KR20080054278A - Synthesis method of biodegradable polyester mixed with aliphatic and aromatic compounds - Google Patents
Synthesis method of biodegradable polyester mixed with aliphatic and aromatic compounds Download PDFInfo
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- 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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Abstract
본 발명은 방향족과 지방족 화합물이 혼재된 생분해성 폴리에스테르의 합성방법에 관한 것으로서, 더욱 상세하게는 디카르복실산(dicarboxylic acid) 및 디올(diol)로 합성된 방향족 에스테르 올리고머와 지방족 락톤 화합물인 락티드 또는 카프로락톤의 개환 중합에 의한 방향족과 지방족 화합물이 한 분자내에 혼재하는 생분해성 폴리에스테르의 합성방법에 관한 것이다.The present invention relates to a method for synthesizing a biodegradable polyester mixed with an aromatic and aliphatic compound, and more particularly, an aromatic ester oligomer and an aliphatic lactone compound synthesized from dicarboxylic acid and diol. A method for synthesizing biodegradable polyesters in which an aromatic and aliphatic compound is mixed in one molecule by ring-opening polymerization of tide or caprolactone.
본 발명에 따르면, 에스테르 올리고머내에 존재하는 디카르복실산(dicarboxylic acid) 및 디올(diol)을 조합화학적으로 변화시킴으로써 다양하고 우수한 물성을 가지는 생분해성 폴리에스테르를 합성할 수 있다.According to the present invention, biodegradable polyester having various and excellent physical properties can be synthesized by combinatorially changing the dicarboxylic acid and diol present in the ester oligomer.
Description
도 1은 방향족 에스테르 올리고머와 락티드의 개환 중합에 의한 폴리에스테르 합성 반응식을 나타낸 것이다.1 shows a polyester synthesis reaction scheme by ring-opening polymerization of an aromatic ester oligomer and lactide.
도 2는 방향족 에스테르 올리고머와 카프로락톤의 개환 중합에 의한 폴리에스테르 합성 반응식을 나타낸 것이다.2 shows a polyester synthesis reaction scheme by ring-opening polymerization of an aromatic ester oligomer and caprolactone.
발명의 분야Field of invention
본 발명은 방향족과 지방족 화합물이 혼재된 생분해성 폴리에스테르의 합성방법에 관한 것으로서, 더욱 상세하게는 디카르복실산(dicarboxylic acid) 및 디올(diol)로 합성한 방향족 에스테르 올리고머와 지방족 락톤 화합물인 락티드 또는 카프로락틴의 개환 중합에 의해 방향족과 지방족 화합물이 한 분자내에 혼재하는 생분해성 폴리에스테르의 합성방법에 관한 것이다.The present invention relates to a method for synthesizing a biodegradable polyester mixed with an aromatic and aliphatic compound, and more particularly, an aromatic ester oligomer and an aliphatic lactone compound synthesized from dicarboxylic acid and diol. A method for synthesizing biodegradable polyesters in which aromatic and aliphatic compounds are mixed in one molecule by ring-opening polymerization of tide or caprolactin.
배경기술Background
생분해성 고분자 소재는 고유한 분해 특성으로 인하여 의학, 농학, 환경 등 여러 분야에서 각광받고 있는 소재이며, 특히 환경 및 의학 분야에서의 그 가치가 급격히 증대되고 있는 물질이다. Biodegradable polymer materials are in the spotlight in various fields such as medicine, agriculture, and the environment due to their inherent decomposition properties, and in particular, their values are rapidly increasing in the fields of environment and medicine.
생분해성 고분자는 크게 천연 생분해성 고분자와 합성 생분해성 고분자로 나뉘어 진다. 이 중에서 천연 생분해성 고분자는 원료가 천연물이므로 환경에 대한 친화력이 높고, 물리적인 성능이나 생명체에 대한 적응성이 높아 유력한 물질로서 인식되어지고 있으나, 고가이며 천연 물질의 특성상 그 물성을 임의대로 조절하기 어려운 것이 큰 단점으로 지적되고 있다. 반면, 합성 생분해성 고분자는 천연 생분해성 고분자가 가지지 못한 점을 인위적으로 조절하여 보완할 수 있다는 장점이 있어, 최근 들어 그 상업적 가치가 매우 높게 평가되고 있다.Biodegradable polymers are largely divided into natural biodegradable polymers and synthetic biodegradable polymers. Among them, natural biodegradable polymers are recognized as potential materials because they have high affinity for the environment and high physical performance and adaptability to living organisms because they are natural, but they are expensive and difficult to control their properties arbitrarily due to the characteristics of natural materials. It is pointed out as a big disadvantage. On the other hand, synthetic biodegradable polymers have the advantage that they can be compensated by artificially controlling the points that natural biodegradable polymers do not have, and the commercial value of these has been highly evaluated in recent years.
이들 합성 생분해성 고분자 소재 중 폴리락티드(PLA)는 비교적 그 성능이 우수하고, 환경 또는 생체에 대한 안정성 및 무독성 등으로 인하여 의학 분야에서 각종 용도로 다양하게 이용되고 있다. Among these synthetic biodegradable polymer materials, polylactide (PLA) is relatively excellent in performance, and is widely used in various fields in the medical field due to stability and nontoxicity to the environment or a living body.
기존에 적용되던 폴리에틸렌테레프탈릭산(PET:polyethylene terephthalic acid)나 PPT, PBT, 폴리에틸렌 2,6-나프탈렌(PEN:polyethylene 2,6-naphthalene)과 같은 테레프탈릭산(terephthalic acid), 나프탈렌디카르복실산(naphthalene dicarboxylic acid), 퓨란-2,5-디카르복실산(furane-2,5-dicarboxylic acid)과 같 은 방향족이 함유된 고분자 수지는 생분해성이 결여되어 있어 미생물에 의한 분해가 가능하도록 아디픽산(adipic acid), 숙신산(succinic acid)과 같은 지방족 카르복실산(dicarboxylic acid)을 첨가하여 생분해성을 증가시킨 다양한 수지들이 개발되었다 (예, BASF Ecoflex®, Ecovio®, DuPont Biomax®). 또한 천연자원인 탄수화물의 발효에 의해 생성된 젖산을 락티드 형태로 만들어 개환중합한 폴리락티드(PLA)는 지방족 화합물로 이루어진 생분해성 폴리에스테르로 생분해성이 높으나 제조원가가 비싸고, 물성 면에서 가공이나 사용이 제한적인 단점이 있었다.Polyethylene terephthalic acid (PET), terephthalic acid (naphthalene dicarboxylic acid) such as PPT, PBT, polyethylene 2,6-naphthalene (PEN) Polymer resins containing aromatics, such as naphthalene dicarboxylic acid and furane-2,5-dicarboxylic acid, lack biodegradability and can be decomposed by microorganisms. Various resins have been developed that increase the biodegradability by addition of aliphatic carboxylic acids such as adipic acid and succinic acid (eg BASF Ecoflex ® , Ecovio ® , DuPont Biomax ® ). In addition, polylactide (PLA), which is ring-opened and polymerized by lactic acid produced by the fermentation of carbohydrates, which is a natural resource, is a biodegradable polyester made of aliphatic compounds. There was a drawback of limited use.
일본공개특허 2004-506773는 락톤을 베이스로 하는 지방족 폴리에스테르와 지방족 및 방향족 블록을 베이스로 하는 부분 방향족 코폴리에스테르로 구성된 생분해성 폴리머 블랜드를 개시하고 있다. 그러나 상기 코폴리에스테르는 방향족 및 지방족 디카르복실산과 디올 성분의 중축합에 의해 형성되고, 이러한 축합반응은 부산물이 생성되어 공정이 매우 복잡하다는 단점이 있다.Japanese Laid-Open Patent Publication No. 2004-506773 discloses a biodegradable polymer blend composed of aliphatic polyesters based on lactones and partially aromatic copolyesters based on aliphatic and aromatic blocks. However, the copolyester is formed by polycondensation of aromatic and aliphatic dicarboxylic acids and diol components, and this condensation reaction has a disadvantage in that a by-product is generated and the process is very complicated.
따라서 생분해성 폴리에스테르를 범용으로 사용하기 위해서 기존의 고분자와 혼합(blend), 결정화를 유도하는 화합물의 첨가에 의한 물성변화, 스테레오블럭 폴리락티드(stereoblock PLA)등 다양한 물성 향상 방법이 시도되고 있다. Therefore, in order to use biodegradable polyester for general purposes, various physical properties improvement methods such as blending with existing polymers and addition of compounds that induce crystallization and stereoblock PLA are being tried. .
이에, 본 발명자들은 다양한 물성을 가지는 생분해성 폴리에스테르를 개발하기 위하여 예의 노력한 결과, 방향족 락톤 화합물로서 사이클릭 에스테르 올리고머 와 지방족 락톤 화합물인 락티드 또는 카프로락톤의 개환중합에 의해 방향족과 지방족이 혼재하는 폴리에스테르가 합성되는 것을 확인하고, 본 발명을 완성하게 되었다.Therefore, the present inventors have made intensive efforts to develop biodegradable polyesters having various physical properties. As a result, aromatic and aliphatic mixtures are mixed by ring-opening polymerization of cyclic ester oligomers and aliphatic lactone compounds, such as lactide or caprolactone, as aromatic lactone compounds. It confirmed that polyester was synthesize | combined and came to complete this invention.
결국, 본 발명의 주된 목적은 디카르복실산(dicarboxylic acid) 및 디올(diol)로 합성한 방향족 에스테르 올리고머와 지방족 화합물을 개환중합시키는 것을 특징으로 하는 방향족과 지방족 화합물이 한 분자내에 혼재하는 생분해성 폴리에스테르의 제조방법을 제공하는 데 있다.After all, the main object of the present invention is the biodegradability in which aromatic and aliphatic compounds are mixed in one molecule, which is characterized by ring-opening polymerization of an aromatic ester oligomer and an aliphatic compound synthesized with dicarboxylic acid and diol. It is to provide a method for producing a polyester.
본 발명의 다른 목적은 상기 제조방법에 의하여 제조된 생분해성 폴리에스테르를 제공하는 데 있다.Another object of the present invention to provide a biodegradable polyester produced by the above production method.
상기 목적을 달성하기 위하여, 본 발명은 디카르복실산(dicarboxylic acid) 및 디올(diol)로 합성된 방향족 에스테르 올리고머와 지방족 화합물을 개환중합시키는 것을 특징으로 하는 방향족과 지방족 화합물이 한 분자내에 혼재하는 생분해성 폴리에스테르의 제조 방법을 제공한다.In order to achieve the above object, the present invention is an aromatic and aliphatic compound mixed in one molecule, characterized in that the ring-opening polymerization of the aromatic ester oligomer and aliphatic compound synthesized with dicarboxylic acid and diol (diol) Provided are methods of making biodegradable polyesters.
본 발명에 있어서, 상기 카르복실산은 테레프탈릭산(terephthalic acid), 이소테레프탈릭산(isoterephthalic acid), 시클로헥산디카르복실산(cyclohexane dicarboxylic acid), 나프탈렌디카르복실산(naphthalene dicarboxylic acid) 및 퓨란-2,5-디카르복실산(furane-2,5-dicarboxylic acid)으로 이루어진 군에서 선택되는 것을 특징으로 할 수 있고, 상기 디올(diol)은 에틸렌글리콜(ethylene glycol), 1,3-프로판디올(1.3-propanediol), 1,4-부타네디올(1,4-butanediol), 시클로헥산네디메탄올(cyclohexanedimethanol), 이소솔비드(isosorbide), 2,5-비스-하이드록시메틸푸란(2,5-bis-hydroxymethyl furan) 및 2-비스-하이드록시메틸테드라하이드록시푸란(2-bis-hydroxymethyl tetrahydroxyfuran)으로 이루어진 군에서 선택되는 것을 특징으로 할 수 있으며, 상기 지방족 화합물은 카프로락톤, 락티드, 카프로락틴 및 락티드로 이루어진 군에서 선택되는 것을 특징으로 할 수 있다.In the present invention, the carboxylic acid is terephthalic acid (terephthalic acid), isoterephthalic acid (isoterephthalic acid), cyclohexane dicarboxylic acid (cyclohexane dicarboxylic acid), naphthalene dicarboxylic acid (naphthalene dicarboxylic acid) and furan-2 , 5-dicarboxylic acid (furane-2,5-dicarboxylic acid) may be selected from the group consisting of, the diol (diol) is ethylene glycol (ethylene glycol), 1,3-propanediol ( 1.3-propanediol), 1,4-butanediol (1,4-butanediol), cyclohexanedimethanol, isosorbide, 2,5-bis-hydroxymethylfuran (2,5- bis-hydroxymethyl furan) and 2-bis-hydroxymethyl tetrahydroxyfuran (2-bis-hydroxymethyl tetrahydroxyfuran) may be selected from the group consisting of, and the aliphatic compound is caprolactone, lactide, car Sun in the group consisting of prolactin and lactide That may be characterized.
본 발명에 있어서, 상기 개환중합 반응시 촉매를 더 첨가하는 것을 특징으로 할 수 있고, 상기 촉매는 틴(II)비스-2-에틸헥사노익산(틴옥토에이트)(tin (II) bis-2-ethylhexanoic acid (tinn octoate)) 또는 디조르티타늄테트라알콕사이드(Tyzor titanium tetraalkoxide)인 것을 특징으로 할 수 있다. In the present invention, the ring-opening polymerization may be further added to the catalyst, the catalyst is tin (II) bis-2-ethylhexanoic acid (tin octoate) (tin (II) bis-2 -ethylhexanoic acid (tinn octoate)) or dizortitanium tetraalkoxide (Tyzor titanium tetraalkoxide) may be characterized.
본 발명은 또한, 다음 화학식Ⅱ로 표시되는 생분해성 폴리에스테르를 제공한다:The present invention also provides a biodegradable polyester represented by the following formula (II):
[화학식Ⅱ][Formula II]
본 발명은 또한, 다음 화학식Ⅲ로 표시되는 생분해성 폴리에스테르를 제공한다:The present invention also provides a biodegradable polyester represented by the following formula III:
[화학식Ⅲ][Formula III]
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 기존의 접근방식과는 달리 직접 폴리에스테르 분자내에 방향족과 지방족이 혼재하도록 개환중합반응을 사용한다. 도 1에 나타난 바와 같이, 디카르복실산과 디올로 사이클릭 에스테르 올리고머를 합성한 다음, 지방족 화합물인 락티드와 개환 중합시켜 지방족과 방향족 화합물이 혼재된 생분해성 폴리에스테르를 제조할 수 있다.In the present invention, unlike the conventional approach, the ring-opening polymerization reaction is used to directly mix aromatic and aliphatic in polyester molecules. As shown in FIG. 1, a dicarboxylic acid and a diol cyclic ester oligomer may be synthesized and then ring-opened polymerized with an aliphatic lactide to prepare a biodegradable polyester having a mixture of aliphatic and aromatic compounds.
본 발명에서, 상기 사이클릭 에스테르 올리고머 합성시, 디카르복실산과 디올의 함량 비율에 따라 최종 생분해성 폴리에스테르의 물성을 다양하게 변화시킬 수 있고, 사이클릭 에스테르 올리고머와 락티드의 함량 비율에 따라 다양한 물성을 가질 수 있다. In the present invention, when synthesizing the cyclic ester oligomer, the physical properties of the final biodegradable polyester can be variously changed according to the content ratio of the dicarboxylic acid and the diol, and the content varies depending on the content ratio of the cyclic ester oligomer and the lactide. It may have physical properties.
상기 사이클릭 에스테르 올리고머는 디카르복실산(dicarboxylic acid) 및 디올(diol)에 의해서 합성되고, 상기 카르복실산은 테레프탈릭산(terephthalic acid), 이소테레프탈릭산(isoterephthalic acid), 시클로헥산디카르복실산(cyclohexane dicarboxylic acid), 나프탈렌디카르복실산(naphthalene dicarboxylic acid) 및 퓨란-2,5-디카르복실산(furane-2,5-dicarboxylic acid)으로 이루어진 군에서 선택하여 사용할 수 있고, 상기 디올(diol)은 에틸렌글리 콜(ethylene glycol), 1,3-프로판디올(1.3-propanediol), 1,4-부타네디올(1,4-butanediol), 시클로헥산네디메탄올(cyclohexanedimethanol), 이소솔비드(isosorbide), 2,5-비스-하이드록시메틸푸란(2,5-bis-hydroxymethyl furan) 및 2-비스-하이드록시메틸테드라하이드록시푸란(2-bis-hydroxymethyl tetrahydroxyfuran)으로 이루어진 군에서 선택하여 사용할 수 있다. The cyclic ester oligomer is synthesized by dicarboxylic acid (dicarboxylic acid) and diol (diol), the carboxylic acid is terephthalic acid (terephthalic acid), isoterephthalic acid (isoterephthalic acid), cyclohexanedicarboxylic acid ( cyclohexane dicarboxylic acid), naphthalene dicarboxylic acid (naphthalene dicarboxylic acid) and furan-2,5-dicarboxylic acid (furane-2,5-dicarboxylic acid) can be selected from the group consisting of, the diol (diol ) Is ethylene glycol, 1,3-propanediol (1.3-propanediol), 1,4-butanediol (1,4-butanediol), cyclohexanedimethanol, isosorbide ), 2,5-bis-hydroxymethyl furan and 2-bis-hydroxymethyl tetrahydroxyfuran Can be.
상기 락티드는 L,L-락티드, D,L-락티드, D,D-락티드로부터 선택하여 사용할 수 있다. The lactide may be selected from L, L-lactide, D, L-lactide, and D, D-lactide.
상기 지방족 화합물은 카프로락톤, 락티드, 카프로락톤 및 락티드로 이루어진 군에서 선택하여 사용할 수 있다.The aliphatic compound may be selected from the group consisting of caprolactone, lactide, caprolactone and lactide.
또한, 상기 개환중합 반응시 사용되는 촉매는 일반적으로 락톤의 개환중합촉매로 사용될 수 있는 촉매라면 제한없이 사용 가능하고, 대표적으로 틴(II)비스-2-에틸헥사노익산(틴옥토에이트)[tin (II) bis-2-ethylhexanoic acid (tinn octoate)] 또는 디조르티타늄테트라알콕사이드(Tyzor titanium tetraalkoxide)를 사용할 수 있다.In addition, the catalyst used in the ring-opening polymerization reaction can be generally used without limitation as long as it can be used as a ring-opening polymerization catalyst of lactone. tin (II) bis-2-ethylhexanoic acid (tinn octoate)] or Tyzor titanium tetraalkoxide.
개환중합에 의한 고분자의 합성 방법은 다음과 같다. L,L-락티드, D,L-락티드, D,D-락티드와 사이클릭 에스테르 올리고머의 공중합체는 틴 옥틸레이트(tin octylate)의 촉매 존재에서 상기의 다양한 두 모노머를 넣고, 질소로 채운 다음, 마개를 한 뒤 180도에서 30분 내지 1시간 반응하여 얻을 수 있다. 상기 방법으로 얻어진 고분자를 GPC로 분석하여 수평균 분자량을 얻을 수 있다. 카프로락톤과 사이클릭 에스테르 올리고머의 공중합체 또는 L,L-락티드, D,L-락티드, D,D-락티드, 카프로락톤, 사이클릭 에스테르 올리고머의 공중합체도 틴 옥틸레이트(tin octylate)의 촉재 존재에서 동일한 방법으로 합성할 수 있다. The synthesis method of the polymer by ring-opening polymerization is as follows. Copolymers of L, L-lactide, D, L-lactide, D, D-lactide and cyclic ester oligomers are prepared by adding these two monomers in the presence of a catalyst of tin octylate, After filling, stopper may be obtained by reacting at 180 degrees for 30 minutes to 1 hour. The polymer obtained by the above method can be analyzed by GPC to obtain a number average molecular weight. Copolymers of caprolactone and cyclic ester oligomers or copolymers of L, L-lactide, D, L-lactide, D, D-lactide, caprolactone, and cyclic ester oligomers may also be octylates (tin octylate). Synthesis can be carried out in the same manner in the presence of a catalyst.
이상에서 상세히 설명하고 입증하였듯이, 디카르복실산(dicarboxylic acid) 및 디올(diol)로 합성한 방향족 에스테르 올리고머와 지방족 락톤 화합물인 락티드 또는 카프로락톤의 개환 중합에 의해 방향족과 지방족 화합물이 한 분자내에 혼재하는 생분해성 폴리에스테르의 합성방법을 제공하는 효과가 있다. As described and demonstrated in detail above, the aromatic and aliphatic compounds are contained in one molecule by ring-opening polymerization of the aromatic ester oligomer synthesized with dicarboxylic acid and diol and the aliphatic lactone compound lactide or caprolactone. There is an effect of providing a method for synthesizing mixed biodegradable polyester.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013183874A1 (en) * | 2012-06-05 | 2013-12-12 | 에스케이케미칼주식회사 | Polyester resin and method for manufacturing same |
| KR20190073117A (en) * | 2017-12-18 | 2019-06-26 | 한국생산기술연구원 | Lactone-based polymer through ring opening reaction and method for preparing the same |
| WO2025127436A1 (en) * | 2023-12-11 | 2025-06-19 | 코오롱인더스트리 주식회사 | Polyester resin and preparation method therefor |
| WO2025143662A1 (en) * | 2023-12-27 | 2025-07-03 | 코오롱인더스트리 주식회사 | Polyester resin composition and method for predicting properties thereof |
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| KR100537211B1 (en) | 2003-03-04 | 2005-12-16 | 학교법인 한양학원 | Biodegradable aliphatic polyester ionomeric resin and its preparing method |
| KR100525476B1 (en) * | 2003-06-19 | 2005-11-02 | 도레이새한 주식회사 | Preparing method of Biodegradable polyester copoly with improved cutting property and mechar |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013183874A1 (en) * | 2012-06-05 | 2013-12-12 | 에스케이케미칼주식회사 | Polyester resin and method for manufacturing same |
| US9279033B2 (en) | 2012-06-05 | 2016-03-08 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
| KR20190073117A (en) * | 2017-12-18 | 2019-06-26 | 한국생산기술연구원 | Lactone-based polymer through ring opening reaction and method for preparing the same |
| WO2025127436A1 (en) * | 2023-12-11 | 2025-06-19 | 코오롱인더스트리 주식회사 | Polyester resin and preparation method therefor |
| WO2025143662A1 (en) * | 2023-12-27 | 2025-07-03 | 코오롱인더스트리 주식회사 | Polyester resin composition and method for predicting properties thereof |
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