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WO2013010290A1 - 一种可用土壤掩埋法进行生物分解的组合物及其制品 - Google Patents

一种可用土壤掩埋法进行生物分解的组合物及其制品 Download PDF

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Publication number
WO2013010290A1
WO2013010290A1 PCT/CN2011/001178 CN2011001178W WO2013010290A1 WO 2013010290 A1 WO2013010290 A1 WO 2013010290A1 CN 2011001178 W CN2011001178 W CN 2011001178W WO 2013010290 A1 WO2013010290 A1 WO 2013010290A1
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composition
acid
poly
polyhydroxyalkanoate
hydroxybutyrate
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PCT/CN2011/001178
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English (en)
French (fr)
Inventor
吕渭川
张谦
胡文艳
程曼
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Tianjin Greenbio Material Co Ltd
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Tianjin Greenbio Material Co Ltd
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Priority to PCT/CN2011/001178 priority Critical patent/WO2013010290A1/zh
Publication of WO2013010290A1 publication Critical patent/WO2013010290A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a composition which is biodegradable and belongs to the field of polymer technology, and more particularly to a composition which can be decomposed in a common soil environment; the present invention also relates to an article of the composition.
  • Polylactic acid is a polymer obtained by artificial chemical synthesis of lactic acid produced by biological fermentation, which maintains good biocompatibility and biodegradability.
  • Polylactic acid has similar impermeability to polyester, has similar gloss, clarity and processability to polystyrene, and provides lower temperature heat sealability than polyolefin. It can be processed by melt processing technology.
  • Various packaging plastics such as plastic profiles for plastics and construction, films, and non-woven fabrics and polyester fibers for chemical and textile industries.
  • the production energy of polylactic acid is only 20%_50% of that of traditional petrochemical products, and only 50% of the carbon dioxide gas is produced.
  • Polylactic acid materials can be completely decomposed under composting conditions, but it takes a long time, which is far from meeting people's increasingly demanding environmental protection, not to mention decomposition in general soil. What is more serious is that compost decomposition needs to establish specific Composting facilities also need to provide compostable organic matter, which greatly increases the cost of waste disposal. In real life, it is very difficult for plastics to be completely recycled. There is still a large amount of plastic waste left in the environment, which seriously pollutes the living environment of residents. How to improve the degradation rate of waste polylactic acid products and reduce the cost of waste disposal is one of the problems to be solved in environmental protection work today.
  • the present invention provides a composition formed by blending polylactic acid and a polyhydroxyalkanoate, which can be treated by a soil burying method, and the composition is very It completely decomposes in the soil quickly, which not only increases the decomposition rate of the polylactic acid material, but also reduces the processing cost of the polylactic acid product.
  • the present invention also provides an article of the composition comprising a heat-shrinkable film of a food package, a plastic sheet, a foamed material, a woven product, which can be quickly decomposed in a natural environment after being discarded.
  • Polyhydroxyalkanoate is a class of biodegradable materials that can be completely decomposed into carbon dioxide and water in the natural environment. Decomposition is first of all under certain conditions, a variety of microorganisms attached to the surface of the polymer to release a specific decomposing enzyme, under the catalysis of the enzyme, the polymer is broken down into small segments, when the molecular weight drops to a certain extent, it will be very It is easily absorbed by microorganisms and digested. Many factors have an impact on the decomposition process of the material. In a sense, the structure of the material determines the strength of biodegradability.
  • a composition which can be biodegraded by soil burying method comprising polylactic acid and polyhydroxyalkanoate, the polyhydroxyalkanoate accounting for 20%-90 of the mass fraction of the composition. %.
  • the polyhydroxyalkanoate comprises from 25% to 75% of the mass fraction of the composition.
  • the polyhydroxyalkanoate is selected from the group consisting of poly(3-hydroxybutyric acid-CO-3-hydroxyvaleric acid), poly(3-hydroxybutyric acid-CO-3-hydroxyhexanoic acid), poly(3) - hydroxyvaleric acid -CO-3-hydroxyhexanoic acid), one of poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester.
  • the polyhydroxyalkanoate is poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester, wherein a component of the monomer unit 4-hydroxybutyric acid accounts for the poly(3-hydroxyl group) 5% to 20% by mass ratio of butyric acid-CO-4-hydroxybutyrate), and the poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester has a weight average molecular weight of 300,000 to 400,000 The crystallinity is between 43% and 53%.
  • the polylactic acid is L-polylactic acid having a molecular weight of between 180,000 and 250,000.
  • the polyhydroxyalkanoate of the present invention is selected from the group consisting of poly(3-hydroxybutyric acid-CO-3-hydroxyvaleric acid) and poly(3-hydroxybutyric acid-CO-3-hydroxyl group).
  • One of hexanoic acid), poly(3-hydroxyvaleric acid-CO-3-hydroxyhexanoic acid), and poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester is preferred, which can be produced in various microorganisms and can be decomposed by various microorganisms, and has good Biodegradability and biocompatibility.
  • the copolymerization unit 4-hydroxybutyric acid has a great influence on the properties of P(3HB-4HB).
  • the difference in the composition of 4HB determines whether the copolymer is crystalline or elastomer, and its mechanical properties are greatly changed. It is important that the 4HB content has a large effect on the rate of decomposition of the copolymer.
  • the molecular arrangement of the PLA material is relatively regular and the crystallinity is high, so the biodegradation rate is relatively slow.
  • PHA PHA
  • the microorganism first erodes the surface of the PHA.
  • the enzyme secreted by the microorganism then acts on the ester bond in the PHA to cause decomposition.
  • the small molecular intermediates and microbial secretions produced during the decomposition of PHA can be used as a nutrient or growth promoter for degrading PLA microorganisms, promoting their rapid growth and reproduction, forming the advantage of degrading PLA micro-ecological regions, thus destroying the entire crystal.
  • titanate coupling agent may be added, and the titanate coupling agent is titanium monoalkoxy fatty acid or titanium monoalkoxy phosphate. It can bend and entangle the long, soft aliphatic carbon chain and organic binder, enhance the bonding force with the binder, improve their compatibility, cause the surface energy of the filler to change, resulting in a significant decrease in viscosity, and improve the filler. And the melt flow and processing of the binder system.
  • a free radical initiator such as benzoyl peroxide may be added, and the radical initiator is selected from one of benzoyl peroxide, peroxydicarbonate, and azobisisobutyronitrile.
  • PLA-PHA graft or block copolymer Under heating conditions, it promotes radical polymerization of the free radical chain formed by homopolymerization of the covalent bond of the polymer to form a PLA-PHA graft or block copolymer. Since PHA is easily decomposed by microorganisms, when PHA is degraded in the block copolymer, more polar end groups are left in the copolymer matrix, which accelerates the decomposition of PLA.
  • FIGS. 1 to 10 are views showing states of different burying times when a first embodiment of the present invention is buried at 20 cm.
  • 11 to 20 are views showing states of different burying times when the first embodiment of the present invention is buried at 40 cm.
  • 21 to 30 are views showing states of different burying times when the second embodiment of the present invention is buried at 20 cm.
  • 31 to 40 are views showing states of different burying times when the second embodiment of the present invention is buried at 40 cm.
  • 41 to 50 are views showing states of different burying times when the third embodiment of the present invention is buried at 20 cm.
  • 51 to 60 are views showing states of different burying times when the third embodiment of the present invention is buried at 40 cm.
  • 61 to 70 are views showing states of different burying times when the fourth embodiment of the present invention is buried at 20 cm.
  • 71 to 80 are views showing states of different burying times when the fourth embodiment of the present invention is buried at 40 cm.
  • 81 to 84 show detection views of SEMs of different buried times of the first embodiment of the present invention.
  • 85 to 87 show detection views of SEMs of different buried times of the second embodiment of the present invention.
  • 88 to 90 are diagrams showing the detection of SEM of different buried times in the third embodiment of the present invention.
  • Poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester can be produced according to a conventional production method in which a monomer unit of 4-hydroxybutyric acid accounts for the poly(3-hydroxyl group).
  • the poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester used in this example is derived from Tianjin Guoyun Biomaterial Co., Ltd.
  • Test unit test conditions Test standard mg/cm 1. 2 A method GB/T 1033-2008 Glass transition temperature "C 1 DSC method melting temperature” C 142 GB/T 19466-2004 Melt index g/10min 3. 6 170°C, 2. 16kg GB/T 3682-2000 Tensile strength MPa 33
  • Type 1A specimen lOOmm/min GB/T 1040. 2-2006 Elongation at break % 10 Notched impact strength kj/m 2 9. 2 Cantilever beam: A-notch GB/T 1843-2008 Bending strength MPa 42 Speed: 2 mm/min
  • Polylactic acid is a commercially available L-polylactic acid.
  • Parameter item means the test condition test standard white to pale yellow, regular, columnar particles; no odor density g/cm 1.
  • 25 A Method GB/T 1033-2008 Melt index g/10min 3 170°C, 2. 16kg GB/T 3682-2000 Melting point °C 210 Molecular weight million 22 Vicat softening point °C 90 A 50 method GB/T 1633-2000 Pull Stretching portrait 41
  • the film selected in the examples of the present invention can be produced by a conventional method in which poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester and L-polylactic acid are melted, mixed, and then extruded.
  • the test area size is: 4m X 6m long plot.
  • the test period is from May 2010 to December 2010.
  • the test area is planted with grass seeds and watered regularly.
  • the prepared film strips were filled in the soil landfill experimental zone according to the ratio of different poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) esters, and the filling depth was 20 cm and 40 cm.
  • the film samples were taken for photographing and performance testing.
  • Test items include: photo taking, dimensional measurement, infrared, and electron microscopy.
  • the numbers shown in the figure are, for example, 50-21-20, where 50 is PHA 50%, 21 is the number of days of excavation, and 20 is 20 cm from the ground.
  • a colorant is added to make the composition white.
  • the sample fill depth is 20 cm, and the results are shown in Fig. 61-70.
  • the samples were selected and examined by SEM scanning electron microscopy.
  • Scanning electron microscopy SEM was used as a material observation method to observe the surface morphology and crystal structure of the material.
  • SEM scanning electron microscopy
  • the SEM photo shows that as the decomposition time increases, significant voids and cracks appear on the surface of the material, indicating that the material has decomposed. As shown in Figure 81-90.
  • the film Compared with the film with different landfill time, the film showed a gradual decomposition as the landfill time increased.
  • the decomposition process is the occurrence of decomposed spots, which are gradually broken and broken into smaller pieces.
  • the decomposability of the film gradually increases.
  • the decomposition performance increases with the PHA/PLA ratio, the decomposition of the film becomes more pronounced, and the time required is shorter.
  • the film with a PHA ratio of 25% showed obvious breakage at 105 days. From the results of electron scanning electron microscopy, the intermolecular force had begun to change at 42 days, and it was broken at 126 days. Smaller pieces.
  • the film with a PHA ratio of 50% has been ruptured significantly at 42 days. From the results of its scanning electron microscopy, the surface has become quite rough, indicating that the decomposition effect of the microorganism on the film is already very obvious. A film with a PHA ratio of 75% has been substantially decomposed at 63 days.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种可用土壤掩埋法进行生物分解的组合物，包括聚乳酸和聚羟基烷酸酯，所述聚羟基烷酸酯占所述组合物质量分数比的20%-90%，所述聚羟基烷酸酯为聚(3-羟基丁酸-co-4-羟基丁酸)酯，其中单体单元4-羟基丁酸的组分占所述聚（3-羟基丁酸-co-4-羟基丁酸）酯质量分数比的5%-20%，所述聚（3-羟基丁酸-co-4-羟基丁酸）酯的重均分子量在30万-40万之间，结晶度在43%-53%之间。本发明的组合物在土壤填埋环境下分解时，微生物首先侵蚀PHA的表面，然后微生物分泌出来的酶对聚羟基烷酸酯中的酯键发生作用并使其分解，从而破坏了整个晶体的结构规整性，减小了其分子间作用力，使微生物更容易攻击或切断分子链，大大地提高了组合物的分解速率；更为重要的是，此组合物不需堆肥，在土壤填埋的环境中就很快地完全分解。

Description

一种可用土壤掩埋法进行生物分解的组合物及其制
技术领域 本发明涉及一种可被生物分解的组合物， 属于高分子技术领域， 尤其是一种可在普通的 土壤环境中发生分解的组合物； 本发明还涉及此组合物的制品。
背景技术 塑料工业在方便人类生活的同时， 也加剧了环境的污染。 目前世界每年生产的塑料 约 2. 5亿吨，用后废弃的大约 7000万吨，过多的塑料废品构成了垃圾掩埋坑中渐增的废 料掩埋物。 基于减少每年由消费者产生的固体废弃物要求， 可生物分解的聚合物以及由 可生物分解的聚合物制成的产品正变的日益重要。
聚乳酸（PLA)是由生物发酵生产的乳酸经人工化学合成而得到的聚合物， 其保持着 良好的生物相容性和生物可分解性。 聚乳酸具有与聚酯相似的防渗透性， 同时具有与聚 苯乙烯相似的光泽度、 清晰度和加工性， 而且提供了比聚烯烃更低温度的可热合性， 可 采用熔融加工技术加工成各种包装用塑料， 如农业、 建筑业用的塑料型材、 薄膜， 以及 化工、 纺织业用的无纺布、 聚酯纤维等。 聚乳酸的生产耗能只相当于传统石油化工产品 的 20%_50%， 产生的二氧化碳气体只为其 50%。 聚乳酸材料在堆肥条件下可以完全分解， 但需要较长的时间， 远远不能满足人们日益对 环保的要求， 更不用说在一般土壤中分解了； 更为严重的是堆肥分解需要建立特定的堆 肥设施， 还需要提供可堆肥的有机物， 这样的处理方式大大增加了垃圾处理的成本。 现 实生活当中， 塑料要做到完全回收是非常困难的， 依旧有大量的塑料垃圾残留在环境当 中， 严重污染了居民的生活环境。 如何提高废弃的聚乳酸制品的降解速率， 降低其废弃 物处理的成本， 是当今环保工作要解决的难题之一。 发明内容 为了解决现有技术中存在的问题， 本发明提供一种聚乳酸和聚羟基脂肪酸酯共混形 成的组合物， 可以采用土壤掩埋法对其废弃物进行处理， 而且此组合物会很快地在土壤 中完全分解，不但提高了聚乳酸材料的分解速率，而且还降低了聚乳酸制品的处理成本。 本发明还提供此组合物的制品， 包括食品包装的热收縮膜、 塑料片材、 发泡材料、 纺织 制品， 此类制品在使用丢弃后， 可以很快地在自然环境中分解。 聚羟基脂肪酸酯（PHA)是一类生物可分解材料， 可以在自然环境中彻底分解成为二 氧化碳和水。 分解首先是在一定的条件下， 各种附在聚合物表面增殖的微生物释放出特 定的分解酶， 在酶的催化下聚合物分解成很小的段， 当分子量降到一定程度后就会很容 易地被微生物吸收消化。 很多因素对材料的分解过程产生影响。 从某种意义上说材料的 结构决定了可生物分解性能的强弱， 一般认为分子结构排列越规整， 结晶度越高的材料 越难被分解。 聚合物的侧基和取代基也会阻碍酶的作用， 当然结晶和交联也会限制酶的 作用。 微生物降解酶一般先作用于 PHA的非结晶部分的酯键。 本发明的技术方案是： 一种可用土壤掩埋法进行生物分解的组合物， 包含聚乳酸和聚羟 基烷酸酯， 所述聚羟基烷酸酯占所述组合物质量分数比的 20%-90%。 优选的是： 所述聚羟基烷酸酯占所述组合物质量分数比的 25%_75%。 优选的是： 所述聚羟基烷酸酯选自聚 (3-羟基丁酸 -CO-3-羟基戊酸）、 聚 (3-羟基丁酸 -CO-3-羟基己酸）、 聚（3-羟基戊酸 -CO-3-羟基己酸）、 聚（3-羟基丁酸 -CO-4-羟基丁酸） 酯中的一种。 优选的是： 所述聚羟基烷酸酯为聚 (3-羟基丁酸 -CO-4-羟基丁酸)酯， 其中单体单元 4-羟 基丁酸的组分占所述聚（3-羟基丁酸 -CO-4-羟基丁酸）酯质量分数比的 5%_20%， 所述聚 ( 3-羟基丁酸 -CO-4-羟基丁酸） 酯重均分子量在 30万 -40万之间， 结晶度在 43%-53%之 间。 优选的是： 所述聚乳酸为 L-聚乳酸， 其分子量在 18万 -25万之间。 本发明的聚羟基烷酸酯选自聚 (3-羟基丁酸 -CO-3-羟基戊酸）、聚 (3-羟基丁酸 -CO-3-羟基 己酸）、 聚 (3-羟基戊酸 -CO-3-羟基己酸）、 聚 (3-羟基丁酸 -CO-4-羟基丁酸)酯中的一种。 其中优选聚 （3-羟基丁酸 -C0-4-羟基丁酸） 酯 （P [3HB-co-4HB] ) ，它可以在多种微生物 体内生成， 并可被多种微生物分解， 具有良好的生物分解性和生物相容性。 共聚单元 4- 羟基丁酸对 P (3HB-4HB)的性质有很大的影响， 4HB所占组分的不同决定了共聚物是结晶 体还是高弹体， 其力学性质有很大的变化， 更为重要的是， 4HB的含量对共聚物的分解 速率有很大的影响。
PLA材料的分子排列较规整， 结晶度高， 故生物分解速率相对较慢。 当加入 PHA共 混改性后， 微生物首先侵蚀 PHA 的表面。 然后由微生物分泌的酶对 PHA中的酯键发生 作用使其分解。 在 PHA分解过程中产生的小分子中间产物及微生物的分泌物可作为降解 PLA微生物的营养或生长促进剂， 促进其快速生长繁殖， 形成了降解 PLA微生态区域优 势， 这样就破坏了整个晶体的结构规整性， 较小了其分子间作用力， 使微生物更容易攻 击或切断分子链， 大大地提高了组合物中 PLA的分解速率； 更为重要的是， 普通土壤中 的微生物及环境条件已经满足了此组合物快速分解的需求， 并不需要在堆肥的条件下进 行。 而且还可以在海水、 淡水、 污水中完全分解。
优选的是： 还可以加入一些钛酸酯类偶联剂， 所述钛酸酯类偶联剂为单烷氧脂肪酸 钛或单烷氧磷酸酯钛。 它能使较长、 柔软的脂肪族碳链和有机基料进行弯曲缠绕， 增强 和基料的结合力， 提高他们的相容性， 引起填料的表面能变化， 导致粘度大幅度下降， 改善填料和基料体系的熔融流动性和加工工艺。 优选的是： 还可以加入一些过氧化苯甲酰等自由基引发剂， 所述自由基引发剂选自过氧 化苯甲酰、 过氧化二碳酸酯、 偶氮二异丁腈中的一种。 在加热的条件下， 它能促使聚合 物共价键均裂生成的自由基链发生自由基聚合反应， 从而生成 PLA-PHA接枝或嵌段共聚 物。 由于 PHA很容易被微生物分解， 因此当该嵌段共聚物中 PHA被降解后， 会在共聚物 基体中留下更多的极性末端基， 这样就加速了 PLA的分解。
附图说明 图 1-图 10示出了本发明第一实施方式土埋 20cm时不同掩埋时间的状态示意图。 图 11-图 20示出了本发明第一实施方式土埋 40cm时不同掩埋时间的状态示意图。 图 21-图 30示出了本发明第二实施方式土埋 20cm时不同掩埋时间的状态示意图。 图 31-图 40示出了本发明第二实施方式土埋 40cm时不同掩埋时间的状态示意图。 图 41-图 50示出了本发明第三实施方式土埋 20cm时不同掩埋时间的状态示意图。 图 51-图 60示出了本发明第三实施方式土埋 40cm时不同掩埋时间的状态示意图。 图 61-图 70示出了本发明第四实施方式土埋 20cm时不同掩埋时间的状态示意图。 图 71-图 80示出了本发明第四实施方式土埋 40cm时不同掩埋时间的状态示意图。 图 81-图 84示出了本发明第一实施方式不同掩埋时间的 SEM的检测图。 图 85-图 87示出了本发明第二实施方式不同掩埋时间的 SEM的检测图。 图 88-图 90示出了本发明第三实施方式不同掩埋时间的 SEM的检测图。
具体实施方式 聚 （3-羟基丁酸 -CO-4-羟基丁酸） 酯， 可以按照常规生产方法进行生产， 其中， 单 体单元 4-羟基丁酸的组分占所述聚 （3-羟基丁酸 -CO-4-羟基丁酸） 酯质量分数比的 5%-20%, 聚 （3-羟基丁酸 -CO-4-羟基丁酸）酯均聚分子量在 30万 -40万之间， 结晶度在 43%_53%之间。 本实施例选用的聚 （3-羟基丁酸 -CO-4-羟基丁酸） 酯来源于天津国韵生物材料有限 公司， 其具体参数如下表： 项目 单位 指标 测试条件 测试标准 m g/cm 1. 2 A法 GB/T 1033-2008 玻璃化温度 "C 1 DSC法 熔融温度 "C 142 GB/T 19466-2004 熔融指数 g/10min 3. 6 170°C， 2. 16kg GB/T 3682-2000 拉伸强度 MPa 33
1A型试样， lOOmm/min GB/T 1040. 2-2006 断裂伸长率 % 10 缺口冲击强度 kj/m2 9. 2 悬臂梁： A型缺口 GB/T 1843-2008 弯曲强度 MPa 42 速度： 2 mm/min
GB/T 9341-2000 弯曲模量 GPa 1. 8 速度： 1 mm/min 热分解温度 °C 286 升温： 10°C/min TGA法 维卡软化点 °C 134 A50法 GB/T 1633-2000 分子量 万 30
聚乳酸采用的是市售的 L-聚乳酸， 其详细参数如下表: 参数项目 单位 指 测试条件 测试标准 夕卜 观 白色至淡黄色、 规整、 柱状颗粒； 无异味 密 度 g/cm 1. 25 A法 GB/T 1033-2008 熔融指数 g/10min 3 170°C， 2. 16kg GB/T 3682-2000 熔点 °C 210 分子量 万 22 维卡软化点 °C 90 A50法 GB/T 1633-2000 拉伸 纵向 41
MPa
强度 横向 45 II型试样，
GB/T 1040. 3-2006 断裂 纵向 174 lOmm/min
%
伸长率 横向 180 直角撕 纵向 kN/m 109 180瞧 /min QB/T 1130-1991
Figure imgf000008_0001
本发明的实施例选用的薄膜可通过常规方法进行制备， 将聚 （3-羟基丁酸 -CO-4-羟 基丁酸） 酯和 L-聚乳酸熔融后混合， 再挤压成型。
1.实验准备
(1) 试验区
试验区尺寸为： 4m X 6m长条地块。试验时间为 2010年 5月 -2010年 12月。试验区 地面栽种草籽， 并定期浇水。
(2) 样品
将制备好的薄膜样条在土壤填埋实验区内按照不同聚 ( 3-羟基丁酸 -CO-4-羟基丁酸) 酯的配比， 填埋深度为 20cm和 40cm。在 0天、 21天、 42天、 63天、 84天、 105天、 126 天、 154天、 175天和 196天（尚未挖出）试验结束为止， 分别挖取薄膜样品进行拍照和 性能检测。
2.试验内容
(1) 在六个月的试验时间内， 每天记录天气、 温度、 土壤湿度、 是否浇水、 浇水时 间及其他需记录事项等。 及时清理土壤中板结部分， 及时对试验区所做标记和四周土坎 进行检查和整理。
(2) 根据不同分解时间要求， 每隔 15天取出对应的样品进行检测。 检测项目包括: 拍照、 尺寸测量、 红外、 电镜。
图中所示的标号， 如： 50-21-20 ， 其中 50为 PHA50%， 21为挖掘的天数， 20为距 地面深度 20cm处。
3. 试验内容汇总
在六个月的试验时间内， 每天记录天气、 温度、 土壤湿度、 浇水、 浇水时间及其他 需记录事项。 主要对不同的 PHA/PLA配比、 不同填埋深度、 不同填埋分解时间的样品进 行的拍照和 SEM检测， 对结果进行汇总。
实施例 1 ( 3-羟基丁酸 -co-4-羟基丁酸） 酯 /L-聚乳酸 =25/75
a.样品填埋深度为 20cm， 其结果如图 1-图 10所示。
b.样品填埋深度为 40cm， 其结果如图 10-图 20所示。
实施例 2
( 3-羟基丁酸 -co-4-羟基丁酸） 酯 /L-聚乳酸 =50/50
a.样品填埋深度为 20cm， 其结果如图 21-图 30所示。
b.样品填埋深度为 40cm， 其结果如图 31-图 40所示。
实施例 3
( 3-羟基丁酸 -co-4-羟基丁酸） 酯 /L-聚乳酸 =75/25
a.样品填埋深度为 20cm， 其结果如图 41-图 50所示。
b.样品填埋深度为 40cm， 其结果如图 51-图 60所示。
实施例 4
添加着色剂， 使其组合物变成白色。
( 3-羟基丁酸 -co-4-羟基丁酸） 酯 /L-聚乳酸 =25/75
a.样品填埋深度为 20cm， 其结果如图 61-图 70所示。
b.样品填埋深度为 40cm， 其结果如图 71-图 80所示。
挑选其中样品， 进行 SEM电子扫描电镜检测， 扫描电镜作为一种材料微观结构的观 察手段， 能够很好的观测到材料表面形态和晶体结构。 通过对分解材料进行扫描电镜分 析， 可以观测到微生物对材料表面的蚀刻程度， 进而可以证明材料的分解。 SEM 照片显 示， 随着分解时间的增加， 材料表面出现明显空洞和裂纹， 这说明材料已经发生分解。 如图 81-90所示。
对比不同填埋时间的薄膜， 随着填埋时间的增长， 薄膜呈现明显逐渐分解的情况。 分解过程为出现分解的斑点、 逐渐破碎、 破碎为尺寸较小的碎片。 如附图可以得知： 随 着 PHA/PLA比例的增大， 薄膜的可分解性能逐渐增强。 其分解性能随着 PHA/PLA比例的 增大， 薄膜的分解越明显， 所需时间越短。其中， PHA比例为 25%的薄膜在 105天的时候 出现明显的破碎，从电子扫描电镜的结果来看，在 42天的时候其分子间作用力已经开始 变化， 在 126天的时候已经破碎为尺寸较小的碎片。 而 PHA比例为 50%的薄膜在 42天的 时候就已经明显的破裂， 从其电子扫描电镜的结果来看， 其表面已经变的相当粗糙， 这 说明微生物对薄膜的分解效果已经非常明显。 PHA比例为 75%的薄膜在 63天的时候已经 基本分解完毕。

Claims

权利要求书
1.一种可用土壤掩埋法进行生物分解的组合物，其特征是：包含聚乳酸和聚羟基烷酸酯， 所述聚羟基烷酸酯占所述组合物质量分数比的 20%-90%。
2. 根据权利要求 1所述的组合物， 其特征是： 所述聚羟基烷酸酯占所述组合物质量分数 比的 25%_75%。
3. 根据权利要求 2所述的组合物， 其特征是： 所述聚羟基烷酸酯选自聚 (3-羟基丁酸 -CO-3-羟基戊酸）、 聚（3-羟基丁酸 -CO-3-羟基己酸）、 聚（3-羟基戊酸 -CO-3-羟基己酸）、 聚 (3-羟基丁酸 -CO-4-羟基丁酸)酯中的一种。
4.根据权利要求 3所述的组合物，其特征是： 所述聚羟基烷酸酯为聚 (3-羟基丁酸 -CO-4- 羟基丁酸)酯， 其中单体单元 4-羟基丁酸的组分占所述聚（3-羟基丁酸 -CO-4-羟基丁酸) 酯质量分数比的 5%_20%， 所述聚 （3-羟基丁酸 -CO-4-羟基丁酸） 酯重均分子量在 30万 -40万之间， 结晶度在 43%_53%之间。
5. 根据权利要求 4所述的组合物， 其特征是： 所述聚乳酸为 L-聚乳酸， 其分子量在 18 万 -25万之间。
6. 根据权利要求 1所述的组合物， 其特征是： 所述组合物中还含有钛酸酯类偶联剂， 所 述钛酸酯类偶联剂为单烷氧脂肪酸钛或者单烷氧磷酸酯钛。
7. 根据权利要求 1所述的组合物， 其特征是： 所述组合物中还含有自由基引发剂， 所述 自由基引发剂选自过氧化苯甲酰、 过氧化二碳酸酯、 偶氮二异丁腈中的一种。
8. 一种食品包装的热收縮膜， 包含上述权利要求 1-6中任一项所述的组合物。
9. 一种塑料片材， 包含上述权利要求 1-6中任一项所述的组合物。
10. 一种发泡材料， 包含上述权利要求 1-6中任一项所述的组合物。
11. 一种纺织制品， 包含上述权利要求 1-6任一项权利要求所述的组合物。
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Publication number Priority date Publication date Assignee Title
CN1923890A (zh) * 2006-08-29 2007-03-07 天津国韵生物科技有限公司 用于发泡材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101210101A (zh) * 2006-12-29 2008-07-02 天津国韵生物科技有限公司 用于片材、薄膜、管材、纤维材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101387046A (zh) * 2008-09-23 2009-03-18 中国民航大学 可生物完全降解的无纺织物及其专用熔喷装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923890A (zh) * 2006-08-29 2007-03-07 天津国韵生物科技有限公司 用于发泡材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101210101A (zh) * 2006-12-29 2008-07-02 天津国韵生物科技有限公司 用于片材、薄膜、管材、纤维材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
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