KR19980073761A - Tear resistance biodegradable polyester resin and its manufacturing method - Google Patents
Tear resistance biodegradable polyester resin and its manufacturing method Download PDFInfo
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- KR19980073761A KR19980073761A KR1019970009285A KR19970009285A KR19980073761A KR 19980073761 A KR19980073761 A KR 19980073761A KR 1019970009285 A KR1019970009285 A KR 1019970009285A KR 19970009285 A KR19970009285 A KR 19970009285A KR 19980073761 A KR19980073761 A KR 19980073761A
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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
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
본 발명에 의하면 하나 또는 2 이상의 지방족 폴리에스테르 수지 성분에 추가 성분으로 화학식 1의 화합물이 전체 혼합물 기준으로 0.01∼1.0중량% 혼합되어 중합된 내인열성 생분해성 폴리에스테르 수지와 그 제조방법이 제공된다.The present invention provides a tear-resistant biodegradable polyester resin polymerized by mixing 0.01 to 1.0% by weight of the compound of formula 1 as an additional component with one or more aliphatic polyester resin components, based on the total mixture.
[화학식 1][Formula 1]
여기서, R1과 R3는 -OH 또는 -COOH 중에서 선택되는 서로 같거나 다른 기이고, R2는 2가의 기로서 O, CH2또는 SO2 Wherein R1 and R3 are the same or different groups selected from -OH or -COOH, and R2 is a divalent group which is O, CH 2 or SO 2
Description
본 발명은 생분해성 폴리에스테르 수지, 보다 구체적으로는 내인열성의 생분해성 폴리에스테르에 관한 것이다.The present invention relates to biodegradable polyester resins, and more particularly to tear resistant biodegradable polyesters.
최근 환경문제중의 하나인 폐플라스틱의 문제를 해결하기 위한 방안의 하나로서 생분해성 고분자의 연구에 대한 관심이 증대되고 있으며, 대표적인 생분해성 고분자는 지방족 폴리에스테르이다 (대한민국 공개특허 제94-14497호, 제 95-758호 등). 그러나, 지방족 폴리에스테르는 생분해성은 우수하나 쉽게 찢어지는 등 기계적성질이 좋지 못한 단점이 있어 적용범위가 크게 제한된다.Recently, as a way to solve the problem of waste plastic, which is one of the environmental problems, interest in the study of biodegradable polymers is increasing, and representative biodegradable polymers are aliphatic polyesters (Korean Patent Publication No. 94-14497). , 95-758, etc.). However, aliphatic polyester has excellent biodegradability but has a disadvantage of poor mechanical properties such as being easily torn, thereby greatly limiting the scope of application.
지방족 폴리에스테르 수지의 내인열성을 개선하기 위한 방법으로 다음의 두가지 방법을 고려해볼 수 있다. 그 한 방법은 인열성이 좋은 고분자를 소량 섞어 물리적 결합에 의하여 내인열성을 갖게 하는 방법이고, 다른 한 방법은 중합단계에서 인열성이 좋은 화합물을 혼합하여 지방족 폴리에스테르수지에 화학적으로 결합시켜서 인열강도를 증대시키는 방법이다.As a method for improving the tear resistance of the aliphatic polyester resin, the following two methods can be considered. One method is to mix a small amount of good tear-resistant polymer and make it tear resistant by physical bonding, and the other method is to chemically bond to aliphatic polyester resin by mixing a good tearing compound in the polymerization step and tearing steel It is a way to increase the degree.
전자의 경우는 지방족 폴리에스테르에 내인열성이 우수한 고분자와 블렌딩하고, 블랜딩시 온도, 조성에 따라서 상분리구조가 다양한 내인열성 생분해성 지방족 폴리에스테르를 얻을 수 있으며, 이러한 상분리구조의 계면 접착력 및 상용성은 상용화제 첨가에 의하여 조절할 수 있다.In the former case, a tear resistant biodegradable aliphatic polyester having various phase separation structures depending on the temperature and composition at the time of blending is blended with a polymer having excellent tear resistance to the aliphatic polyester, and the interface adhesion and compatibility of the phase separation structure are commercialized. It can be adjusted by the addition.
한편, 후자의 경우는 지방족 폴리에스테르 수지와 개질성분의 화학적결합을 유도하여야 하므로 개질성분이 지방족 디올 및 지방족 디에시드 또는 이들의 에스테르 화합물과 화학적반응을 할 수 있는 관능기를 가져야 하고, 가급적이면 지방족 화합물 보다 인열강도의 향상에 유리한 방향족 화합물이 적합할 것이다.On the other hand, in the latter case, since the chemical bond between the aliphatic polyester resin and the modifying component must be induced, the modifying component must have a functional group capable of chemically reacting with the aliphatic diol and aliphatic dieside or an ester compound thereof, preferably an aliphatic compound. Aromatic compounds that are more advantageous for improving tear strength will be suitable.
본 발명은 후자의 방법으로 생분해성 지방족 폴리에스테르의 물성을 개량하는 것을 목적으로 하는 것으로서, 특히 내인열성이 향상된 내인열성 생분해성 폴리에스테르 수지를 제공하는 것을 목적으로 한다.An object of the present invention is to improve the physical properties of biodegradable aliphatic polyester by the latter method, and in particular, an object of the present invention is to provide a tear resistant biodegradable polyester resin having improved tear resistance.
상기한 목적을 달성하기 위한 본 발명에 의하면, 하나 또는 2 이상의 지방족 폴리에스테르 성분에 추가 성분으로 하기 화학식 1의 화합물이 전체 혼합물 기준으로 0.01∼1.0중량% 혼합되어 중합된 것임을 특징으로 하는 내인열성 생분해성 폴리에스테르 수지가 제공된다.According to the present invention for achieving the above object, tear resistance biodegradation, characterized in that the compound of formula (1) as a further component in one or two or more aliphatic polyester component is polymerized by mixing 0.01 to 1.0% by weight based on the total mixture A polymeric polyester resin is provided.
[화학식1][Formula 1]
여기서, R1과 R3는 -OH 또는 -COOH 중에서 선택되는 서로 같거나 다른 기이고, R2는 2가의 기로서 O, CH2또는 SO2이다.Here, R1 and R3 are the same or different groups selected from -OH or -COOH, and R2 is O, CH 2 or SO 2 as a divalent group.
또한, 본 발명에 의하면 하나 또는 2 이상의 지방족 폴리에스테르 성분에 추가 성분으로 화학식 1의 화합물중 일부를 혼합하여 완전히 용융시키고 지방족 폴리에스테르 성분과 추가성분 사이에서만 선택적으로 축합반응을 진행시킨 다음, 나머지의 상기 화학식 1의 화합물을 추가 투입하고 축중합시키되, 전제 반응에 투입된 화학식 1의 화합물이 지방족 폴리에스테르 수지 성분과 추가성분의 총량 기준으로 0.01∼1.0중량%가 되도록 하는 것을 특징으로 하는 내인열성 생분해성 폴리에스테르 수지의 제조방법이 제공된다.In addition, according to the present invention, one or two or more aliphatic polyester components are mixed with some of the compounds of the formula (1) as additional components to completely melt them, and the condensation reaction is selectively performed only between the aliphatic polyester components and the additional components. Addition of the compound of Formula 1 and condensation polymerization, the compound of formula 1 added to the total reaction is tear-resistant biodegradable, characterized in that 0.01 to 1.0% by weight based on the total amount of the aliphatic polyester resin component and additional components A method for producing a polyester resin is provided.
이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따르는 내인열성 생분해성 폴리에스테르 수지는 지방족 디올, 지방족 디에시드 또는 이들의 에스테르 화합물과 화학식 1의 방향족 화합물이 중합되어 선형, 가지형 또는 망목형으로 중합된 형태를 갖는다.The tear resistant biodegradable polyester resin according to the present invention has a form in which an aliphatic diol, an aliphatic dieside or an ester compound thereof and an aromatic compound of the formula (1) are polymerized into a linear, branched or meshed form.
화학식 1의 방향족 화합물은 벤젠고리의 특성으로 인하여 중합체의 내인열성을 향상시킨다. 그러나 중합체중에 화학식 1의 방향족 화합물이 점유하는 영역이 크게되면 생분해성이 낮아지거나 거의 없게 되므로 지방족 성분 모노머에 비해 상당히 낮은 함량으로 유지시키는 것이 중요하다. 따라서 본 발명에 의하면, 추가성분인 화학식 1의 방향족 화합물의 함량을 지방족 폴리에스테르 수지 성분과 추가성분의 총량 기준으로 0.01∼1.0중량%로 제한한다. 만일, 상기 범위의 상한을 초과하게 되면 생분해성이 저하되는 문제점이 있으며, 그 하한을 밑돌면 강도개선효과가 미미하게 된다. 또한, 후술되는 실시예에서 화학식 1의 화합물이 R1, R2, R3는 전부 OH 또는 COOH 인 것에 대해서만 예시되나, 당분야의 통상의 지식을 가진자라면 R1, R2, R3중 둘만이 같거나 또는 각기 다른 것도 용이하게 적용할 수 있음을 이해할 수 있을 것이다.The aromatic compound of Formula 1 improves the tear resistance of the polymer due to the properties of the benzene ring. However, if the area of the polymer occupied by the aromatic compound of Formula 1 is large, the biodegradability is low or almost absent, so it is important to maintain the content at a considerably lower content than the aliphatic monomer. Therefore, according to the present invention, the content of the aromatic compound of the general formula (1) as an additional component is limited to 0.01 to 1.0% by weight based on the total amount of the aliphatic polyester resin component and the additional component. If the upper limit of the above range is exceeded, there is a problem that the biodegradability is lowered, and below the lower limit, the strength improvement effect is insignificant. In addition, in the following examples, the compounds of Formula 1 are exemplified only for R1, R2, and R3, all of which are OH or COOH, but if one of ordinary skill in the art, only two of R1, R2, and R3 are the same or respectively. It will be appreciated that other things can be readily applied.
또한, 본 발명에서 지방족 폴리에스테르 수지 성분으로 사용되는 지방족 디올과, 지방족 디에시드 또는 이들의 에스테르 화합물은 공지의 생분해성 지방족 폴리에스테르 수지의 제조와 관련하여 잘알려져 있는 통상의 화합물을 사용하면 된다.In addition, the aliphatic diol used as an aliphatic polyester resin component in this invention, and an aliphatic dieside or its ester compound may use the conventional compound well-known in connection with manufacture of a well-known biodegradable aliphatic polyester resin.
본 발명에 따르는 중합체의 제조에 있어서, 지방족 폴리에스테르 수지 성분과 일부 추가성분 사이에서만 선택적으로 축합반응을 진행시킨 다음, 나머지의 상기 화학식 1의 화합물을 추가 투입하고 축중합시키는 것이 목적하는 생분해성 유지와 강도보강을 전부 만족시킬 수 있어 바람직하다.In the preparation of the polymer according to the present invention, the condensation reaction is carried out selectively only between the aliphatic polyester resin component and some additional components, followed by further addition and condensation polymerization of the remaining compound of formula (1). It is preferable to satisfy all of the strength reinforcement.
상기 선택적 축합반응에서는 촉매로서 칼슘트리아세테이트, 정색제로 코발트아세테이트, 열안정제로 포스포릭산 등을 사용할 수 있으며, 또한 중축합반응에서는 촉매로서 안티몬트리아세테이트, 안정제, 1,2,4-트리벤젠아세틱산, 이산화티탄 등을 첨가하고 감압조건에서 반응을 진행시킬 수도 있다.In the selective condensation reaction, calcium triacetate can be used as a catalyst, cobalt acetate as a colorant, phosphoric acid as a heat stabilizer, and antimontriacetate, stabilizer, 1,2,4-tribenzene acetate as a catalyst in the polycondensation reaction. Tic acid, titanium dioxide, and the like may be added, and the reaction may proceed under reduced pressure.
상술한 바와 같은 본 발명의 특징 및 기타의 장점은 후술되는 실시예로부터 보다 명백하게 될 것이다. 하기 실시예는 본 발명을 예시하기 위한 것일뿐 제한하기 위한 것은 아니다.Features and other advantages of the present invention as described above will become more apparent from the embodiments described below. The following examples are intended to illustrate the invention but not to limit it.
〈실시예 1〉<Example 1>
에틸렌 글리콜과 석신산의 1:2 몰비 혼합물로 이루어진 지방족 폴리에스테르 수지 성분에 추가성분으로 하기 표 1에 제시되는 투입량으로 R1과 R3 OH이고 R2가 O인 화학식 1의 화합물을 혼합하여 완전 용융시키고 촉매로서 칼슘트리아세테이트를 400ppm, 정색제로 코발트아세테이트를 60ppm, 열안정제로 포스포릭산을 150ppm를 첨가하여 지방족 폴리에스테르 수지 성분과 화학식 1의 화합물 간에 선택적인 축합반응을 진행시켰다. 결과의 축합반응 생성물에 하기 표 1에 제시되는 투입량으로 상기와 동일한 화학식 1의 화합물을 더 투입하고 촉매로서 안티몬트리아세테이트를 400ppm정도 첨가하여 중합온도 280℃, 0.3㎜Hg의 감압하에서 축중합시켜 고유점도가 0.620(㎗/g)이며 분자량 분포가 3.0인 중합체를 얻었다. 얻어진 중합체의 인열강도와 생분해도를 측정하여 그 결과를 하기 표 1에 나타내었다. 생분해도는 가성매립 30일 후의 무게감량으로 측정하였다.In addition to the aliphatic polyester resin component consisting of a 1: 2 molar ratio mixture of ethylene glycol and succinic acid, as a further component, a compound of the formula (1) in which R 1 and R 3 OH and R 2 is O is mixed and completely melted in the amounts shown in Table 1 As a result, a selective condensation reaction was performed between the aliphatic polyester resin component and the compound of formula 1 by adding 400 ppm of calcium triacetate, 60 ppm of cobalt acetate as a colorant, and 150 ppm of phosphoric acid as a heat stabilizer. Into the resulting condensation reaction product, the compound of the formula (I) as described above was further added to the resulting condensation product, and about 400 ppm of antimontriacetate was added as a catalyst. A polymer having a viscosity of 0.620 (dl / g) and a molecular weight distribution of 3.0 was obtained. The tear strength and biodegradability of the obtained polymer were measured and the results are shown in Table 1 below. Biodegradability was measured by weight loss after 30 days of caustic embedding.
〈실시예 2 내지 6〉<Examples 2 to 6>
추가성분의 종류 및 선택적 축합반응단계와 중축합단계의 투입량을 하기 표 1에 제시되는 바와 같이 변경한 것을 제외하고는 실시예 1과 동일한 절차를 반복하였다.The same procedure as in Example 1 was repeated except that the kinds of additional ingredients and the dosages of the selective condensation reaction step and the polycondensation step were changed as shown in Table 1 below.
〈비교예 1〉<Comparative Example 1>
화학식 1의 화합물을 사용함이 없이 실시예 1과 동일한 지방족 디올과 지방족 디에시드 또는 이들의 에스테르 화합물의 1:2 혼합물을 사용하여 중합체를 제조하였다. 제조된 중합체의 인열강도와 생분해도를 측정하여 그 결과를 하기 표 1에 나타내었다.A polymer was prepared using a 1: 2 mixture of the same aliphatic diols and aliphatic diesides or ester compounds thereof as in Example 1 without using the compound of Formula 1. The tear strength and biodegradation of the prepared polymers were measured and the results are shown in Table 1 below.
[표 1]TABLE 1
상기 표 1로부터 알수 있는 바와 같이, 본 발명에 의하면 생분해성 지방족 폴리에스테르에 비하여 내인열성이 훨씬 우수한 생분해성 수지를 제공하는 것이 가능하게 된다.As can be seen from Table 1, the present invention makes it possible to provide a biodegradable resin having much higher tear resistance than biodegradable aliphatic polyesters.
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KR1019970009285A KR100220223B1 (en) | 1997-03-19 | 1997-03-19 | Boidegradable polyester resin having high tear strength and preparation thereof |
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