본 발명은 섬유, 필름 및 성형품 등에 사용되는 난연성 폴리에스테르의 제조방법에 관한 것이다. 더욱 상세하게는 인계화합물을 반응시킨 중축합촉매를 사용하여 난연성이 향상된 폴리에스테르를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a flame retardant polyester for use in fibers, films and molded articles. More particularly, the present invention relates to a method for producing a polyester having improved flame retardancy by using a polycondensation catalyst reacted with a phosphorus compound.
일반적으로 폴리에스테르는 열적 성질, 기계적 성질, 화학약품에 대한 저항성 및 성형성 등이 우수하여 섬유, 필름 또는 플라스틱 제품으로 많이 이용되고 있다. 그러나 이같은 폴리에스테르는 난연성에 있어서 착화 후에는 급속히 연소하기 쉬운 단점을 갖고 있다. 이 때문에 인테리어 분야의 섬유, 필름, 성형품 및 엔지니어링 플라스틱 등에 있어서는 난연성, 특히 자기소화성을 부여한 폴리에스테르의 개발이 요구되고 있다.In general, polyester is excellent in thermal properties, mechanical properties, chemical resistance and moldability, and is widely used as a fiber, film or plastic product. However, such a polyester has a disadvantage in that it is easy to burn rapidly after ignition in flame retardancy. For this reason, the development of the polyester which gave flame retardancy, especially self-extinguishing property is calculated | required in the fiber, film, molded article, engineering plastics, etc. in the interior field.
종래에는 폴리에스테르에 난연성을 부여하는 방법으로 폴리에스테르 중합시에 완료와 함께 반응형 난연제를 투입하여 난연성을 부여하거나, 성형시에 폴리에스테르 수지와 첨가형 난연제를 혼합하여 난연성을 부여하였다. 그 대표적인 난연제로서는 크게 할로겐함유화합물과 금속 산화물의 혼합물, 질소함유화합물 및 인함유화합물로 나누어지는데 이들 난연제 중에서 어느 것을 사용하여도 제품물성에 좋지 않은 영향을 주는 단점이 있었기 때문에 그때그때의 반응조건에 따라 난연제를 선택하여 사용하였다.Conventionally, in the method of imparting flame retardancy to polyester, a reaction type flame retardant is added with completion to the polyester polymerization to impart flame retardancy, or at the time of molding, a polyester resin and an additive flame retardant are mixed to impart flame retardancy. The representative flame retardants are largely divided into halogen-containing compounds, metal oxide mixtures, nitrogen-containing compounds and phosphorus-containing compounds. Any of these flame retardants may have a disadvantage in adversely affecting product properties. Accordingly, a flame retardant was selected and used.
폴리에틸렌테레프탈레이트의 섬유에 난연성을 부여하기 위한 방법으로는 방사 후에 섬유표면에 난연제를 코팅하거나 표면을 처리하는 방법과 중합 후 방사 이전 단계에서 비반응성 난연제를 첨가하여 혼합방사 하는 방법 등이 이용되어 왔다. 그러나 중합을 한 후에 후처리하는 방법은 경제적인 이점이 있는 반면, 반복 사용할 때 내구성 저하 등의 문제가 있었다. 그 후 연구되어 온 방향은 폴리머 제조시 방염성 물질을 중합공정 중에 투입하여 공중합 내지 블렌드 시켜 원사 자체에 고유한 난연성을 부여하는 기법이 연구되어 오고 있다. 일본특허공개공보 소 60-101144호에는 인계난연제 입자를 형성하지 않게 하면서 망간 및 마그네슘 등의 금속을 넣는 방법이 제시되어 있고, 일본특허공개공보 소 59-1991716호에는 중축합 반응이 어느 정도 진행된 후에 인계 난연제 및 중축합 촉매를 추가로 넣는 방법이 제시되어 있다. 이와 같은 방법은 후처리 방법에 비해 내구성과 난연성이 우수하다고 보고되고 있기는 하지만 반응형 난연제의 종류에 따라 다음과 같은 문제점이 대두되어 있다.As a method for imparting flame retardancy to fibers of polyethylene terephthalate, a method of coating or surface-treating a flame retardant on the surface of the fiber after spinning and a method of mixed spinning by adding a non-reactive flame retardant in the pre-spinning step after polymerization have been used. . However, the method of post-treatment after polymerization has an economical advantage, but there are problems such as deterioration of durability when repeated use. The direction that has been studied since then has been studied a technique of imparting flame retardancy inherent to the yarn itself by copolymerizing or blending flame retardant materials during the polymerization process during polymer production. Japanese Patent Laid-Open Publication No. 60-101144 discloses a method of adding metals such as manganese and magnesium without forming phosphorus-based flame retardant particles, and Japanese Patent Laid-Open Publication No. 59-1991716 discloses some degree of polycondensation reaction. A method of further adding a phosphorus flame retardant and a polycondensation catalyst is provided. Although such a method is reported to be superior in durability and flame retardancy compared to the post-treatment method, the following problems are raised depending on the type of reactive flame retardant.
할로겐계 난연제를 사용하면 난연성이 발현된다 하더라도 공중합체가 착색되고 내광성이 떨어지는 단점이 있고, 인계 난연제를 사용하면 고분자의 물성 및 난연성을 좋다 하더라도 인계 난연제 자체가 열안정성이 떨어지고 반응성이 약하여 첨가량의 상당부분이 중합시에 빠져나오는 단점이 있다. 이러한 점을 극복하기 위해 많은 연구가 진행되고 있으나 아직 공업화에까지는 이르지 못하고 있다.The use of halogen-based flame retardants has the disadvantage that the copolymer is colored and the light resistance is poor even if the flame retardant is expressed. If the phosphorus-based flame retardant is used, even if the physical properties and flame retardancy of the polymer are good, the phosphorus-based flame retardant itself is poor in thermal stability and weak in reactivity. There is a disadvantage that the part comes out during polymerization. Many studies have been conducted to overcome these problems, but they have not yet reached industrialization.
이에 본 발명자들은 중합시에 첨가된 인계 난연제가 중합과정에서 상당부분이 빠져나오는 것을 방지하므로서 중합체 내에 난연제가 충분한 비율로 함유되게 하고, 난연성, 투명성 및 내광성 등이 뛰어나며, 물성저하가 적은 폴리에스테르의 제조방법을 발명하였다.Therefore, the inventors of the present invention prevent the phosphorus-based flame retardant added during the polymerization to prevent a large portion of the escape during the polymerization process, so that the flame retardant is contained in the polymer in a sufficient ratio, and excellent flame retardancy, transparency and light resistance, etc. The manufacturing method was invented.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
폴리에스테르 중축합 전에 일반식(I)로 표시되는 아릴포스피닐카르본산 또는 그 유도체를 중축합 촉매와 미리 반응시켜 반응물을 제조한 후, 이를 폴리에스테르 중축합시에 첨가하는 것을 특징으로 하는 난연성 폴리에스테르의 제조방법에 관한 것이다.Flame-retardant polyester, characterized in that the aryl phosphinylcarboxylic acid represented by the general formula (I) or a derivative thereof is reacted with a polycondensation catalyst to prepare a reactant before polyester polycondensation, and then added during polyester polycondensation. It relates to a manufacturing method of.
구조식 중에서 R1은 수소, 하이디록시에틸 또는 하이드록시프로필기이며, R2은 알킬렌기이고 n=1∼10의 정수이다.In the structural formula, R 1 is hydrogen, hydroxyethyl or hydroxypropyl group, R 2 is an alkylene group and is an integer of n = 1-10.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 인계 난연제인 아릴포스피날카르본산 또는 그 유도체를 중축합 촉매와 미리 반응시켜 반응물을 제조한 후, 제조된 반응물을 폴리에스테르 중축합시에 첨가한다. 아릴포스피닐카르본산 또는 그 유도체를 폴리에스테르 중축합시 먼저 일정시간 교반한 후에 추가로 중축합 촉매를 투입하는 경우와, 아릴포스피닐카르본산 또는 그 유도체와 중축합 촉매를 단순 혼합한 후에 폴리에스테르 중축합시 동시에 첨가하는 경우에는 종축합 촉매가 난연제에 충분히 작용을 하지 못하여 난연제가 반응기 외로 유출되는 현상이 나타난다.The present invention is prepared by reacting arylphosphinylcarboxylic acid or a derivative thereof, which is a phosphorus flame retardant, with a polycondensation catalyst in advance to prepare a reactant, and then adding the prepared reactant during polyester polycondensation. When polycondensation of arylphosphinylcarboxylic acid or its derivatives is first stirred for a predetermined time, and then a polycondensation catalyst is further added, and polyester polycondensation after simple mixing of arylphosphinylcarboxylic acid or its derivatives and polycondensation catalyst In the case of simultaneous addition, the condensation catalyst does not function sufficiently on the flame retardant, and the flame retardant flows out of the reactor.
중축합 촉매로서는 안티몬 또는 안티몬 산화물을 사용한다. 인계 난연제와 촉매 금속원자와 비율은 몰비로 2:1∼3:1이다. 인계 난연제와 촉매 금속 원자의 몰비가 2:1 이 안되는 경우, 즉, 촉매의 비율이 높은 경우는 디에틸렌글리콜 생성 및 말단 카르복실기의 증가와 같은 부반응이 증가하고 분자량 분포가 넓어지는 결과를 초래하고, 몰비가 3:1을 초과하는 경우에는 난연제의 양이 과량으로 되어 중축합 촉매의 활성을 저하시켜 결국 폴리에스테르의 물성저하를 가져온다.Antimony or antimony oxide is used as a polycondensation catalyst. The ratio of the phosphorus flame retardant to the catalyst metal atom is 2: 1 to 3: 1 in molar ratio. When the molar ratio of the phosphorus flame retardant to the catalyst metal atom is less than 2: 1, that is, when the ratio of the catalyst is high, the side reactions such as diethylene glycol production and the increase of the terminal carboxyl group increase and the molecular weight distribution is widened. When the molar ratio exceeds 3: 1, the amount of the flame retardant becomes excessive, which lowers the activity of the polycondensation catalyst, resulting in a decrease in physical properties of the polyester.
공중합된 폴리에스테르 중 인원자의 함량은 500∼5000ppm이 되도록 한다. 인원자의 함량이 500ppm 이하가 되면 난연성이 발휘되기 어려우며, 5000ppm을 초과하면 폴리에스테르의 열적, 기계적 물성이 저하된다.The content of the number of people in the copolymerized polyester is 500 to 5000ppm. If the content of the personnel is less than 500ppm it is difficult to exhibit flame retardancy, if it exceeds 5000ppm the thermal and mechanical properties of the polyester is lowered.
본 발명의 폴리에스테르 합성에 사용되는 제1 및 제2성분으로는 테레프탈산 또는 그 유도체 및 탄소수 2∼12의 α,ω-알킬글리콜이 사용되며, 제3성분으로는 인프탈산, 디페닐설폰산4.4'-디카르본산, 디페닐에테르4.4'-디카르본산, 디페녹시에탄4.4'-디카르본산, 아디핀산, 세바틴산, 스페린산, 글리콜에스테르, 프로필렌글리콜, 부탄디올, 1,4-헥사메틸렌글리콜, 1,4-디클로로헥산디올, 1,4-디클로로핵산디메탄올, 1,4-비스옥시에톡시벤젠, 비스페놀A, 폴리옥시에틸렌글리콜 또는 폴리테트라메틸렌글리콜 등과 같은 화합물을 한가지 이상 소량 첨가하여도 좋다.Terephthalic acid or a derivative thereof and α, ω-alkylglycol having 2 to 12 carbon atoms are used as the first and second components used in the synthesis of the polyester of the present invention, and inphthalic acid and diphenylsulfonic acid 4.4 '-Dicarboxylic acid, diphenyl ether 4.4'-dicarboxylic acid, diphenoxyethane 4.4'-dicarboxylic acid, adipic acid, sebacic acid, sperinic acid, glycol ester, propylene glycol, butanediol, 1,4-hexamethylene One or more small amounts of a compound such as glycol, 1,4-dichlorohexanediol, 1,4-dichloronucleic acid dimethanol, 1,4-bisoxyethoxybenzene, bisphenol A, polyoxyethylene glycol or polytetramethylene glycol Also good.
다음의 실시예 및 비교실시예는 본 발명을 구체적으로 설명하는 것으로서 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples specifically illustrate the present invention and do not limit the scope of the present invention.
[실시예 1]Example 1
아릴포스피닐카르본산(2-페닐-2,5-디옥소-1,2-옥사-포스폴란) 32 중량부 및 삼산화 안티몬 8.5중량부를 에틸렌글리콜 50중량부에 넣고 140℃에서 1시간 교반하여 반응시켜 아릴포스피닐카르본산과 삼산화 안티몬의 반응생성물을 구하고 이를 140℃로 유지시키면서 보관한다.32 parts by weight of arylphosphinylcarboxylic acid (2-phenyl-2,5-dioxo-1,2-oxa-phospholane) and 8.5 parts by weight of antimony trioxide were added to 50 parts by weight of ethylene glycol, followed by stirring at 140 ° C. for 1 hour. The reaction product of arylphosphinylcarboxylic acid and antimony trioxide is obtained and stored at 140 ° C.
디메틸프탈레이트 1600중량부, 에틸렌글리콜 932중량부 및 초산아연 0.72 중량부를 에스테르 교환 반응기에 넣고 가열, 교반을 실시하고 메탄올을 반응기외로 유출시키면서 2시간 후 온도가 230℃까지 올라가도록 가열하여 에스테르 교환반응을 시켜서 에스테르 교환 반응물을 제조한다.1600 parts by weight of dimethyl phthalate, 932 parts by weight of ethylene glycol, and 0.72 parts by weight of zinc acetate were placed in a transesterification reactor, heated and stirred, and heated to a temperature of 230 ° C. after 2 hours while methanol was discharged out of the reactor. To prepare a transesterification reaction.
제조된 에스테르 교환 반응물을 중축합 반응기로 이송하고, 여기서 안정제로 아인산 0.20중량부와 중축합 촉매로 삼산화 안티몬 0.8중량부와 소광제로 산화티탄을 35중량부를 투입한 후, 반응기 온도를 260℃까지 상승시키며 감압반응을 한다. 반응기내 온도가 260℃가 되었을 때 압력을 상압으로 풀고, 140℃에서 보관 중이던 아릴포스피닐카르본산과 삼산화 안티몬의 반응생성물을 반응기내에 첨가하고 다시 280℃까지 가열하면서 압력을 상압에서 2토르(Torr)이하의 고진공으로 감압하여 난연성 폴리에스테르를 공중합하였다.The prepared transesterification reaction was transferred to a polycondensation reactor, where 0.20 parts by weight of phosphorous acid as a stabilizer, 0.8 parts by weight of antimony trioxide as a polycondensation catalyst and 35 parts by weight of titanium oxide as a quencher were added, and the reactor temperature was raised to 260 ° C. Under reduced pressure. When the temperature in the reactor reached 260 ° C, the pressure was released to atmospheric pressure, and the reaction product of arylphosphinylcarboxylic acid and antimony trioxide stored at 140 ° C was added to the reactor and heated up to 280 ° C. The flame-retardant polyester was copolymerized under reduced pressure under a high vacuum.
[실시예 2]Example 2
아릴포스피닐카르본산을 21.3 중량부, 삼산화 안티몬을 5.67중량부 투입한 것 이외에는 모든 조건을 실시예 1과 동일하게 하여 난연성 폴리에스테르를 공중합하였다.A flame-retardant polyester was copolymerized in the same manner as in Example 1 except that 21.3 parts by weight of arylphosphinylcarboxylic acid and 5.67 parts by weight of antimony trioxide were added.
[비교 실시예 1]Comparative Example 1
삼산화 안티몬을 4.25중량부 투입한 것 이외에는 모든 조건을 실시예 1과 동일하게 하여 난연성 폴리에스테르를 공중합하였다.A flame-retardant polyester was copolymerized in the same manner as in Example 1 except that 4.25 parts by weight of antimony trioxide was added.
[비교 실시예 2]Comparative Example 2
아릴포스피닐카르본산을 16중량부 투입한 것 이외에는 모든 조건을 실시예 1과 동일하게 하여 난연성 폴리에스테르를 공중합하였다.A flame-retardant polyester was copolymerized in the same manner as in Example 1 except that 16 parts by weight of arylphosphinylcarboxylic acid was added.
[비교 실시예 3]Comparative Example 3
아릴포스피닐카르본산 32 중량부, 삼산화 안티몬 8.5중량부, 디메틸프탈레이트 1600중량부, 에틸렌글리콜 932중량부 및 초산 0.72중량부에 에스테르 교환 반응기에 넣고 가열, 교반을 실시하고 메탄올을 반응기외로 유출시키면서 2시간 후 온도가 230℃까지 올라가도록 가열하여 에스테르 교환반응을 시켜서 에스테르 교환 반응물을 제조한다. 제조된 에스테르 교환 반응물을 중중합 반응기로 이송하고, 여기서 안정제로 아인산 0.20중량부와 중축합 촉매로 삼산화 안티몬 0.8중량부와 소광제로 산화티탄을 35중량부를 투입한 후, 반응기 온도를 260℃까지 상승시킨 후 감압반응 시켜서 난연성 폴리에스테르를 공중합하였다.32 parts by weight of arylphosphinylcarboxylic acid, 8.5 parts by weight of antimony trioxide, 1600 parts by weight of dimethyl phthalate, 932 parts by weight of ethylene glycol, and 0.72 parts by weight of acetic acid were added to a transesterification reactor, followed by heating and stirring. After a period of time, the temperature is raised to 230 ℃ to undergo a transesterification reaction to prepare a transesterification reaction. The prepared transesterification product was transferred to a polymerization reactor where 0.20 parts by weight of phosphorous acid as a stabilizer, 0.8 parts by weight of antimony trioxide as a polycondensation catalyst and 35 parts by weight of titanium oxide as a quencher were added, and the reactor temperature was raised to 260 ° C. After reacting under reduced pressure, flame retardant polyester was copolymerized.
실시예 1∼2 및 비교실시예 1∼3에서 제조된 난연성 폴리에스테르를 아래 평가 방법으로 각각의 물성을 평가하였다, 그 평가 결과는 표 1과 같다.The physical properties of the flame retardant polyesters prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were evaluated by the following evaluation methods, and the evaluation results are shown in Table 1 below.
· 고유점도Intrinsic viscosity
30℃의 오르토클로로페놀 용액 중에서 측정하였다.It measured in 30 degreeC orthochlorophenol solution.
· 착색정도Coloring degree
색차계를 이용하여 L값 (명도) 및 b값(황도)를 측정하였다.L value (brightness) and b value (yellowness) were measured using the color difference meter.
· 인함량· Phosphorus content
아이씨피(ICP)를 이용하여 정량하였다.Quantification using ICP (ICP).
· 난연성(한계산소지수(LOI))Flame retardant (LOI)
에이에스티엠 디-2863-70(ASTM D-2863-70)에 의거한 산소계수 가연성 게이지로 측정하였다.It was measured with an oxygen coefficient flammability gauge based on ATS D-2863-70 (ASTM D-2863-70).
· 접염 횟수· Number of infections
제이아이에스 엘-1092 디(JIS L-1092 D)법에 의거 마이크로 버너에 의한 45°코일법으로 평가하였다.It evaluated by the 45 degree coil method by the micro burner based on JLS-L-1092D (JIS L-1092D) method.
실시예 및 비교실시예로 보아 아릴포스피닐카르본산과 안티몬 산화물의 몰비가 2:1∼3:1의 범위를 벗어난 경우는 색상이 불량하고 난연성이 떨어지는 결과를 보이고, 공지의 공정으로 중합한 경우(비교실시예 3)는 인의 투입량에 대비하여 잔존 인이 양의 현저하게 낮아진 것을 알수 있다. 반면에 본 발명에 의해 제조된 난연성 폴리에스테르는 난연성 및 색상이 우수하고, 인화합물의 잔존률이 현저하게 높음을 알 수 있다.In Examples and Comparative Examples, when the molar ratio of arylphosphinylcarboxylic acid and antimony oxide is outside the range of 2: 1 to 3: 1, the color is poor and the flame retardancy is poor, and the polymerization is performed by a known process. In Comparative Example 3, it can be seen that the amount of remaining phosphorus was significantly lowered compared to the amount of phosphorus injected. On the other hand, the flame retardant polyester produced by the present invention is excellent in flame retardancy and color, it can be seen that the residual ratio of the phosphorus compound is remarkably high.
Claims (4)
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| KR100365813B1 (en) * | 2000-11-27 | 2002-12-27 | 주식회사 코오롱 | Manufacturing method of polybutyleneterephthalate |
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| KR100365813B1 (en) * | 2000-11-27 | 2002-12-27 | 주식회사 코오롱 | Manufacturing method of polybutyleneterephthalate |
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