KR930000117B1 - Preparation for polybutylene terephathalate - Google Patents

Preparation for polybutylene terephathalate Download PDF

Info

Publication number
KR930000117B1
KR930000117B1 KR1019880017957A KR880017957A KR930000117B1 KR 930000117 B1 KR930000117 B1 KR 930000117B1 KR 1019880017957 A KR1019880017957 A KR 1019880017957A KR 880017957 A KR880017957 A KR 880017957A KR 930000117 B1 KR930000117 B1 KR 930000117B1
Authority
KR
South Korea
Prior art keywords
reaction
butanediol
terephthalic acid
tetrahydrofuran
polybutylene terephthalate
Prior art date
Application number
KR1019880017957A
Other languages
Korean (ko)
Other versions
KR900009753A (en
Inventor
김충부
송석정
박인보
이수창
Original Assignee
주식회사 코오롱
이상철
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 코오롱, 이상철 filed Critical 주식회사 코오롱
Priority to KR1019880017957A priority Critical patent/KR930000117B1/en
Publication of KR900009753A publication Critical patent/KR900009753A/en
Application granted granted Critical
Publication of KR930000117B1 publication Critical patent/KR930000117B1/en

Links

Classifications

    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

A polybuthylene terephthalate is prepared by esterifying and polycondensating terephthalic acid and 1,4-butanediol in the presence of an esterification catalyst. The esterification catalyst is composed of a quaternary ammonium salt and at least one compound selected from organic titanium compounds and organic tin compounds. The quaternary ammonium salt is tetramethyl ammonium, tetraethyl ammonium or tetrapropyl ammonium. Specifically, the formation of tetrahydrofuran is restrained by the addition of the catalyst.

Description

폴리부틸렌테레프탈레이트의 제조방법Method for producing polybutylene terephthalate

본 발명은 폴리부틸렌 테레프탈레이트(PBT)의 제조방법에 관한 것이다.The present invention relates to a process for preparing polybutylene terephthalate (PBT).

폴리부틸렌 테레프탈레이트는 통상적으로 테레프탈산과 1,4-부탄디올을 중합원료로 하여 제조하되, 특히 일반적인 폴리에스테르의 제조방법, 예컨대 테레프탈산과 에틸렌글리콜을 사용하여 폴리에틸렌 테레프탈레이트를 제조하는 방법을 그대로 적용하여 제조할 수 있다. 그러나, 그와 같이 폴리부틸렌 테레프탈레이트를 제조하는 경우에는 반응속도가 매우 느릴뿐 아니라 일정 수준이상으로는 반응이 전혀 진행되지 않게 되는 단점이 있었다. 그 원인은 중합원료로 사용된 1,4-부탄디올이 열에 의해 반응계내에서 환상에테르인 테트라히드로퓨란으로 전환되고, 또한 반응생성물인 올리고머의 카르복시에스테르말단기도 폐환반응하여 환상화합물을 형성하면서 테트라하이드로퓨란으로 전환되기 때문인 것으로 밝혀졌다. 즉, 처음에 투입한 1,4-부탄디올의 상당량이 상술한 바와 같이 테트라하이드로퓨란으로 전환되기 때문에 테레프탈산성분과 반응할 수 있는 1,4-부탄디올의 양은 상대적으로 줄어들게 되고 이로 인해 반응이 더 이상 진행되지 않게 되는 것이다.Polybutylene terephthalate is usually prepared by using terephthalic acid and 1,4-butanediol as a polymerization raw material, and in particular, a method of preparing a polyester such as polyethylene terephthalate using terephthalic acid and ethylene glycol is applied as it is. It can manufacture. However, in the case of preparing the polybutylene terephthalate as described above, the reaction rate is very slow and there is a disadvantage that the reaction does not proceed at all above a certain level. The reason is that 1,4-butanediol used as a polymerization raw material is converted into tetrahydrofuran, which is a cyclic ether, in the reaction system by heat, and tetrahydrofuran is formed by ring-closing the carboxyester terminal of the reaction product oligomer to form a cyclic compound. It turns out that it is because That is, since a considerable amount of 1,4-butanediol initially introduced is converted to tetrahydrofuran as described above, the amount of 1,4-butanediol that can react with terephthalic acid components is relatively reduced, which causes the reaction to proceed further. It will not be.

이와 같은 문제점을 개선하기 위한 종래방법으로는, 예컨대 일본특공소53-9796호, 소55-7853호, 소55-19253호, 소55-30010호 등에 기재된 바와 같이 특정한 유기티탄계 화합물 또는 유기주석계 화합물을 사용하는 방법이 알려져 있다. 그러나, 상기 방법을 사용하는 경우에는 에스테르화반응의 속도를 개선시키는데에 효과는 있으나, 가장 문제시되었던 테트라하이드퓨란의 발생을 억제시키지는 못하는 단점이 있었다.As a conventional method for improving such a problem, a specific organotitanium-based compound or an organic tin-based compound is described, for example, as described in JP 53-9796, 55-7853, 55-19253, 55-30010, etc. Methods of using the compounds are known. However, the above method is effective in improving the rate of esterification, but has a disadvantage in that it does not inhibit the generation of tetrahydrofuran, which has been most problematic.

이에 본 발명자들은 종래의 이러한 문제점들을 해결하기 위해 예의 연구해온 결과 다음과 같은 사실을 알게 되어 그에 기초하여 본 발명을 완성하게 되었다.Accordingly, the present inventors have made diligent researches to solve these problems in the related art, and have come to know the following facts to complete the present invention.

즉, 테레프탈산과 1,4-부탄디올을 사용하여 통상적인 방법에 따라 폴리부틸렌테레프탈레이트를 제조하는 경우, 반응이 진행되는 도중에 부탄디올이 테트라하이드로퓨란으로 전환되는 반응의 매카니즘은 다음 반응식과 같은데,That is, when polybutylene terephthalate is prepared according to a conventional method using terephthalic acid and 1,4-butanediol, the reaction mechanism of converting butanediol to tetrahydrofuran during the reaction is as follows.

Figure kpo00001
Figure kpo00001

이 반응은 산촉매의 작용으로 인하여 매우 빠른 속도로 반응이 진행되게 된다. 그러므로, 테레프탈산 반응계 자체가 테레프탈산의 산도에 의해 부반응이 촉진되게 되고 아울러 테트라하이드로퓨란이 생성이 현저하게 증가하게 되는 원인이 되는 것이다.The reaction proceeds very rapidly due to the action of the acid catalyst. Therefore, the terephthalic acid reaction system itself causes the side reaction to be promoted by the acidity of terephthalic acid and also causes the production of tetrahydrofuran to increase significantly.

또한, 본 발명자들은 종래에 반응촉매로 사용되었던 유기티탄계 화합물과 유기주석계 화합물의 부탄디올용액은 pH측정결과 용액의 pH가 약산성으로 밝혀졌는 바, 이로 인하여 테트라하이드로퓨란의 생성억제 효과가 저하된 것을 알수 있었다.In addition, the present inventors have found that the butanediol solution of the organotitanium compound and the organotin compound, which has been used as a reaction catalyst in the past, was found to have a weak acidity as a result of pH measurement, thereby reducing the inhibitory effect of tetrahydrofuran production. Could know.

따라서, 본 발명의 목적은 폴리부틸렌테레프탈레이트의 제조에 있어서 종래의 문제시 되었던 테트라하이드로퓨란의 생성을 억제시켜서 낮은 부탄디올/테레프탈산의 몰비에서 효과적으로 폴리부틸렌테레프탈레이트를 제조하는 방법을 제공하는데 있다.Accordingly, it is an object of the present invention to provide a method for producing polybutylene terephthalate effectively at a low molar ratio of butanediol / terephthalic acid by inhibiting the production of tetrahydrofuran, which has been a conventional problem in the production of polybutylene terephthalate. .

이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 테레프탈산과 1,4-부탄디올을 중합원료로 하여 에스테르화 반응 및 중축합반응시켜서 폴리부틸렌테레프탈레이트를 제조함에 있어서, 에스테르화촉매로서 유기티탄계 화합물과 유기주석계 화합물중에서 선택되는 적어도 1종이상과 4급 암모늄염을 사용하여서 제조함을 그 특징으로 한다.In the present invention, in the production of polybutylene terephthalate by esterification and polycondensation reaction using terephthalic acid and 1,4-butanediol as a polymerization raw material, at least one selected from an organotitanium compound and an organotin compound as an esterification catalyst It is characterized by the manufacture using paper and quaternary ammonium salts.

이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명에 따르면, 폴리부틸렌테레프탈레이트의 제조를 위해 테레프탈산과 1,4-부탄디올을 에스테르화반응시킴에 있어서, 에스테르화촉매로서 유기티탄계 화합물 및 유기주석계 화합물들 중에서 선택되는 적어도 1종이상의 화합물뿐 아니라 일반식 R4N+OH-(여기서, R은 탄소원자수 1 내지 3의 저급알킬기이다)로 pH를 약염기성으로 유지시켜 줌으로써 종래 문제시되었던 테트라하이드로퓨란의 생성을 효과적으로 억제시킬 수 있다.According to the present invention, in the esterification reaction of terephthalic acid and 1,4-butanediol for the production of polybutylene terephthalate, at least one compound selected from organotitanium compounds and organotin compounds as an esterification catalyst as well as the general formula R 4 N + OH - it is possible to suppress the generation of the prior question tetrahydrofuran was by giving to maintain the pH (where, R is a lower alkyl group of 1 to 3 carbon atoms) with a weakly basic effectively.

본 발명에서 특징으로 하는 4급암모늄염으로는, 예컨대 테트라메틸암모늄하이드록사이드, 테트라에틸암모늄 하이드록사이드, 테트라프로필암모늄 하이드록사이드 등을 들 수 있으며, 그 첨가량은 제조되는 중합체에 대하여 0.05 내지 0.1중량%로 사용하는 것이 바람직하다.The quaternary ammonium salts featured in the present invention include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and the addition amount thereof is 0.05 to 0.1 based on the polymer to be produced. Preference is given to using by weight.

또한, 본 발명에서 사용할 수 있는 유기티탄계 화합물로는, 예컨대 테트라메틸티타네이트, 테트라프로필티타네이트, 테트라부틸티타네이트 등과 같은 테트라알킬티타테이트화합물들이 있고, 유기주석게 화합물로는 디부틸틴옥사이드, 메틸페닐틴옥사이드, 부틸틴옥사이드, 디부틸틴클라이드 및 모노부틸틴트리클로라이드 등이 있다. 이와 같은 유기티탄계 화합물과 유기주석계 화합물은 단독으로 사용하거나 또는 그들 중 1종이상을 선택하여 사용할 수도 있는데, 상기 어느 경우에나 동일하게 그 첨가량은 제조되는 중합체에 대하여 0.01 내지 0.2중량%로 사용하는 것이 좋다.In addition, examples of the organotitanium compounds that can be used in the present invention include tetraalkyl titanate compounds such as tetramethyl titanate, tetrapropyl titanate, tetrabutyl titanate, and the like. , Methylphenyl tin oxide, butyl tin oxide, dibutyl tin clyde and monobutyl tin trichloride. Such organotitanium compounds and organotin compounds may be used singly or in combination with one or more of them. In any of the above cases, the amount is added in an amount of 0.01 to 0.2% by weight based on the polymer to be produced. It is good.

상술한 바와 같이 본 발명의 방법에 따라 에스테르화반응을 실행한 후, 이어서 중축합반응시키게 되면 목적하는 폴리부틸렌테레프탈레이트를 효과적으로 제조할 수 있다.As described above, if the esterification reaction is carried out according to the method of the present invention, followed by the polycondensation reaction, the desired polybutylene terephthalate can be effectively produced.

이하 본 발명을 실시예에 의거하여 더욱 상세히 설명하면 다음과 같으며, 실시예에서 유출액중에 포함된 테트라하이드로퓨란의 양은 가스크로마토그래피법에 의해 분석한 값이다.Hereinafter, the present invention will be described in more detail with reference to Examples. The amount of tetrahydrofuran contained in the effluent in the Examples is a value analyzed by gas chromatography.

[실시예 1]Example 1

테레프탈산 166g 및 부탄디올 113g[몰비(부탄디올/테레프탈산)=1.25]과, 테트라부틸티타네이트 0.1g, 테트라에틸암모늄 하이드록사이드 0.03g을 반응관에 투입한 후, 반응관 내 온도를 230℃까지 서서히 승온시키면서 생성되는 액을 유출시켰다.166 g of terephthalic acid and 113 g of butanediol [molar ratio (butanediol / terephthalic acid) = 1.25], 0.1 g of tetrabutyl titanate and 0.03 g of tetraethylammonium hydroxide were added to the reaction tube, and the temperature in the reaction tube was gradually raised to 230 ° C. The resulting liquid was flowed out.

반응계가 투명해지는 싯점에서 에스테르화반응을 종결시키고, 이어서 테트라부틸티타네이트 0.05g을 첨가하고 250℃의 온도 및 1토르 이하의 진공하에서 중축합반응시켜서 고유점도가 0.67인 중합체를 얻었다.At the point where the reaction system became transparent, the esterification reaction was terminated, followed by addition of 0.05 g of tetrabutyl titanate and polycondensation at a temperature of 250 ° C. and vacuum of 1 Torr or less to obtain a polymer having an intrinsic viscosity of 0.67.

이때, 에스테르화반응에 소요된 시간은 130분이었고, 유출용액중에 포함된 테트라하이드로퓨란의 양은 8%였다.At this time, the time required for the esterification reaction was 130 minutes, the amount of tetrahydrofuran contained in the effluent solution was 8%.

[실시예 2]Example 2

에스테르화촉매로서 테트라부틸티타네이트 0.1g과

Figure kpo00002
테트라에틸암모늄 하이드록사이드 0.05g을 사용하는 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.0.1 g of tetrabutyl titanate as esterification catalyst
Figure kpo00002
The same procedure as in Example 1 was carried out except that 0.05 g of tetraethylammonium hydroxide was used.

이때, 제조된 중합체의 고유점도는 0.69이었고, 에스테르화반응에 소요된 시간은 120분, 유출용액중에 포함된 테트라하이드로퓨란의 양은 3%였다.At this time, the inherent viscosity of the polymer was 0.69, the time required for the esterification reaction 120 minutes, the amount of tetrahydrofuran contained in the effluent solution was 3%.

[실시예 3]Example 3

에스테르화촉매로

Figure kpo00003
과 테트라에틸암모늄하이드록사이드 0.05g을 사용하는 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.With esterification catalyst
Figure kpo00003
And tetraethylammonium hydroxide 0.05g was used in the same manner as in Example 1 above.

이때, 제조된 중합체의 고유점도는 0.65이었고, 에스테르화 반응에 소요되는 시간은 130분, 유출액중에서 포함된 테트라하이드로퓨란의 양은 5%였다.At this time, the intrinsic viscosity of the polymer was 0.65, the time required for the esterification reaction 130 minutes, the amount of tetrahydrofuran contained in the effluent was 5%.

[비교예 1]Comparative Example 1

에스테르화촉매로 테트라부틸티타네이트 0.1g만을 사용하는 것을 제외하고는 상기 실시예 1과 동일하다.It is the same as Example 1 except using only 0.1 g of tetrabutyl titanate as an esterification catalyst.

그런데, 4시간이상을 반응시켜도 반응계는 투명해지지 않았고, 더 이상의 반응이 진행되지 않았다.However, the reaction system did not become transparent even after reacting for 4 hours or more, and no further reaction proceeded.

이때, 유출액중에 포함된 테트라하이드로퓨란의 양은 42%였다.At this time, the amount of tetrahydrofuran contained in the effluent was 42%.

[비교예 2]Comparative Example 2

테레프탈산 166g 및 부탄디올 153g[몰비(부탄디올/테레프탈산)=1.7]과, 테트라부틸티타네이트 0.1g, C4

Figure kpo00004
을 사용하여 상기 실시예 1과 동일하게 실시한 결과, 고유점도가 0.65인 중합체를 얻었다.166 g of terephthalic acid and 153 g of butanediol [molar ratio (butanediol / terephthalic acid) = 1.7], 0.1 g of tetrabutyl titanate, C 4
Figure kpo00004
As a result of performing the same procedure as in Example 1, the polymer having an intrinsic viscosity of 0.65 was obtained.

이때, 에스테르화반응에 소요된 시간은 130분이었고, 유출액중에 포함된 테트라하이드로퓨란의 양은 23%였다.At this time, the time required for the esterification reaction was 130 minutes, the amount of tetrahydrofuran contained in the effluent was 23%.

Claims (2)

테레프탈산과 1,4-부탄디올을 중합원료로 하여 에스테르화반응 및 중축합반응시켜서 폴리부틸렌테레프탈레이트를 제조함에 있어서, 에스테르화촉매로서 유기티탄계 화합물과 유기주석계 화합물중에서 선택되는 적어도 1종이상과 4급암모늄염을 사용하여서 제조함을 특징으로 하는 폴리부틸렌테레프탈레이트의 제조방법.In the preparation of polybutylene terephthalate by esterification and polycondensation reaction using terephthalic acid and 1,4-butanediol as a polymerization raw material, at least one selected from an organotitanium compound and an organotin compound as esterification catalyst A process for producing polybutylene terephthalate, characterized in that it is prepared using a quaternary ammonium salt. 제1항에 있어서, 4급암모늄염으로서 테트라알킬암모늄 하이드록사이드류를 사용함을 특징으로 하는 폴리부틸렌테레프탈레이트의 제조방법.The method for producing polybutylene terephthalate according to claim 1, wherein tetraalkylammonium hydroxides are used as quaternary ammonium salts.
KR1019880017957A 1988-12-30 1988-12-30 Preparation for polybutylene terephathalate KR930000117B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019880017957A KR930000117B1 (en) 1988-12-30 1988-12-30 Preparation for polybutylene terephathalate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019880017957A KR930000117B1 (en) 1988-12-30 1988-12-30 Preparation for polybutylene terephathalate

Publications (2)

Publication Number Publication Date
KR900009753A KR900009753A (en) 1990-07-05
KR930000117B1 true KR930000117B1 (en) 1993-01-09

Family

ID=19280956

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019880017957A KR930000117B1 (en) 1988-12-30 1988-12-30 Preparation for polybutylene terephathalate

Country Status (1)

Country Link
KR (1) KR930000117B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012051177A3 (en) * 2010-10-11 2012-07-12 Tbl Licensing Llc Suspension heel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012051177A3 (en) * 2010-10-11 2012-07-12 Tbl Licensing Llc Suspension heel
US8539697B2 (en) 2010-10-11 2013-09-24 Tbl Licensing Llc Suspension heel

Also Published As

Publication number Publication date
KR900009753A (en) 1990-07-05

Similar Documents

Publication Publication Date Title
EP0826713B1 (en) Process for producing polyethylene terephthalate using a specific catalyst stabilizer system
US6472500B2 (en) Crystalline polyester resins and processes for their preparation
JP6505917B6 (en) Process for preparing cyclic oligomers, and cyclic oligomers obtained thereby
US3936421A (en) Process of preparing polytetramethylene terephthalate
US4656241A (en) Method for producing polybutylene terephthalate
CA1079895A (en) Production of polyesters
EP0046670B1 (en) Process for the preparation of polybutylene terephthalate
KR930000117B1 (en) Preparation for polybutylene terephathalate
US4511708A (en) Process for manufacturing polytetramethylene terephthalate
CN111087583A (en) Preparation method of low-end carboxyl PBT resin
US4107150A (en) High impact terephthalate copolyesters using 1,4-butanediol and 1,4-cyclohexanedimethanol
US4439597A (en) Process for the preparation of polybutylene terephthalate
US4049635A (en) Production of tetramethylene terephthalate polymers using 225° to 248° C. polycondensation temperature
US5811513A (en) Process for producing polyethylene naphthalate
US3718621A (en) Solid state polymerization process
EP1386937B1 (en) Method for preparing poly(cyclohexane-1, 4-dicarboxylate)s
US3756986A (en) Process for preparing polyesters from acyloxyethyl terephthalates
JP4552243B2 (en) Process for producing polybutylene terephthalate
KR0175204B1 (en) Method for producing high molecular weight polybutylene terephthalate
JPS60208325A (en) Production of polyester
US4119614A (en) Process for making polyester polymer
JPH07138253A (en) Production of lactide
US3268482A (en) Preparation of polyesters
US3313846A (en) Polyethers and method of making same
JP3873428B2 (en) Process for producing polybutylene terephthalate

Legal Events

Date Code Title Description
A201 Request for examination
G160 Decision to publish patent application
G160 Decision to publish patent application
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20060103

Year of fee payment: 14

LAPS Lapse due to unpaid annual fee