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WO2008028344A1 - The composition containing polyhydroxyalkanoate copolymer and polylactic acid used for foam - Google Patents

The composition containing polyhydroxyalkanoate copolymer and polylactic acid used for foam Download PDF

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Publication number
WO2008028344A1
WO2008028344A1 PCT/CN2006/002706 CN2006002706W WO2008028344A1 WO 2008028344 A1 WO2008028344 A1 WO 2008028344A1 CN 2006002706 W CN2006002706 W CN 2006002706W WO 2008028344 A1 WO2008028344 A1 WO 2008028344A1
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Prior art keywords
copolymer
acid
composition
parts
monomer unit
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PCT/CN2006/002706
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English (en)
French (fr)
Inventor
Weichuan Lu
Mei Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Greenbio Material Co Ltd
Civil Aviation University of China
Original Assignee
Tianjin Greenbio Material Co Ltd
Civil Aviation University of China
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Application filed by Tianjin Greenbio Material Co Ltd, Civil Aviation University of China filed Critical Tianjin Greenbio Material Co Ltd
Priority to EP06804930A priority Critical patent/EP2060605A4/en
Priority to US12/439,506 priority patent/US8586643B2/en
Priority to JP2009525894A priority patent/JP5103686B2/ja
Priority to KR1020097006230A priority patent/KR101399802B1/ko
Publication of WO2008028344A1 publication Critical patent/WO2008028344A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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

Definitions

  • the present invention relates to the field of polymer technology, and more particularly, to a biodegradable material for a foamed material.
  • a polymer composition can be widely used in packaging products. BACKGROUND OF THE INVENTION While the plastics industry is convenient for human life, it also leads to an increase in environmental pollution. At present, about 140 million tons of plastics are produced every year in the world, and about 10%-60% of the production is discarded after use. The most serious concentration of environmental pollution in China is the use of disposable tableware, plastic packaging boxes, bags and films and medical products.
  • the disposable products currently used on the market are mainly polyethylene, polypropylene, polypropylene/starch blends and polyphenyl foamed products, and none of these foamed disposable products can be biodegraded to co 2 and 3 ⁇ 4 ⁇ .
  • polypropylene/starch is only a physical method to incorporate starch into a polypropylene polymer. It is not really grafted onto the polypropylene macromolecular chain. Although the starch is degraded and the polypropylene polymer is still not degraded, the macroscopically seen product has been broken. However, in essence, the geometry of the polypropylene material is reduced, and the polypropylene macromolecules do not undergo fundamental changes, which in turn accelerates the quality of the soil and environmental pollution.
  • Polyhydroxydecanoate copolymer such as copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid P(3HB-co-4HB), copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid P (3HB-co -3HV), a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid (3HB- CO- 3Ifflb, 3-hydroxybutyric acid and 3-hydroxydecanoic acid P(3HB-co-3HD) are more flexible than Good, and in the natural environment such as seawater, sewage or bacteria-intensive soil, it can completely decompose into carbon dioxide and water after 3-6 months. Moreover, these polymers are produced by fermentation, the production process is clean, and the environment is clean. No pollution.
  • the above polyhydroxyalkanoate copolymer is usually a semi-crystalline thermoplastic polyester compound, It has low crystallinity and melting point. It has a slow crystallization rate during processing and adheres together after cooling, which affects the normal collection and production yield of the product. At present, the cost of this biocopolyester is relatively high.
  • the inventors of the present invention have conducted a large number of experiments and selected another biodegradable polylactic acid (PLA) to be blended with the above polyhydroxyalkanoate copolymer to form a composition, and further, Adding polylactic acid and foaming agent and other auxiliary agents to the above polyhydroxyalkanoate copolymer to form a blending composition to change its processing property, and obtaining a foamed product suitable for packaging materials, which can satisfy the conventional processing.
  • PLA biodegradable polylactic acid
  • the invention discloses a composition applicable to a foaming material, comprising a polyhydroxyalkanoate copolymer, a polylactic acid and a foaming agent, wherein the polyhydroxyalkanoate copolymer is a polyhydroxy group containing two kinds of irregular repeating units.
  • polyhydroxyalkanoate copolymer is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid P (3HB-co-4HB), 3-hydroxybutyric acid and 3-hydroxypentane Copolymerization of acid copolymer p (3HB-CO-3HV), copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid P (3HB-co-3HHx), 3-hydroxybutyric acid and 3-hydroxydecanoic acid P
  • the polyhydroxyalkanoate copolymer is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid P (3HB-co-4HB), 3-hydroxybutyric acid and 3-hydroxypentane Copolymerization of acid copolymer p (3HB-CO-3HV), copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid P (3HB-co-3HHx), 3-hydroxybutyric acid and 3-hydroxydecanoic acid P
  • One of the substances (3HB-C0-3HD)).
  • the above composition disclosed in the present invention wherein the polyhydroxyalkanoate copolymer is a copolymer P (3HB-co-4HB) of 3-hydroxybutyric acid and 4-hydroxybutyric acid.
  • the blowing agent may be one of azodicarbonamide, butane, carbon dioxide, water, nitrogen, preferably azodicarbonamide or butyl hydrazine. 5 ⁇
  • the composition of the present invention, wherein the mass ratio of the mass ratio of the poly-based phthalic acid ester copolymer, the polylactic acid, the foaming agent is 100, 100 ⁇ 700, 0. 2 ⁇ 1.
  • the composition disclosed by the present invention further contains organic and/or inorganic additives, and the organic and/or inorganic additives are nanometer-micron particles, wherein the organic additive is an organic solid, which may be starch, a degradable fatty acid such as glycerolipid, protein.
  • One of the inorganic additives may be one of oxygen compounds of talc, calcium carbonate, silicon, and titanium. 5 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 0 ⁇ 60.
  • the composition disclosed in the present invention further contains other auxiliary agents, and the auxiliary agent may be one of stearic acid and calcium stearate. ⁇ 1.
  • composition of the present invention wherein the mass ratio of the mass ratio of the polyhydroxyalkanoate copolymer, the polylactic acid, the foaming agent, the organic and or inorganic additives, and other auxiliaries is 100, 100 ⁇ 700, 0. 2 ⁇ 1. 5, 0 ⁇ 60, 0 ⁇ 5.
  • the main components of the blend compositions disclosed herein are biodegradable polyhydroxyalkanoate copolymers and biodegradable polylactic acid (PLA).
  • the polyhydroxyalkanoate copolymer disclosed in the present invention is a polyhydroxyalkanoate copolymer containing two kinds of random repeating units, wherein the first monomer unit has the formula (I)
  • R 1 is H, or or ( 2 fluorenyl, and n is 1 or 2, and the second monomer unit has the formula (II)
  • R 2 is d-. alkyl, Or the second monomer unit has the formula ( ⁇ )
  • the biodegradable polylactic acid (PLA) of the present invention has the formula:
  • the blowing agent is azodicarbonamide, butane, carbon dioxide, water, nitrogen, wherein azodicarbonamide (AC) is used as a chemical foaming agent, and water, butane, carbon dioxide and nitrogen are used as physical hair. Foaming agent.
  • an organic and/or inorganic additive to the composition, and the addition of these organic and/or inorganic additives can provide lubrication and reduce cost, preferably in the form of nanometers to micrometers.
  • the organic additive may be one of starch, protein, a degradable fatty acid such as glycerolipid.
  • the inorganic additive may be one of silicon, titanium oxygen compound, talc, and calcium carbonate.
  • it is more preferred to add other auxiliary agents to the composition which may be one of stearic acid and calcium stearate.
  • the inventors of the present invention conducted a large number of experiments, and obtained mass fraction ratios of polyhydroxyphthalic acid ester copolymer, polylactic acid, foaming agent, organic and or inorganic additives, and other auxiliary agents to 100, 100-700, 0.2- 1.5, 0 ⁇ 60, 0-5 can obtain foaming materials as packaging materials that meet different needs.
  • the present invention also discloses a method of preparing a foamed material using the composition of the present invention, which can be produced by processing using a conventional extrusion manufacturing apparatus.
  • the raw materials are prepared according to the formula ratio, dry and mixed
  • the composition pellets are then melted and extruded at a certain temperature in a product extrusion apparatus, and shaped into various desired products by an auxiliary machine.
  • the foamed sheet is a cast flat or T-shaped extruder head, and the foam is cooled by a tubular head, cooled on a water-cooled or polished metal roll, and the finished product is collected.
  • the obtained finished product is tested by impact strength, elongation at break, and expansion ratio.
  • Different formulations can obtain foamed materials with different impact strength, different elongation at break and expansion ratio, which have flexibility, strength, and Insulation, general solvent resistance, imperviousness, non-toxicity, etc., in line with the actual use requirements of fast food hot food and frozen food packaging.
  • the processing and molding method is simple, the molding cycle is continuous production, low energy consumption, high yield efficiency, easy operation and industrialization popularization and production.
  • the finished waste is biodegradable and can be degraded into co 2 and 3 ⁇ 40 in a dense area of microbial strain such as muddy water, soil, seawater, etc., and it is environmentally friendly material without secondary pollution to the environment.
  • the polyhydroxyalkanoate copolymer is from Tianjin Guoyun Biotechnology Co., Ltd.
  • Example 10 100 parts by weight of P (3HB-co-40mol% 4HB), 600 parts of PLA, 30 parts of starch; 2.5 parts of talc; 0.2 parts of stearic acid; blending and granulating all raw materials; Foaming, adding 1.0 part of butyl hydrazine; 9 parts of monoglyceride; forming foamed sheet; 100 parts by weight of P (3HB-co-40mol% 4HB), 300 parts of PLA, 10 parts of starch; 1.0 part of talc; 1.2 parts of fatty acid; and all raw materials are blended and granulated; The foaming was carried out, and 1.5 parts of nitrogen gas was added; 8 parts of monoglyceride; a foamed sheet was molded; and it was molded into a product by suction molding.
  • Example 10 100 parts by weight of P (3HB-co-40mol% 4HB), 600 parts of PLA, 30 parts of starch; 2.5 parts of talc; 0.2 parts of stearic acid; blending and granulating all raw materials;
  • Example 12 100 parts by weight of p (3HB-co-3HV), 200 parts of PLA, 1.0 part of talc, and 0.2 parts of stearic acid; all raw materials are blended and extruded into granules; 0.8 parts; 1 part of monoglyceride; molded foamed sheet; re-molded into a product.
  • Examples 1 to 13 of the present invention were subjected to tensile strength, elongation at break and degradation experiments, wherein tensile strength and elongation at break were tested according to national standard GB/T1040-92, and degradation experiments were carried out under natural conditions. (in sewage or seawater or sludge), for three to six months.
  • the physical properties of the product are:
  • the foamed material prepared by the composition containing the polyhydroxybutyrate copolymer and the polylactic acid disclosed in the present invention achieves the object of the present invention, and has good tensile strength and elongation at break. Rate, completely biodegradable in the natural environment, can be widely used in the packaging field.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

用于发泡材料的含聚羟基烷酸酯共聚物和聚乳酸的组合物 技术领域 本发明属于高分子技术领域， 更具体地， 本发明公开了一种用于发泡材料 的可生物降解的高分子聚合物的组合物， 可广泛用于包装制品。 背景技术 塑料工业在方便人类生活的同时， 也导致了环境污染的加剧。 目前全世界 每年生产塑料约 1.4亿吨， 用后废弃的大约占生产量的 50%-60%。 而我国对环 境污染最严重的集中表现为一次性餐具、 塑料包装盒、 袋和薄膜及医用制品的 使用。
现在市场上使用的一次性制品主要是聚乙烯、 聚丙烯、 聚丙烯 /淀粉共混物 和聚苯发泡制品， 这些发泡一次性制品任何一种都不能达到生物降解成为 co2 和 ¾◦的目的。 如聚丙烯 /淀粉仅仅是物理方法将淀粉掺在聚丙烯聚合物中， 没 有真正接枝在聚丙烯大分子链上， 虽导致淀粉降解而聚丙烯聚合物仍然没有降 解， 宏观上看制品已经碎了， 但本质上是聚丙烯物质几何尺寸减小， 而聚丙烯 大分子没有发生根本变化， 这样反而加速影响土壤的质量和环境污染。
聚羟基垸酸酯共聚物例如 3- 羟基丁酸和 4- 羟基丁酸的共聚物 P(3HB-co-4HB)、 3-羟基丁酸和 3-羟基戊酸的共聚物 P (3HB-co-3HV)、 3—羟 基丁酸和 3—羟基已酸的共聚物 P(3HB-CO-3Ifflb 、 3—羟基丁酸和 3—羟基癸酸 P(3HB-co-3HD)都具有柔韧性较好， 而且在自然环境如海水、污水或细菌密集的 土壤中经过 3-6个月的时间能够完全降解成二氧化碳和水的优点。而且这些聚合 物是利用发酵方法生产， 生产过程清洁， 对环境不造成污染。
由于上述的聚羟基烷酸酯共聚物通常是半结晶性的热塑性聚酯化合物， 具 有低的结晶度和熔点， 在加工中结晶速率慢， 同时冷却后也会粘附在一起， 影 响了制品的正常收集及生产产量， 而且目前这种生物共聚酯的成本还相对较高。
因此， 如何利用上述的聚羟基烷酸酯共聚物具有的可生物降解的特性并克 服其低结晶度和熔点， 得到成本市场可以接受的能用现有的发泡塑料生产设备 进行批量生产的生物可降解的发泡材料， 从而使其广泛地应用于包装领域一直 是本领域所着力解决的问题。
发明内容
为了解决上述问题， 本发明的发明人经过了大量的实验， 选择了另一种生 物可降解的聚乳酸（PLA)与上述的聚羟基烷酸酯共聚物共混形成组合物，更迸 一步， 在上述的聚羟基烷酸酯共聚物中添加聚乳酸和发泡剂及其它助剂制成共 混组合物以改变它的加工性能， 得到适用于包装材料的发泡制品， 具有可以满 足传统加工方法和正常使用性并可生物降解的优点。 本发明公开了一种可用于发泡材料的组合物， 含有聚羟基烷酸酯共聚物、 聚乳酸和发泡剂， 其中聚羟基烷酸酯共聚物为含有两种无规则重复单元的聚羟 基链烷酸酯共聚物， 其中第一单体单元具有式（I)
Figure imgf000003_0001
其中 1^为11、 或(^或( 2垸基， 且 n为 1或 2， 和第二单体单元具有式 （Π)
Figure imgf000004_0001
其中！^为^-^。烷基， 或者所述第二单体单元具有式 （III)
0
-0-(CH2)m-C
(Π1) 其中 m为 2 - 9， 第一单体单元和第二单体单元的摩尔比为 5: 95-98： 2。 本发明公开的上述组合物， 其中聚羟基垸酸酯共聚物第一单体单元 R1为 -C¾， n为 1。 本发明公开的上述组合物，其中聚羟基烷酸酯共聚物为 3-羟基丁酸和 4- 羟基丁酸的共聚物 P (3HB- co- 4HB)、 3-羟基丁酸和 3-羟基戊酸的共聚物 p (3HB-CO-3HV), 3—羟基丁酸和 3—羟基已酸的共聚物 P (3HB- co- 3HHx)、 3—羟 基丁酸和 3—羟基癸酸 P的共聚物 (3HB-C0- 3HD) )之一。 本发明公开的上述组合物，其中聚羟基烷酸酯共聚物为 3-羟基丁酸和 4- 羟基丁酸的共聚物 P (3HB-co- 4HB)。 本发明公开的上述组合物， 其中发泡剂可为偶氮二甲酰胺、 丁烷 、 二氧 化碳、 水、 氮气之一， 优选偶氮二甲酰胺或丁垸。 本发明公开的上述组合物，其中聚轻基垸酸酯共聚物、聚乳酸、发泡剂的 质量份数比为 100、 100〜700、 0. 2〜1. 5。 本发明公开的组合物，还含有有机和 /或无机添加剂，这些有机和 /或无机 添加剂为纳米〜微米级颗粒， 其中有机添加剂为有机固体， 可以为淀粉、 可降 解的脂肪酸如甘油脂、 蛋白质之一， 无机添加剂可以为滑石粉、 碳酸钙、 硅、 钛的氧化合物之一。 本发明公开的组合物， 其中聚羟基烷酸酯共聚物、 聚乳酸、发泡剂、有机 和或无机添加剂的质量份数比为 100、 100〜700、 0. 2〜1. 5、 0〜60。 本发明公开的组合物， 还含有其它助剂， 助剂可以为硬脂酸、 硬脂酸钙 之一。 本发明公开的组合物， 其中聚羟基烷酸酯共聚物、 聚乳酸、 发泡剂、有机 和或无机添加剂、其它助剂的质量份数比为 100、 100〜700、 0. 2〜1. 5、 0〜60、 0〜5。 ' 本发明公开的共混组合物的主要成分是生物可降解的聚羟基烷酸酯共聚 物和可生物降解的聚乳酸（PLA)。本发明公开的聚羟基烷酸酯共聚物为含有两 种无规则重复单元的聚羟基链烷酸酯共聚物， 其中第一单体单元具有式 （I)
Figure imgf000005_0001
其中 R1为 H、 或 或( 2垸基， 且 n为 1或 2， 和第二单体单元具有式 （II)
-O- ,rr、
Figure imgf000005_0002
其中 R2为 d- 。烷基， 或者所述第二单体单元具有式 （ΠΙ )
「 o Ί
II
-0-(CH2)m-C-
其中 m为 2-9， 第一单体单元和第二单体单元的摩尔比为 5: 95-98： 2。 本发明中可生物降解的聚乳酸 (PLA)， 具有通式：
Figure imgf000006_0001
本发明中发泡剂为偶氮二甲酰胺、 丁烷、 二氧化碳、 水、 氮气， 其中偶氮 二甲酰胺（AC)用做化学发泡剂， 水、 丁烷、 二氧化碳、 氮气用做物理发泡剂。
在本发明中， 优选在组合物中加入有机和 /或无机添加剂， 加入这些有机和 / 或无机添加剂可以起到润滑作用并能降低成本， 优选为纳米〜微米级颗粒状。 有机添加剂可以为淀粉、 蛋白质、 可降解的脂肪酸如甘油脂之一。 无机添加剂 可以为硅、 钛的氧化合物、 滑石粉、 碳酸钙之一。 在本发明中， 更优选在组合物中加入其它助剂， 可以为硬脂酸、硬脂酸钙 之一。 本发明的发明人进行了大量实验， 得到了聚羟基焼酸酯共聚物、 聚乳酸、 发泡剂、有机和或无机添加剂、其它助剂的质量份数比为 100、 100-700, 0.2-1.5, 0~60、 0-5时可以得到符合不同需求的作为包装材料的发泡材料。
本发明还公开了利用本发明的组合物制备发泡材料的方法， 可通过使用传 统的挤出制造设备进行加工生产。 首先将原料按照配方比例配制， 干燥混合挤 出组合物粒料， 然后在产品挤出设备中， 控制一定温度熔融挤出， 通过辅机定 型成为各种所需制品。 发泡片材采用平板流延或 T字挤出机头， 发泡采用管状 机头， 水冷却或抛光金属轧辊上冷却， 收集成品。
得到的成品经过冲击强度、 断裂伸长率、 发泡倍率实验， 配方不同可以得 到耐不同的冲击强度、 具有不同的断裂伸长率和发泡倍率的发泡材料， 其有柔 韧性、 强度、 隔热性、 耐普通溶剂、 不透水、 无毒等特点， 符合快餐热食物和 冷冻食物的包装品的实际使用要求。 其加工成型方法简单， 成型周期是连续化 生产， 能耗低、 产量效益高， 易于操作及工业化普及推广生产。 成品废弃物具 有生物可降解性， 可以在污泥浊水、 土壤、 海水等微生物菌种密集区经过数月 全部降解为 co2和 ¾0，对环境没有二次污染属于环境友好材料。
具体实施方式
以下实施例、 实验例仅对本发明进行更进一步的说明， 不应构成对本发明 的限制。
聚羟基烷酸酯共聚物来自天津国韵生物技术有限公司。
其他成分如未言明均为市售。 实施例 发泡材料的制备 发泡剂配方如下：
按质量份数计，并以主体成分聚羟基烷酸酯共聚物为基准（ 100质量份）， 各 成分比例如下： 聚羟基垸酸酯共聚物 100份
聚乳酸 （PLA ) 100〜700份 发泡剂： 0.2〜1.5份 有机和 /或无机添加剂 0〜60份
其它助剂： 0〜5份
加工方法： 将所有原料共混， 挤出造粒。 然后挤出发泡成型片材， 温度控 制在 140°C〜180°C， 螺杆转速 20〜： 150转 / min， 水冷成型。 发泡片材再到吸塑 机上吸塑成型为制品。 实施例 1 :
按质量份数计， P (3HB-co-5mol%4HB) 100份， PLA700份， AC为 1.5 份； 将所有原料共混挤出造粒； 然后挤出发泡片材； 再吸塑成型为制品。 实施例 2:
按质量份数计选 P (3HB-co-95mol%4HB) 100份， PLA400份， AC为 1.0 份， 硬脂酸钙 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡片材； 再吸塑成 型为制品。 实施例 3:
按质量份数计选 P ( 3HB-co- 10mol%4HB ) 100份， PLA700份， AC为 1.0 份， 玉米淀粉 50份； 滑石粉 3.0份； 硬脂酸 4.0份； 将所有原料共混挤出造粒； 然后挤出发泡片材； 再吸塑成型为制品。 实施例 4:
按质量份数计选 P (3HB-co-10mol%4HB) 100份， PLA500份， AC为 0.6 份， 滑石粉 2.5份； 硬脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡片 材； 再吸塑成型为制品。 实施例 5 :
按质量份数计选 P (3HB-co-40mol%4HB) 100份， PLA500份， AC为 1.0 份， 玉米淀粉 20份; 滑石粉 1.0份； 硬脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡片材； 再吸塑成型为制品。 实施例 6:
按质量份数计选 P (3HB-co-40mol%4HB) 100份， PLA200份， AC为 1.0 份， 滑石粉 0.5份； 硬脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡片 材； 再吸塑成型为制品。 实施例 Ί
按质量份数计选 P (3HB-co-10mol%4HB) 100份， PLA700份，滑石粉 3.0 份 玉米淀粉 30份； 硬脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发 泡， 加入丁烷 0.5份； 单甘酯 10份； 成型发泡片材； 再吸塑成型为制品。 实施例 8:
按质量份数计选 P (3HB-co-40mol%4HB) 100份， PLA600份， 淀粉 30份； 滑石粉 2.5份； 硬脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡， 加入 丁垸 1.0份； 单甘酯 9份； 成型发泡片材； 再吸塑成型为制品。 按质量份数计选 P (3HB-co-40mol%4HB) 100份， PLA300份， 淀粉 10 份； 滑石粉 1.0份； fi更脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡， 加入氮气 1.5份； 单甘酯 8份； 成型发泡片材； 再吸塑成型为制品。 实施例 10:
按质量份数计选 P (3HB-co-40mol%4HB) 100份， PLA200份， 滑石粉 0.5 份； 硬脂酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡，加入丁烷 0.2份； 单甘酯 1份； 成型发泡片材； 再吸塑成型为制品。 实施例 11 :
按质量份数计选 p (3HB-co-3HV) 100份， PLA200份， 滑石粉 1.0份； 硬脂 酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡，加入丁垸 0.8份； 单甘酯 1 份； 成型发泡片材； 再吸塑成型为制品。 实施例 12:
按质量份数计选 P(3HB-co-3HHx)100份， PLA200份， 滑石粉 0.5份； 硬脂 酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡，加入丁烷 1.2份； 单甘酯 1 份； 成型发泡片材； 再吸塑成型为制品。 实施例 13:
按质量份数计选 P(3HB-co-3HD)100份， PLA200份， 滑石粉 1.5份； 硬脂 酸 0.2份； 将所有原料共混挤出造粒； 然后挤出发泡，加入丁烷 1.0份； 单甘酯 1 份； 成型发泡片材； 再吸塑成型为制品。 实验例：
将本发明实施例 1~13所得到的产品进行拉伸强度、断裂伸长率和降解实验， 其中拉伸强度与 断裂伸长率实验按国标 GB/T1040— 92进行， 降解实验在自然 环境下 （污水或海水或污泥中）进行， 时间为三到六个月。
实验结果如下
产品的物理性能为：
拉伸强度 （MPa) ^3.45
断裂伸长率 （％) 30
降解实验： 完全生物降解
从上述实验结果可以看出， 本发明公开的含聚羟基丁酸酯共聚物和聚乳酸的 组合物制备的发泡材料达到了本发明的目的， 其具有较好的拉伸强度、 断裂伸 长率， 在自然环境下可以完全生物降解， 可广泛地应用于包装领域。

Claims

权 利 要 求 书
1. 一种可用于发泡材料的组合物，含有聚羟基烷酸酯共聚物、聚乳酸和发泡剂， 其中聚羟基烷酸酯 0=共聚物为含有两种无规则重复单元的聚羟基链烷酸酯共聚 物， 其中第一单体单元具有式 （I)
Figure imgf000012_0001
其中 1^为11、 或 (^或 垸基， 且 n为 1或 2， 和第二单体单元具有式 （II)
Figure imgf000012_0002
其中 R2为 C 烷基， 或者所述第二单体单元具有式 （III)
-0-(CH2)m-C-
(ΙΠ) 其中 m为 2-9， 第一单体单元和第二单体单元的摩尔比为 5: 95-98： 2：
2. 权利要求 1所述的组合物，其中聚羟基烷酸酯共聚物第一单体单元 R1为 -C n为 1。
3. 权利要求 2所述的组合物， 其中聚轻基垸酸酯共聚物为 3-羟基丁酸和 4- 羟基丁酸的共聚物 P (3HB- co- 4HB)、 3-羟基丁酸和 3-羟基戊酸的共聚物 p (3HB-CO-3HV), 3—羟基丁酸和 3—羟基已酸的共聚物 P (3HB-co_3HHx)、 3—羟 基丁酸和 3—羟基癸酸 P的共聚物 (3HB- co- 3HD) )之一。
4. 权利要求 3所述的组合物， 其中聚羟基垸酸酯共聚物为 3-羟基丁酸和 4- 羟基丁酸的共聚物 P (3HB- C0-4HB)。
5. 权利要求 1所述的组合物， 其中发泡剂可为偶氮二甲酰胺、 丁烷 、 二氧化 碳、 水、 氮气之一。
6. 权利要求 5所述的组合物， 其中发泡剂为偶氮二甲酰胺。
7. 权利要求 5所述的组合物， 其中发泡剂为丁垸。
8. 权利要求 1所述的组合物，其中聚羟基烷酸酯共聚物、聚乳酸、发泡剂的质 量份数比为 100、 100〜700、 0. 2〜L 5。
9. 权利要求 1所述的组合物， 还含有有机和 /或无机添加剂， 其中有机添加剂 可以为淀粉、 可降解的脂肪酸如甘油脂、 蛋白质之一， 无机添加剂可以为滑石 粉、 碳酸钙、 硅、 钛的氧化合物之一。
10. 权利要求 9所述的组合物， 其中聚羟基垸酸酯共聚物、 聚乳酸、 发泡剂、 有机和或无机添加剂的质量份数比为 100、 100〜700、 0. 2〜1. 5、 0〜60。
11. 权利要求 9所述的组合物， 还含有其它助剂， 助剂可以为硬脂酸、 硬脂酸 钙之一。
12. 权利要求 11所述的组合物， 其中聚羟基烷酸酯共聚物、 聚乳酸、 发泡剂、 有机和或无机添加剂、其它助剂的质量份数比为 100、 100〜700、 0. 2〜1. 5、 0〜 60、 0〜5。
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CN1923890A (zh) 2007-03-07
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EP2060605A4 (en) 2012-10-24
US8586643B2 (en) 2013-11-19
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KR20090054457A (ko) 2009-05-29

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