KR100435510B1 - A process for preparing poly(butylene terephthalate) resin - Google Patents

A process for preparing poly(butylene terephthalate) resin Download PDF

Info

Publication number
KR100435510B1
KR100435510B1 KR1020000017894A KR20000017894A KR100435510B1 KR 100435510 B1 KR100435510 B1 KR 100435510B1 KR 1020000017894 A KR1020000017894 A KR 1020000017894A KR 20000017894 A KR20000017894 A KR 20000017894A KR 100435510 B1 KR100435510 B1 KR 100435510B1
Authority
KR
South Korea
Prior art keywords
polybutylene terephthalate
terephthalate resin
optical fiber
resin
extrusion
Prior art date
Application number
KR1020000017894A
Other languages
Korean (ko)
Other versions
KR20010094303A (en
Inventor
신경무
홍명혁
이준희
Original Assignee
주식회사 삼양사
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 삼양사 filed Critical 주식회사 삼양사
Priority to KR1020000017894A priority Critical patent/KR100435510B1/en
Publication of KR20010094303A publication Critical patent/KR20010094303A/en
Application granted granted Critical
Publication of KR100435510B1 publication Critical patent/KR100435510B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/07—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/03—Drawing means, e.g. drawing drums ; Traction or tensioning devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H2701/00—Handled material; Storage means
    • B65H2701/30—Handled filamentary material
    • B65H2701/31—Textiles threads or artificial strands of filaments
    • B65H2701/312—Fibreglass strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H54/00—Winding, coiling, or depositing filamentary material
    • B65H54/02—Winding and traversing material on to reels, bobbins, tubes, or like package cores or formers
    • B65H54/28—Traversing devices; Package-shaping arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H54/00—Winding, coiling, or depositing filamentary material
    • B65H54/02—Winding and traversing material on to reels, bobbins, tubes, or like package cores or formers
    • B65H54/40—Arrangements for rotating packages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H59/00—Adjusting or controlling tension in filamentary material, e.g. for preventing snarling; Applications of tension indicators
    • B65H59/38—Adjusting or controlling tension in filamentary material, e.g. for preventing snarling; Applications of tension indicators by regulating speed of driving mechanism of unwinding, paying-out, forwarding, winding, or depositing devices, e.g. automatically in response to variations in tension
    • B65H59/384—Adjusting or controlling tension in filamentary material, e.g. for preventing snarling; Applications of tension indicators by regulating speed of driving mechanism of unwinding, paying-out, forwarding, winding, or depositing devices, e.g. automatically in response to variations in tension using electronic means
    • B65H59/388—Regulating forwarding speed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

본 발명은 폴리부틸렌 테레프탈레이트 수지의 제조방법에 관한 것으로서, 더욱 상세하게는 통상의 폴리부틸렌 테레프탈레이트 수지의 단량체에 2개 이상의 수산기가 함유된 다관능성 분지제 및 다음 화학식 1로 표시되는 핵제를 첨가하여 용융혼합 후 고상중합을 통하여 제조함으로써, 분자량, 점도 및 용융장력이 높고 빠른 결정화 속도를 갖도록 하는 폴리부틸렌 테레프탈레이트 수지의 제조방법에 관한 것이다. 이에, 상기 제조방법에 의해 제조된 폴리부틸렌 테레프탈레이트 수지가 광섬유 자케팅에 적용하는 경우, 광섬유 자켓팅 공정중 발생하는 편심(광섬유가 자켓의 중심에서 벗어나는 현상) 및 높은 압출부하를 해결하여 고속압출이 가능하도록 개선하게 되는 특징이 있다.The present invention relates to a method for producing a polybutylene terephthalate resin, and more particularly, a polyfunctional branching agent containing two or more hydroxyl groups in a monomer of a conventional polybutylene terephthalate resin and a nucleating agent represented by the following Chemical Formula 1 The present invention relates to a method for producing a polybutylene terephthalate resin having a high crystallization rate and high molecular weight, viscosity and melt tension by melting through mixing followed by solid phase polymerization. Therefore, when the polybutylene terephthalate resin prepared by the above manufacturing method is applied to optical fiber jacketing, eccentricity (phenomena in which the optical fiber deviates from the center of the jacket) and high extrusion load generated during the optical fiber jacketing process are solved at high speed. There is a feature that improves to enable extrusion.

상기 화학식 1에서; R은 C1∼ C4의 알킬기를 나타내고; Ar 또는 Ar'는 서로 같거나 다른 것으로서, 벤젠 고리 또는 나프탈렌 고리를 나타낸다.In Chemical Formula 1; R represents an alkyl group of C 1 to C 4 ; Ar or Ar ', the same or different from each other, represents a benzene ring or a naphthalene ring.

Description

폴리부틸렌 테레프탈레이트 수지의 제조방법{A process for preparing poly(butylene terephthalate) resin}A process for preparing poly (butylene terephthalate) resin

본 발명은 폴리부틸렌 테레프탈레이트 수지의 제조방법에 관한 것으로서, 더욱 상세하게는 통상의 폴리부틸렌 테레프탈레이트 수지의 단량체에 2개 이상의 수산기가 함유된 다관능성 분지제 및 다음 화학식 1로 표시되는 핵제를 첨가하여 용융혼합 후 고상중합을 통하여 제조함으로써, 분자량, 점도 및 용융장력이 높고 빠른 결정화 속도를 갖도록 하는 폴리부틸렌 테레프탈레이트 수지의 제조방법에 관한 것이다. 이에, 상기 제조방법에 의해 제조된 폴리부틸렌 테레프탈레이트 수지가 광섬유 자케팅에 적용하는 경우, 광섬유 자켓팅 공정중 발생하는 편심(광섬유가 자켓의 중심에서 벗어나는 현상) 및 높은 압출부하를 해결하여 고속압출이 가능하도록 개선하게 되는 특징이 있다.The present invention relates to a method for producing a polybutylene terephthalate resin, and more particularly, a polyfunctional branching agent containing two or more hydroxyl groups in a monomer of a conventional polybutylene terephthalate resin and a nucleating agent represented by the following Chemical Formula 1 The present invention relates to a method for producing a polybutylene terephthalate resin having a high crystallization rate and high molecular weight, viscosity and melt tension by melting through mixing followed by solid phase polymerization. Therefore, when the polybutylene terephthalate resin prepared by the above manufacturing method is applied to optical fiber jacketing, eccentricity (phenomena in which the optical fiber deviates from the center of the jacket) and high extrusion load generated during the optical fiber jacketing process are solved at high speed. There is a feature that improves to enable extrusion.

화학식 1Formula 1

상기 화학식 1에서; R은 C1∼ C4의 알킬기를 나타내고; Ar 또는 Ar'는 서로 같거나 다른 것으로서, 벤젠 고리 또는 나프탈렌 고리를 나타낸다.In Chemical Formula 1; R represents an alkyl group of C 1 to C 4 ; Ar or Ar ', the same or different from each other, represents a benzene ring or a naphthalene ring.

일반적으로 폴리부틸렌 테레프탈레이트(이하, PBT)는 폴리에틸렌 테레프탈레이트와 유사한 것으로, 이전에는 유리전이 온도가 너무 낮아서 실용적인 합성섬유로는 적합지 못한 것으로 간주되었다가 근래 엔지니어링용으로 개발되어 본격적으로 사용되고 있다.In general, polybutylene terephthalate (hereinafter referred to as PBT) is similar to polyethylene terephthalate, and was previously considered to be unsuitable as a practical synthetic fiber because the glass transition temperature is too low.

현재 PBT는 흡습성, 치수 안정성 및 내마모성 등의 기계적 특성과 가공성이 우수하기 때문에 아라미드계 수지와 더불어 광섬유 자켓팅용으로 사용되고 있으며, 전자 통신망의 확충 및 교체의 증가와 더불어 그 사용량이 매우 빠르게 증가하고 있는 추세이다. 그러나, 이러한 수지들을 광섬유 자켓팅에 응용하는 경우 압출 공정중 편심(광섬유가 자켓의 중심에서 벗어나는 현상)으로 인한 불량 발생률이 매우 높게 나타난다.PBT is used for optical fiber jacketing along with aramid resin because of its excellent mechanical properties such as hygroscopicity, dimensional stability and abrasion resistance, and its usage is increasing very rapidly with the expansion and replacement of electronic communication networks. to be. However, when these resins are applied to the optical fiber jacketing, the failure rate due to the eccentricity (the phenomenon in which the optical fiber deviates from the center of the jacket) during the extrusion process is very high.

통상적으로 이용되는 광섬유 자켓팅용 수지는 용융혼합 후 고상중합(solid-state polymerization)을 통해 고유점도가 1.25 ∼ 1.30 ㎗/g 정도로 고점도인 PBT 수지가 사용되고 있다. 그러나, 편심 및 고속압출시 압출부하로 인한 압출 속도저하의 문제점이 남아 있는 실정이다.As the commonly used resin for optical fiber jacketing, PBT resin having high intrinsic viscosity of about 1.25 to 1.30 g / g through solid-state polymerization after melt mixing is used. However, there is a problem that the extrusion speed decreases due to the extrusion load during eccentricity and high-speed extrusion.

지금까지 알려진 PBT 수지는 미국특허 제4,917,845호 및 제5,536,810호에서 제안된 바에 의하면 빠른 고상중합으로 고분자량을 얻는 방법 또는 가장 적당한 고상중합 온도를 구하는 방법 등에 대해서 언급되어 있다. 또한, 미국특허제5,334,343호에서는 결정화 속도를 향상시켜 압출에 응용하는 방법에 대해 언급되어 있고, 미국특허 제5,229,432호, 제4,034,013호 및 제4,071,503호에서는 용융장력을 향상시켜 블로우 몰딩에 사용되는 수지의 제조에 관해서 언급된 바 있다.PBT resins known so far have been mentioned in U.S. Pat.Nos. 4,917,845 and 5,536,810 to mention methods for obtaining high molecular weight with fast solid-state polymerization or for obtaining the most suitable solid-state polymerization temperature. In addition, U.S. Patent No. 5,334,343 mentions a method of improving the crystallization rate and applying it to extrusion, and U.S. Patent Nos. 5,229,432, 4,034,013 and 4,071,503 improve the melt tension of resins used for blow molding. Mention has been made with regard to manufacturing.

그러나, 상기의 것을 포함한 이제까지의 문헌을 살펴보면, 고점도의 PBT 수지를 제조하는 고상중합 방법 및 고상중합을 빠르게 하는 방법 등에 대한 연구는 많이 공지되어 있는 반면에, PBT 수지의 점도 및 용융장력을 향상시킴과 동시에 고속 압출능을 개선할 수 있는 방법에 대해서는 아직까지 알려진 바가 없다.However, when looking at the literatures including the above, the studies on the solid phase polymerization method for producing a high viscosity PBT resin and the method for increasing the solid phase polymerization are well known, while improving the viscosity and melt tension of the PBT resin At the same time, it is not known how to improve the high-speed extrusion capacity.

종래 폴리부틸렌 테레프탈레이트 수지는 고상중합 후 고속 압출공정시 압출부하가 매우 높고 낮은 용융장력을 나타내기 때문에 광섬유 자케팅 공정에서 편심이 발생하는 문제점이 있다.Conventional polybutylene terephthalate resin has a problem that the eccentricity occurs in the optical fiber jacketing process because the extrusion load is very high and exhibits a low melt tension during the high-speed extrusion process after the solid state polymerization.

따라서, 본 발명에서는 상기의 문제점을 개선하기 위하여 기존의 폴리부틸렌 테레프탈레이트 수지의 원료 단량체에 2개 이상의 수산기가 함유된 다관능성 분지제 및 핵제를 함유시켜 폴리부틸렌 테레프탈레이트수지를 제조함으로써, 용융장력을 높이고 빠른 결정화 속도를 유지시켜 고속압출을 가능하도록 개선된 폴리부틸렌 테레프탈레이트 수지의 제조방법을 제공하는데 그 목적이 있다.Therefore, in the present invention, in order to improve the above problems by preparing a polybutylene terephthalate resin by containing a polyfunctional branching agent and a nucleating agent containing two or more hydroxyl groups in the raw material monomer of the conventional polybutylene terephthalate resin, It is an object of the present invention to provide a method for producing a polybutylene terephthalate resin improved to enable high-speed extrusion by increasing melt tension and maintaining a fast crystallization rate.

본 발명은 디메틸테레프탈레이트와 1,4-부탄디올을 용융중합한후 고상중합하여 제조하는 폴리부틸렌 테레프탈레이트 수지의 제조방법에 있어서,The present invention is a method for producing a polybutylene terephthalate resin prepared by melt-polymerizing dimethyl terephthalate and 1,4-butanediol and then solid-phase polymerization,

2개 이상의 수산기가 함유된 다관능성 분지제를 상기 디메틸테레프탈레이트 1몰에 대하여 0.1 ∼ 5 몰%, 그리고0.1-5 mol% of the polyfunctional branching agent containing two or more hydroxyl groups with respect to 1 mol of said dimethyl terephthalates, and

다음 화학식 1로 표시되는 핵제를 디메틸테레프탈레이트, 1,4-부탄디올 및 다관능성 분지제의 혼합물 조성에 대하여 1 ∼ 5 중량%를 첨가하여 용융중합한 후, 고상중합 반응을 수행하여 제조하는 것을 특징으로 하는 폴리부틸렌 테레프탈레이트 수지의 제조방법을 그 특징으로 하고 있다.Next, the nucleating agent represented by Chemical Formula 1 is melt-polymerized by adding 1 to 5% by weight, based on the mixture composition of dimethyl terephthalate, 1,4-butanediol, and polyfunctional branching agent, followed by solid phase polymerization. The manufacturing method of the polybutylene terephthalate resin which sets it as the feature is characterized.

화학식 1Formula 1

상기 화학식 1에서; R은 C1∼ C4의 알킬기를 나타내고; Ar 또는 Ar'는 서로 같거나 다른 것으로서, 벤젠 고리 또는 나프탈렌 고리를 나타낸다.In Chemical Formula 1; R represents an alkyl group of C 1 to C 4 ; Ar or Ar ', the same or different from each other, represents a benzene ring or a naphthalene ring.

이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명은 기존의 폴리부틸렌 테레프탈레이트(이하, PBT) 수지에 다관능성 분지제 및 핵제를 함유시켜 용융중합한후 고상중합하여 PBT 수지의 용융장력을 높이고 기존의 고점도 PBT 수지에 비해 압출 속도가 빠른 고점도 수지를 제조하는 방법으로써, 이와 같은 방법으로 제조된 고점도 PBT 수지는 기존의 고점도 PBT 수지에 비해 압출속도를 향상시킬 수 있음을 그 특징으로 하고 있다.The present invention contains a polyfunctional branching agent and a nucleating agent in the polybutylene terephthalate (hereinafter referred to as PBT) resin to melt-polymerize and then solidify the polymer to increase the melt tension of the PBT resin, and the extrusion rate is higher than that of the conventional high viscosity PBT resin. As a method of producing a fast high viscosity resin, the high viscosity PBT resin prepared in this way is characterized in that the extrusion speed can be improved compared to the existing high viscosity PBT resin.

본 발명에서 사용되는 PBT 수지는 통상적으로 PBT 수지 제조에 사용되는 단량체인 디메틸테레프탈레이트와 1,4-부탄디올을 용융중합한 후 고상중합하여 제조한다.The PBT resin used in the present invention is prepared by melt polymerization of dimethyl terephthalate and 1,4-butanediol, which are monomers used in the manufacture of PBT resin, and then solid phase polymerization.

특히, 본 발명에 사용되는 2개 이상의 수산기가 함유된 다관능성 분지제는 PBT 수지의 압출공정시 용융장력을 높이고 압출부하를 낮추는 역할을 한다. PBT 수지를 광섬유 자케팅에 적용하는 경우에 광섬유가 자켓의 정중앙에 위치해야 하는데, 고속압출을 실시할 경우 용융장력이 부족하거나 느린 결정화속도에 의하여 광섬유가 자켓의 중앙에서 벗어나는 편심현상이 발생한다. 따라서, 고속압출을 실시할 경우 용융장력과 결정화 속도의 제어가 2개 이상의 수산기가 함유된 다관능성 분지제와 핵제를 첨가함으로 효과적으로 이루어지게 된다.In particular, the multifunctional branching agent containing two or more hydroxyl groups used in the present invention serves to increase the melt tension and lower the extrusion load during the extrusion process of the PBT resin. When PBT resin is applied to the optical fiber jacketing, the optical fiber should be located at the center of the jacket. When high-speed extrusion is performed, eccentricity may occur due to the lack of melt tension or the slow crystallization rate. Therefore, when the high-speed extrusion is carried out, the control of the melt tension and the crystallization rate is effectively achieved by adding a multifunctional branching agent and a nucleating agent containing two or more hydroxyl groups.

본 발명에서 사용되는 2개 이상의 수산기가 함유된 다관능성 분지제로는 글리세롤, 트리메틸올 프로판, 펜타에리쓰리톨, 디펜타에리쓰리톨, 소르비톨 및 1,2,6-헥산 트리올(1,2,6-hexane triol)로 탄소수가 2 ∼ 10의 폴리올 중에서 선택된 것을 사용한다. 본 발명에서 사용되는 다관능성 분지제의 함량은 본 발명에서 특별히 한정하지는 않지만 PBT 수지의 단량체인 디메틸테레프탈레이트에 대하여 0.1 ∼ 5 몰%, 바람직하게는 0.2 ∼ 1 몰%로 첨가한다. 이때, 그 함량이 0.1 몰% 미만이면 용융장력이나 전단점도 저하 면에서 큰 효과가 나타나지 않으며, 5 몰%가 초과되면 용융장력은 증가하나 분자간 가교의 형성으로 오히려 전단점도가 높아져 가공성이 저하되는 문제점이 발생하게 된다.Polyfunctional branching agents containing two or more hydroxyl groups used in the present invention include glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, sorbitol and 1,2,6-hexane triol (1,2, 6-hexane triol) is selected from polyols having 2 to 10 carbon atoms. Although the content of the polyfunctional branching agent used by this invention is not specifically limited in this invention, 0.1-5 mol%, Preferably it is 0.2-1 mol% with respect to the dimethyl terephthalate which is a monomer of a PBT resin. At this time, if the content is less than 0.1 mol%, there is no great effect in terms of melting tension or shear viscosity, and if it exceeds 5 mol%, the melt tension is increased, but the shear viscosity is increased due to the formation of intermolecular crosslinking. This will occur.

또한, 본 발명에서 분지제를 첨가하여 발생되는 결정화 속도의 저하를 최소화하기 위하여 핵제가 첨가된다. 본 발명에서 사용되는 핵제로는 상기 화학식 1로써 표시되는 것으로, 바람직하기로는 디메틸 테레프탈로일디옥시디벤조에이트In addition, in the present invention, a nucleating agent is added to minimize the decrease in the crystallization rate caused by adding the branching agent. Nucleating agent used in the present invention is represented by the formula (1), preferably dimethyl terephthaloyldioxydibenzoate

(dimethyl-terephthaloyl dioxy-dibenzoate) 및 디메틸테레프탈로일디옥시나프토에이트(dimethyl-terephtaloyl dioxy-naphtoate) 등이 사용된다.(dimethyl-terephthaloyl dioxy-dibenzoate) and dimethyl terephthaloyl dioxy-naphtoate and the like are used.

본 발명에서 사용되는 핵제의 함량은 전체 조성물에 대하여 1 ∼ 5 중량%로, 만일 그 함량이 1 중량% 미만이면 결정화 속도의 저하를 기대할 수 없으며 5 중량%가 초과되면 더 이상 결정화 속도가 증가하지 않게 된다.The content of the nucleating agent used in the present invention is 1 to 5% by weight based on the total composition, if the content is less than 1% by weight can not be expected to decrease the rate of crystallization, if more than 5% by weight does not increase the rate of crystallization Will not.

이에, 상기 조성 및 함량으로 PBT, 분지제 및 핵제를 함유시켜 용융중합하여 마스터 뱃치를 제조한 다음 고상중합을 한다. 상기 고상중합의 방법은 본 발명에서 특별히 한정하지는 않지만 170 ∼ 190℃의 온도범위에서 10 ∼ 13 시간동안 중합반응을 유지하는 것이 바람직하다. 이러한 방식으로 제조된 PBT 수지는 용융 유동지수가 7 ∼ 15의 범위로서 이는 압출공정에 있어서 압출부하를 줄일 수 있다.Thus, PBT, a branching agent, and a nucleating agent are contained in the composition and content to melt-polymerize to prepare a master batch, followed by solid phase polymerization. The solid phase polymerization method is not particularly limited in the present invention, but it is preferable to maintain the polymerization reaction for 10 to 13 hours in the temperature range of 170 to 190 ° C. The PBT resin produced in this way has a melt flow index in the range of 7 to 15, which can reduce the extrusion load in the extrusion process.

이와 같은 본 발명을 실시예에 의거 상세히 설명하겠는 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited by an Example.

실시예 1 ∼ 6 및 비교예 1 ∼ 2Examples 1-6 and Comparative Examples 1-2

다음 표 1의 조성을 가지도록 준비한 다음, 메틸테레프탈레이트(이하, DMT) 및 1,4-부탄디올(이하 1,4-BD)에 분지제로 글리세롤, 핵제로 디메틸테레프탈로일디옥시디벤조에이트 또는 디메틸테레프탈로일디옥시나프토에이트를 용융중합하여 마스터뱃치를 제조하였다. 상기 제조된 마스터뱃치를 원료로 회전식 증발건조기Prepared to have the composition of the following Table 1, then methyl terephthalate (hereinafter referred to as DMT) and 1,4-butanediol (hereinafter referred to as 1,4-BD) as a branching agent glycerol, nucleating agent dimethyl terephthaloyldioxydibenzoate or dimethyl terephthalate Masterbatches were prepared by melt polymerizing loyldioxynaphthoate. Rotary evaporator dryer as a raw material of the prepared master batch

(rotary evaporator)를 사용하여 185℃에서 12 시간동안 고상중합을 실시하여 PBT수지를 제조하였다.PBT resin was prepared by performing solid phase polymerization at 185 ° C. for 12 hours using a rotary evaporator.

시험예 : 용융장력 및 결정화 속도 상수Test Example: Melt Tension and Crystallization Rate Constant

상기 실시예 1 ∼ 6 및 비교예 1∼ 2에서 제조한 마스터 뱃치의 용융장력을 비교하기 위하여 캐필러리 유량계(capillary rheometer)를 이용하여 245℃의 온도에서 용융장력을 측정하였다.In order to compare the melt tension of the master batches prepared in Examples 1 to 6 and Comparative Examples 1 and 2, the melt tension was measured at a temperature of 245 ° C. using a capillary rheometer.

결정화 속도는 시차열분석기를 사용하여 실험하고, 아브라미식으로 속도상수를 이용하여 계산하였다. 결정화 속도상수의 측정은 테스트 시료를 샘플링한 후 시차열분석기에 넣고 상온에서 250℃까지 가열하여 충분히 용융한 후, 다시 195℃로 급속히 냉각하여 등온 상태에서 결정화하여 측정하였다.The crystallization rate was tested using a differential thermal analyzer, and calculated using the rate constant in Abrami's formula. The measurement of the crystallization rate constant was measured by sampling a test sample, placing it in a differential thermal analyzer, heating it to 250 ° C. at room temperature, melting it sufficiently, and then rapidly cooling to 195 ° C. to crystallize it in an isothermal state.

이와 같은 측정결과를 다음 표 1에 나타내었다.The measurement results are shown in Table 1 below.

상기 표 1에 나타낸 바와 같이, 분지제 및 핵제를 첨가하지 않은 비교예 1의 경우에는 용융장력이 실시예에 비해 현저히 낮음을 알 수 있다. 또한, 분지제만을 첨가하고, 핵제를 첨가하지 않은 비교예 2의 경우에는 용융장력은 실시예의 것들과 유사하나, 결정화 속도상수가 매우 낮음을 알 수 있다.As shown in Table 1, in the case of Comparative Example 1 without the addition of a branching agent and a nucleating agent it can be seen that the melt tension is significantly lower than the Example. In addition, in the case of Comparative Example 2 in which only the branching agent was added and the nucleating agent was not added, the melt tension is similar to those of the examples, but it can be seen that the crystallization rate constant is very low.

따라서, 분지제와 함께 적당량의 핵제를 첨가하여 제조할 경우, 고속 압출가공시 빠른 결정화 속도를 유지하면서 용융장력을 향상시킴으로써 생산성을 향상시킬 수 있다.Therefore, when the appropriate amount of nucleating agent is added together with the branching agent, the productivity can be improved by improving the melt tension while maintaining a fast crystallization rate during high-speed extrusion.

상술한 바와 같이, 본 발명에 따른 폴리부틸렌 테레프탈레이트 수지의 제조시 적당량의 분지제와 함께 핵제를 첨가함으로써, 빠른 결정화 속도를 유지시키고 용융장력이 높아 고속압출시 편심이 발생하는 것을 방지하여 고속압출을 가능케 할 수 있다. 따라서, 본 발명에 의해 제조된 고점도의 PBT 수지를 이용하여 광섬유 자켓팅용으로 적합하게 사용할 수 있다.As described above, in the preparation of the polybutylene terephthalate resin according to the present invention by adding a nucleating agent with an appropriate amount of branching agent, it maintains a fast crystallization rate and high melt tension to prevent the occurrence of eccentricity during high-speed extrusion high speed Extrusion may be possible. Therefore, it can be suitably used for optical fiber jacketing using the high viscosity PBT resin manufactured by this invention.

Claims (1)

디메틸테레프탈레이트와 1,4-부탄디올을 사용하여 제조하는 폴리부틸렌 테레프탈레이트 수지의 제조방법에 있어서,In the manufacturing method of polybutylene terephthalate resin manufactured using dimethyl terephthalate and 1, 4- butanediol, 2개 이상의 수산기가 함유된 다관능성 분지제를 상기 디메틸테레프탈레이트 1몰에 대하여 0.1 ∼ 5 몰%, 그리고0.1-5 mol% of the polyfunctional branching agent containing two or more hydroxyl groups with respect to 1 mol of said dimethyl terephthalates, and 다음 화학식 1로 표시되는 핵제를 디메틸테레프탈레이트, 1,4-부탄디올 및 다관능성 분지제의 혼합물 조성에 대하여 1 ∼ 5 중량%를 첨가하여 용융중합한 후, 고상중합 반응을 수행하여 제조하는 것을 특징으로 하는 폴리부틸렌 테레프탈레이트 수지의 제조방법.Next, the nucleating agent represented by Chemical Formula 1 is melt-polymerized by adding 1 to 5% by weight, based on the mixture composition of dimethyl terephthalate, 1,4-butanediol, and polyfunctional branching agent, followed by solid phase polymerization. The manufacturing method of polybutylene terephthalate resin made into. 화학식 1Formula 1 상기 화학식 1에서; R은 C1∼ C4의 알킬기를 나타내고; Ar 또는 Ar'는 서로 같거나 다른 것으로서, 벤젠 고리 또는 나프탈렌 고리를 나타낸다.In Chemical Formula 1; R represents an alkyl group of C 1 to C 4 ; Ar or Ar ', the same or different from each other, represents a benzene ring or a naphthalene ring.
KR1020000017894A 2000-04-06 2000-04-06 A process for preparing poly(butylene terephthalate) resin KR100435510B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020000017894A KR100435510B1 (en) 2000-04-06 2000-04-06 A process for preparing poly(butylene terephthalate) resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020000017894A KR100435510B1 (en) 2000-04-06 2000-04-06 A process for preparing poly(butylene terephthalate) resin

Publications (2)

Publication Number Publication Date
KR20010094303A KR20010094303A (en) 2001-10-31
KR100435510B1 true KR100435510B1 (en) 2004-06-10

Family

ID=19662105

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020000017894A KR100435510B1 (en) 2000-04-06 2000-04-06 A process for preparing poly(butylene terephthalate) resin

Country Status (1)

Country Link
KR (1) KR100435510B1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4184033A (en) * 1975-05-05 1980-01-15 General Electric Company Melt polymerization process for increasing the molecular weight of poly(1,4-butylene terephthalate)
KR940014512A (en) * 1992-12-29 1994-07-18 구창남 Method for preparing polybutylene terephthalate
US5688898A (en) * 1993-10-18 1997-11-18 E. I. Du Pont De Nemours And Company Polyesters production process
KR20010036052A (en) * 1999-10-05 2001-05-07 김윤 A process for preparing polybutylene terephthalate resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4184033A (en) * 1975-05-05 1980-01-15 General Electric Company Melt polymerization process for increasing the molecular weight of poly(1,4-butylene terephthalate)
KR940014512A (en) * 1992-12-29 1994-07-18 구창남 Method for preparing polybutylene terephthalate
US5688898A (en) * 1993-10-18 1997-11-18 E. I. Du Pont De Nemours And Company Polyesters production process
KR20010036052A (en) * 1999-10-05 2001-05-07 김윤 A process for preparing polybutylene terephthalate resin

Also Published As

Publication number Publication date
KR20010094303A (en) 2001-10-31

Similar Documents

Publication Publication Date Title
KR20210029500A (en) Polyester resion for preparing cation dye-PET fiber, Composite resin containing the same, Cation dye-PET fiber using the same, and Manufacturing method thereof
KR102079522B1 (en) Copolymerized polyester and polyester fiber formed from same
CA1153857A (en) Process for injection molding a polyester with improved crystallization thereof
CN110564124B (en) Composite material for improving compatibility and crystallinity of PLLA/PMMA and preparation method thereof
CN111808274A (en) Spinning filament type low-melting-point polyester chip and preparation method thereof
CN113272376A (en) Resin composition, molded body, optical lens, and optical lens unit
CN112662139B (en) High-melt-strength liquid crystal polyester resin composition for film and preparation method thereof
KR100435510B1 (en) A process for preparing poly(butylene terephthalate) resin
Misra et al. Block copolymers of poly (ethylene terephthalate–polybutylene terephthalate). I. Preparation and crystallization behavior
AU610306B2 (en) Elastomeric polymers
JPH10513210A (en) Copolyetherester
KR100446473B1 (en) High Viscosity Poly(butylene terephthalate) for high speed extrusion
JPS6410606B2 (en)
KR20010036052A (en) A process for preparing polybutylene terephthalate resin
CA1051626A (en) Polyurethane hard fiber
CN112135857A (en) Copolyester composition
JPH11323658A (en) Polyester fiber and its production
KR102564978B1 (en) Novel Polyester fiber for binder
US5232778A (en) Polyester fibers containing liquid crystal copolymer containing alkoxy-substituted para-phenylene terephthalate groups
KR100547355B1 (en) Polyester resin excellent in hydrophilicity and a method of manufacturing the same
JPS60126322A (en) Manufacture of blended polyurethane fiber
KR100323611B1 (en) Manufacturing method of high shrinkage polyester bland
CN116096778A (en) Low melting copolyetherester
CN113638071A (en) Preparation method of polyolefin composite fiber
JPH03243649A (en) Modified polyester composition

Legal Events

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

Payment date: 20130228

Year of fee payment: 10

FPAY Annual fee payment

Payment date: 20140312

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20150310

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20160304

Year of fee payment: 13

FPAY Annual fee payment

Payment date: 20170306

Year of fee payment: 14

FPAY Annual fee payment

Payment date: 20180305

Year of fee payment: 15