KR100215637B1 - Process for preparing flame-retardant polyester - Google Patents

Process for preparing flame-retardant polyester Download PDF

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Publication number
KR100215637B1
KR100215637B1 KR1019960049871A KR19960049871A KR100215637B1 KR 100215637 B1 KR100215637 B1 KR 100215637B1 KR 1019960049871 A KR1019960049871 A KR 1019960049871A KR 19960049871 A KR19960049871 A KR 19960049871A KR 100215637 B1 KR100215637 B1 KR 100215637B1
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South Korea
Prior art keywords
polyester
flame
flame retardant
retardant
producing
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KR1019960049871A
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Korean (ko)
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KR19980030465A (en
Inventor
최태근
박인수
윤경근
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구광시
주식회사코오롱
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Priority to KR1019960049871A priority Critical patent/KR100215637B1/en
Publication of KR19980030465A publication Critical patent/KR19980030465A/en
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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
    • C08G63/863—Germanium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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'
    • 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
    • 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

[청구범위에 기재된 발명이 속하는 기술분야][TECHNICAL FIELD OF THE INVENTION]

섬유, 필름 및 성형품 등에 사용되는 난연성이 향상된 폴리에스테르를 제조하는 방법에 관한 것이다.To a method for producing a polyester having improved flame retardancy, which is used for fibers, films, molded articles and the like.

[발명이 해결하려고 하는 기술적 과제][Technical Problems to be Solved by the Invention]

폴리에스테르 중합시 착색이 되는 문제점을 보완하여 난연성 및 색상이 우수한 폴리에스테르의 제조방법을 제공한다.The present invention also provides a process for producing a polyester having excellent flame retardancy and color by complementing the problem of coloration in polyester polymerization.

[발명이 해결방법의 요지][Summary of the Invention]

인계 난연제를 사용하여 폴리에스테르를 제조할 때, 중축합 촉매로서 게르마늄 옥사이드를 사용하여 중합한다.When a polyester is produced using a phosphorus flame retardant, polymerization is carried out using germanium oxide as a polycondensation catalyst.

[발명의 중요한 용도][Important Application of the Invention]

본 발명의 난연성 폴리에스테르는 섬유, 필름 및 성형품 등으로 사용된다.The flame-retardant polyester of the present invention is used as fibers, films, molded products and the like.

Description

난연성 폴리에스테르의 제조방법Manufacturing method of flame retardant polyester

본 발명은 섬유, 필름 및 성형품 등에 사용되는 난연성 폴리에스테르의 제조방법에 관한 것이다. 더욱 상세하게는 인계 난연제를 첨가하여 폴리에스테르를 제조할 때, 중축합 촉매로서 게르마늄 옥사이드를 사용하여 색상이 우수하고 난연성이 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 a polyester having excellent color and improved flame retardancy by using germanium oxide as a polycondensation catalyst when a polyester is produced by adding a phosphorus flame retardant.

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 시장으로부터 요구되고 있다.Polyesters are generally used as fibers, films or plastic products because of their excellent thermal properties, mechanical properties, resistance to chemicals and moldability. However, such a polyester has a disadvantage that it is likely to burn rapidly after ignition in flame retardance. For this reason, in the field of fibers, films, molded products and engineering plastics in the interior field, development of a polyester imparting flame retardancy, particularly self-extinguishing properties, is required from the market.

종래에는 폴리에스테르에 난연성을 부여하는 방법으로 플리에스테르 중합시에 원료와 함께 반응형 난연제를 투입하여 난연성을 부여하거나, 성형시에 폴리에스테르수지와 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, a method of imparting flame retardancy to polyesters, flame retardance is imparted by feeding reactive flame retardant together with raw materials at the time of polyester polymerization, or polyester resin and addition type flame retardant are mixed at the time of molding to impart flame retardancy. 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 혼합방사 하는 방법등이 이용되어 왔다. 그러나 중합을 한 후에 후처리하는 방법은 경제적인 이점이 있는 반면, 반복 사용할 때 내구성 저하 등의 문제가 있었다.Methods for imparting flame retardancy to the fibers of polyethylene terephthalate include 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- . However, the post-treatment method after polymerization has an economical advantage, but has a problem of durability deterioration when repeatedly used.

그 후 연구되어 은 방향은 폴리머 제조시 방염성 물질을 중합공정 중에 투입하여 공중합 내지 블렌드 시켜 원사 자체에 고유한 난연성을 부여하는 기법이 연구되어 오고 있다. 그러나, 후처리 방법에 비해 중합공정 자체를 변형하는 것은 내구성과 난연 성능이 우수하다고 보고되어 있지만, 반응형 난연제의 종류에 따라 많은 문제점이 대두되어 왔다. 할로겐계 난연제를 사용하면 난연성이 발현된다 하더라도 공중합체가 착색되고, 내광성이 떨어지는 단점이 있다. 또한 인계 난연제를 사용할 때에도 난연제 자체의 열적 안정성이 낮기 때문에 공중합체가 변색이 되는 단점이 있다. 이러한 점을 극복하기 위하여 일본특허공개공보 소 57-212251호와 특허공개공보 소 59-191716호 등에서는 폴리에스테르 공중합시 중축합반응이 어느 정도 진행된 후에 난연제와 중축합 촉매를 넣는 방법을 제시하고 있으나 위와 같은 문제점을 완전히 해결하지는 못하였다.Thereafter, techniques for imparting flame retardancy inherent to the yarn itself by copolymerizing or blending the flame retardant material during the polymerization process have been studied. However, it has been reported that the durability and the flame retardant performance are superior to the post-treatment method in modifying the polymerization process itself, but there have been many problems depending on the type of the reactive flame retardant. The use of the halogen-based flame retardant has a disadvantage in that the copolymer is colored and the light resistance is poor even if flame retardancy is expressed. In addition, when the phosphorus flame retardant is used, there is a disadvantage that the copolymer is discolored because the thermal stability of the flame retardant itself is low. In order to overcome this problem, JP-A-57-212251 and JP-A-59-191716 disclose a method of adding a flame retardant and a polycondensation catalyst after the polycondensation reaction proceeds to some extent in polyester copolymerization The above problems have not been completely solved.

본 발명은 상기와 같은 문제점, 특히 공중합체에 착색이 되는 단점을 보완하기 위하여 폴리에스데르 제조과정 중에 인계 난연제를 투입하여 공중합시길 때, 중축합 촉매로서 게르마늄 옥사이드를 사용하여 난연성 뿐만 아니라 색상이 우수한 난연성 폴리에스테를 제조한다.It is an object of the present invention to provide a flame retardant which is excellent in flame retardancy as well as flame retardancy by using germanium oxide as a polycondensation catalyst when copolymerizing a phosphorus- To produce flame retardant polyester.

본 발명은 폴리에스테르의 중축합시에 일반식(I)로 표시되는 인계 난연제와 중축합 촉매인 게르마늄 옥사이드를 첨가하여 색상이 우수한 난연성 폴리에스테르를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a flame retardant polyester having excellent color by adding a phosphorus flame retardant represented by the general formula (I) and germanium oxide as a polycondensation catalyst at the time of polycondensation of the polyester.

1One 22

Claims (2)

폴리에스테르를 공중합항에 있어서, 일반식(I)로 표시되는 인계 난연제 중축합 촉매로서 게르마늄 옥사이드를 폴리에스테르에 대해 50∼200ppm 첨가함을 특징으로 하는 난연성 폴리에스테르의 제조방법.A process for producing a flame-retardant polyester characterized by adding 50 to 200 ppm of germanium oxide as a phosphorus-based flame retardant polycondensation catalyst represented by the general formula (I) in the copolymerization reaction of polyester. 구조식에서 Rl, R2는 같거나 서로 다른기로서 수소, 하이드록시에틸 또는 하이드록시프로필기이다.In the structural formula, R 1 and R 2, which may be the same or different, are hydrogen, hydroxyethyl or hydroxypropyl groups. 1항에 있어서, 인계 난연제는 3-히드록시페닐포스피닐프로판카르본산 또는 (2'-히드록시에털 ) -3-히드록시페닐포스피닐프로판 에스테르임을 특징으로 하는 난연성 폴리에스테르의 제조방법.The method for producing a flame-retardant polyester according to claim 1, wherein the phosphorus-based flame retardant is 3-hydroxyphenylphosphinylpropanecarboxylic acid or (2'-hydroxyethy) -3-hydroxyphenylphosphinylpropane ester.
KR1019960049871A 1996-10-30 1996-10-30 Process for preparing flame-retardant polyester KR100215637B1 (en)

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KR100215637B1 true KR100215637B1 (en) 1999-08-16

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100365813B1 (en) * 2000-11-27 2002-12-27 주식회사 코오롱 Manufacturing method of polybutyleneterephthalate
KR100616185B1 (en) * 2004-04-27 2006-08-25 주식회사 코오롱 Fire retardant Polyester resin composite for wig-hair
KR101139848B1 (en) * 2009-05-25 2012-04-30 주식회사 휴비스 Multi filament with absorbtion, quick dry characteristic and flame retardant property

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100365813B1 (en) * 2000-11-27 2002-12-27 주식회사 코오롱 Manufacturing method of polybutyleneterephthalate
KR100616185B1 (en) * 2004-04-27 2006-08-25 주식회사 코오롱 Fire retardant Polyester resin composite for wig-hair
KR101139848B1 (en) * 2009-05-25 2012-04-30 주식회사 휴비스 Multi filament with absorbtion, quick dry characteristic and flame retardant property

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Publication number Publication date
KR19980030465A (en) 1998-07-25

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