KR100244911B1 - Polymerization method of polyester polymer - Google Patents
Polymerization method of polyester polymer Download PDFInfo
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- KR100244911B1 KR100244911B1 KR1019950066478A KR19950066478A KR100244911B1 KR 100244911 B1 KR100244911 B1 KR 100244911B1 KR 1019950066478 A KR1019950066478 A KR 1019950066478A KR 19950066478 A KR19950066478 A KR 19950066478A KR 100244911 B1 KR100244911 B1 KR 100244911B1
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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
- C08G63/02—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
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Abstract
본 발명은 폴리에틸렌테레프탈레이트를 주반복 단위로 하는 폴리에스터 폴리머의 중합에 있어서 디카르복실산 성분과 디올성분의 에스테르화 반응중에 발생하는 지방족 디올을 에스테르화 반응기로 환류시키면서 폴리에스터 폴리머의 디에틸렌글리콜의 함량을 조절함을 특징으로 하는 폴리에스터 폴리머의 중합방법에 관한 것으로, 개별 제품에 요구되는 물성의 폴리에스테르를 하나의 연속공중합기에서 제조하는 것이 가능하므로 설비비 및 제조원가를 절감할 수 있는 장점이 있다.The present invention relates to diethylene glycol of a polyester polymer while refluxing an aliphatic diol generated during the esterification reaction between a dicarboxylic acid component and a diol component in the polymerization of a polyester polymer containing polyethylene terephthalate as a main repeating unit to an esterification reactor. The present invention relates to a polymerization method of a polyester polymer characterized by controlling the content of, and it is possible to manufacture polyester of physical properties required for individual products in one continuous copolymerizer, which has the advantage of reducing equipment cost and manufacturing cost. have.
Description
본 발명은 폴리에스테르 원사, 필름, 산업용사, 보틀(bottle)등을 제조함에 있어서, 상기 각 제품에 요구되는 물성의 폴리에스테르 폴리머를 하나의 연속공중합기에서 제조하는 폴리에스테르 폴리머의 제조방법에 관한 것이다.The present invention relates to a method for producing a polyester polymer in the production of polyester yarns, films, industrial yarns, bottles, etc., the polyester polymer of the physical properties required for each of the products in one continuous copolymerizer. will be.
보다 상세하게는, 폴리에틸렌 테레프탈레이트(Polyethylene Terephtha-late : 이하 폴리에스테르라 함)로 연속중합공정에서 폴리에스테르 원사, 필름, 산업용사, 보틀용 폴리머을 제조함에 있어서, 원료, 촉매등을 변경하거나 설비를 개조하지 않고도 폴리에스테르 제조전에 에스테르화 반응에 의해 발생되는 올리고머의 물성을 콘트롤함으로써 하나의 연속중합기에서도 각 제품에 요구되는 폴리에스테르 폴리머를 제조할 수 있는 폴리머 중합방법에 관한 것이다.More specifically, in the production of polyester yarns, films, industrial yarns, and bottles for polymers in a continuous polymerization process with polyethylene terephtha-late (hereinafter, referred to as polyester), raw materials, catalysts, or the like may be changed. The present invention relates to a polymer polymerization method capable of producing polyester polymers required for each product even in one continuous polymerizer by controlling physical properties of oligomers generated by esterification before polyester production without modification.
종래, 폴리에스테르 연속중합기에서는 다양한 제품을 생산해내지 못하고 한가지 품목만 계속 생산하기 때문에 다른 제품을 생산하기 위해서는 원료나 촉매를 변경하거나 설비를 개조해야 하므로 설비비 및 제조원가의 상승을 야기할 뿐만 아니라, 운전조건을 변경할 경우 제품의 손실 및 에너지 상승을 초래하는 등의 문제점이 있었다.Conventionally, polyester continuous polymerizers cannot produce various products and continue to produce only one item. Therefore, in order to produce other products, it is necessary to change raw materials or catalysts or to remodel facilities, resulting in an increase in equipment costs and manufacturing costs. If the conditions were changed, there were problems such as loss of product and increase of energy.
따라서 본 발명의 목적은 연속식 중합기를 이용하여 폴리에스테르를 제조함에 있어서 원료, 촉매조성, 설비 및 전체 운전조건의 변경없이 원사, 필름, 산업용사, 보틀등 각 용도의 제품이 요구하는 물성의 폴리에스테르를 제조하기 위한 방법을 제공하는 데 있다.Accordingly, an object of the present invention is to prepare a polyester by using a continuous polymerizer, and to obtain a poly-polymer of physical properties required for each application such as yarn, film, industrial yarn, and bottle without changing raw materials, catalyst composition, equipment, and overall operating conditions. It is to provide a method for preparing an ester.
즉, 본 발명에서 언급되는 물성중 일반적으로 보틀은 유연하고 연신율이 우수한 특성을, 산업용사는 고강력성 및 저수축성이 우수한 특성을, 또한 원사 및 필름은 중간 정도의 적당한 연신성과 소프트감이 우수한 물성의 폴리에스테르를 필요로 하게 되는데, 본 발명에 있어서는 각 제품에 요구되는 물성중 각 제품의 용도에 맞게 특별히 첨가되는 부원료에 의한 물성은 제외되는 것을 전제로 하여 원료, 촉매조성, 설비개조 및 전체 운전조건 변경없이 하나의 연속반응기에서 상기의 물성을 발현시키는 폴리에스테르를 제조하기 위한 폴리머 중합방법에 관한 것이다.That is, among the physical properties mentioned in the present invention, the bottle is generally flexible and excellent in elongation, the industrial yarn is excellent in high strength and low shrinkage, and the yarn and film have moderate moderate elongation and softness. In the present invention, raw materials, catalyst composition, facility modification, and overall operation are premised on the premise that the physical properties of the subsidiary ingredients added specifically for the purpose of each product are excluded from the physical properties required for each product. It relates to a polymer polymerization method for producing a polyester expressing the above physical properties in one continuous reactor without changing the conditions.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 폴리에스테르는 주로 테레프탈산 또는 이의 유도체로 이루어진 디카르복실산 성분과 탄소수 2 내지 8의 지방족 디올을 1.1∼1.3몰(mole)비로 반응시켜 제조하며 하기 일반식으로 표현될 수 있다.The polyester of the present invention is prepared by reacting a dicarboxylic acid component mainly consisting of terephthalic acid or a derivative thereof and an aliphatic diol having 2 to 8 carbon atoms in a ratio of 1.1 to 1.3 moles, and may be represented by the following general formula.
상기 일반식(I)에서 R은 주로 테레프탈산 또는 이의 유도체로 이루어진 디카르복실산이고, R1은 주로 탄소수가 2∼8이고, 분자량이 250이하인 에틸렌 글리콜로써, 이외에 프로필렌 글리콜, 테트라메틸렌 글리콜, 펜타메틸렌 글리콜, 2,2-디메틸 트리메틸렌 글리콜, 헥사메틸렌 글리콜과 같은 지방족 디올과 사이클로 헥산 디메탄올도 사용될 수 있다.In the general formula (I), R is a dicarboxylic acid mainly composed of terephthalic acid or a derivative thereof, and R 1 is mainly ethylene glycol having 2 to 8 carbon atoms and a molecular weight of 250 or less, in addition to propylene glycol, tetramethylene glycol, penta Aliphatic diols such as methylene glycol, 2,2-dimethyl trimethylene glycol, hexamethylene glycol and cyclohexane dimethanol may also be used.
상기 일반식에서 n은 90∼110이다.In the general formula, n is 90 to 110.
본 발명에 사용되는 연속중합기는 크게 원료를 섞는 슬러리관, 에스테르화 반응기 1∼2개, 축중합반응기 2∼3개로 이루어져 있으며, 이 중에서 에스테르화 반응기에는 보조기기로써 에스테르 반응시 발생되는 부산물인 물과 에스테르화 반응의 원료인 지방족 디올의 증기를 분리시켜 주는 정류탑이 설치되어 있다. 정류탑의 상부에서는 응축된 물을 제거해주고 하부에는 지방족 디올이 응축되어 모여 있는데, 이 지방족 디올의 처리방법에 따라 요구하는 폴리에스테르를 얻을 수 있다.The continuous polymerizer used in the present invention is composed of slurry tubes for mixing raw materials, 1 to 2 esterification reactors and 2 to 3 condensation polymerization reactors, among which water is a by-product generated during the ester reaction as an auxiliary device. And a rectification column for separating vapor of aliphatic diol, which is a raw material for the esterification reaction, is provided. At the top of the tower, condensed water is removed, and at the bottom, aliphatic diols are condensed.
보다 상세하게는 정류탑 하부에 모여있는 지방족 디올을 생산량 대비하여 전량 에스테르화 반응기로 환류 시키거나 1.0중량% 까지 드레인시키고 잔량을 환류시키면 제조되는 폴리에스테르는 디에틸글리콜함량이 1.5∼1.7중량%정도 포함된 유연한 폴리에스테르가 되어 보틀용으로 사용하게 되며, 지방족 디올은 2.4∼4.5중량%까지 드레인 시키고 잔량을 환류시키면 제조되는 폴리에스테르는 디에틸렌글리콜함량이 0.9∼1.2중량%정도 포함된 중간 정도 특성의 폴리에스테르로서 원사 및 필름용으로 사용될 수 있으며, 5,4∼6.0중량%이상 드레인 시키고 잔량을 환류시키면 제조되는 폴리에스테르는 디에틸렌글리콜함량이 0.8중량% 이하로 포함된 고강력의 폴리에스테르를 제조할 수 있어 산자용으로 사용될 수 있는 것이다.More specifically, the aliphatic diols collected at the bottom of the rectification column are refluxed to the total amount of esterification reactor or drained to 1.0% by weight, and the remaining amount is refluxed to yield a diethyl glycol content of about 1.5 to 1.7% by weight. It becomes a flexible polyester included and is used for the bottle, and the aliphatic diol is 2.4 to 4.5% by weight drained and the remaining amount refluxed polyester is produced in the intermediate properties containing 0.9 to 1.2% by weight of diethylene glycol It can be used for yarn and film as a polyester, and the polyester produced by draining 5,4 ~ 6.0% by weight or more and refluxing the residual amount of high strength polyester containing diethylene glycol content of 0.8% by weight or less It can be prepared and can be used for living.
본 발명에서는 사용되는 디카르복실산 성분의 함량을 기준으로 디올 성분을 1.1∼1.3 몰비로 에스테르화 반응기에 투입하고 240∼265℃의 온도에서 n=3∼10이 될때까지 반응시키며, 이때 본 반응기의 보조기기인 정류탑 하부에 모인 지방족 디올의 드레인량을 용도에 따라 조절함으로써 각 제품에 요구되는 폴리에스테르를 제조하는 것이다.In the present invention, the diol component is introduced into the esterification reactor at a molar ratio of 1.1 to 1.3 based on the content of the dicarboxylic acid component used, and reacted at a temperature of 240 to 265 ° C until n = 3 to 10, wherein the reactor is It is to prepare the polyester required for each product by adjusting the drain amount of aliphatic diol collected in the bottom of the rectification column, which is an auxiliary device of the product according to the use.
본 발명에서 정류탑 하부에 모인 지방족 디올의 드레인량은 0중량%에서 약 8중량%까지가 유효하며 8∼10중량% 에서는 운전가능한 수준이고 10중량% 이상이 되면 반응의 난조(Hunting)가 심하여 폴리에스테르 전체 물성이 변화 되므로 유효하지 못하다.In the present invention, the amount of drainage of aliphatic diols collected at the bottom of the rectification column is effective from 0% by weight to about 8% by weight. It is not effective because the physical properties of the polyester change.
본 발명에 따른 폴리에스터의 제조방법은 생산품목을 교체하여 생산할 경우에도 운전조건이나 촉매등의 변경없이 생산품목이 요하는 물성을 지닌 폴리 에스터를 제조할 수 있으므로 설비비, 제조원가 절감 및 에너지를 절약할 수 있는 장점이 있다.The polyester manufacturing method according to the present invention can produce a polyester having the properties required by the production item without changing the operating conditions or catalyst even when the production product is replaced by the production item, saving equipment cost, manufacturing cost and energy There are advantages to it.
이하 실시예를 들어 본 발명을 설명한다.The present invention will be described with reference to the following Examples.
[실시예 1-12][Example 1-12]
디카르복실산 성분으로서 테레프탈산을, 지방족 디올성분으로서는 에틸렌 글리콜을 사용하여 반응시키되, 정류탑 하부에 모인 에틸렌 글리콜의 드레인량을 조절시켜가면서 반응을 시킨 후 수득한 폴리머를 펠렛화하여 디에틸렌글리콜함량의 변화를 측정하였다.Terephthalic acid was reacted as a dicarboxylic acid component and ethylene glycol was used as an aliphatic diol component, but the reaction was performed while controlling the drain amount of ethylene glycol collected at the bottom of the column, and then the obtained polymer was pelletized to diethylene glycol content. The change of was measured.
[표 1]TABLE 1
상기 표 1 에서 나타난 바와 같이, 정류탑 하부 에틸렌 글리콜의 드레인량을 변화시켜가며 반응시킨 결과 에틸렌 글리콜을 전량 에스테르화 반응기로 투입하거나 1.0중량%까지 드레인 시키면 디에틸렌글리콜 함량이 1.5∼1.7중량%로서 보틀용에 알맞고, 2.4∼4.5중량%까지 드레인 시키면 디에틸렌글리콜함량이 0.9∼1.2중량%로서 원사용, 필름용에 알맞고, 5.4중량% 이상 드레인 시키면 디에틸렌글리콜함량이 0.8중량% 이하로서 산업용사에 알맞다는 것을 확인 할 수 있다.As shown in Table 1, as a result of reacting while changing the drain amount of the ethylene glycol at the bottom of the distillation column, when the total amount of ethylene glycol was added to the esterification reactor or drained to 1.0% by weight, the diethylene glycol content was 1.5 to 1.7% by weight. It is suitable for bottle and diethylene glycol content is 0.9 ~ 1.2% by weight when it is drained up to 2.4 ~ 4.5% by weight. It is suitable for raw materials and film use. When it is drained more than 5.4% by weight, diethylene glycol content is 0.8% by weight or less. You can confirm that it is suitable for.
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| KR1019950066478A KR100244911B1 (en) | 1995-12-29 | 1995-12-29 | Polymerization method of polyester polymer |
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| KR1019950066478A KR100244911B1 (en) | 1995-12-29 | 1995-12-29 | Polymerization method of polyester polymer |
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| KR100244911B1 true KR100244911B1 (en) | 2000-02-15 |
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| US4097468A (en) * | 1977-03-15 | 1978-06-27 | Allied Chemical Corporation | Process for preparing polyesters |
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| US4097468A (en) * | 1977-03-15 | 1978-06-27 | Allied Chemical Corporation | Process for preparing polyesters |
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