KR930002208B1 - Process for the preparation of polyester - Google Patents
Process for the preparation of polyester Download PDFInfo
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- KR930002208B1 KR930002208B1 KR1019870015600A KR870015600A KR930002208B1 KR 930002208 B1 KR930002208 B1 KR 930002208B1 KR 1019870015600 A KR1019870015600 A KR 1019870015600A KR 870015600 A KR870015600 A KR 870015600A KR 930002208 B1 KR930002208 B1 KR 930002208B1
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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
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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
- C08G63/80—Solid-state polycondensation
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Abstract
Description
제1도 및 제2도는 본발명 고중합도 폴리에스터의 제조방법에 대한 공정개략 예시도로서, 부호에 대한 설명을 가하면 다음과 같다.1 and 2 is a schematic view showing the process of the manufacturing method of the present invention, a high degree of polymerization polyester, the description of the reference is as follows.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 용융 중합조 2 : 용융 프리폴리머 스트링1: melt polymerization tank 2: melt prepolymer string
3 : 불활성액체 냉각조 3' : 수냉각조3: inert liquid cooling tank 3 ': water cooling tank
4 : 결정화 프리폴리머 스트링 5 : 펠레타이저4: crystallization prepolymer string 5: pelletizer
6 : 칩6: chip
본 발명은 고중합도 폴리에스터의 제조방법에 관한 것이다. 상세하게는 용융중합조에서 배출되는 폴리에스터 프리폴리머 스트링(String)을 고온의 불활성 액체나 물에서 서서히 냉각시켜 프리폴리머 스트링을 결정화시킴으로써 고상중합시 별도의 결정화 단계를 생략할 수 있고 칩의 스티킹(Sticking) 방지 및 고상중합시간을 단축할 수 있는 고중합도 폴리에스터의 제조방법에 관한 것이다.The present invention relates to a method for producing a high degree of polymerization polyester. Specifically, the polyester prepolymer string discharged from the melt polymerization tank is gradually cooled in a high temperature inert liquid or water to crystallize the prepolymer string so that a separate crystallization step can be omitted during solid phase polymerization and sticking of chips. The present invention relates to a method for producing a high degree of polymerization polyester capable of preventing and shortening the time of solid phase polymerization.
일반적으로 폴리에스터는 자체의 우수한 물성으로 인해 섬유, 필름, 병(Bottle)등의 제조에 광범위하게 이용되고 있다. 그런데 산업용으로 쓰이는 섬유, 병등 강한 물성을 요구하는 용도로 사용될 경우 중합도가 높은 폴리에스터를 필요로 하게되며, 이를 위해서 통상 용융중합후 프리폴리머를 칩으로 만들고 이것을 고상중합시켜 중합도를 높이고 있다.In general, polyester is widely used in the manufacture of fibers, films, bottles, etc. because of its excellent physical properties. However, when it is used for industrial applications such as fibers, bottles, etc. that require strong physical properties, a high degree of polymerization is required for polyester. To this end, prepolymerization is usually made after melting polymerization into chips and solidified to increase the degree of polymerization.
또한 종래의 경우 고상중합은 테레프탈산과 에틸렌 글리콜을 용융중합한 다음 극한 점도가 0.3dl/gr이상인 프리폴리머를 제조하고 이를 스트링 상태로 배출하여 냉수조에서 급냉시켜 비정형 상태로 한다음 절단하여 칩화한후 고상중합을 실시하였다. 그러나 상기의 방법에 따라 제조된 칩은 비정형인 관계로 고상중합공정에서 온도를 급격히 상승시킬 경우 비정형의 칩간에 스티킹이 일어나 칩들이 괴형(塊形)화 되기 때문에 고상중합속도가 저하되고, 덩어리가 커질경우 취급이 또한 어렵게 되기 때문에 고상중합전 칩을 별도의 결정화조나 고상중합기내에서 결정화시킨 다음 고상중합을 실시하여야 하였다.In the conventional case, the solid phase polymerization is a melt polymerization of terephthalic acid and ethylene glycol, and then a prepolymer having an intrinsic viscosity of 0.3 dl / gr or more is prepared, discharged in a string state, quenched in a cold water tank to be in an amorphous state, cut into chips, and then solidified. The polymerization was carried out. However, chips manufactured according to the above method are atypical, so if the temperature is rapidly increased in the solid-state polymerization process, sticking occurs between the atypical chips, resulting in agglomeration of the chips. Since the handling becomes difficult, the chips had to be crystallized in a separate crystallization tank or solid-state polymerizer and then subjected to solid-state polymerization.
그런데 상기의 방법에 의할경우 칩을 결정화 하는데 상당한 시간이 소요될 뿐만 아니라 결정화 완료시까지 칩의 승온속도를 빠르게 할수 없어 고상중합을 수행할 수 있는 적정온도까지의 승온시간에 장시간이 소요되어 고상중합을 완료하는데는 많은 시간이 소비되는 문제점이 있었다.However, according to the above method, it takes not only a considerable time to crystallize the chip, but also a long time in the temperature rise time to a proper temperature to perform the solid phase polymerization because the temperature rise rate of the chip cannot be increased until the crystallization is completed. There was a problem that takes a lot of time to complete.
따라서 본 발명자들은 이같은 종래의 문제점을 해결하기 위해 비정형 폴리에스터 프리폴리머 칩의 결정화현상을 예의 주시하여 연구한 결과 용융 중합후 프리폴리머 스트링을 냉수에 급냉시켜 비정형 상태로 만드는 종래의 방법을 탈피하여 용융 중합조로부터 배출되는 프리폴리머 스트링을 140 내지 190℃인 고온의 불활성 액체(비점 140 내지 210℃)로 채워진 냉각조를 이용 서냉시키거나, 60 내지 100℃의 물로 채워진 냉각조를 잠깐 통과시켜 스트링 상태를 만든후 대기중에서 서냉시켜 프리폴리머 스트링을 결정화하고 이를 칩상으로 절단하여 고상중합을 실시하는 것을 특징으로한 본 발명을 완성하게 되었다.Therefore, the present inventors have carefully studied the crystallization phenomenon of the amorphous polyester prepolymer chip to solve such a conventional problem, and as a result, the molten polymerization tank is removed from the conventional method of quenching the prepolymer string in cold water and making it into an amorphous state after melt polymerization. The prepolymer string discharged from the mixture is slowly cooled using a cooling tank filled with a high temperature inert liquid (boiling point 140 to 210 ° C.), or briefly passed through a cooling tank filled with water at 60 to 100 ° C. to form a string state. The present invention has been accomplished by crystallizing a prepolymer string by cooling in air and cutting it into chips to perform solid phase polymerization.
본 발명의 방법에 있어서 불활성 액체가 채워진 냉각조의 길이는 2.0 내지 3.0m인 것이 적당하며, 물로 채워진 냉각조를 통과하는 시간은 1 내지 5초의 범위가 바람직하다. 사용될 수 있는 불활성 액체로는 듀렌, 노멀부틸 벤젠, 이소듀렌, 인데칸, 도데칸, 트리데칸, 테트라데칸 등이다.In the method of the present invention, the length of the cooling tank filled with the inert liquid is suitably 2.0 to 3.0 m, and the time for passing through the cooling tank filled with water is preferably in the range of 1 to 5 seconds. Inert liquids that may be used are durene, normal butyl benzene, isdurene, indecane, dodecane, tridecane, tetradecane and the like.
본 발명에 따라 고중합도 폴리에스터를 제조할 경우 종래의 방법에 비해 폴리에스터의 물성저하 없이 고상중합의 생산효율을 향상시킬 수 있을 뿐만 아니라 고상중합 주기를 단축시킬수가 있다. 이하 본 발명을 첨부된 도면 및 실시예에 의거 상세히 설명한다.According to the present invention, when manufacturing a high degree of polyester, the production efficiency of the solid phase polymerization can be improved as well as the solid phase polymerization cycle can be shortened without deteriorating the physical properties of the polyester compared to the conventional method. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and examples.
[실시예 1]Example 1
제1도에서 보는바와 같이 데레프탈산과 에틸렌 글리클 및 중합촉매, 열안정제를 회분식 용융중합조(1)에서 용융중합한후 원형의 배출노즐을 통해 극한점도가 0.55dl/gr인 폴리에스터 프리폴리머(2)를 도데칸으로 채워진 길이 2.5m 온도 140℃의 불활성 액체 냉각조(3)로 배출시켜 서냉시킨후 펠레타이저(5)를 이용 4×4×2mm의 칩(6)으로 만들었다. 수득한 칩을 회분식 고상중합기에 투입하여 0.5mmHg의 감압하에서 200℃까지 승온(승온시간 5시간, 200℃이상 유지시간 6시간) 시켜 고상중합시킨후 3시간 정도 쿨링시켜 180℃가 되게하여 고상중합기에서 칩을 배출시킨 결과 칩간의 융착현상이 발견되지 않았으며, 도데칸 용액도 고상중합 반응시 고온, 강압으로 인해 칩으로 부터 완전히 제거되었음을 알수 있었다.As shown in FIG. 1, a polyester prepolymer having an ultimate viscosity of 0.55 dl / gr through a circular discharge nozzle after melt-polymerizing a derephthalic acid, ethylene glycol, a polymerization catalyst, and a thermal stabilizer in a batch melt polymerization tank (1) 2) was discharged into an inert liquid cooling bath 3 having a length of 2.5 m and a temperature of 140 ° C. filled with dodecane, and then cooled slowly to form a chip 6 of 4 × 4 × 2 mm using a pelletizer 5. The obtained chips were put into a batch solid-state polymerizer and heated to 200 ° C. under a reduced pressure of 0.5 mmHg (5 hours of elevated temperature, 6 hours of holding time over 200 ° C.), and then subjected to solid phase polymerization for 3 hours to be cooled to 180 ° C. in solid phase. As a result of discharging the chip from the agitator, fusion between chips was not found, and the dodecane solution was completely removed from the chip due to high temperature and pressure during solid phase polymerization.
[실시예 2]Example 2
냉각조의 온도를 160℃로 한것외에는 (실시예 1)과 동일하게 실시하였다.It carried out similarly to (Example 1) except having made the temperature of the cooling tank 160 degreeC.
[실시예 3]Example 3
[실시예 1]과 같이 폴리에스터 프리폴리머를 중합하되 제2도와 같이 냉각조(3')에 물을 채워 85℃로 가열시킨후 용융중합조(1)로 부터 배출되는 프리폴리머(2)를 3초간 통과시킨다음 대기중에서 서냉시켜 펠레타이저(5)를 이용 4×4×2mm의 칩(6)으로 만들어 [실시에 1]과 동일한 방법으로 고상중합을 실시하였다.Polymerization of the polyester prepolymer as shown in Example 1, but filled with water in the cooling tank (3 ') as shown in Figure 2 and heated to 85 ℃ and the prepolymer (2) discharged from the melt polymerization tank (1) for 3 seconds After passing through, it was cooled slowly in the air, and the pelletizer 5 was used to make a chip 6 of 4 × 4 × 2 mm, and solid-phase polymerization was carried out in the same manner as in [Example 1].
[비교예 1-2]Comparative Example 1-2
[실시예 1]과 같은 방법으로 폴리에스터 프리폴리머를 중합한후 온도가 15℃인 물로 채워진 냉각조로 배출시켜 프리폴리머를 급냉시킨후 칩화하여 고상중합을 실시하였다.After polymerizing the polyester prepolymer in the same manner as in [Example 1], it was discharged into a cooling tank filled with water having a temperature of 15 ° C. to quench the prepolymer, and then chipped to conduct solid phase polymerization.
이상의 실시예 및 비교에 결과를 하기표에 정리하였다.The results in the above examples and comparisons are summarized in the table below.
[표][table]
(참고) (1) 극한 점도 : 페놀 1, 1, 2, 2-테트라 클로로 에탄(3/2 중량비) 혼합용애에 칩을 용해시킨후 25℃에서 우베로드 점도계로 측정(Reference) (1) Intrinsic Viscosity: After dissolving the chip in the mixture of phenol 1, 1, 2, 2-tetrachloroethane (3/2 weight ratio), measure with Uberod viscometer at 25 ℃
(2) 카복실말단기 농도(CEG) : 어낼리티컬 케미스트리 제26권 1614페이지(1954)에 기재되어 잇는 폴(Phol)의 방법에 의해 측정(2) Carboxyl terminal concentration (CEG): measured by the method of Phol described in Analytic Chemical Chemistry, Volume 26, page 1614 (1954).
(3)결정화도(3) crystallinity
Dx : 칩의 밀도Dx: chip density
Da : 폴리에스터 완전 비정형의 밀도.Da: density of polyester complete amorphous.
Dc : 폴리에스터 완전 결정형의 밀도.Dc: density of polyester fully crystalline form.
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KR1019870015600A KR930002208B1 (en) | 1987-12-31 | 1987-12-31 | Process for the preparation of polyester |
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KR1019870015600A KR930002208B1 (en) | 1987-12-31 | 1987-12-31 | Process for the preparation of polyester |
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KR930002208B1 true KR930002208B1 (en) | 1993-03-27 |
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