KR950002608B1 - Method of producing poly-glycolic acid with excellent heat resistance - Google Patents
Method of producing poly-glycolic acid with excellent heat resistance Download PDFInfo
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- KR950002608B1 KR950002608B1 KR1019910015750A KR910015750A KR950002608B1 KR 950002608 B1 KR950002608 B1 KR 950002608B1 KR 1019910015750 A KR1019910015750 A KR 1019910015750A KR 910015750 A KR910015750 A KR 910015750A KR 950002608 B1 KR950002608 B1 KR 950002608B1
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- glycolide
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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Abstract
Description
본 발명은 폴리글리콜산의 제조방법에 판한 것으로서, 더욱 상세하게는 종래에는 사용하지 않았던 토코페롤을 글리콜라이드에 첨가하므로써 의료 수술용 흡수성 합성 봉합사를 만들기 적절한 내열성이 우수한 폴리글리콜산을 제조하는 방법에 관한 것이다.The present invention is directed to a method for producing polyglycolic acid, and more particularly, to a method for producing polyglycolic acid having excellent heat resistance suitable for making an absorbent synthetic suture for medical surgery by adding tocopherol, which has not been used conventionally, to glycolide. will be.
종래에 폴리글리콜산을 제조하는 방법으로서 일본 공개 특허 소 58-13624호에서는 글리콜라이드에 대하여 옥탄산 제일주석을 0.01-0.05중량% 사용하여 100-180℃의 저온에서 폴리글리콜산을 얻는 방법을 제시하였으나, 이는 섬유상의 봉합사 제조시 방사 공정에서 많은 열분해가 수반되어 봉합사의 강도가 저하되는 문제점을 안고있다.Conventionally, Japanese Patent Application Laid-Open No. 58-13624 discloses a method for obtaining polyglycolic acid at a low temperature of 100-180 ° C. using 0.01-0.05% by weight of octanoic acid tin tin relative to glycolide. However, this has a problem in that the strength of the suture is accompanied by a lot of pyrolysis in the spinning process when manufacturing the fibrous suture.
또한, 미국특허 제3442871호와 제3468853호에서는 글리콜라이드에 촉매로서 염화제일주석을 사용하는 방법을 제시하였으나, 이 방법에서는 스케일업(scale up)하였을 경우 글리콜라이드의 열분해 현상이 발생하여 고점도의 폴리글리콜산을 얻을 수 없는 단점이 있다.In addition, US Pat. Nos. 3,428,71 and 3468853 propose a method of using tin chloride as a catalyst for glycolide, but in this method, pyrolysis of glycolide occurs when scaled up. There is a disadvantage that glycolic acid cannot be obtained.
따라서, 본 발명은 내열성이 우수하며 분자량이 매우 큰 폴리글리콜산을 제조하는 방법으로서, 토코페롤을 글리콜라이드에 대하여 소량 첨가하여 고온 중합 반응시 글리콜라이드가 열분해되는 것을 억제하므로써 내열성이 우수한 고분자량의 폴리글리콜산을 제조하는 방법을 제공하는데 그 목적이 있다.Accordingly, the present invention is a method for producing a polyglycolic acid having excellent heat resistance and very high molecular weight, by adding a small amount of tocopherol to the glycolide to suppress the thermal decomposition of the glycolide during high-temperature polymerization, thereby providing a high molecular weight poly with excellent heat resistance. It is an object to provide a method for preparing glycolic acid.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 글리콜라이드를 중합하여 폴리글리콜산을 제조함에 있어서, 글리콜라이드에 다음 구조식(I)로 표시되는 토코페롤을 글리콜라이드에 대하여 0.005-0.5중량%를 첨가하여 중합하는 것을 특징으로 한다.The present invention is characterized in that in the preparation of polyglycolic acid by polymerizing glycolide, tocopherol represented by the following structural formula (I) is added to glycolide by adding 0.005-0.5% by weight relative to glycolide.
상기 식에서 R1,R2는 서로 같거나 다른 것으로서 각각 H 또는 CH3이다.Wherein R 1 and R 2 are the same as or different from each other, or H or CH 3, respectively.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
일반적으로 토코페롤은 사람의 혈장 중에 약 0.9-1.2mg/100m1 존재하는 물질로서 비타민 A, 지방 둥의 산화방지제로 작용하며 의약품으로 널리 쓰이고 있다.In general, tocopherol is a substance present in the human plasma of about 0.9-1.2mg / 100m1 and acts as an antioxidant for vitamin A and fat, and is widely used as a medicine.
본 발명은 폴리글리콜산을 제조하는데 있어서 층분히 정제되고 건조된 글리콜라이드에 촉매로써 옥탄산 제일주석 0.0001-0.001중량%와 함께 산화방지제인 토코페롤을 글리콜라이드 성분에 대하여 0.005-0.5중량% 첨가하여 반응시키므로써 내열성이 우수한 고점도의 폴리글리콜산을 제조할 수 있는 것이다.The present invention reacts by adding 0.005-0.5% by weight of antioxidant tocopherol with respect to the glycolide component with 0.0001-0.001% by weight of octanoic acid as a catalyst to the purified and dried glycolide in polyglycolic acid. By doing so, it is possible to produce a high viscosity polyglycolic acid having excellent heat resistance.
토코페롤을 첨가하지 않고 제조한 폴리글리콜산은 글리콜라이드의 열분해로 인해 점도가 낮을 뿐만 아니라 방사할때 또다시 상당한 열분해가 수반되어 방사 후 최종 실의 강도가 저하되어 봉합사로서 사용하기에 바람직하지 않게 된다.Polyglycolic acid prepared without the addition of tocopherol not only has a low viscosity due to the thermal decomposition of glycolide, but also involves significant thermal decomposition during spinning, which lowers the strength of the final yarn after spinning, making it undesirable for use as a suture.
그러나 토코페롤을 글리콜라이드에 대하여 바람직하기로는 0.005∼0.5중량%, 더욱 바람직하게는 0.01-0.1중량% 첨가하여 폴리글리콜산을 제조한후, 이 폴리머를 적당한 크기로 분쇄하여 240℃에서 용융점도를 측정하여 본 결과, 의료수술용 흡수성 합성 봉합사 제조에 알맞은 내열성이 우수한 고점도의 폴리글리콜산을 얻을 수 있었다.However, polycolic acid is prepared by adding tocopherol to the glycolide, preferably from 0.005 to 0.5% by weight, more preferably from 0.01 to 0.1% by weight, and then pulverizing the polymer to an appropriate size to measure the melt viscosity at 240 ° C. As a result, a high viscosity polyglycolic acid having excellent heat resistance suitable for the manufacture of absorbent synthetic sutures for medical surgery was obtained.
여기서 글리콜라이드에 대하여 토코페롤의 첨가량이 0.005중량% 보다 적으면 산화방지제의 작용을 충분히 하지 못하여 내열성이 좋지않은 저점도의 폴리글리콜산이 제조되어 방사시 많은 열분해가 일어난다.Here, when the amount of tocopherol added to the glycolide is less than 0.005% by weight, a low viscosity polyglycolic acid having poor heat resistance due to insufficient action of an antioxidant is produced, which causes a lot of thermal decomposition during spinning.
또한, 글리콜라이드에 대하여 토코페롤의 첨가량이 0.5중량% 보다 많으면 글리콜라이드의 중합속도가 현저하게 늦고 봉합사 제조에 바람직한 고점도의 폴리글리콜산을 얻을 수 없다.In addition, when the amount of tocopherol added to the glycolide is more than 0.5% by weight, the polymerization rate of the glycolide is remarkably slow, and a high viscosity polyglycolic acid suitable for suture production cannot be obtained.
한편, 본 발명에서 촉매로서는 옥탄산제일주석 등을 사용하면 더욱 효과적으로 폴리글리콜산을 중합시킬 수 있다.On the other hand, in the present invention, the use of stannic octanoate as the catalyst can be more effectively polymerized polyglycolic acid.
상기의 방법에 의하여 제조된 본 발명의 폴리글리콜산은 의료수술용 흡수성 합성봉합사를 제조할 경우 매우 유용한 장점이 있다.Polyglycolic acid of the present invention prepared by the above method has a very useful advantage when preparing the absorbent synthetic suture for medical surgery.
이하, 본 발명을 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
본 실시예에서 용융점도는 RDS7700(Rheometrics Dynamic Spectrometer) 기기를 사용하여 240℃에서 각 속도 10rad/sec일때 측정한 것이며, 열분해도는 Perkin-Elmer 4열분석기를 써서 240℃에서 등온으로 30분동안 측정한 것이다.In this example, the melt viscosity was measured at 240 ° C. using a RDS7700 (Rheometrics Dynamic Spectrometer) instrument at an angular rate of 10 rad / sec, and the thermal decomposition rate was measured at 240 ° C. for 30 minutes using a Perkin-Elmer 4 thermal analyzer. It is.
실시예 1Example 1
충분히 정제되고 건조된 글리콜라이드 500g과 이것에 대하여 촉매로써 옥탄산 제일주석 0.0004중량%를 중합반응기에 투입하고 이와 함께 글리콜라이드에 대하여 토코페롤 0.05중량%를 첨가하였다.500 g of sufficiently purified and dried glycolide and 0.0004% by weight of stannic octanoate as a catalyst were added to the polymerization reactor, and 0.05% by weight of tocopherol was added to the glycolide.
그런다음 반응기를 밀폐시키고 질소분위기에서 반응물을 저어주며 230℃에서 반응시켰다. 이와 같이 하여 제조한 폴리글리콜산을 적당한 크기로 분쇄한 다음 110℃에서 6시간 이상 건조한후 용융점도를 측정한 결과 다음 표 1과 같이 240℃에서 41,000 포아스(poise)였다.The reactor was then sealed and reacted at 230 ° C. with stirring of the reactants in a nitrogen atmosphere. The polyglycolic acid thus prepared was pulverized to a suitable size and then dried at 110 ° C. for 6 hours or more, and the melt viscosity was measured. As a result, it was 41,000 poise at 240 ° C. as shown in Table 1 below.
그리고 융점은 225℃였으며, 열분해시작온도는 266℃였다. 또한, 240℃에서 30분간 동안 열분해도를 측정한 결과 1.5중량%였다. 이와 같이 하여 얻은 폴리글리콜산을 방사하였을때 강도 6.7g/d, 신도 14%인 우수한 의료수술용 합성 흡수성 봉합사를 제조할 수 있었다.And melting point was 225 ℃, pyrolysis start temperature was 266 ℃. In addition, the thermal decomposition degree was measured at 240 ° C. for 30 minutes, and the result was 1.5 wt%. When the polyglycolic acid thus obtained was spun off, an excellent absorbable suture for medical surgery having a strength of 6.7 g / d and an elongation of 14% could be prepared.
실시예 2∼5Examples 2-5
글리콜라이드에 대하여 다만 토코페롤의 첨가비율을 다음 표 1과 같이 변화시켜 가면서 실시예 1과 동일한 방빕으로 중합반응을 행하였다.For the glycolide, the polymerization reaction was carried out in the same chamber as in Example 1 while changing the addition ratio of tocopherol as shown in Table 1 below.
비교예 1∼6Comparative Examples 1 to 6
글리콜라이드에 대하여 토코페롤의 첨가량이 폴리글리콜산의 내열성 향상에 미치는 영향을 알아보기 위하여 실시예 1과 같은 방법드로 다만 토코페롤의 첨가량을 달리하여 중합반응을 행하였다.In order to investigate the effect of the addition amount of tocopherol to the glycolide on the heat resistance improvement of the polyglycolic acid, polymerization was carried out in the same manner as in Example 1 except that the amount of tocopherol was changed.
표 1Table 1
(주) 측정방법 : PGA Chip을 110℃에서 6시간 건조후 250℃에서 방사하였다. 방사노즐은 10Hole이며 연신비는 3.4, 연신속도는 750m/min로 하여 최종제품을 3d/10f로 하여 제사성, 신도 및 강도를 측정하였다.(Note) Measurement method: PGA Chip was dried at 110 ℃ for 6 hours and then spun at 250 ℃. The spinning nozzle was 10Hole, the drawing ratio was 3.4, the drawing speed was 750m / min, and the final product was 3d / 10f.
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