KR100436576B1 - Melt blend composite of biodegradable polybutylene succinate having superior mechanical and thermal properties - Google Patents
Melt blend composite of biodegradable polybutylene succinate having superior mechanical and thermal properties Download PDFInfo
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Abstract
본 발명은 자연상태에서 썩거나 분해되는 즉, 환경친화적이면서도 기계적강도 및 내열성이 우수한 폴리부틸렌석시네이트의 용융블렌드 조성물에 관한 것으로, 지방족 폴리에스테르 고분자인 폴리부틸렌석시네이트 60 ~ 90 중량부, 몬모릴로나이트 2 ~ 25 중량부 및 에틸렌비닐아세테이트 2 ~ 25 중량부를 용융블렌드하여 구성되는 것을 특징으로 한다.The present invention relates to a melt blend composition of a polybutylene succinate that is rotting or decomposed in a natural state, that is, environmentally friendly and excellent in mechanical strength and heat resistance, wherein the aliphatic polyester polymer is 60 to 90 parts by weight of polybutylene succinate, 2 to 25 parts by weight of montmorillonite and 2 to 25 parts by weight of ethylene vinyl acetate.
Description
본 발명은 생분해성 고분자 조성물에 관한 것으로, 보다 상세하게는 자연상태에서 썩거나 분해되는 즉, 환경친화적이면서도 기계적강도 및 내열성이 우수한 폴리부틸렌석시네이트의 용융블렌드 조성물에 관한 것이다.The present invention relates to a biodegradable polymer composition, and more particularly, to a melt blend composition of polybutylene succinate that is decomposed or decomposed in a natural state, that is, environmentally friendly and excellent in mechanical strength and heat resistance.
최근 공해물질에 대한 엄격한 규제 및 환경오염 가능성이 있는 제품에 대한 법적규제가 부각되고 있다. 규제 대상으로 많이 거론되고 있는 플라스틱은 인간의 의식주 생활을 개선하기 위해 끊임없이 개발되어 그 사용량 또한 계속 증가추세에 있다.Recently, strict regulations on pollutants and legal regulations on products with possible environmental pollution have been highlighted. Plastics, which are widely considered to be regulated, are constantly being developed to improve human life, and their consumption is on the rise.
한 예로서 플라스틱 필름은 포장용도로서 종이를 대체하여 꾸준히 그 성장을 계속하여 플라스틱만이 가능한 새로운 시장을 개척하여 왔으나 무제한적인 사용으로 인하여 사용 후에 심각한 공해문제를 발생시키고 있다. 이러한 플라스틱 폐기물은 바다의 어류, 조류 및 해초류 등의 먹이사슬을 파괴하고 토양의 원활한 호흡기관을 단절시켜 토양을 썩게 하는 원인이 되고 있다.As an example, plastic film has been steadily growing by replacing paper as a packaging purpose, and pioneering a new market only plastic, but causing unlimited pollution after use due to unlimited use. These plastic wastes cause food chains such as fish, algae, and seaweeds in the sea and cause the soil to rot by breaking down the smooth respiratory organs of the soil.
이와 같은 환경문제가 대두됨에 따라 이들 플라스틱의 사용비중을 줄이는 노력 이외에 플라스틱의 후처리를 위한 연구가 진행되고 있다. 그 방법의 일환으로서 플라스틱이 그 용도를 다하고 버려졌을 때, 자연 상태에서 썩거나 분해되는 플라스틱을 합성하거나 그러한 플라스틱을 이용하여 가공하는 방법에 대해 꾸준한 연구가 진행되어 왔다.As such environmental problems are raised, research for post-treatment of plastics in addition to efforts to reduce the use of these plastics is being conducted. As a part of the method, when plastic is used up and discarded, steadily researches have been conducted on how to synthesize or process plastics that decay or degrade in nature.
이러한 플라스틱의 문제를 해결하고자 하는 연구는 크게 두 가지로 진행되었는데 첫번째는 100% 완전생분해성을 띄는 고분자를 합성하거나 완전생분해성 고분자끼리의 블렌드를 통하여 기존의 플라스틱을 대체하는 방법이다. 하지만, 100% 생분해성을 갖는 고분자는 대부분 물성이 취약한 단점이 있다.There are two major researches to solve the problem of plastics. The first method is to synthesize 100% biodegradable polymers or to replace existing plastics through blending of fully biodegradable polymers. However, most polymers having 100% biodegradability have disadvantages of poor physical properties.
두번째는 보다 현실적인 방법으로써 생분해성 고분자와 비분해성 고분자의 블렌드를 통하여 물성을 보완하는 방법이다. 이러한 고분자를 100% 완전생분해성고분자와 구별하기 위하여 별도로 생붕괴성고분자라 부른다.The second is a more realistic method of supplementing physical properties through blends of biodegradable and non-degradable polymers. These polymers are separately called biodegradable polymers to distinguish them from 100% fully biodegradable polymers.
생분해성을 갖는 합성고분자로서 가장 체계적으로 연구된 것이 지방족 폴리에스테르이며 그 제조방법 중의 하나는 디카르복실에시드(dicarboxylic acid)와 디올(diol)을 이용한 축중합 반응이 있다.As the biodegradable synthetic polymers, the most systematic studies are aliphatic polyesters, and one of the preparation methods is a polycondensation reaction using dicarboxylic acid and diol.
생분해성 지방족 폴리에스테르는 완전히 생분해되는 것으로 알려져 있어 환경오염 문제를 해결할 수 있는 효과적인 재료 중의 하나로 알려져 있다. 하지만 PBS는 올레핀계 고분자에 비해 기계적 물성이 떨어지는 단점이 있어 그 사용에 제약을 받고 있고 따라서 물성의 보완이 요구된다.Biodegradable aliphatic polyesters are known to be fully biodegradable and are therefore known as one of the effective materials that can solve environmental pollution problems. However, PBS has a disadvantage in that its mechanical properties are inferior to those of olefinic polymers, and thus, PBS is limited in use, and thus, supplementation of physical properties is required.
일반적으로 사용되는 디카르복실에시드로는 석시닉에시드(succinic acid),아디픽에시드(adipic acid) 등이 있으며, 디올은 에틸렌글리콜(ethylene glycol), 1,4-부탄디올(1,4-butanediol), 헥산디올(hexanediol) 등이 있다. 이들 축중합 반응에 의해 합성된 지방족 폴리에스테르의 가공성을 용이하게 하려면 용융온도의 조절이 무엇보다 중요한 인자가 된다. 또한, 최종제품의 물성을 자유롭게 조절하기 위해서는 높은 분자량의 지방족 폴리에스테르를 합성할 필요가 있다.Commonly used dicarboxylic acids include succinic acid and adipic acid, and diols include ethylene glycol and 1,4-butanediol. And hexanediol. In order to facilitate the processability of the aliphatic polyester synthesized by these polycondensation reactions, the control of the melting temperature is the most important factor. In addition, in order to freely control the physical properties of the final product it is necessary to synthesize a high molecular weight aliphatic polyester.
최근 일본의 쇼와고분자(Showa High Polymer)는 고분자량의 지방족 폴리에스테르를 합성하는데 성공하여 이를 특허등록 받았으며 Bionolle로 명명하였다. 이 중 1,4-부탄디올과 석시닉에시드에 의해 합성된 poly(butylene succinate)(PBS)는 분해성이 우수하며 융점이 폴리에틸렌(polyethylene)과 유사하나 기계적 물성이 올레핀계열의 고분자에 비해 취약하다는 단점이 있다.Recently, Showa High Polymer of Japan succeeded in synthesizing high molecular weight aliphatic polyester and registered it and named it Bionolle. Among these, poly (butylene succinate) (PBS) synthesized by 1,4-butanediol and succinic acid has excellent degradability and similar melting point to polyethylene, but its mechanical properties are weaker than that of olefin polymers. have.
즉, PBS는 우수한 생분해성을 가지고 있어 식품포장용필름 등 지금까지 환경오염의 주범으로 꼽히는 플라스틱의 용도 중 일부를 대체할 수 있는 가능이 있음에도 불구하고 기계적 물성이 비교적 취약하여 사용이 극히 제한적이었다. 따라서, 이의 기계적물성 보완이 시급한 형편이다.In other words, PBS has excellent biodegradability, and although it is possible to replace some of the plastics used as the main cause of environmental pollution such as food packaging films, its use is limited due to its relatively weak mechanical properties. Therefore, its mechanical properties are urgently needed.
상기와 같은 단점을 보완하고자 생분해성을 띄지 않는 물성이 우수한 고분자 물질과 블렌드를 하거나 유리섬유(glass fiber)와 블렌드 하였으나 계면에서의 접착력이 약하여 물성의 향상에는 별다른 효과를 거두지는 못하였다.In order to make up for the above drawbacks, the polymers were blended with high biomaterials having no biodegradability or blended with glass fibers, but the adhesive strength at the interface was weak.
최근 도요타 자동차에서 나일론6(nylon6)에 스멕타이트계 클레이의 일종인 몬모릴로나이트를 용융블렌드하여 나노복합재를 합성함으로써 자동차 엔진커버로 사용할 수 있을 정도의 급격한 기계적 강도 및 내열성의 상승효과를 나타낸 바 있다.Recently, Toyota has melted and blended montmorillonite, a kind of smectite-based clay, to nylon 6 (nylon6) to synthesize a nanocomposite material, which has shown a rapid mechanical strength and heat resistance synergistic effect that can be used as an automobile engine cover.
PBS에도 역시 섬유보강방법을 이용하여 기계적 물성의 향상을 시도하였으나 별다른 효과를 보지 못하였다. 이러한 노력의 한 가지 방법으로 최근 활발히 연구되고 있는 2:1 층간구조(2 ~ 8면체형의 3층구조)를 갖고 있는 몬모릴로나이트를 사용하여 복합재를 합성하여 물성을 측정한 결과 기계적 강도 및 내열성이 향상되었으나 신율 및 충격강도가 급격히 저하되어 PBS의 주된 용도인 필름의 용도로는 사용이 불가능하다고 판단되었다.PBS also tried to improve mechanical properties by using fiber reinforcement method, but did not see any effect. One way of this effort is to improve the mechanical strength and heat resistance of composites using montmorillonite, which has a 2: 1 interlayer structure (two-octahedral three-layer structure), which has been actively studied recently. However, the elongation and impact strength were drastically lowered, which made it impossible to use the film, which is the main use of PBS.
본 발명은 상기와 같은 문제점을 해결하기 위하여 창작된 것으로서, 본 발명의 목적은 자연상태에서 썩거나 분해되는 즉, 환경친화적이면서도 기계적강도 및 내열성이 우수한 생분해성 폴리부틸렌석시네이트의 용융블렌드 조성물을 제공하는 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to melt or decompose in a natural state, that is, environmentally friendly melt blend composition of biodegradable polybutylene succinate excellent mechanical strength and heat resistance To provide.
상기와 같은 본 발명의 목적은, 지방족 폴리에스테르 고분자인 폴리부틸렌석시네이트 60 ~ 90 중량부, 몬모릴로나이트 2 ~ 25 중량부 및 에틸렌비닐아세테이트 2 ~ 25 중량부를 용융블렌드하여 구성되는 것을 특징으로 하는 기계적강도 및 내열성이 우수한 생분해성 폴리부틸렌석시네이트(PBS)의 용융블렌드 조성물에 의하여 달성된다.An object of the present invention as described above, the mechanically characterized in that it is composed by melting and blending 60 to 90 parts by weight of polybutylene succinate, an aliphatic polyester polymer, 2 to 25 parts by weight of montmorillonite and 2 to 25 parts by weight of ethylene vinyl acetate. A melt blended composition of biodegradable polybutylene succinate (PBS) with good strength and heat resistance is achieved.
고분자의 복합재를 만드는 목적에는 가격을 낮추기 위한 경제적인 목적과 물성의 보완을 위한 목적 등 크게 두 가지가 있다. 기계적강도를 높이기 위해서는 주로 유리섬유(glass fiber), 나일론(nylon), 폴리에틸렌 테레프탈레이트(polyethyleneterephthalate; PET) 등의 섬유를 보강시키거나 무기물을 첨가하는 방법이 사용되는데 이때 물성의 보강을 위해서는 고분자 매트릭스(matrix)와 보강되는 물질간의 계면접착력 및 모폴로지(morphology)가 중요한 영향을 미친다.There are two main purposes of making composites of polymers: economical to lower prices and complementary properties. In order to increase the mechanical strength, a method of reinforcing fibers such as glass fiber, nylon, polyethylene terephthalate (PET), or adding an inorganic material is used. The interfacial adhesion and morphology between the matrix and the material being reinforced have an important effect.
본 발명에서는 PBS에 몬모릴로나이트의 2원계 용융블렌드물을 제조하여 기계적 물성을 측정한 결과 인장강도 및 모듈러스는 상승되었으나 신율 및 충격강도가 심하게 저하되어 PBS/몬모릴로나이트의 2원계 블렌드 조성만으로는 물성의 보완이 어려우므로 제 3성분인 EVA를 추가적으로 소량 첨가하여 블렌드물을 제고한 결과 인장강도와 모듈러스의 감소없이 신율과 충격강도 및 내열성을 획기적으로 개선할 수 있어 PBS/스멕타이트/EVA 3원계 조성물을 사용하면 기계적 물성이 극히 우수한 필름용도의 제품제조에 활용할 수 있다.In the present invention, the binary melt blend of montmorillonite was prepared in PBS, and the mechanical properties were measured, but tensile strength and modulus were increased, but elongation and impact strength were severely reduced. Therefore, as a result of improving the blend by adding an additional small amount of the third component EVA, it is possible to dramatically improve elongation, impact strength and heat resistance without decreasing tensile strength and modulus, and thus, mechanical properties can be improved by using PBS / Smectite / EVA tertiary composition. It can be used to manufacture products of this extremely excellent film use.
즉, 제 3성분으로 에틸렌비닐아세테이트를 사용한 경우, 몬모릴로나이트만을 첨가하였을 때와 비슷한 인장강도와 모듈러스를 띄면서도 신율과 충격강도를 극대화하여 물성의 획기적인 개선을 할 수 있도록 하였다.That is, when ethylene vinyl acetate was used as the third component, the tensile strength and modulus similar to those when only montmorillonite was added, while the elongation and impact strength were maximized to drastically improve the physical properties.
본 발명의 그 밖의 목적, 특정한 장점 및 신규한 특징들은 첨부된 도면들과 연관되어지는 이하의 발명의 상세한 설명과 바람직한 실시예로부터 더욱 분명해질 것이다.Other objects, specific advantages, and novel features of the present invention will become more apparent from the following detailed description of the invention and the preferred embodiments in connection with the accompanying drawings.
이하 본 발명에 따른 상기 기계적강도 및 내열성이 우수한 생분해성 폴리부틸렌석시네이트의 용융블렌드 조성물의 구성에 대하여 설명하기로 한다.Hereinafter, the configuration of the melt blend composition of the biodegradable polybutylene succinate excellent in mechanical strength and heat resistance according to the present invention will be described.
상기 용융블렌드는 트윈스크루 압출기(twin-screw extruder)를 사용하여 145℃에서 60rpm의 회전속도로 실시되었다. 사용된 PBS는 수평균 분자량이 58,000 g/mol 이었고, 중량평균 분자량은 150,000 g/mol 이었다. PSB는 60 ~ 90 중량부이며 몬모릴로나이트는 southern clay (USA)사의 유기 몬모릴로나이트인 cloisite 30B를 2 ~ 25 중량부를 사용하였으며 에틸렌비닐 아세테이트는 2 ~ 25 중량부를 사용하였다. 상기 에틸렌비닐 아세테이트 100 중량부 중에는 비닐아세테이트 함량이 50 ~ 90 중량부 포함되어 있다.The melt blend was carried out at a rotational speed of 60 rpm at 145 ° C. using a twin-screw extruder. The PBS used had a number average molecular weight of 58,000 g / mol and a weight average molecular weight of 150,000 g / mol. PSB is 60 to 90 parts by weight, montmorillonite is 2 to 25 parts by weight of cloisite 30B, organic montmorillonite of southern clay (USA), and 2 to 25 parts by weight of ethylene vinyl acetate. In 100 parts by weight of the ethylene vinyl acetate, vinyl acetate content is contained 50 to 90 parts by weight.
몬모릴로나이트의 표면은 친수성을 띄므로 고분자사슬과의 친화력이 좋지 못하여 고분자가 층간으로 쉽게 삽입되기 힘들다. 따라서 고분자 사슬이 쉽게 삽입되게 하기 위하여 이온교환반응을 통하여 몬모릴로나이트의 표면을 개질하여 사용하는 것이 보통이다.Since the surface of montmorillonite is hydrophilic, its affinity with the polymer chain is poor, making it difficult to easily insert the polymer into the interlayer. Therefore, it is common to modify the surface of montmorillonite through ion exchange reaction in order to easily insert the polymer chain.
본 발명에 사용된 몬모릴로나이트는 표면이 메틸타로우비스-2-히드록시에틸암모늄(methyl tallow bis-2-hydroxyethyl ammonium)으로 치환되어 있으며 이의 유기치환체 농도(modifier concentration)는 75 ~ 130 meq/100g 이다.The montmorillonite used in the present invention is substituted with methyl tallow bis-2-hydroxyethyl ammonium on its surface and its organic substituent concentration is 75 to 130 meq / 100 g. .
압출기를 통과하여 나온 블렌드물은 펠렛타이저(pelletizer)를 사용하여 펠렛으로 만들어졌고 150℃에서 3분 동안 핫프레스(hot press)를 사용하여 필름으로 만든 뒤 인장시험을 위하여 가로 10mm, 길이 50mm, 두께 0.2mm의 크기로 만들었다. 비교시험을 위하여는 유리섬유(glass fiber)와 몬모릴로나이트를 사용하여 같은 방법으로 용융블렌드를 실시하였다.The blend from the extruder was pelleted using a pelletizer, made into a film using a hot press for 3 minutes at 150 ° C, and then 10 mm wide and 50 mm long for tensile testing. Made to a size of 0.2 mm thick. For the comparative test, the melt blend was performed in the same manner using glass fiber and montmorillonite.
또한, 본 발명에서는 열안정성을 알아보기 위해서는 각 샘플 10mg 정도를 열분석기(thermal gravimetry analyzer)를 사용하여 분당 20℃의 승온속도로 측정하였다.In addition, in the present invention, in order to determine the thermal stability, about 10 mg of each sample was measured at a temperature rising rate of 20 ° C. per minute using a thermal gravimetry analyzer.
PBS에 유리섬유가 첨가된 경우에는 인장강도와 인장모듈러스가 상승하였으나 그다지 뚜렷한 물성의 향상은 보이지 않았다. 특히 신율의 감소가 뚜렷하게 나타나서 식품포장 등의 필름용으로의 사용에는 적합하지 않다고 판단되었다.When glass fiber was added to PBS, tensile strength and tensile modulus were increased, but there was no significant improvement in physical properties. In particular, the decrease in elongation was obvious, and it was judged that the elongation was not suitable for use in films such as food packaging.
유기화제로 치환된 몬모릴로나이트를 사용한 경우에는 유리섬유가 보다 휠씬 소량이 첨가됨에도 불구하고 인장강도와 인장모듈러스의 상승이 뚜렷하게 나타났으나 신율의 저하가 매우크게 나타났다. 뿐만 아니라 충격강도 역시 급격한 감소현상이 나타났다. 이의 보완을 위하여 비닐아세트의 함량이 70%인 에틸렌비닐 아세테이트를 사용하여 PBS/몬모릴로나이트/에틸렌비닐아세테이트의 3성분계를 만든 결과 인장강도, 인장모듈러스, 신율, 충격강도, 노화 후 기계적강도가 모두 획기적으로 개선되었다.In the case of using montmorillonite substituted with an organizing agent, although a much smaller amount of glass fiber was added, the tensile strength and tensile modulus were clearly increased, but the elongation was greatly decreased. In addition, the impact strength also decreased drastically. To compensate for this, three-component system of PBS / montmorillonite / ethylenevinylacetate was used using ethylene vinyl acetate containing 70% vinylacetate. Improvements were made.
표 1에서는 상기 용융블렌드 조성물의 배합성분을 나타내었으며 표 2에서는 물성평가 결과를 나타내었다.Table 1 shows the blending components of the melt blend composition and Table 2 shows the results of the physical property evaluation.
* 몬모릴로나이트는 M(Al4xMgx)Si8O20(OH)4의 구조식을 띄고 있으며 M은 1가의양이온을 띄는 금속, x는 구조상 치환정도(degree of isomorphous substition)를 나타내는 값으로 0.5 에서 1.3 사이의 값을 갖는다.* Montmorillonite has a structural formula of M (Al4 x Mg x ) Si 8 O 20 (OH) 4 , M is a monovalent cation metal, x is a degree of isomorphous substition, and is 0.5 to 1.3. Has a value between
* 유리섬유는 직경이 0.12 ㎛, 길이 5 mm의 제품을 사용하였음.* Glass fiber used was 0.12 ㎛ in diameter and 5 mm in length.
* EVA는 중량평균분자량이 285,000 g/mol의 제품을 사용하였고 비닐아세테이트의 함량은 70%이다.* EVA has a weight average molecular weight of 285,000 g / mol and the vinyl acetate content is 70%.
* 노화는 70℃의 오븐에서 48시간 동안 진행하였음.Aging was carried out for 48 hours in an oven at 70 ℃.
* Tmax는 열분석기(thermal gravimetry analyzer) 상에서 98%의 중량을 유지하는 온도임.* T max is the temperature of 98% on a thermal gravimetry analyzer.
상기 언급한 바와 같이 본 발명에 따른 기계적강도 및 내열성이 우수한 생분해성 폴리부틸렌석시네이트의 용융블렌드 조성물에 의하면, 인장강도, 인장모듈러스 및 내열성이 우수하며 신율, 충격강도, 노화 후 인장잔율, 노화 후 신장잔율이 획기적으로 개선되었다.As mentioned above, according to the melt blend composition of biodegradable polybutylene succinate having excellent mechanical strength and heat resistance according to the present invention, it has excellent tensile strength, tensile modulus and heat resistance, and has elongation, impact strength, tensile residual after aging, and aging. Afterwards, the residual height improved dramatically.
비록 본 발명이 상기 언급된 바람직한 실시예와 관련하여 설명되어졌지만, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 따라서 첨부된 특허청구범위는 본 발명의 요지에 속하는 이러한 수정이나 변형을 포함한다.Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims include such modifications and variations as fall within the spirit of the invention.
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| US5731402A (en) * | 1995-04-25 | 1998-03-24 | Tokuyama Corporation | Biodegradable aliphatic polyester, melt-extrusion film thereof, and process for the production thereof |
| US5750218A (en) * | 1994-06-22 | 1998-05-12 | Tokuyama Corporation | Biodegradable aliphatic polyester, melt-extrusion film thereof, and process for the production thereof |
| KR19980083265A (en) * | 1997-05-13 | 1998-12-05 | 김윤 | Method for preparing biodegradable aliphatic polyester resin |
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| US5783271A (en) * | 1993-10-29 | 1998-07-21 | Tokuyama Corporation | Biodegradable alipathic polyster, melt-extrusion film thereof, and process for the production thereof |
| US5750218A (en) * | 1994-06-22 | 1998-05-12 | Tokuyama Corporation | Biodegradable aliphatic polyester, melt-extrusion film thereof, and process for the production thereof |
| US5731402A (en) * | 1995-04-25 | 1998-03-24 | Tokuyama Corporation | Biodegradable aliphatic polyester, melt-extrusion film thereof, and process for the production thereof |
| KR19980083265A (en) * | 1997-05-13 | 1998-12-05 | 김윤 | Method for preparing biodegradable aliphatic polyester resin |
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