KR20010049104A - Polymerization apparatus for polyester - Google Patents

Polymerization apparatus for polyester Download PDF

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Publication number
KR20010049104A
KR20010049104A KR1019990054049A KR19990054049A KR20010049104A KR 20010049104 A KR20010049104 A KR 20010049104A KR 1019990054049 A KR1019990054049 A KR 1019990054049A KR 19990054049 A KR19990054049 A KR 19990054049A KR 20010049104 A KR20010049104 A KR 20010049104A
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South Korea
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reactor
prepolymer
inert gas
polyester
ethylene glycol
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KR1019990054049A
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Korean (ko)
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이귤섭
최영찬
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조정래
주식회사 효성
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Priority to KR1019990054049A priority Critical patent/KR20010049104A/en
Publication of KR20010049104A publication Critical patent/KR20010049104A/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
    • C08G63/02—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
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/785—Preparation processes characterised by the apparatus used
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings

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  • 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

PURPOSE: A polyester polymerizing device is provided which increases a polymerizability of prepolymer and has a simple structure. CONSTITUTION: The device, which produces polyester polymer by directly esterifying terephthalic acid or ester-forming derivative thereof and ethylene glycol or ester-forming derivative to prepare a prepolymer and then performing a polycondensation of the prepolymer, comprises: (i) a DE heater(1); (ii) a DE evaporator(2); (iii) a DE column(3); (iv) a DE condenser(4); (v) a filter(5); (vi) an oligomer line(6); (vii) an additive manufacturing device(7); (viii) a PC-1 reactor(8) which is a prepolymerization reactor; (ix) an inert gas supplying device(9); (x) a scrubber(10); (xi) an ejector(11); and (xii) an absorber(12), where the inert gas supplying device is connected to the PC-1 reactor.

Description

폴리에스테르 중합장치 {Polymerization apparatus for polyester}Polyester polymerization apparatus for polyester

본 발명은 폴리에스테르의 중합장치에 관한 것으로, 더욱 상세하게는 써멀 싸이폰(Thermal syphon)방식을 채택한 루프 반응기에서 테레프탈산과 에틸렌글리콜을 원료로 하여 직접 에스테르화법으로 에스테르화 반응을 시키고, 중축합 반응기에서 중축합 촉매의 존재하에서 중축합 반응을 일으켜서 폴리에스테르를 제조하는데 있어서, 프리폴리머(prepolymer)를 제조하는 PC-1 반응기에 불활성 기체를 불어넣어 주어 반응물의 혼합성(mixing성)을 향상시켜 줌으로서 다음 단계로 이송되는 중합물의 중합도를 높여줄 수 있게 한 것을 특징으로 하는 폴리에스테르 중합장치에 관한 것이다.The present invention relates to a polymerization apparatus of polyester, and more particularly, to a esterification reaction by a direct esterification method using terephthalic acid and ethylene glycol as a raw material in a loop reactor adopting a thermal syphon method, and a polycondensation reactor. In the polycondensation reaction in the presence of a polycondensation catalyst at to prepare a polyester, by inert gas is blown into the PC-1 reactor to prepare a prepolymer to improve the mixing properties of the reactants It relates to a polyester polymerization apparatus characterized in that it is possible to increase the degree of polymerization of the polymer to be transferred to the next step.

일반적으로 폴리에스테르를 제조하는 방법은 테레프탈산과 에틸렌글리콜을 원료로 하여 에스테르화 반응을 시키며 이때 생성되는 물을 증류탑을 통해 제거하면서 에스테르화 반응율이 90 ∼ 98% 정도의 올리고머를 얻은 다음 생성된 올리고머를 중축합 반응기로 이송하고 여기에 중축합 반응 촉매를 첨가하고 270 ∼ 300℃의 고온, 고진 공하에서 중축합 반응을 수행하여 최종 제품의 폴리에스테를 얻는다.In general, a method for preparing polyester is an esterification reaction using terephthalic acid and ethylene glycol as raw materials. At this time, water produced is removed through a distillation column to obtain an oligomer having an esterification rate of about 90 to 98%, and then the resulting oligomer Transfer to a polycondensation reactor, to which a polycondensation reaction catalyst is added, and polycondensation reaction is performed under high temperature and high vacuum of 270-300 degreeC, and the polyester of a final product is obtained.

에스테르화 반응에서는 고체상태의 테레프탈산과 액상의 에틸렌글리콜의 유동성을 좋게 하기 위해 이론적으로 요구되는 필요량보다 에틸렌글리콜을 1.1 ∼ 2.0 의 몰비로 많이 사용하게 된다. 이때 과잉의 에틸렌글리콜은 반응기로 순환시키거나 계외로 빼내어 원료 에틸렌글리콜과 혼합하여 원료로 재사용 한다. 에스테르화 반응시 부산물로 물이 생기는바 이 물을 빨리 제거해야 정반응으로 반응이 잘 이루어지며 이를 위해 정류탑을 설치하여 에틸렌글리콜과 물을 분리하여 상부에서 물을 유출시킨다.In the esterification reaction, ethylene glycol is used in a molar ratio of 1.1 to 2.0 more than the theoretically required amount in order to improve the fluidity of the solid terephthalic acid and the liquid ethylene glycol. At this time, the excess ethylene glycol is circulated to the reactor or taken out of the system and mixed with the raw material ethylene glycol and reused as raw materials. Water is generated as a by-product during the esterification reaction, and the water must be removed quickly so that the reaction is well performed. For this purpose, a rectification tower is installed to separate the ethylene glycol and the water and to drain the water from the top.

에스테르화 반응을 마친 올리고머는 프리폴리머리제이션(prepolymerization)을 수행하는 반응기로 이송되어서 중합도 30정도의 프리폴리머(prepolymer)를 생성시키는 바, 본 발명처럼 에스테르화 반응공정에서 루프 반응기를 사용하는 공정에서는 공급되는 올리고머의 중합도가 낮기 때문에 프리폴리머리제이션(prepolymerization) 반응기에서 프리폴리머의 중합도를 올리는데는 한계가 있다. 이와 같은 이유 때문에 그 뒷단계의 중축합 반응기에서 좀더 가혹한 조건으로 중축합 반응을 수행하게 되므로 분해반응을 촉진시켜 최종 제품의 품질을 떨어뜨리게 된다.After completion of the esterification reaction, the oligomer is transferred to a reactor that performs prepolymerization to produce a prepolymer having a degree of polymerization of about 30. In the process of using a loop reactor in an esterification process as in the present invention, the oligomer is supplied. Due to the low degree of polymerization of the oligomers, there is a limit to raising the degree of polymerization of the prepolymer in the prepolymerization reactor. For this reason, the polycondensation reaction is carried out in more severe conditions in the polycondensation reactor in the later stage, thereby promoting decomposition reactions and degrading the quality of the final product.

종래에는 이와 같은 문제점을 해결하기 위해 최종 반응장치에 불활성 기체를 불어주어 폴리머의 순도를 높여주고 있으나, 이 방법은 투입되는 프리폴리머의 중합도가 일반적인 수준인 30이상에서 실시해야 효과가 있으며 또한 최종 중합장치를 새롭게 제조하여야만 실시할 수 있는 방법이므로 본 발명의 중합장치에 적용하기는 어렵다.Conventionally, in order to solve this problem, inert gas is blown into the final reactor to increase the purity of the polymer. However, this method is effective only when the degree of polymerization of the prepolymer to be introduced is at a general level of 30 or more. It is difficult to apply to the polymerization apparatus of the present invention because it is a method that can be carried out only when newly manufactured.

본 발명은 상기한 바와 같은 문제점을 개선하기 위하여 프리폴리머의 중합도를 높여줄 수 있으며 구조가 간단한 프리폴리머리제이션 반응기를 제공하는데 그 목적이 있는 것이다.The present invention is to provide a prepolymerization reactor that can increase the degree of polymerization of the prepolymer and has a simple structure in order to improve the problems as described above.

도 1 은 본 발명 중합장치의 개략도1 is a schematic view of the polymerization apparatus of the present invention

* 도면의 주요 부분에 대한 부호 설명 *Explanation of symbols on the main parts of the drawings

1 : 디이 히터(DE Heater), 2 : 디이 증발기(DE Evaporater),1: DE Heater, 2: DE Evaporater,

3 : 디이 정류탑(DE Column), 4 : 디이 콘덴서(DE Condenser),3: DE column, 4: DE condenser,

5 : 필터, 6 : 올리고머 라인(Oligomer line),5: filter, 6: oligomer line,

7 : 첨가제 제조장치, 8 : PC-1 반응기,7: additive manufacturing apparatus, 8: PC-1 reactor,

9 : 불활성 기체 공급장치, 10 : 스쿠루버(Scrubber),9: inert gas supply device, 10: Scrubber (Scrubber),

11 : 이젝터(Ejector), 12 : 흡착기(Absorber).11: Ejector, 12: Absorber.

도 1 은 에스테르화 반응장치와 프리폴리머리제이션 반응장치로 구성되어 있는 본 발명의 개략도 이다. 테레프탈산과 에틸렌글리콜의 슬러리는 디이 히터(1) 하단부로 부터 공급받아 에스테르화 반응을 시키며 이후 디이 증발기(2)로 이송된다. 디이 증발기(2)에서 유출되는 올리고머는 다시 디이 히터(1)로 공급되어 계속 순환시키면서 일정한 비중에 다달았을때 프리폴리머리제이션 반응기로 이송하게 된다. 반응중 발생한 물과 에틸렌글리콜은 디이 정류탑(3)에서 분리하여 물은 디이 콘덴서(4)에서 응축하여 계외로 빠져 나가게 된다.1 is a schematic diagram of the present invention consisting of an esterification reactor and a prepolymerization reactor. Slurry of terephthalic acid and ethylene glycol is fed from the lower end of the die heater (1) for the esterification reaction and then transferred to the die evaporator (2). The oligomer exiting from the evaporator (2) is supplied to the Dee heater (1) again and continues to circulate and is transferred to the prepolymerization reactor when a certain specific gravity is reached. Water and ethylene glycol generated during the reaction are separated in the DI rectification tower (3), and water is condensed in the DI condenser (4) to exit the system.

디이 증발기(2)에서 유출된 올리고머는 필터(5)를 거쳐 첨가제 제조장치(7)에서 공급된 첨가제와 함께 올리고머 라인(6)에서 합쳐진 후 프리폴리머리제이션 반응기인 PC-1 반응기(8)로 이송된다. 이때 PC-1 반응기(8) 하단에 불활성 기체 공급장치(9)에서 제조한 질소와 같은 불활성 기체를 불어 넣어 주어서 반응기내에서의 혼합성을 좋게 해 준다. 생성된 프리폴리머는 다음 단계의 중축합 반응기로 이송되며 반응중 생성된 에틸렌글리콜은 스쿠루버(10), 이젝터(11)를 거쳐 탄소입자가 충전되 있는 흡착기(12)를 통과하게 된다. 이때 흡착기(12)에서 저분자량의 올리고머와 기타 불순물들은 흡수되므로 유출된 에틸렌글리콜은 깨끗한 상태로 첨가제 제조장치(7)에 다시 공급해 사용하게 되며, 질소가스는 불활성 기체 공급장치(9)로 들어가 순환시켜 사용하게 된다.The oligomer outflow from the DI evaporator (2) is combined in the oligomer line (6) together with the additive supplied from the additive manufacturing apparatus (7) via the filter (5) and then transferred to the PC-1 reactor (8), which is a prepolymerization reactor. do. At this time, an inert gas such as nitrogen produced by the inert gas supply device 9 is blown to the bottom of the PC-1 reactor 8 to improve the mixing property in the reactor. The produced prepolymer is transferred to the polycondensation reactor of the next step, and the ethylene glycol produced during the reaction passes through the squeuber 10 and the ejector 11 to the adsorber 12 in which carbon particles are charged. At this time, since the low molecular weight oligomer and other impurities are absorbed by the adsorber 12, the ethylene glycol leaked out is supplied to the additive manufacturing apparatus 7 in a clean state, and nitrogen gas enters the inert gas supply apparatus 9 and circulates. Will be used.

실시예 1∼6 및 비교예Examples 1-6 and Comparative Examples

테레프탈산 24kg/hr, 에틸렌글리콜 15kg/hr의 유량으로 슬러리를 조제해 디이 히터(1) 하단부에 투입하면서 디이 히터(1) 온도는 280℃로 유지시키고 디이 증발기(2)는 281℃로 유지시키면서 임펠러로 교반시켰다. 상기 상태에서 3시간 30분 동안 반응물을 디이 히터(1)와 디이 증발기(2)간에 순환시키고 발생된 물과 에틸렌글리콜은 디이 정류탑(3)에서 분리하였다. 첨가제로는 소광제인 이산화 티탄(TiO2)와 촉매인 삼산화 안티몬(Sb2O3)를 250ppm, 300ppm의 농도로 공급하였고, PC-1 반응기(8)는 283℃로 유지시키며 1시간 동안 반응시켰다. 이때 PC-1 반응기(8) 하단에 공급하는 질소가스는 285℃로 가열하여 3m/분의 속력으로 불어 넣어 주었으며 생성된 에틸렌글리콜은 첨가제 제조장치(7)에 재공급 하였다. 질소가스 공급조건에 따른 물성차를 보기 위해 표 1 과 같이 여러 조건으로 제조하였다.The slurry was prepared at a flow rate of 24 kg / hr of terephthalic acid and 15 kg / hr of ethylene glycol and injected into the lower part of the die heater 1, while the die heater 1 temperature was maintained at 280 ° C. and the die evaporator 2 was kept at 281 ° C. with an impeller. Stirred. In the above state, the reaction was circulated between the Dee Heater 1 and the Dee Evaporator 2 for 3 hours 30 minutes, and the generated water and ethylene glycol were separated from the Dee rectifier 3. As an additive, titanium dioxide (TiO 2 ) as a quencher and antimony trioxide (Sb 2 O 3 ) as a catalyst were supplied at a concentration of 250 ppm and 300 ppm, and the PC-1 reactor 8 was maintained at 283 ° C. for 1 hour. . At this time, the nitrogen gas supplied to the bottom of the PC-1 reactor 8 was heated to 285 ℃ and blown at a speed of 3m / min and the produced ethylene glycol was re-supplied to the additive manufacturing apparatus (7). In order to see the difference in physical properties according to the nitrogen gas supply conditions were prepared under various conditions as shown in Table 1.

생성된 프리폴리머의 중합도, 카르복실 말단기를 측정한 결과는 표 1 과 같다.The result of measuring the polymerization degree and carboxyl end group of the produced prepolymer is shown in Table 1.

주)1. 실시예 1∼2는 질소투입량만 변경, 3∼4는 투입 속도만 변경, 5∼6은 온도만 변경함.Note 1 Examples 1 to 2 only changed the nitrogen input amount, 3 to 4 only the input rate, and 5 to 6 only the temperature.

표 1 로 알수 있는 바와 같이 질소가스를 공급한 경우는 공급하지 않은 경우에 비하여 수평균 중합도가 5이상 올라갔으며 카르복실 말단기도 10meq/kg 이상 줄어들어 고중합도의 프리폴리머를 얻을 수 있었다.As can be seen from Table 1, when the nitrogen gas was supplied, the number average degree of polymerization was increased by 5 or more compared with the case where the nitrogen gas was not supplied, and the carboxyl end group was reduced by 10 meq / kg or more, thereby obtaining a high degree of polymerization.

본 발명의 중합장치를 사용했을 때 프리폴리머의 중합도는 기존보다 5 ∼ 10 정도 올라 갔으며 카르복실 말단기도 10 ∼ 20meq/kg 정도 줄어 들었다. 아울러 유출된 에틸렌글리콜은 정제된 후 재사용 되므로 원가절감을 통한 생산성을 높일 수 있었고 환경 오염의 원인이 되는 유기 불순물을 계내에서 제거해 줌으로 환경 친화적인 이점도 있다.When the polymerization apparatus of the present invention was used, the degree of polymerization of the prepolymer was increased by 5 to 10 and the carboxyl end group was reduced by about 10 to 20 meq / kg. In addition, the spilled ethylene glycol can be purified and reused to increase productivity through cost reduction, and also have an environmentally-friendly advantage by removing organic impurities that cause environmental pollution in the system.

Claims (2)

테레프탈산 또는 그 에스테르형성성 유도체와 에틸렌글리콜 또는 그 에스테르형성성 유도체를 원료로 사용하여 직접 에스테르화하고 프리폴리머를 제조한 후 중축합 시켜서 폴리에스테르 중합체를 제조하는 폴리에스테르 중합장치에 있어서, 프리폴리머리제이션(prepolymerization) 반응기인 PC-1 반응기(8)에 불활성 기체를 불어넣어 주는 불활성 기체 공급장치(9)를 연결시킨 것을 특징으로 하는 폴리에스테르 중합장치.In the polyester polymerization apparatus which produces a polyester polymer by directly esterifying using terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative as a raw material, preparing a prepolymer, and then polycondensing it, the prepolymerization ( A polyester polymerization apparatus characterized by connecting an inert gas supply device (9) for blowing an inert gas into a PC-1 reactor (8), which is a prepolymerization reactor. 제 1 항에 있어서 불활성 기체의 이송라인에 저비점 유기물들을 흡수할 수 있는 흡착기(12)를 연결시킨 것을 특징으로 하는 폴리에스테르 중합장치.The polyester polymerization apparatus as claimed in claim 1, wherein an adsorber (12) capable of absorbing low-boiling organics is connected to a transfer line of inert gas.
KR1019990054049A 1999-11-30 1999-11-30 Polymerization apparatus for polyester KR20010049104A (en)

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