WO2013071802A1 - 一种可快速降解的聚酯类聚合物及其制备方法和应用 - Google Patents

一种可快速降解的聚酯类聚合物及其制备方法和应用 Download PDF

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WO2013071802A1
WO2013071802A1 PCT/CN2012/082770 CN2012082770W WO2013071802A1 WO 2013071802 A1 WO2013071802 A1 WO 2013071802A1 CN 2012082770 W CN2012082770 W CN 2012082770W WO 2013071802 A1 WO2013071802 A1 WO 2013071802A1
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substituted
unsubstituted
degradable
polyester
segment
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English (en)
French (fr)
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黄斌
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MOLECON (SUZHOU) NOVEL MATERIALS CO Ltd
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MOLECON (SUZHOU) NOVEL MATERIALS CO Ltd
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Priority to EP12849611.4A priority Critical patent/EP2767554B9/en
Priority to JP2014534932A priority patent/JP5998224B2/ja
Priority to US14/350,513 priority patent/US9018316B2/en
Priority to PL12849611T priority patent/PL2767554T3/pl
Priority to ES12849611.4T priority patent/ES2654574T3/es
Priority to DK12849611.4T priority patent/DK2767554T5/en
Publication of WO2013071802A1 publication Critical patent/WO2013071802A1/zh
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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
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • 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
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • 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
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • 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
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/78—Preparation processes
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • Polyester polymer which can be rapidly degraded, preparation method and application thereof
  • the invention relates to a polyester polymer which can be rapidly degraded and a preparation method and application thereof, in particular to a polyester polymer embedded with a degradable small segment in a polymer main chain and preparation thereof
  • the method and application belong to the technical field of functional polymer materials.
  • Polyester is a general term for polymerized books obtained by polycondensation of polyhydric alcohols and polybasic acids.
  • Aromatic polyesters represented by polyethylene terephthalate (PET) have excellent chemical stability, good mechanics and hygiene. Performance and transparency have been widely used in the chemical fiber, packaging and other industries.
  • PET polyethylene terephthalate
  • the polyester bottle has a humidity of 45% ⁇ 100% and a temperature of 20 °C for 30 to 40 years, and its performance is only 50% loss; under the same conditions, the polyester film can exist for 90 to 100 years. . To this end, a large amount of polyester waste will put tremendous pressure on the environment.
  • polyester waste can solve environmental pollution problems and realize the full utilization of resources. It is the preferred method adopted by countries in the world.
  • a variety of PET-based polyester recycling technologies have been developed. Simple regeneration can be after the polyester waste is purified and remelted to produce relatively low-grade products, such as toys, detergent bottles, etc.; higher-grade polyester regeneration is the use of polyester materials to polycondensate macromolecules. It can be degraded, re-polymerized or used as a chemical raw material, etc.
  • there are methods such as oiling technology, recycling of fuel, and incineration of energy together with other wastes.
  • polyester waste cannot be the ultimate solution to the problem of environmental pollution, because: First, the polyester waste that can be recycled has certain limitations, contains a large amount of additives or contains other hard-to-remove impurities and has been repeatedly Recycled products are very difficult to recycle. Secondly, a large number of inconveniently collected polyester products, such as agricultural film and garbage bags, are not suitable for recycling. Finally, it is not worth recycling products that are too costly or have no recycling value. Recycling. Therefore, it is necessary to modify the environmental degradability of the polyester used in the production of such products, so that the waste can be naturally decomposed into small molecular products in a certain period of time in nature, and finally returned. The material cycle of nature.
  • the chemical factors affecting the degradation properties of the material include the hydrophilicity, morphology, molecular mass and composition of the polymer.
  • the polymer has strong hydrophilicity and is easy to be hydrolyzed, and is also beneficial to biodegradation under the action of microorganisms.
  • the hydrolase has a strong effect on ester bonds, amide bonds and carbamic acid bonds; the amorphous region of the polymer is more crystalline than the crystallization.
  • the zone is more susceptible to damage by water and microorganisms; the molecular chain is soft, the glass transition temperature is low, which is favorable for degradation; the degradability is also enhanced with the decrease of molecular mass; the composition of the polymer, such as blending and copolymerization, can also affect it. Degradation performance.
  • PET polyesters contain ester bonds that are susceptible to damage by microbial enzymes and water molecules. In the molten state, the presence of traces of moisture can cause rapid cracking of the polyester bond. For this reason, in the production and processing of polyester, the moisture content of the chips must be strictly controlled.
  • PET polyester has good chemical stability and is difficult to degrade under natural conditions. This is related to the regular structure of the PET macromolecular backbone and the aromatic ring contained in the main chain. The presence of the aromatic ring increases the polarity of the regular molecular chain, which reduces the flexibility and improves the crystallization performance. Higher crystallinity has an inhibitory effect on hydrolysis because water does not easily penetrate into the crystalline phase. PET is a semi-crystalline polymer.
  • the initial stage of degradation occurs in the relatively loose structure of the structure and the edge of the crystallization zone.
  • the hydrolysis of the linked molecular chain between the crystal particles and the occurrence of chain cracking lead to the amorphous zone.
  • the crystallinity is significantly increased, thereby hindering the further occurrence of hydrolysis; on the other hand, the molecular chain rigidity is increased, the mobility of the macromolecule is inevitably lowered, and the glass transition temperature is higher, thereby also causing the polymer pair
  • the sensitivity to hydrolysis is diminished. Therefore, unlike the molten state, degradation in the solid state becomes a complex process that depends on the activity of the molecular chain and the permeability.
  • the way to reduce the crystallinity of polyester can be started from the post-processing technology of controlling the polymer material, or through the concept of molecular design to some extent from the rigid regular structure with strong polarity of the PET macromolecule.
  • the crystallization properties of the PET-based polyester can be fundamentally changed by introducing a flexible or third functional monomer unit having a specific functional group.
  • the introduction method mainly includes the addition of a modified third monomer copolymerization and reactive blending with an aliphatic polyester.
  • an object of the present invention is to provide a polyester polymer which can be rapidly degraded and a preparation method and application thereof for realizing rapid degradation of a polyester polymer such as PET under specific conditions. To solve the environmental pollution problems caused by the application of such polymers.
  • a rapidly degradable polyester polymer is a polyester polymer obtained by polycondensation of a repeating structural unit composed of a non-degradable segment A and a degradable segment B; characterized by:
  • the non-degraded segment A has the following chemical structural formula:
  • p, m, s, r, and u are integers greater than 0 and less than 11;
  • t is an integer greater than 1, less than 31;
  • n is an integer greater than one
  • R, Ri R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkane
  • the R, Ri R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from H or ⁇ .
  • An alkyl group; the R 7 is selected from H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or not Any of the substituted aryl groups.
  • the R, Ri R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl. Any one of tert-butyl groups; said R 7 being selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted hetero Any of the cycloalkyl groups.
  • the R is a methyl group
  • a method for preparing the above rapidly degradable polyester polymer comprises the following steps:
  • R, Ri R 2 , R 3 , R 4 , R 5 , R 6 , 1 7 and m, s, r, u, t, n are as defined above;
  • X is selected from Cl, Br, I, NH 2 or OH.
  • the synthesis of the non-degraded segment A comprises the following steps:
  • Another preparation method of the above rapidly degradable polyester polymer comprises the following steps:
  • degradable segments are uniformly distributed throughout the polymer chain.
  • first melt-condensed into non-degradable segments or oligomers for example: at 240 to 290 ° C under vacuum for 2 to 7 hours
  • the degradable segment continues to melt polymerize (for example: at 240 to 290 ° C, the reaction is continued under vacuum for 2 to 7 hours).
  • the non-degradable segment contains more moles of hydroxyl groups than the number of moles of carboxylate groups contained in the degradable segment, since excess non-degraded segments can be removed under high temperature and vacuum.
  • the ethylene glycol molecule undergoes a self-condensation reaction to form a high molecular weight polymer.
  • the polyester-based polymer provided by the present invention has a structurally different degradation segment inserted in the polymer main chain, thereby destroying its crystallinity and making its melting temperature compared to conventional polyester.
  • the polymer is more reduced; and the soft segment is lengthened due to the insertion of the degradation segment, so that the glass transition temperature is also lowered compared to the conventional polyester polymer; therefore, the polyester polymerization provided by the present invention
  • the material not only has good machinability, but also can be rapidly degraded into a plurality of short-chain non-degraded chains in a suitable environment (for example, in an alkaline solution), and then further degradation of the non-degraded chain occurs completely and effectively.
  • FIG. 1 is a DSC curve of the polyester-based polymer mPET (MeGSGMe) prepared in Example 1.
  • FIG. 2 is a degradation performance curve of the polyester-based polymer mPET (MeGSGMe) prepared in Example 1.
  • FIG. 2 The relationship between the intrinsic viscosity of the prepared PET oligomer and the polymerization time.
  • PET standard assay for the industry According to the standards of the Plastics Industry Association (SPI's) for PET, the polymer is used in a mixed solution of phenol/1,1,2,2-tetrachloroethane (60:40 by weight). The measurement was carried out by an Ubbelohde viscometer at a measurement temperature of 25 °C.
  • SPI's Plastics Industry Association
  • the structure and composition of the polyester-based polymer prepared by the present invention were measured by solution nuclear magnetic resonance, and the temperature of the nuclear magnetic resonance was measured at 20 ° C.
  • the solvent was deuterated chloroform.
  • the thermal properties of the polyester-based polymer prepared by the present invention were measured in a differential scanning calorimeter Q20 of TA Instruments.
  • the tensile strength test was determined by the Shanghai Institute of Organic Chemistry of the Chinese Academy of Sciences in accordance with the method of ASTM D638-97.
  • Fig. 1 is a DSC graph obtained by performing thermal performance test (heating rate of 10 ° C / min) on the obtained polymer. It can be seen from Fig. 1 that the obtained polymer has a glass transition temperature of 56 ° C and a melting temperature of 216 °. C, the recrystallization temperature during the heating process is 121 °C; It can be further confirmed from Fig. 1 that the polyester-based polymer provided by the present invention destroys its crystallization by inserting a structurally different degradation segment into the main chain of the polymer. The degree of melting is much lower than that of conventional PET; and because of the insertion of the degradation segment, the soft segment is lengthened, and its glass transition temperature is also lowered compared to conventional PET.
  • the viscosity of the polymer obtained in a mixed solution of phenol /1,1,2,2-tetrachloroethane (60:40 by weight) according to the standards of the Plastics Industry Association (SPI's) was 0.57 dL/g.
  • the regular PET chain length is the regular PET chain length.
  • the polyester-based polymer obtained in this example was found to have an elastic modulus of 910 MPa and a tensile stress of 57 MPa in accordance with the test standard of ASTM D638-97.
  • Fig. 2 is a view showing the weight loss of the polyester-based polymer obtained in the present embodiment after stirring for 1 hour at 100 ° C in a 5% aqueous sodium hydroxide solution. It can be seen from Fig. 2 that the polycondensation obtained in this example After the ester polymer was stirred in an alkali solution for 120 minutes, the weight loss percentage reached 49.78%; after stirring for 240 minutes, the weight loss percentage reached 83.84%; After stirring for 480 minutes, the weight loss percentage reached 92.24%; further illustrating that the polyester-based polymer of the present invention has rapid degradation characteristics under specific conditions.
  • the degradation segment synthesized in the first step is added, and then the polymerization is continued at 275 ° C for 1 to 3 hours to a predetermined degree of polymerization (intrinsic viscosity).
  • Table 1 shows the performance test results of the polyester-based polymer of the present invention obtained by the molar ratio of the degraded segment to the non-degraded segment in the present embodiment of 1:5, 1:7, and 1:9.
  • the polyester-based polymer provided by the invention not only has good machinability, but also can be rapidly degraded in a suitable environment (for example, in an alkaline solution). It can effectively solve the environmental pollution problems caused by the application of such polymers, and meet the wide application requirements of such polymers, especially to ensure that the polymers are in beverage bottles, food packaging films, shopping bags and other food packaging containers.
  • the preparation method of the invention is simple, the cost is low, the raw materials are cheap and easy to obtain, and it is suitable for large-scale production, and has strong practical value and popularization and application prospect.

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Wrappers (AREA)

Abstract

公开了可快速降解的聚酯类聚合物及其制备方法和应用，其中所述聚合物是由非降解链段A与可降解链段B进行缩聚反应而获得的。所述制备方法包括：a）由卤代链烷酸（或酯）（如溴乙酸甲酯或氯代乙酸甲酯）或羟基（或氨基）链烷酸（或酯）与脂肪族二元酸（如丁二酸）进行反应来合成可降解链段Β，然后b）使非降解链段A（如双（2-羟烷基）对苯二甲酸酯BHET）与可降解链段B进行缩聚反应。聚酯类聚合物不仅具有良好的加工性能，而且在适当的环境中快速地降解，尤其可保证在饮料瓶、食物包装膜、购物袋及其它食品包装容器中的应用。

Description

一种可快速降解的聚酯类聚合物及其制备方法和应用 技术领域
本发明涉及一种可快速降解的聚酯类聚合物及其制备方法和应用， 具体说， 是涉 及一种在聚合物主链中嵌有可降解小链段的聚酯类聚合物及其制备方法和应用， 属于 功能高分子材料技术领域。
说 背景技术
聚酯是由多元醇和多元酸縮聚而得的聚合书物总称， 以聚对苯二甲酸乙二酯 (PET) 为代表的芳香族聚酯以其优异的化学稳定性、 较好的力学和卫生性能以及透明性能等 在化纤、 包装等行业得到了广泛应用。 目前， 聚酯产量和销售量仍保持强有力的增长 势头， 特别是在碳酸饮料的包装方面； 随着聚酯阻隔性能研究的突破， 在啤酒、 食品 以及化妆品等领域的应用将使聚酯的市场进一步扩大。 但 PET聚酯废弃物在自然界中 很难自然降解。 聚酯瓶在湿度为 45%〜100%， 温度为 20 °C的环境中存在 30〜40年， 其 性能仅有 50%的损失； 相同条件下， 聚酯胶片可以存在 90〜100年之久。 为此大量的聚 酯废弃物将给环境带来巨大压力。
聚酯废弃物的回收再生既可以解决环境污染问题又实现了资源的充分利用， 是世 界各国优先采用的方法。 已经开发出多种 PET类聚酯的回收利用技术。 简单再生可以 是将聚酯废料经净化处理后， 重新熔融加工制成档次相对较低的产品， 例如玩具、 洗 涤剂用瓶等； 比较高档次的聚酯再生是利用聚酯材料是縮聚大分子， 可以进行降解处 理， 再次聚合或用作化工原料等； 另外还有油化技术、 回收燃料以及连同其他垃圾一 起焚烧回收能量等方法。
但聚酯废弃物的回收再利用并不能成为解决其环境污染问题的最终方法， 因为： 首先， 可以进行再生的聚酯废料有一定限制， 含有大量添加剂或含有其他难以去除杂 质以及已经是多次再生的产品， 回收再利用有很大困难； 其次， 大量不便收集的聚酯 产品， 如农膜、 垃圾袋等也不适合回收再生； 最后， 回收代价太大或没有回收价值的 产品也不值得回收再利用。 因此， 就有必要对用于这类产品生产的聚酯进行环境可降 解性改性， 使其废弃物在自然界中一定时间内能够自然分解为小分子产物， 最终回到 自然界的物质循环。
有效控制 PET类聚酯废弃物在自然界中的存在时间， 避免它对环境的污染， 这对 提高 PET类聚酯材料的环保性能， 从而促进其长远发展十分有利。
影响材料降解性能的化学因素有高分子的亲水性、 形态结构、 分子质量以及高聚 物的组成等。 高分子的亲水性强， 容易水解， 也有利于微生物作用下发生生物降解， 水解酶对酯键、 酰胺键以及氨基甲酸键等都有较强的作用； 高聚物的无定性区比结晶 区更容易受到水以及微生物的破坏； 分子链柔软、 玻璃化温度低有利于降解； 可降解 性能还随分子质量的降低而增强； 高聚物的组成， 如共混、 共聚等也可影响其降解性 能。
PET聚酯含有容易受微生物酶以及水分子破坏的酯键。 熔融状态下， 微量水分的 存在便可以引起聚酯键的迅速开裂。 为此在聚酯的生产加工中， 必须严格控制切片的 含水率。 但在通常条件下， PET聚酯却有着良好的化学稳定性， 自然条件下很难发生 降解。 这与 PET大分子主链的规整性结构以及主链中含有的芳香环有关。 芳香环的存 在增加了规整性分子链的极性， 使其柔性降低， 结晶性能提高。 较高的结晶度对水解 具有阻碍作用， 因为水不易侵入结晶相。 PET为半结晶性高聚物， 其降解的初始阶段 发生在结构相对比较疏松的无定型区以及结晶区的边缘， 结晶微粒之间的连接分子链 水解、 发生链开裂后， 会导致无定型区进一步结晶， 使结晶度明显增加， 从而阻碍了 水解的进一步发生； 另一方面， 分子链刚性提高， 大分子的活动能力必然降低， 表现 在玻璃化温度较高， 由此也会使聚合物对水解的敏感性减弱。 所以与熔融态不同， 固 态时的降解变成一个依赖于分子链活性以及穿透性的复杂过程。
由以上对 PET聚酯可降解性控制因素的分析可知： 为改进 PET聚酯的可降解性就 需要降低聚合物的结晶性能以及玻璃化温度。 聚酯玻璃化温度的降低可以提高分子链 的活动能力并减少改变状态所需要的能量， 进而提高聚酯对水解的敏感性。 结晶度的 降低可以使水分子或微生物有效侵入材料的内部对其薄弱的酯键攻击。
降低聚酯结晶度的途径既可以从控制高聚物材料的后加工工艺着手， 也可以通过 分子设计的观念一定程度上从改变 PET大分子原来的极性较强的刚性规整结构实现。 通过引入柔性或含有特殊官能团第三单体结构单元的方法可以从根本上改变 PET类聚 酯的结晶性能。 引入方法主要有加入改性第三单体共聚和与脂肪族聚酯类进行反应性 共混两种。
尽管从理论上已经明确改善 PET类芳香族聚酯环境可降解性的途径， 但在生产实 际中得到应用的还很有限。 PET类聚酯作为合成树脂中广泛应用的材料， 充分考虑其 环境可降解性能以消除其废弃物对环境的影响， 必将对其长远发展具有重要意义。 发明内容
针对现有技术存在的上述问题， 本发明的目的是提供一种可快速降解的聚酯类聚 合物及其制备方法和应用， 以实现例如 PET等聚酯类聚合物在特定条件下的快速降解， 解决因该类聚合物的应用所产生的环境污染问题。
为实现上述发明目的， 本发明采用的技术方案如下：
一种可快速降解的聚酯类聚合物， 是由非降解链段 A与可降解链段 B构成的重 复结构单元经縮聚反应得到的聚酯类聚合物一 ^ ^T ; 其特征在于：
所述的非降解链段 A具有如下化学结构通式：
Figure imgf000005_0001
其巾：
p、 m、 s 、 r 和 u 均是大于 0、 小于 11的整数;
t 是大于 1、 小于 31的整数；
n 是大于 1的整数；
R、 Ri R2、 R3、 R4、 R5、 R6、 R7分别独立选自 H、 取代或未取代的烷基、 取代 或未取代的杂烷基、 取代或未取代的环烷基、 取代或未取代的杂环烷基、 取代或未取 代的芳基、 取代或未取代的杂芳基、 取代或未取代的烷氧基、 酯基、 硝基、 氨基、 酰 胺基、 硫醇基中的任意一种。
作为一种优选方案， 所述 R、 Ri R2、 R3、 R4、 R5、 R6分别独立选自 H或 〜 。 烷基； 所述 R7选自 H、 取代或未取代的烷基、 取代或未取代的杂烷基、 取代或未取代 的环烷基、 取代或未取代的杂环烷基、 取代或未取代的芳基中的任意一种。
作为进一步优选方案， 所述 R、 Ri R2、 R3、 R4、 R5、 R6分别独立选自 H、 甲基、 乙基、 丙基、 异丙基、 正丁基、 异丁基、 叔丁基中的任意一种； 所述 R7选自 H、 取代 或未取代的烷基、 取代或未取代的杂烷基、 取代或未取代的环烷基、 取代或未取代的 杂环烷基中的任意一种。
作为更进一步优选方案， 所述 R为甲基， 所述 Ri、 R2、 R3、 R4、 R5、 R6、 R7均为 H， p=2; m和 s 分别独立选自 1、 2、 3、 4、 5中的任意一位数； t 是大于 1、 小于 31 的整数； r=l或 2; u=l或 2; n是大于 2的整数。
一种制备上述可快速降解的聚酯类聚合物的方法， 包括如下步骤：
a) 合成可降解链段 B :
Figure imgf000006_0001
b 通过溶液聚合或熔融聚合使非降解链段 A与可降解链段 B进行縮聚反应:
Figure imgf000006_0002
其中的 R、 Ri R2、 R3、 R4、 R5、 R6、 1 7及 、 m、 s、 r、 u、 t、 n的定义均同上所述;
X选自 Cl、 Br、 I、 NH2或 OH。 作为一种优选方案， 所述非降解链段 A的合成包括如下步骤:
Figure imgf000007_0001
上述可快速降解的聚酯类聚合物的另一种制备方法， 包括如下步骤:
Figure imgf000007_0002
Figure imgf000008_0001
为了确保可降解链段均一地分布在整个聚合物链中， 首先采用熔融缩聚合成非降 解链段或低聚物 （例如： 在 240〜290 °C、 真空下反应 2〜7小时）， 然后加入可降解链 段继续熔融聚合 （例如： 在 240〜290 °C、 真空下继续反应 2〜7小时）。
为了获得高分子量的聚合物， 只要使非降解链段含有的羟基摩尔数大于可降解链 段含有的羧酸酯基摩尔数即可， 因为过量的非降解链段能在高温和真空下脱除乙二醇 分子发生自缩合反应， 使形成高分子量聚合物。
与现有技术相比， 由于本发明提供的聚酯类聚合物在高分子主链中插入了结构不 同的降解链段， 因而破坏了它的结晶度， 使其熔融温度相比于常规聚酯类聚合物降低 较多； 而且由于降解链段的插入， 柔性链段加长， 使其玻璃化转变温度相比于常规聚 酯类聚合物也发生了降低； 因此， 本发明提供的聚酯类聚合物不仅具有良好的机械加 工性能， 而且可在适当的环境中 （例如， 碱性溶液中）， 可快速地降解为多个短链的非 降解链， 然后发生非降解链的进一步降解完全， 有效解决了该类聚合物的应用导致的 环境污染问题，满足了该类聚合物的广泛应用要求，尤其可保证该类聚合物在饮料瓶、 食物包装膜、 购物袋及其它食品包装容器中的应用； 另外， 本发明的制备方法简单， 成本低， 原料价廉易得， 适合规模化生产， 具有极强的实用价值和推广应用前景。 附图说明
图 1是实施例 1所制备的聚酯类聚合物 mPET(MeGSGMe)的 DSC曲线； 图 2是实施例 1所制备的聚酯类聚合物 mPET(MeGSGMe)的降解性能曲线； 图 3是实施例 2制备的 PET低聚物的特性粘度与聚合时间的关系曲线。 具体实施方式
下面结合实施例对本发明作进一步详细、 完整地说明。 下述实施例中所述实验方 法， 如无特殊说明， 均为常规方法； 所述试剂和材料， 如无特殊说明， 均可从商业途 径获得。
本发明中所采用的化学分析方法和分析仪器具体说明如下：
一、 特性粘度 （IV) 测定
工业界的 PET标准测定法： 根据塑料工业协会 （SPI's ) 关于 PET的标准测量所 得聚合物在苯酚 /1, 1,2,2-四氯乙烷 （60:40重量比） 混合溶液中， 用乌氏粘度计测定， 测定温度为 25°C。
因 PET的聚合度通过以下公式计算得到： DPn = 1.19 X IV - 7; 其中， IV的单位是 毫升 /克 (mL/g)， 因此本发明中的聚酯的链长采用相同的计算进行估算。
二、 化学组成与结构
本发明制备得到的聚酯类聚合物的结构与组成通过溶液核磁共振测定， 核磁共振 的测定温度为摄氏 20度， 溶剂为氘代氯仿。
三、 热性能测试
本发明制备得到的聚酯类聚合物的热性能是在 TA Instruments的示差扫描量热仪 Q20中测定得到的。
四、 降解性能测试
测试本发明制备得到的聚酯类聚合物在 100°C、5%的氢氧化钠水溶液中搅拌 n 小 时后的失重百分比。
五、 力学性能测试
拉伸强度测试由中科院上海有机所按照 ASTMD638-97 方法测定。
实施例 1
一、 合成可降解链段： MeGSGMe
将 23.62g (0.20mol)丁二酸和 56mL (0.4mol)三乙胺溶于 50mL无水乙腈中； 向上 述混合溶液中滴加 73.43g (0.48mol)溴乙酸甲酯； 滴毕， 室温搅拌 5小时； 当出现白色 沉淀时， 加入 lOOmL无水乙腈； 搅拌 24小时后， 过滤， 浓縮滤液； 将残渣在 50°C、 3mmHg下真空干燥 16小时以除去过量的溴乙酸甲酯；然后将残渣溶于 200mL乙酸乙 酯中， 用水洗涤残余的氨； 用无水硫酸镁干燥， 过滤， 浓縮滤液， 得到 41.43g固体， 即为所述的可降解链段： MeGSGMe; 摩尔收率 79%。
1HNMR (CDC13 , 400 Μζ) δ 4.66 (D, 4H); δ 3.77 (S, 6H); δ 2.80 (T， 4H)。
二、 制备本发明所述的聚酯类聚合物
将 71.19g双 (2-羟乙基）对苯二甲酸酯（BHET)、 10.49g可降解链段 MeGSGMe及 Sb203加入不锈钢压力容器中， 其中： 双 (2-羟乙基)对苯二甲酸酯 (BHET)与可降解链段 MeGSGMe的摩尔比为 7: 1， Sb203的加入量为总质量的 0.01wt% ; 反复抽三次真空后 充入氮气， 并将真空抽至 2 mmHg 左右， 再加热至 275 °C搅拌反应 5小时； 加入干冰 使反应体系温度快速冷却到室温； 收集得到 57.2g固体， 即为本发明所述的可快速降解 的聚酯类聚合物， 记为： mPET(MeGSGMe)。
图 1是对得到的聚合物进行热性能测试 （升温速度 10 °C/分钟） 得到的 DSC曲线 图， 由图 1可见： 所得聚合物的玻璃化转变温度为 56°C， 熔融温度为 216 °C， 升温过 程中重结晶温度为 121 °C ; 由图 1可进一步证明本发明提供的聚酯类聚合物由于在高 分子主链中插入了结构不同的降解链段， 因而破坏了它的结晶度， 使得其熔融温度相 比于常规 PET降低较多； 而且由于降解链段的插入， 柔性链段加长， 使其玻璃化转变 温度相比于常规 PET也发生了降低。
根据塑料工业协会 （SPI's ) 关于 PET的标准测量所得聚合物在苯酚 /1 , 1,2,2-四氯 乙烷 （60:40重量比） 混合溶液中的粘度为 0.57dL/g。
另外， 根据 B. Gantillon的公式计算得知本实施例所获得的聚酯类聚合物的链长 相当于聚合度为：
DPn = 1.19 X IV - 7=1.19 X (0.57 X 100)-7 = 61
的常规 PET的链长。
按照 ASTMD638-97的测试标准测得本实施例所获得的聚酯类聚合物的弹性模量 为 910MPa， 拉伸应力为 57MPa。
图 2体现了本实施例所制得的聚酯类聚合物在 100 °C、 5%的氢氧化钠水溶液中搅 拌 n 小时后的失重情况， 由图 2可见： 本实施例所制得的聚酯类聚合物在碱溶液中搅 拌 120分钟后，失重百分比达到 49.78% ;在搅拌 240分钟后，失重百分比达到 83.84% ; 在搅拌 480分钟后， 失重百分比达到 92.24% ; 进一步说明了本发明所述的聚酯类聚合 物在特定条件下具有快速降解特性。
实施例 2
一、 合成可降解链段： MeGSGMe
将 23.62g (0.20mol)丁二酸和 84mL (0.6mol)三乙胺溶于 50mL二氯甲烷中； 向上 述混合溶液中滴加 65. llg (0.6mol)氯代乙酸甲酯； 滴毕， 室温搅拌 5小时； 当出现白 色沉淀时， 加入 lOOmL二氯甲烷； 搅拌 24小时后， 过滤， 用水洗涤滤液中残余的氨； 用无水硫酸镁干燥， 过滤， 浓縮滤液， 得到 47.20g 固体， 即为所述的可降解链段： MeGSGMe; 摩尔收率 90%。
1HNMR (CDC13 , 400 Μζ) δ 4.66 (D, 4H); δ 3.77 (S, 6H); δ 2.80 (T， 4H)。
二、 合成非降解链段： PET低聚物
将 100 克 (0.393mol)双 (2-羟乙基)对苯二甲酸酯 (BHET) 和 0.02 克 Sb203 置于
250mL 反应器中。 将系统抽真空充氮气反复三次后抽真空并在 45分钟内加热到 275 °C ; 将系统在 3mmHg真空下维持在 275°C至需要的时间 （2〜7小时)， 即可得到各种 特性粘度的 PET低聚物。 获得的 PET低聚物用乌氏粘度计在苯酚 /1、 1、 2、 2四氯乙烷 ( 60:40重量比）混合溶液中测定其特性粘度， 图 3是 PET低聚物的特性粘度与聚合时 间的关系曲线。
三、 制备本发明所述的聚酯类聚合物
向步骤二制备的 PET低聚物中加入步骤一所合成的降解链段， 然后继续在 275°C 聚合 1〜3 小时至所定聚合度 （特性粘度） 时终止。 按此方法可合成降解链段 /非降解 链段 =1:5， 1:7 , 1:9 等不同摩尔比 【即 t = 5， 7， 9】 的聚合物。
表 1是本实施例按降解链段与非降解链段的摩尔比为 1 :5， 1:7 , 1:9所制得的本发 明所述的聚酯类聚合物的性能测试结果。
表 1 不同聚合物的性能表征结果
Figure imgf000011_0001
1 :9 0.713 63 213 930 57.5 综上所述可见： 本发明提供的聚酯类聚合物不仅具有良好的机械加工性能， 而且可 在适当的环境中 （例如， 碱性溶液中） 可快速地降解， 能有效解决该类聚合物的应用 导致的环境污染问题， 满足了该类聚合物的广泛应用要求， 尤其可保证该类聚合物在 饮料瓶、 食物包装膜、 购物袋及其它食品包装容器中的应用； 另外， 本发明的制备方 法简单， 成本低， 原料价廉易得， 适合规模化生产， 具有极强的实用价值和推广应用 前景。
最后有必要在此说明的是： 以上实施例只用于对本发明的技术方案作进一步详细 地说明， 不能理解为对本发明保护范围的限制， 本领域的技术人员根据本发明的上述 内容作出的一些非本质的改进和调整均属于本发明的保护范围。

Claims

权 利 要 求 书
1、 一种可快速降解的聚酯类聚合物， 是由非降解链段 A与可降解链段 B构成的 重复结构单元经縮聚反应得到的聚酯类聚合物一 ^"； 其特征在于：
所述的非降解链段 A具有如下化学结构通式：
Figure imgf000013_0001
其巾：
p、 m、 s 、 r 和 u 均是大于 0、 小于 11的整数；
t 是大于 1、 小于 31的整数；
n 是大于 1的整数；
R、 Ri R2、 R3、 R4、 R5、 R6、 R7分别独立选自 H、 取代或未取代的烷基、 取代 或未取代的杂烷基、 取代或未取代的环烷基、 取代或未取代的杂环烷基、 取代或未取 代的芳基、 取代或未取代的杂芳基、 取代或未取代的烷氧基、 酯基、 硝基、 氨基、 酰 胺基、 硫醇基中的任意一种。
2、根据权利要求 1所述的可快速降解的聚酯类聚合物， 其特征在于： 所述 R、 Ri R2、 R3、 R4、 R5、 R6分别独立选自 H或 〜^。烷基； 所述 R7选自 H、 取代或未取代的 烷基、 取代或未取代的杂烷基、 取代或未取代的环烷基、 取代或未取代的杂环烷基、 取代或未取代的芳基中的任意一种。
3、根据权利要求 2所述的可快速降解的聚酯类聚合物， 其特征在于： 所述 R、 R2、 R3、 R4、 R5、 R6分别独立选自 H、 甲基、 乙基、 丙基、 异丙基、 正丁基、 异丁基、 叔丁基中的任意一种； 所述 R7选自 H、 取代或未取代的烷基、 取代或未取代的杂烷基、 取代或未取代的环烷基、 取代或未取代的杂环烷基中的任意一种。
4、 根据权利要求 3所述的可快速降解的聚酯类聚合物， 其特征在于： 所述 R为甲 基， 所述 Ri、 R2、 R3、 R4、 R5、 R6、 R7均为 H， p=2; m和 s 分别独立选自 1、 2、 3、 4、 5中的任意一位数； t 是大于 1、 小于 31 的整数； r=l或 2 ; u=l或 2 ; n是大于 2 的整数。
5、 一种制备权利要求 1所述的可快速降解的聚酯类聚合物的方法， 其特征在于， 包括如下步骤：
a) 合成可降解链段 B
Figure imgf000014_0001
其中的 R、 Ri R2、 R3、 R4、 R5、 R6、 1 7及 、 m、 s、 r、 u、 t、 n的定义均同权利要求 1中所述； X选自 Cl、 Br、 I、 NH2或 OH。
6、 根据权利要求 5所述的方法， 其特征在于， 所述非降解链段 A的合成包括如 下步骤：
Figure imgf000015_0001
7、 一种制备权利要求 1所述的可快速降解的聚酯类聚合物的方法， 其特征在于， 包括如下步骤：
Figure imgf000015_0002
Figure imgf000016_0001
9、根据权利要求 5和 7所述的方法， 其特征在于， 首先采用熔融聚合合成非降解 链段或低聚物， 然后加入可降解链段继续熔融聚合。
10、根据权利要求 9所述的方法， 其特征在于， 进行熔融聚合的条件为： 在 240〜 290°C、 真空下反应 2〜7小时。
11、 根据权利要求 5和 7所述的方法， 其特征在于： 非降解链段含有的羟基摩尔 数大于可降解链段含有的羧酸酯基摩尔数。
12、 权利要求 1至 4中任一项所述的可快速降解的聚酯类聚合物在饮料瓶、 食物 包装膜、 购物袋及其它食品包装容器中的应用。
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