KR20000013473A - Process for preparing high transparent polytrimethylene terephthalate - Google Patents

Process for preparing high transparent polytrimethylene terephthalate Download PDF

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KR20000013473A
KR20000013473A KR1019980032344A KR19980032344A KR20000013473A KR 20000013473 A KR20000013473 A KR 20000013473A KR 1019980032344 A KR1019980032344 A KR 1019980032344A KR 19980032344 A KR19980032344 A KR 19980032344A KR 20000013473 A KR20000013473 A KR 20000013473A
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polytrimethylene terephthalate
catalyst
terephthalate
dmt
polymer
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KR1019980032344A
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Korean (ko)
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이주문
정훈
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김윤
주식회사 삼양사
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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
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Abstract

PURPOSE: Polytrimethylene terephthalate is prepared which has an excellent color and high viscosity. CONSTITUTION: 2.328g of dimethyl terephthalate(DMT) and 1.8mole ratio of 1,3-propane diol of the dimethyl terephthalate are esterified at 150-230 degree C for 3-4 hours in the presence of cobalt acetate as an ester exchange catalyst, followed by polymerization at 255 degree C for 2-3 hours with 0.01-0.2 weight % of £MHTi(OR)6; R is C1-C6 alkyl group, aryl or arylalkyl; M is sodium, magnesium, manganese or cobalt| of the polymer to give the polytrimethylene terephthalate.

Description

고투명성 폴리트리메틸렌테레프탈레이트의 제조방법Manufacturing method of high transparency polytrimethylene terephthalate

본 발명은 고투명성, 고점도의 폴리트리메틸렌테레프탈레이트의 제조방법에 관한 것으로, 보다 상세하게는 산성분으로 디메틸테레프탈레이트(이하 "DMT"라함)와 디올성분으로 1,3-프로판디올를 사용하여 폴리트리메틸렌테레프탈레이트를 제조함에 있어서, 에스테르 교환반응 촉매로서 코발트 아세테이트를 사용하고, 중축합반응 촉매로서 하기 일반식(1)으로 표시되는 혼합촉매를 사용함으로써 투명성이 우수한 고점도의 폴리트리메틸렌테레프탈레이트를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a high transparency, high viscosity polytrimethylene terephthalate, more specifically, using a dimethyl terephthalate (hereinafter referred to as "DMT") as an acid component and 1,3-propanediol as a diol component In preparing trimethylene terephthalate, a high viscosity polytrimethylene terephthalate having excellent transparency is obtained by using cobalt acetate as a transesterification catalyst and using a mixed catalyst represented by the following general formula (1) as a polycondensation catalyst. It relates to a manufacturing method.

[ MHTi(OR)6] .......... (1)[MHTi (OR) 6 ] .......... (1)

여기서, R은 탄소수 1∼6개인 알킬기, 아릴기 또는 아릴알킬기이고,R is an alkyl group having 1 to 6 carbon atoms, an aryl group or an arylalkyl group,

M은 소듐, 마그네슘, 포타슘, 망간 또는 코발트M is sodium, magnesium, potassium, manganese or cobalt

특히, 섬유용 폴리트리메틸렌테레프탈레이트는 점도(IV) 0.8이상이어야 하는데 폴리트리메틸렌테레프탈레이트 폴리머의 점도개선과 투명성 개선방법이 제안되어 왔다.In particular, the polytrimethylene terephthalate for fibers should have a viscosity (IV) of 0.8 or more, and a method of improving the viscosity and transparency of the polytrimethylene terephthalate polymer has been proposed.

미국특허 제 3,671,379호 에서는 에스테르 교환반응 촉매와 중축합 반응촉매로 나트륨과 테트라부칠티타네이트를 혼합한것을 촉매로 사용하는 방법이 개시되어 있고, 미국특허 제 5,340,909호에서는 에스테르 교환반응 촉매로 테트리부칠티타내이트를 사용하고, 중축합촉매로 부틸틴에시드를 사용하는 방법이 개시되어 있으나, 이들은 점도면에서 다소 개선되었으나 색상이 불선명하여 섬유를 제조함에 부적당하였다.U.S. Patent No. 3,671,379 discloses a method using a mixture of sodium and tetrabuty titanate as a transesterification catalyst and a polycondensation reaction catalyst as a catalyst, and U.S. Pat. The use of titanite and the use of butyl tin acid as polycondensation catalysts have been disclosed, but these have been somewhat improved in terms of viscosity but unsuitable for making fibers due to unclear color.

폴리트리메틸렌테레프탈레이트 섬유는 기존의 폴리에틸렌테레프탈레이트와 폴리부틸렌레프탈레이트로부터 제조한 섬유와 많은 특성차이가 있다. 특히 연신된 폴리트리메틸렌테레프탈레이트 섬유는 나이론 섬유와 같은 반발탄성이 매우 우수하고 촉감이 뛰어난 장점이 있기 때문에 카페트용 및 섬유용 필라멘트로 이용가치가 높고, 열안정제와 피그먼트를 사용하여 색상과 점도를 개선하고 있으나, 이방법들은 색상면에서 만족 할만한 수준을 얻을수는 없었다.Polytrimethylene terephthalate fibers have a number of characteristic differences from fibers made from conventional polyethylene terephthalate and polybutylene lephthalate. In particular, the stretched polytrimethylene terephthalate fiber has a high rebound elasticity such as nylon fiber and has excellent touch. Therefore, the polytrimethylene terephthalate fiber has high use value as a filament for carpet and fiber, and it has a color and viscosity using heat stabilizer and pigment. However, these methods could not achieve satisfactory level of color.

따라서 본 발명은 색상이 우수한 섬유로 사용이 가능한 고점도 폴리트리메틸렌테레프탈레이트를 제조하는데 그 목적이 있다.Therefore, an object of the present invention is to produce a high viscosity polytrimethylene terephthalate that can be used as a fiber having excellent color.

상기 목적을 달성하기 위해서 본 발명은 폴리트리메틸렌테레프탈레이트 고분자 제조시 색가의 현저한 개선을 위하여 코발트 아세테이트를 에스테르 교환반응촉매로 사용하고, 하기 일반식(1)으로 표시되는 혼합촉매를 중축합 촉매로 하며 열안정제를 첨가하여 중축합함을 특징으로 한다.In order to achieve the above object, the present invention uses cobalt acetate as a transesterification catalyst for the remarkable improvement of color value in the preparation of polytrimethylene terephthalate polymer, and the mixed catalyst represented by the following general formula (1) as a polycondensation catalyst And polycondensation by adding a heat stabilizer.

[ MHTi(OR)6] ..........(1)[MHTi (OR) 6 ] .......... (1)

여기서, R은 탄소수 1∼6개인 알킬기, 아릴기 또는 아릴알킬기이고,R is an alkyl group having 1 to 6 carbon atoms, an aryl group or an arylalkyl group,

M은 소듐, 마그네슘, 포타슘, 망간 또는 코발트M is sodium, magnesium, potassium, manganese or cobalt

즉, 본 발명은 DMT와 1,3-프로판디올을 반응시켜서 폴리에스테르를 제조 함에 있어서, 에스테르 교환반응 촉매로서 코발트 아세테이트를 DMT에 대하여 0.3∼1.5 x 10-4몰비로 사용하고, 중축합 촉매로서 상기 일반식(1)의 혼합촉매를 폴리머에 대하여 0.01∼0.2 중량%로 사용하는 것을 특징으로 한다.That is, in the present invention, in the preparation of polyesters by reacting DMT with 1,3-propanediol, cobalt acetate is used as a transesterification catalyst at a molar ratio of 0.3 to 1.5 x 10 -4 to DMT, and as a polycondensation catalyst. It is characterized in that the mixed catalyst of the formula (1) is used at 0.01 to 0.2% by weight relative to the polymer.

본 발명에서 사용한 중축합 촉매인 일반식(1)의 혼합촉매의 제조방법은 다음과 같다.The preparation method of the mixed catalyst of the general formula (1) which is a polycondensation catalyst used in the present invention is as follows.

12.9g의 소듐 아세테이트(무수)에 20Oml 메탄올을 첨가하고 2시간 환류 시킨 후 반응물을 식히고 나서 44.4ml의 티티늄 테트라 부톡사이드와 150ml의 1,4-부탄디올을 첨가 한 후 다시 1시간 동안 교반하여 혼합촉매를 얻는다.20Oml methanol was added to 12.9 g of sodium acetate (anhydrous) and refluxed for 2 hours. After cooling the reaction, 44.4 ml of titanium tetrabutoxide and 150 ml of 1,4-butanediol were added, followed by stirring for 1 hour. Obtain a catalyst.

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

본 발명에서 고점도, 고투명성의 폴리트리메틸렌테레프탈레이트 폴리에스테르를 제조하기 위해서는 산성분으로서 DMT, 디올성분으로서 1,3-프로판디올을 사용하되 이때 사용되는 1,3-프로판디올의 양은 DMT에 대하여 1.5-1.8배의 비율로 사용하여 폴리에스테르를 얻게 된다.In the present invention, in order to prepare a high viscosity, high transparency polytrimethylene terephthalate polyester, DMT is used as an acid component and 1,3-propanediol is used as a diol component, but the amount of 1,3-propanediol used is DMT. Polyesters are obtained at a rate of 1.5-1.8 times.

이와 같은 혼합 조성물에 에스테르 교환반응의 촉매로서 코발트아세테이트를 0.3∼1.5 x 10-4몰/DMT 몰비로 첨가하여 에스테르 교환 반응을 완결한다. 에스테르 교환반응이 끝난후 여기에 중축합 촉매로서 상기 일반식(1)의 혼합촉매를 최종합성 되는 폴리머에 대하여 0.01∼0.2 중량%로 첨가하여 중축합 함으로서 목적하는 고점도 및 고투명의 폴리트리메틸렌테레프탈레이트를 얻는다. 이때 열안정제로는 어느것을 사용해도 상관없으나 3,5-디-테셔리부틸-4-히드록시 벤질 포스포닉산을 사용하는 것이 좋으며, 그 사용량은 특별한 제한은 없으나 최종합성 되는 폴리머에 대하여 0.03∼0.3 중량% 첨가하는 것이 바람직하다.Cobalt acetate is added to this mixed composition as a catalyst for the transesterification reaction at a molar ratio of 0.3 to 1.5 x 10 -4 mol / DMT to complete the transesterification reaction. After completion of the transesterification reaction, the mixed catalyst of the formula (1) as a polycondensation catalyst is added to 0.01 to 0.2% by weight based on the polymer to be finally synthesized to polycondensate the desired high viscosity and high transparency polytrimethylene terephthalate Get At this time, any of the thermal stabilizers may be used, but it is preferable to use 3,5-di-tetrabutylbutyl-hydroxybenzyl phosphonic acid, and the amount of use thereof is not particularly limited, but 0.03∼ It is preferable to add 0.3 weight%.

그러나 이때 첨가되는 일반식(1)의 혼합촉매의 양이 상기 범위보다 적을 경우 반응속도가 지나치게 느려지고, 상기 범위보다 많을 경우 촉매 환원에 의한 폴리머의 착색 현상이 발생하고, 부반응이 촉진되어 중합도 및 투명성이 저하되는 현상이 발생된다. 또한 열안정제의 사용량이 너무 과다하면 중축합 촉매의 활성을 저해하여 폴리머의 중합도가 올라가지 않는 문제점이 있다.However, if the amount of the mixed catalyst of the general formula (1) added at this time is less than the above range, the reaction rate is too slow, and if more than the above range, the coloration of the polymer due to catalytic reduction occurs, and the side reaction is promoted to promote polymerization and transparency. This deterioration phenomenon occurs. In addition, when the amount of the thermal stabilizer is excessively used, there is a problem that the degree of polymerization of the polymer does not increase by inhibiting the activity of the polycondensation catalyst.

본 발명에서 특이할 만한 사실은 폴리트리메틸렌테레프탈레이트를 중합할때 중합 온도에 각별한 주의를 기울여야 한다는 것이며 폴리트리메틸레프탈레이트는 열에 의하여 열분해가 잘 일어나 변색하게 된다. 일반적으로 폴리에틸렌테레프탈레이트는 270℃ 이상의 고온에서도 큰 점도 저하도 없고 색상도 변하지 않는 특징을 가지고 있는 반면에 폴리트리메틸렌테레프탈레이트이 260℃ 이상의 온도에서 열분해가 잘 일어나기 때문에 중합시에도 가능한한 온도를 260℃ 이하에서 실시하는 것이 바람직하다.What is particular to the present invention is that when polymerizing polytrimethylene terephthalate, special attention should be paid to the polymerization temperature, and polytrimethylene phthalate is thermally decomposed due to heat and discolors. In general, polyethylene terephthalate has a characteristic of no significant decrease in viscosity and color change even at a high temperature of 270 ° C. or higher, while polytrimethylene terephthalate is thermally decomposed at a temperature of 260 ° C. or higher. It is preferable to carry out below.

상술한 바와같이 본 발명에 의하면 고투명성의 폴리테트리메틸렌테레프탈레이트를 제조할 수 있고 중합에 소요되는 시간을 단축시킬수 있고 생산원가를 낮출 수 있으며, 일정 점도(IV=8 이상)가 요구되는 섬유용으로 사용 가능한 고점도의 폴리에폴리테트라메틸렌테레프탈레이트를 얻을 수 있다.As described above, according to the present invention, a highly transparent polytetrimethylene terephthalate can be prepared, the time required for polymerization can be shortened, the production cost can be reduced, and a fiber having a certain viscosity (IV = 8 or more) is required. A high viscosity polypolytetramethylene terephthalate which can be used for the purpose can be obtained.

이하, 실시예를 들어서 본 발명을 구체적으로 설명한다.Hereinafter, an Example is given and this invention is demonstrated concretely.

본 발명은 이들 실시예에 한정되어지는 것은 아니며 실시예는 다음과 같은폴리머의 물성평가 방법을 채택하였다.This invention is not limited to these Examples, The Example adopted the following physical property evaluation method of a polymer.

(1) 고유점도의 측정(1) Measurement of intrinsic viscosity

폴리머를 페놀과 사염화에탄의 혼합용액에 0.5 g/dl의 농도로 희석후 20℃의 항온조에서 우벨로우드 점도계를 이용하여 고유점도로 환산 측정 하였다.The polymer was diluted to a concentration of 0.5 g / dl in a mixed solution of phenol and ethane tetrachloride, and then measured in terms of intrinsic viscosity using a Ubellowood viscometer in a 20 ° C. constant temperature bath.

(2) 색가의 측정방법(2) How to measure color value

폴리머를 분쇄 또는 펠렛화 한 다음 색차계를 이용하여 밝기는 L (Lightness)치로서, 황색도는 b(Yellowness)가로써 측정 하였다.After pulverizing or pelletizing the polymer, the brightness was measured as L (Lightness) value and the yellowness as b (Yellowness) value using a color difference meter.

실시예 1∼3, 비교예 1∼5Examples 1-3 and Comparative Examples 1-5

(에스테르 교환반응)(Ester exchange reaction)

환류가 가능 하도록 설계된 응축기와 교반장치가 설치된 스테인레스스틸 반응기에 DMT 2,328g (11.99 몰), 그리고 1,3-프로판디올이 DMT에 대하여 1.8몰 비가 되도록 한 다음 에스테르 교환반응 촉매를 첨가하고, 가열 교반하여 150℃에 이르면 반응이 시작되고 온도를 230℃까지 점차 올리면서 최종 반응률이 95∼98%에 이르게 한다. 이때 반응에 소요되는 시간은 3∼4시간 정도이다.In a stainless steel reactor equipped with a condenser and agitator designed to reflux, 2,328 g (11.99 moles) of DMT and 1,3-propanediol should be 1.8 molar ratio to DMT, and then a transesterification catalyst is added and heated and stirred. When the temperature reaches 150 ° C, the reaction starts and the final reaction rate reaches 95-98% while gradually raising the temperature to 230 ° C. At this time, the time required for the reaction is about 3 to 4 hours.

(중축합 반응)(Polycondensation reaction)

에스테르 교환반응이 완결되면 중축합 촉매와 열안정제를 첨가하고 온도를 서서히 올려 최종 온도가 255℃가 되게하며, 서서히 감압하여 최종 감압도가 0.2torr 이하에서 반응이 진행 되도록 하여 목적하는 점도의 폴리머가 얻어지면 질소로 가압하여 불출한다. 이때 소요되는 중축합 반응시간은 약 2∼3 시간 정도이다.Upon completion of the transesterification reaction, a polycondensation catalyst and a heat stabilizer are added and the temperature is gradually raised to a final temperature of 255 ° C. The pressure is gradually reduced to allow the reaction to proceed at a final pressure of 0.2torr or less. When obtained, it is pressurized with nitrogen and discharged. The polycondensation reaction time required at this time is about 2 to 3 hours.

이때 에스테르 교환반응 촉매와 중축합 촉매 그리고 열안정제를 다음의 표 1과 같은 조건으로 사용 하였으며, 이들의 물성 및 평가는 다음의 표 2와 같으며 이들 물성의 각각의 항목에 대한 개별 평가기준은 다음의 표 3과 같으며, 이들 물성이 균형을 이루는 정도에 따라 각각 우수, 양호, 보통, 불량의 등급으로 평가 하였다.At this time, the transesterification catalyst, the polycondensation catalyst, and the heat stabilizer were used under the conditions shown in Table 1 below, and their properties and evaluations are shown in Table 2 below. Table 3 is as follows, and evaluated according to the grade of excellent, good, normal, and poor, respectively, according to the balance of these properties.

표 1Table 1

DMT : 디메틸테레프탈레이트DMT: Dimethyl Terephthalate

PDO : 1,3-프로판디올PDO: 1,3-propanediol

열안정제 : 3,5-디 테셔리부틸-4-히드록시 벤질 포스포닉산Thermal Stabilizer: 3,5-Di-butylbutyl-4-hydroxy benzyl phosphonic acid

표 2TABLE 2

표 3TABLE 3

본 발명은 에스테르 교환반응 촉매로서 코발트 아세테이트를 사용하고 중축합 촉매로서 일반식(1)으로 표시되는 혼합촉매를 사용하여 중축합함으로써 종래의 방법 보다 촉매의 첨가량이 적으면서도 중합에 소요되는 시간을 단축시킬수 있고 생산원가가 저렴한 섬유용 폴리트리메틸렌테레프탈레이트를 얻을수 있게 된다.In the present invention, polycondensation is carried out using cobalt acetate as a transesterification catalyst and a mixed catalyst represented by the general formula (1) as a polycondensation catalyst, thereby shortening the time required for polymerization while adding less catalyst than the conventional method. It is possible to obtain polytrimethylene terephthalate for fiber which can be produced and inexpensive.

Claims (1)

디메틸테레프탈레이트(DMT)와 1,3-프로판디올을 중합시켜 폴리트리메틸렌테레프탈레이트를 제조하는 방법에 있어서, 에스테르 교환반응 촉매로서 코발트 아세테이트를 DMT에 대하여 O.3∼1.5×10-4몰비로 사용하고 중축합반응 촉매로서 하기 일반식(1)으로 표시되는 혼합촉매를 폴리머에 대하여 0.01∼0.2 중량%를 사용함을 특징으로 하는 고투명성 폴리트리메틸렌테레프탈레이트의 제조방법.In the method for preparing polytrimethylene terephthalate by polymerizing dimethyl terephthalate (DMT) and 1,3-propanediol, cobalt acetate as a transesterification catalyst in a molar ratio of 0.3 to 1.5 x 10 & lt ; -4 & gt ; A method for producing a highly transparent polytrimethylene terephthalate, wherein the mixed catalyst represented by the following general formula (1) is used as a polycondensation reaction catalyst in an amount of 0.01 to 0.2% by weight based on the polymer. [ MHTi(OR)6] ..........(1)[MHTi (OR) 6 ] .......... (1) 여기서, R은 탄소수 1∼6개인 알킬기, 아릴기 또는 아릴알킬기이고, M은 소듐, 마그네슘, 포타슘, 망간 또는 코발트Wherein R is an alkyl group having 1 to 6 carbon atoms, an aryl group or an arylalkyl group, and M is sodium, magnesium, potassium, manganese or cobalt
KR1019980032344A 1998-08-10 1998-08-10 Process for preparing high transparent polytrimethylene terephthalate KR20000013473A (en)

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