KR100371488B1 - A preparation method of catalytic solution - Google Patents

A preparation method of catalytic solution Download PDF

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Publication number
KR100371488B1
KR100371488B1 KR10-2000-0002659A KR20000002659A KR100371488B1 KR 100371488 B1 KR100371488 B1 KR 100371488B1 KR 20000002659 A KR20000002659 A KR 20000002659A KR 100371488 B1 KR100371488 B1 KR 100371488B1
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South Korea
Prior art keywords
ethylene glycol
antimony
solvent
xylene
antimony triacetate
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KR10-2000-0002659A
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Korean (ko)
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KR20000076494A (en
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다나까요시오
토끼야마야스히로
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주식회사 삼양사
다나까 엔지니어링 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • 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
    • 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

Abstract

본 발명은 고순도의 삼초산 안티몬의 에틸렌 글리콜 용액을 저가로, 또한 제조시 및 사용시에 작업 환경을 악화시키는 것 없이 제조하는 방법을 제공하는 것이다.The present invention provides a method for producing a high-purity ethylene glycol solution of antimony triacetic acid at low cost and without deteriorating the working environment at the time of manufacture and use.

삼산화 안티몬을 톨루엔, 크실렌 등의 용매에 현탁시켜, 그 용매의 비점으로 환류시키면서, 무수 초산을 반응시킨다. 반응물로부터 용매를 제거하고, 계산량의 에틸렌 글리콜을 첨가하여, 삼초산 안티몬의 에틸렌 글리콜 용액을 얻는다.Antimony trioxide is suspended in a solvent such as toluene or xylene, and acetic anhydride is reacted while refluxing to the boiling point of the solvent. The solvent is removed from the reaction and a calculated amount of ethylene glycol is added to obtain an ethylene glycol solution of antimony triacetate.

Description

촉매용액의 제조방법{A preparation method of catalytic solution}A preparation method of catalytic solution

본 발명은 폴리폴리에틸렌 테레프탈레이트 종류의 중축합 촉매용액을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a polycondensation catalyst solution of the polypolyethylene terephthalate type.

삼초산 안티몬은, 폴리에스테르 중축합 촉매로서 공지되어 있다. 이것은 통상, 톨루엔 또는 크실렌을 용매로 하여, 삼산화 안티몬에 무수 초산을 반응시켜 생성된 삼초산 안티몬을 원심분리, 진공 건조한 후, 포장하여, 출하된다. 한편, 폴리에스테르 공장에서는, 이것을 에틸렌 글리콜에 용해하여, 삼초산 안티몬으로서 약 5%의 용액화 한 후, 중축합기에 투입한다.Antimony triacetate is known as a polyester polycondensation catalyst. This is usually packaged and shipped after centrifugation and vacuum drying of antimony triacetate produced by reacting antimony trioxide with acetic anhydride using toluene or xylene as a solvent. On the other hand, in a polyester factory, this is melt | dissolved in ethylene glycol, about 5% solution as antimony triacetate, and it introduces into a polycondensation machine.

삼초산 안티몬은, 공기 중의 수분과도 반응하여 초산과 삼산화 안티몬으로 분해되고, 강렬한 초산 냄새가 작업 환경을 나쁘게 할뿐만 아니라, 이 가수분해 반응에 의해, 본래 삼초산 안티몬 촉매로서의 삼산화 안티몬에 대한 우위성도 정도의 차가 있지만, 우위성이 떨어진다.Antimony triacetate reacts with water in the air to decompose into acetic acid and antimony trioxide, and the strong odor of acetic acid makes the working environment worse, and by this hydrolysis reaction, the superiority to antimony trioxide as an antimony triacetic acid catalyst is inherent. There is a degree of difference, but the advantage is inferior.

2Sb(CH3COO)3+ 3H2O → Sb2O3+ 6CH3COOH2Sb (CH 3 COO) 3 + 3H 2 O → Sb 2 O 3 + 6CH 3 COOH

본 발명의 목적의 하나는, 이 가수분해를 방지하고, 고순도의 삼초산 안티몬을, 직접 에틸렌 글리콜 용액으로 하여, 중축합 반응기에 투입할 수 있도록 하는 것을 특징으로 하는, 촉매용액의 제조 방법을 제공하는 것이다. 또 다른 목적은 제조현장 및 사용현장에서 초산 냄새로 인한 작업환경 악화를 방지하고, 또한 삼초산 안티몬의 제조 비용을 낮추는데 있다.One of the objects of the present invention is to provide a method for producing a catalyst solution, wherein the hydrolysis is prevented and high purity antimony triacetate is directly added to the polycondensation reactor as an ethylene glycol solution. It is. Another object is to prevent the deterioration of the working environment due to acetic acid smell in the manufacturing and use sites, and also to lower the production cost of antimony triacetate.

삼초산 안티몬은, 통상 다음 화학식 2로 표시되는 반응식에 의해 합성된다. 용매로서는, 톨루엔과 크실렌이 일반적이다.Antimony triacetate is normally synthesize | combined by the reaction formula represented by following General formula (2). Toluene and xylene are common as a solvent.

Sb2O3+ 3(CH3CO)2O → 2Sb(CH3COO)3 Sb 2 O 3 + 3 (CH 3 CO) 2 O → 2Sb (CH 3 COO) 3

통상, 얻어진 반응 혼합물을 냉각하여, 고체 삼초산 안티몬을 석출시킨 후 원심분리, 진공건조, 포장한 후에 출하된다. 한편, 수요자에 있어서, 상기 포장을 제거한 후 계량하여, 약 5%의 에틸렌 글리콜 용액으로서 중축합 반응기에 투입한다.Usually, the obtained reaction mixture is cooled to precipitate solid antimony triacetate, followed by centrifugation, vacuum drying and packaging before shipping. On the other hand, in the consumer, the packaging is removed and then weighed and put into the polycondensation reactor as about 5% ethylene glycol solution.

본 발명에서는, 삼산화 안티몬과 무수 초산을 반응시켜, 삼초산 안티몬의 맑은 용액으로 하여, 로터리 증발기(rotary evaporator)와 같은, 회전식 진공건조기를 사용하여 해당 용매를 제거하고, 계산량의 에틸렌 글리콜을 첨가하고, 필요하다면 다시 한번 가열교반하여 목적하는 삼초산 안티몬의 에틸렌 글리콜 용액을 제조하고, 삼초산 안티몬이 결정화되지 않도록 보온하고, 또 건조 질소를 봉입하여 가수분해가 일어나지 않게 하여, 폴리에스테르 중축합기에 직접 투입한다.In the present invention, antimony trioxide and acetic anhydride are reacted to form a clear solution of antimony triacetate, the solvent is removed using a rotary vacuum dryer such as a rotary evaporator, and a calculated amount of ethylene glycol is added. If necessary, by heating and stirring once more to prepare the desired ethylene glycol solution of antimony triacetate, insulate the antimony triacetate from crystallization, and encapsulate dry nitrogen to prevent hydrolysis from occurring. Input.

본 발명법에 의하면, 주원료의 하나인 삼산화 안티몬을 반응기에 투입한 후, 삼초산 안티몬의 에틸렌 글리콜 용액을 얻을 때까지의 전공정이, 밸브 펌프의 조작만으로 운전되므로, 종래 기술에서처럼, 원심분리, 건조, 포장, 저장, 수송, 재용해 할 시에 우려되는 가수분해는 없다.According to the method of the present invention, after the antimony trioxide, which is one of the main raw materials, is introduced into the reactor, the whole process until the ethylene glycol solution of antimony triacetate is obtained is operated only by the operation of the valve pump. There is no hydrolysis concern when packing, storing, transporting or remelting.

본 발명에 사용되는 용매, 상기 화학식 2의 용매로서는 톨루엔,o-크실렌,m-크실렌.p-크실렌 또는 혼합 크실렌, 및 초산이 있다.As the solvent used in the present invention, the solvent of the formula (2) is toluene, o -xylene, m -xylene. p -xylene or mixed xylenes, and acetic acid.

실시예 1Example 1

1ℓ의 삼구 플라스크에 0.5몰의 삼산화 안티몬, 1.6몰의 무수 초산 및 300g의 톨루엔을 가하여, 비점에서 2시간 환류시켜 삼초산 안티몬의 약 50중량%의 톨루엔 용액을 얻었다. 반응 생성물 100g을, 1ℓ의 로터리 증발기로 옮기고, 수류 펌프로 초산을 진공 증류하여 제거한다. 증류를 완성한 후, 950g의 에틸렌 글리콜을 첨가하고, 가열교반하는 것에 의해, 삼초산 안티몬으로서 약 5%의 에틸렌 글리콜 용매를 얻었다.0.5 mol of antimony trioxide, 1.6 mol of anhydrous acetic acid and 300 g of toluene were added to a 1 L three-necked flask, and the mixture was refluxed at a boiling point for 2 hours to obtain a solution of about 50% by weight of toluene of antimony triacetate. 100 g of the reaction product is transferred to a 1 L rotary evaporator and acetic acid is removed by vacuum distillation with a water pump. After completion of the distillation, 950 g of ethylene glycol was added and the mixture was heated and stirred to obtain about 5% of an ethylene glycol solvent as antimony triacetate.

실시예 2Example 2

용매를 톨루엔 대신에 초산으로 한 이외의 방법으로서는 실시예 1과 같은 방법으로 삼초산 안티몬의 약 5%의 에틸렌 글리콜 용액을 얻었다.As a method other than using acetic acid instead of toluene, an ethylene glycol solution of about 5% of antimony triacetate was obtained in the same manner as in Example 1.

본 발명에 의해 삼초산 안티몬을 고순도이면서, 가수분해의 현상 없이 에틸렌 글리콜 용액으로서, 중축합기에 투입될 수 있는 것이 가능하게 되었고, 반응성 및 폴리머 특성이 개량되고, 또한 제조 비용이 저렴하게 되며, 또 제조시, 사용시의 초산 냄새에 의한 작업환경 악화를 막을 수가 있다.The present invention makes it possible to introduce antimony triacetate as a ethylene glycol solution with high purity and without the phenomenon of hydrolysis, and to improve the reactivity and polymer properties, and also to lower the production cost, At the time of manufacture, it can prevent the deterioration of the working environment by the acetic acid smell at the time of use.

Claims (2)

톨루엔,o-크실렌,m-크실렌,p-크실렌, 및 초산으로 이루어진 군으로부터 선택된 용매 존재 하에서 삼산화 안티몬과 무수 초산을 반응시켜 삼초산 안티몬을 생성시키고, 생성된 삼초산 안티몬을 결정화하지 않고 필요량의 에틸렌 글리콜을 첨가하거나 또는 필요량의 에틸렌 글리콜에 첨가하는 것에 의해, 삼초산 안티몬의 에틸렌 글리콜 용액을 제조하는 것을 특징으로 하는 폴리에틸렌 테레프탈레이트 종류의 중축합 촉매용액을 제조하는 방법.Antimony trioxide and acetic anhydride are reacted in the presence of a solvent selected from the group consisting of toluene, o -xylene, m -xylene, p -xylene, and acetic acid to produce antimony triacetate, and the resulting amount of antimony triacetate is crystallized without crystallization. A method for producing a polycondensation catalyst solution of polyethylene terephthalate type, characterized by producing an ethylene glycol solution of antimony triacetate by adding ethylene glycol or adding to a required amount of ethylene glycol. 제 1항에 있어서, 용매가 초산인 것을 특징으로 하는 방법.The method of claim 1 wherein the solvent is acetic acid.
KR10-2000-0002659A 1999-04-12 2000-01-20 A preparation method of catalytic solution KR100371488B1 (en)

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JP11142216A JP2000290360A (en) 1999-04-12 1999-04-12 Preparation of catalyst solution
JP1999/142216 1999-04-12

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935170A (en) * 1973-08-24 1976-01-27 Nl Industries, Inc. Trivalent antimony catalyst
JPH04114032A (en) * 1990-09-04 1992-04-15 Fuji Photo Film Co Ltd Preparation of catalyst by dissolution thereof
JPH08311188A (en) * 1995-05-17 1996-11-26 Kanebo Ltd Polymerization catalyst solution for polyester resin
KR0122003B1 (en) * 1994-05-27 1997-11-11 하기주 Method for manufacturing polyester

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935170A (en) * 1973-08-24 1976-01-27 Nl Industries, Inc. Trivalent antimony catalyst
JPH04114032A (en) * 1990-09-04 1992-04-15 Fuji Photo Film Co Ltd Preparation of catalyst by dissolution thereof
KR0122003B1 (en) * 1994-05-27 1997-11-11 하기주 Method for manufacturing polyester
JPH08311188A (en) * 1995-05-17 1996-11-26 Kanebo Ltd Polymerization catalyst solution for polyester resin

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JP2000290360A (en) 2000-10-17

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