KR980009312A - Manufacturing method of flame retardant polyester - Google Patents
Manufacturing method of flame retardant polyester Download PDFInfo
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- KR980009312A KR980009312A KR1019960026903A KR19960026903A KR980009312A KR 980009312 A KR980009312 A KR 980009312A KR 1019960026903 A KR1019960026903 A KR 1019960026903A KR 19960026903 A KR19960026903 A KR 19960026903A KR 980009312 A KR980009312 A KR 980009312A
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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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
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)로 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 촉매중의 안티몬 원자의 비율이 몰비로 2 : 1∼3 : 1 이 되도록 한다.The present invention relates to a process for producing a polycondensation product by reacting an arylphosphinylcarboxylic acid or a derivative thereof represented by the general formula (I) with a polycondensation catalyst of antimony or antimony oxide in advance before polyester polycondensation, Lt; / RTI > Here, the molar ratio of the arylphosphinyl carboxylic acid or its derivative, which is a phosphorus flame retardant, to the antimony atom in the polycondensation catalyst is 2: 1 to 3: 1.
(구조식 중에서,. R1은 수소, 하이드록시에틸 또는 하이드록시프로필기이며, R2는 알킬렌기이고 n=1~10의 정수이다.)(Wherein R 1 is hydrogen, hydroxyethyl or hydroxypropyl, R 2 is an alkylene group and n is an integer of 1 to 10)
이와 같이 제조된 난연성 폴리에스테르는 인함량이 500∼5000ppm이고, 색상, 난연성, 투명성 및 내광성이 우수하다.The flame retardant polyester thus produced has a phosphorus content of 500 to 5000 ppm and is excellent in hue, flame retardance, transparency and light resistance.
Description
본 발명은 섬유, 필름 및 성형품 등에 사용되는 난연성 폴리에스테르의 제조방법에 관한 것이다. 더욱 상세하게는 인계화합물을 반응시킨 중축합촉매를 사용하여 향상된 폴리에스테르를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a flame-retardant polyester used for fibers, films, molded articles and the like. More particularly, the present invention relates to a method for producing an improved polyester using a polycondensation catalyst obtained by reacting a phosphorus compound.
일반적으로 플리에스테르는 열적 성질, 기계적 성질, 화학약품에 대한 저항성 및 성형성 등이 우수하여 섬유, 필름, 또는 플라스틱으로 많이 이용되고 있다. 그러나 이 같은 폴리에스테르는 난연성에 있어서 착화후에는 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, fliesters are excellent in thermal properties, mechanical properties, resistance to chemicals, moldability, and are widely used as fibers, films, or plastics. However, such a polyester has a disadvantage that it is likely to burn rapidly after ignition because of flame retardance. For this reason, development of a polyester imparting flame retardancy, particularly self-extinguishing properties, has been demanded in textiles, films, molded products and engineering plastics in the interior field.
종래에는 폴리에스테르에 난연성을 부여하는 방법으로 폴리에스테르 중합시에 원료와 함께 반응형 난연제를 투입하여 난연성을 부여하거나, 성형시에 폴리에스테르수지와 첨가형 난연제를 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 그때 그때의 반응조건에 따라 난연제를 선택하여 사용하였다.Conventionally, a method of imparting flame retardancy to a polyester has been proposed in which a reaction type flame retardant is added together with a raw material at the time of polyester polymerization to impart flame retardancy, or a polyester resin and an additive type flame retardant are added at the time of molding. The representative flame retardants are classified into a mixture of a halogen-containing compound and a metal oxide, a nitrogen-containing compound, and a phosphorus-containing compound. Any of these flame retardants has a disadvantage in adversely affecting the physical properties of the product. The 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 혼합방사하는 방법 등이 이용되어 왔다. 그러나 중합을 한 후에 후처리하는 방법은 경제적인 이점이 있는 반면, 반복 사용할 때 내구성 저하 등의 문제가 있었다. 그후 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 인계 난연제 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 the fibers of polyethylene terephthalate, a method of coating the surface with a flame retardant on the surface of the fiber after spinning and a method of mixing the non-reactive flame retardant in the pre-spinning step after polymerization are used come. However, the post-treatment method after polymerization has an economical advantage, but has a problem of durability deterioration when repeatedly used. Thereafter, a technique has been studied in which a flame retardant substance is added to the yarn itself through copolymerization or blending by adding a flame retardant substance in the polymerization process during the production of the polymer. Japanese Unexamined Patent Publication (Kokai) No. 60-101144 discloses a method of adding metals such as manganese and magnesium while not forming phosphorus flame retardant particles. Japanese Patent Laid-Open Publication No. 59-1991716 discloses a method in which a polycondensation reaction proceeds to some extent A phosphorus flame retardant and a polycondensation catalyst are additionally introduced. Although this method has been reported to have superior durability and flame retardancy as compared with the post-treatment method, the following problems are caused depending on the type of the reactive flame retardant.
할로겐계 난연제를 사용하면 난연성이 발현된다 하더라도 공중합체가 착색되고 내광성이 떨어지는 단점이 있고, 인계 난연제를 사용하면 고분자의 물성 및 난연성은 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.When a halogen-based flame retardant is used, there is a disadvantage in that the copolymer is colored and the light resistance is poor even if the flame retardancy is expressed. When the phosphorus flame retardant is used, the thermal stability and the reactivity of the phosphorus flame retardant itself are poor, There is a disadvantage in that the part is exited at the time of polymerization. Many studies have been carried out to overcome this point, but it has not reached the industrialization yet.
이에 본 발명자들은 중합시에 첨가된 인계 난연제가 중합과정에서 상당부분이 빠져나오는 것을 방지함으로써 중합체 내에 난연제가 충분한 비율로 함유되게 하고, 난연성, 투명성, 및 내광성 등이 뛰어나며, 물성저하가 적은 폴리에스테르의 제조방법을 발명하였다.Accordingly, the present inventors have found that a phosphorus-based flame retardant added during polymerization prevents a substantial part of the phosphorus flame retardant from escaping from the polymerization process, thereby allowing the flame retardant to be contained in a sufficient proportion in the polymer, and excellent in flame retardance, transparency, light resistance, . ≪ / RTI >
본 발명을 상세히 설명하면 다음과 같다.The present invention will be 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.Characterized in that an arylphosphinyl carboxylic acid or a derivative thereof represented by the general formula (I) is reacted with a polycondensation catalyst in advance before polyester polycondensation to prepare a reaction product and then added at the time of polycondensation of the polyester And a method for producing the same.
(구조식 중에서, R1은 수소, 하이드폭시에틸 또는 하이드록시프로필기이며, R2는 알킬렌기이고 n=1∼10의 정수이다.)(In the structural formula, R 1 is hydrogen, a hydroxypolyethyl or a hydroxypropyl group, R 2 is an alkylene group and n is an integer of 1 to 10)
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 인계 난연제인 아릴포스피닐카르본산 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 중축합 촉매가 난연제에 충분히 작웅을 하지 못하여 난연제가 반응기 외로 유출되는 현상이 나타난다.The present invention relates to a process for producing a reaction product by reacting an arylphosphinyl carboxylic acid or a derivative thereof, which is a phosphorus flame retardant, with a polycondensation catalyst in advance, and then adding the reactant at the time of polycondensation of the polyester. The arylphosphinyl carboxylic acid or its derivative is firstly stirred in the polyester polycondensation for a certain period of time and then the polycondensation catalyst is further added, and the aryl phosphinyl carboxylic acid or its derivative and the polycondensation catalyst are simply mixed, When the polycondensation catalyst is added at the same time, the polycondensation catalyst does not sufficiently work on the flame retardant, and the flame retardant flows out of the reactor.
중축합 촉매로서는 안티몬 또는 안티몬 산화물을 사용한다. 인계 난연제와 촉매 금속원자의 비율은 몰비로 2 : 1∼ 3 : 1이다. 인계 난연제와 촉매 금속원자의 몰비가 2 : 1이 안되는 경우, 즉, 촉매의 비율이 높은 경우는 디에틸렌글리콜 생성 및 말단 카르욕실기의 증가와 같은 부반응이 증가하고 분자량 분포가 넓어지는 결과를 초래하고, 몰비가 3 : 1을 초과하는 경우에는 난연제의 양이 과량으로 되어 중축합 촉매의 활성을 저하시겨 결국 폴리에스테르의 물성저하를 가져온다. 공중합된 폴리에스테르 중 인원자의 함량은 500 ∼ 5000ppm이 되도록 한다. 인원자의 함량이 500ppm 이하가 되면 난연성이 발휘되기 어려우며, 5000ppm을 초과하면 폴리에스테르의 열적, 기계적 물성이 저하된다.As the polycondensation catalyst, antimony or antimony oxide is used. The molar ratio of phosphorus flame retardant to catalytic metal atom is 2: 1 to 3: 1. When the molar ratio of the phosphorus flame retardant to the catalytic metal atom is less than 2: 1, that is, when the ratio of the catalyst is high, the side reaction such as the formation of diethylene glycol and the increase of the terminal carbamo group is increased and the molecular weight distribution is widened , And when the molar ratio exceeds 3: 1, the amount of the flame retardant is excessively decreased to lower the activity of the polycondensation catalyst, resulting in deterioration of the physical properties of the polyester. The content of phosphorus in the copolymerized polyester is set to be 500 to 5000 ppm. When the content of phosphorus is less than 500 ppm, the flame retardancy is difficult to exhibit. When the content exceeds 5000 ppm, the thermal and mechanical properties of the polyester are deteriorated.
본 발명의 폴리에스테르 합성에 사용되는 계1 및 제2성분으로는 테레프탈산 또는 그 유도체 및 탄소수 2∼12의 α,ω-알킬글리콜이 사용되며, 제3성분으로는 인프탄산, 디페닐설폰 4,4'-디카르본산, 디페닐에테르 4,4-디카르본산, 디페녹시에탄 4,4'-디카르본산, 아디핀산, 세바틴산, 스페린산, 글리콜에스테르, 프로필렌글리콜, 부탄디올, 1,4-헥사메틸렌글리콜, 1,4-디클로로헥산디올, 1,4-디클로로헥산디메탄올, 1,4-비스옥시에톡시벤젠, 비스페놀A, 폴리옥시에틸렌글리콜 또는 폴리테트라메틸렌글리콜 등과 같은 화합물을 한가지 이상 소량 첨가하여도 좋다.Terephthalic acid or a derivative thereof and?,? - alkyl glycols having 2 to 12 carbon atoms are used as the system 1 and the second component used in the polyester synthesis of the present invention, and as the third component, Dicarboxylic acid, 4,4'-dicarboxylic acid, diphenyl ether 4,4-dicarboxylic acid, diphenoxyethane 4,4'-dicarboxylic acid, adipic acid, sebacic acid, spesic acid, glycol ester, propylene glycol, butanediol, A compound such as 4-hexamethylene glycol, 1,4-dichlorohexanediol, 1,4-dichlorohexanedimethanol, 1,4-bisoxyethoxybenzene, bisphenol A, polyoxyethylene glycol or polytetramethylene glycol May be added in a small amount.
다음의 실시예 및 비교실시예는 본 발명을 구체적으로 설명하는 것으로서 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples illustrate the present invention in detail and do not limit the scope of the present invention.
[실시예 1][Example 1]
아릴포스피털카르본산(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. 디메틸프탈레이트 1600중량부, 에틸렌글리콜 932중량부 및 초산 0.72중량부를 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 중축합 반응기로 이송하고, 여기서 안정제로 아인산 0.20중량부와 중축합 촉매로 삼산화 안티몬 0.8중량부와 소광제로 산화티탄을 35중량부를 투입한 후, 반응기 온도를 2607까지 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.32 parts by weight of arylphosphate carboxylic acid (2-phenyl-2,5-dioxo-1,2-oxa-phospholane) and 8.5 parts by weight of antimony trioxide were placed in 50 parts by weight of ethylene glycol, And the reaction product of arylphosphinylcarboxylic acid and antimony trioxide is obtained and kept at 140 ° C. 1,600 parts by weight of dimethyl phthalate, 932 parts by weight of ethylene glycol, and 0.72 parts by weight of acetic acid were placed in an ester exchange reactor, heated and stirred, and methanol was discharged out of the reactor while heating for 2 hours, To prepare an ester exchange reaction product. The prepared transesterification reaction product was transferred to a polycondensation reactor where 0.20 part by weight of phosphorous acid as a stabilizer, 0.8 part by weight of antimony trioxide as a polycondensation catalyst and 35 parts by weight of titanium oxide as a quencher were added, The decompression reaction is carried out. When the temperature in the reactor reached 260 ° C, the pressure was released to normal pressure. The reaction product of arylphosphinyl carboxylic acid and antimony trioxide, which had been stored at 140 ° C, was added to the reactor and heated again to 280 ° C while maintaining the pressure at 2 Torr ) To obtain a copolymer of the flame-retardant polyester.
[실시예 2][Example 2]
아릴포스피닐카르본산을 21.3중량부, 삼산화 안티몬을 5.67중량부 투입한 것 이외에는 모든 조건을 실시예 1과 동일하게 하여 난연성 폴리에스테르를 공중합하였다.21.3 parts by weight of arylphosphinylcarboxylic acid and 5.67 parts by weight of antimony trioxide were charged, and the flame-retardant polyester was copolymerized in the same manner as in Example 1 under all conditions.
[비교실시예 1][Comparative Example 1]
삼산화 안티몬을 4.25중량부 투입한 것 이외에는 모든 조건을 실시예 1과 동일하게 하여 난연성 폴리에스테르를 공중합하였다.The 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.
[비교실시예 2][Comparative Example 2]
아릴포스피닐카르본산을 16중량부 투입한 것 이외에는 모든 조건을 실시예 1과 동일하게 하여 난연성 폴리에스테르를 공중합하였다.Flame-retardant polyester was copolymerized in the same manner as in Example 1 except that 16 parts by weight of arylphosphinyl carboxylic acid was added.
[비교실시예 3][Comparative Example 3]
아릴포스피닐카르본산 32중량부, 삼산화 안티몬 8.5중량부, 디메틸프탈레이트 1600중량부, 에틸렌글리콜 932중량부 및 초산 0.72중량부를 에스테르 교환 반응기에 넣고 가열, 교반을 실시하고 메탄올을 반응기외로 유출시켜면서 2시간 후 온도가 230℃까지 올라가도록 가열하여 에스테르 교환반응을 시켜서 에스테르 교환 반응물을 제조한다. 제조된 에스테르 교환 반응물을 중축할 반응기로 이송하고, 여기서 안정제로 아인산 0.20중량부와 중축합 촉매로 삼산화 안티몬 0.8중량부와 소광제로 산화티탄을 35중량부을 투입한 후 반응기 온도를 260℃까지 상승시킨 후 감압반응을 시켜서 난연성폴리에스테르를 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 part by weight of acetic acid were placed in an ester exchange reactor and heated and stirred. After the reaction, the reaction temperature is elevated to 230 DEG C to effect an ester exchange reaction to prepare an ester exchange reaction product. The prepared transesterification reaction product was transferred to a reactor to be polycondensed, where 0.20 part by weight of phosphorous acid as a stabilizer, 0.8 part by weight of antimony trioxide as a polycondensation catalyst and 35 parts by weight of titanium oxide as a quencher were added, Followed by post-decompression reaction to copolymerize the flame-retardant polyester.
실시예1∼2 및 비교실시예1∼3에서 제조된 난연성 폴리에스테르를 아래 평가 방법으로 각각의 물성을 평가하였다. 그 평가 결과는 표 1 과 같다.The properties of the flame-retardant polyesters prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated by the following evaluation methods. The evaluation results are shown in Table 1.
· 고유점도· Intrinsic viscosity
30℃이 오르토클로로페놀 용액 중에서 측정하였다.30 C was measured in an orthochlorophenol solution.
· 책색정도· Degree of development
색차계를 이용하여 L값(명도) 및 b값(황도)을 측정하였다.L value (brightness) and b value (ecliptic) were measured using a color difference meter.
· 인함량· Phosphorus content
아이씨피(ICP)를 이용하여 정량하였다.And quantified using ICP (ICP).
· 난연성· Flammability
에이에스티엠 디-2863-70 (ASTM D-2863-70)에 의거한 산소계수 가연성 게이지로 측정하였다.Oxygen coefficient based on ASTM D-2863-70 (ASTM D-2863-70) was measured with a flammability gauge.
· 점염횟수· Number of spotting
제이아이에스엠엘-1092 디(JIS L-1092 D)법에 의거 마이크로 버너에 의한 45° 코일법으로 평가하였다.Was evaluated by a 45 ° coil method using a micro-burner according to JIS L-1092 D method.
[표 1] 물성 측정 결과[Table 1] Measurement results of physical properties
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 인의 양이 현저하게 낮아진 것을 알 수 있다. 반면에 본 발명에 의해 제조된 난연성 폴리에스테르는 난연성 및 색상이 우수하고, 인화합물의 잔존율이 현저하게 높음을 알 수 있다.When the molar ratio of the arylphosphinyl carboxylic acid to the antimony oxide was out of the range of 2: 1 to 3: 1 in the examples and comparative examples, the color was poor and the flame retardancy was poor. (Comparative Example 3), the amount of residual phosphorus was remarkably lowered in comparison with the input amount of phosphorus. On the other hand, it can be seen that the flame retardant polyester produced by the present invention has excellent flame retardancy and color, and the residual ratio of the phosphorus compound is remarkably high.
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