WO2019228273A1 - 一种可生物降解聚合物组合物及其应用 - Google Patents

一种可生物降解聚合物组合物及其应用 Download PDF

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WO2019228273A1
WO2019228273A1 PCT/CN2019/088370 CN2019088370W WO2019228273A1 WO 2019228273 A1 WO2019228273 A1 WO 2019228273A1 CN 2019088370 W CN2019088370 W CN 2019088370W WO 2019228273 A1 WO2019228273 A1 WO 2019228273A1
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polyester composition
parts
weight
aliphatic
biodegradable polyester
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PCT/CN2019/088370
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English (en)
French (fr)
Inventor
欧阳春平
焦建
麦开锦
董学腾
杨晖
区伟达
熊凯
卢昌利
曾祥斌
蔡彤旻
黄险波
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Priority to KR1020207006302A priority Critical patent/KR102309430B1/ko
Priority to US16/644,459 priority patent/US11370909B2/en
Priority to EP19810046.3A priority patent/EP3660095A4/en
Priority to JP2020533341A priority patent/JP7548816B2/ja
Priority to AU2019100561A priority patent/AU2019100561A4/en
Publication of WO2019228273A1 publication Critical patent/WO2019228273A1/zh
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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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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

Definitions

  • the invention belongs to the technical field of polymer material modification, and particularly relates to a biodegradable polymer composition and application thereof.
  • Biodegradable polyesters are a class of polymer materials based on biological resources. Compared to petroleum-based polymers based on petrochemical resources, biodegradable polyesters can occur during biological or biochemical processes or in the biological environment. Degradation is one of the most active degradation materials in the current research of biodegradable plastics and market applications.
  • polyester compositions based on aliphatic polyesters or aliphatic-aromatic copolyesters are widely used in fields such as shopping bags and kitchen waste bags.
  • the vertical and horizontal tearing performance of the film is an important index for evaluating the performance of the prepared shopping bags, food waste bags and other products.
  • one of the drawbacks of starch-based biodegradable bags currently on the market is the lack of uniformity of mechanical properties, especially tear strength in the transverse and longitudinal directions.
  • the film is still too pliable or brittle at a thickness of 18 ⁇ m to 20 ⁇ m, so that it cannot withstand a certain limit weight.
  • Chinese patent CN 101522797 B uses starch with an average size of less than 0.3 ⁇ m as a dispersed phase, and rigid and brittle polymers with a modulus of more than 1000 MPa as another dispersed phase; at the same time, by using the composition in this reduced Processed in an extruder or other machine under temperature and shear conditions to obtain a small particle size starch dispersed phase and a rigid and brittle polymer dispersed phase with a typical layered structure.
  • the above method improves the uniformity of the vertical and horizontal tearing properties of the material, it has the following problems.
  • the use of nano starch as a dispersed phase on the one hand, is easy to agglomerate because of the small starch particles.
  • specific Processing equipment and processes are not universal; on the other hand, nano-starch is more expensive than ordinary-sized starch, resulting in a lower cost performance of the product.
  • Chinese patent CN 102639594 B uses an aliphatic-aromatic copolyester with an aromatic acid content of 48 to 70 mol% based on the total molar content of the dicarboxylic acid, and uses a starch with an average size of 1 ⁇ m as the dispersed phase.
  • the mechanical properties of the polyester composition are improved to a certain extent.
  • Muller et al. (Angew. Chem., Int. Ed (1999), 38, 1438-1441) reported poly-succinate-adipate-co-terephthalate with a molar fraction of terephthalic acid of 42%.
  • the formate type copolymer was completely biodegraded in the compost within 12 weeks, while the product with a mole fraction of terephthalate of 51% had a biodegradation percentage of less than 40%.
  • the present invention has surprisingly discovered through research that an aliphatic-aromatic copolyester having a total amount of aromatic carboxylic acids in the diacids of 44 to 48 mol% is used as a matrix resin, and the aliphatic-aromatic copolymerization
  • the ester crystallization peak width D is 5 ° C to 16 ° C.
  • Starch having a particle diameter D (50) of 2 ⁇ m to 12 ⁇ m is used as another phase.
  • a specific content of a processing aid is added to prepare a polyester composition having excellent properties. Horizontal and vertical tear strength, and the polyester composition satisfies industrial composting, and during a 12-week degradation test process, the biodegradation rate reaches more than 90%.
  • a primary object of the present invention is to provide a biodegradable polyester composition having excellent transverse and longitudinal tear strength, and the polyester composition Satisfy industrial compost. During the 12-week degradation test, the biodegradation rate reached more than 90%.
  • a biodegradable polyester composition in terms of parts by weight, includes the following components:
  • the biodegradable polyester composition includes, by weight parts, the following components:
  • the total amount of aromatic carboxylic acids in the aliphatic-aromatic copolyester is 44 mol% to 48 mol%, and the aliphatic-aromatic copolyester is The crystal peak width D is 5 ° C to 16 ° C, and preferably 8 ° C to 12 ° C.
  • the polyester will not be caused by too low terephthalic acid content.
  • the mechanical properties of the composition are deteriorated, and the biodegradability of the polyester composition is not greatly affected because the terephthalic acid content is too high.
  • the crystalline peak width D of the aliphatic-aromatic copolyester to be 5 ° C. to 16 ° C., the prepared polyester composition has better crystallization properties.
  • the present invention requires mechanical properties of materials according to different application fields. The amount of aliphatic-aromatic copolyester added was screened.
  • the aliphatic-aromatic copolyester is selected from the group consisting of polybutylene adipate terephthalate PBAT, polybutylene sebacate terephthalate PBSeT One or a mixture thereof.
  • starch is used as component ii) of the polyester composition, and starch is considered as a polymer of natural origin, which has the characteristics of low cost and low toxicity.
  • Blending starch with an aliphatic-aromatic copolyester can not only The mechanical properties of the polyester composition are improved, and the cost of the composition can be greatly reduced; meanwhile, starch as a polymer of natural origin helps to improve the biodegradability of the polyester composition.
  • the particle diameter D (50) of the starch is 2 ⁇ m to 12 ⁇ m, preferably 3 ⁇ m to 11 ⁇ m, and more preferably 5 ⁇ m to 10 ⁇ m. It is beneficial to disperse the polyester composition; however, when the starch particle size D (50) exceeds 12 ⁇ m, the starch particles are too large, which affects the surface characteristics (roughness) of the film product, resulting in the polyester composition requiring more High processing temperature to plasticize the material, and too high processing temperature will lead to degradation of the aliphatic-aromatic copolyester, which affects the performance of the material; at the same time, too high processing temperature will also lead to too high Energy consumption and processing costs.
  • the processing aid is selected from water, glycerin, polyglycerin, epoxy soybean oil, citrate, acetylcitrate, ethylene glycol, and a mixture of one or more of polyethylene glycol, preferably water, glycerin Or a mixture of one or more of the polyglycerols.
  • the biodegradable polymer composition includes, based on parts by weight, the biodegradable polymer composition further comprises 0 to 20 parts by weight of an organic or inorganic filler.
  • the organic filler is selected from a mixture of one or more of natural fibers, straw, and wood flour; the inorganic filler is selected from talc, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, and conductive carbon black , Calcium chloride, iron oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber or a mixture of mineral fibers.
  • a biodegradable polymer composition according to the present invention further includes 0 to 4 parts by weight of the following other auxiliary agents: parting agent, surfactant, wax, etc. , Antistatic agents, dyes, anti-UV additives or other plastic additives.
  • the release agent is: silicone masterbatch, montan wax, erucamide, oleic acid amide;
  • the surfactant is one or a mixture of two or more of polysorbate, palmitate or laurate;
  • the wax is one or a mixture of two or more of stearamide, behenic acid amide, beeswax or beeswax ester;
  • the antistatic agent is a permanent antistatic agent, and specific examples include one or a mixture of two or more of PELESTAT-230, PELESTAT-6500, and SUNNICO ASA-2500;
  • the dye is one or a mixture of two or more of carbon black, black species, titanium dioxide, zinc sulfide, phthalocyanine blue, and fluorescent orange.
  • Anti-UV additives include UV absorbers and UV stabilizers
  • the UV absorber is one or more of UV-944, UV-234, UV531, and UV326;
  • the UV stabilizer is one or more of UV-123, UV-3896, and UV-328;
  • the other plastic additives may be a nucleating agent, an anti-fogging agent, a lubricant (such as calcium stearate), a primary antioxidant, a secondary antioxidant, a plasticizer, and the like.
  • the 12 ⁇ m ⁇ 1 ⁇ m film prepared by the polyester composition of the present invention has excellent transverse and vertical tear strength, and the longitudinal tear strength is greater than or equal to 1000 mN; preferably greater than or equal to 1100 mN, and more preferably greater than or equal to 1200 mN ; Transverse tear strength ⁇ 2400mN; preferably ⁇ 2600mN, more preferably ⁇ 2800mN;
  • the 12 ⁇ m ⁇ 1 ⁇ m film prepared by the polyester composition according to the present invention is tested according to the standard ISO 16929 (2013), and the biodegradation rate after 12 weeks is greater than 90%.
  • the polyester composition according to the invention is biodegradable in industrial compost according to the standard EN 13432.
  • the invention also discloses that the biodegradable polyester composition is used for preparing shopping bags, compost bags, mulch films, protective cover films, silo films, film tapes, fabrics, non-woven fabrics, textiles, fishing nets, load-bearing bags or garbage bags. Application.
  • the present invention has the following beneficial effects:
  • the present invention has surprisingly discovered through research that an aliphatic-aromatic copolyester having a total amount of aromatic carboxylic acids in the diacids of 44 to 48 mol% is used as a matrix resin, and the aliphatic-aromatic copolymerization
  • the ester crystallization peak width D is 5 ° C to 16 ° C.
  • Starch having a particle diameter D (50) of 2 ⁇ m to 12 ⁇ m is used as another phase.
  • a specific content of a processing aid is added to prepare a polyester composition having excellent properties. Horizontal and vertical tear strength, and the polyester composition satisfies industrial composting, and during a 12-week degradation test process, the biodegradation rate reaches more than 90%.
  • the raw materials used in the examples and comparative examples of the present invention are as follows:
  • Component i) PBAT-1 is selected: the aromatic carboxylic acid accounts for 46 mol% of the total diacid, and the crystalline peak width D is 11 ° C;
  • PBAT-2 Aromatic carboxylic acid accounts for 44 mol% of the total diacid, and the crystalline peak width D is 8 ° C;
  • PBAT-3 the total amount of aromatic carboxylic acid is 48 mol%, and the width D of the crystalline peak is 15 ° C;
  • PBAT-4 the total amount of aromatic carboxylic acid is 38 mol%, and the width D of the crystalline peak is 11 ° C;
  • PBAT-5 aromatic carboxylic acid accounts for 58 mol% of the total diacid, and the crystalline peak width D is 11 ° C;
  • PBAT-6 Aromatic carboxylic acid accounts for 46 mol% of the total amount of the diacid, and the crystalline peak width D is 4 ° C;
  • PBAT-7 the total amount of aromatic carboxylic acid is 46 mol%, and the width D of the crystalline peak is 25 ° C;
  • PBAT-8 the total amount of aromatic carboxylic acid is 58 mol%, and the width D of the crystalline peak is 25 ° C;
  • PBSeT the total amount of aromatic carboxylic acid is 46 mol%, and the width D of the crystalline peak is 11 ° C;
  • Component ii) select starch-1 with a particle size D (50) of 4 ⁇ m;
  • citrate is used as the plasticizer
  • palmitate is used as the surfactant
  • DSC differential scanning calorimeter
  • test method for the particle diameter D (50) of the starch according to the present invention is determined with reference to the method of GB / T 19077.1 "particle size analysis laser diffraction method".
  • the polyester composition is prepared into a 12 ⁇ m ⁇ 1 ⁇ m film and obtained according to the standard ASTM D-882 / 88 test;
  • Biodegradation rate of the polyester composition after 12 weeks The polyester composition was prepared into a 12 ⁇ m ⁇ 1 ⁇ m film and obtained by testing according to the standard ISO 16929 (2013).
  • Table 1 The distribution ratio and performance test results (parts by weight) of each group in the examples and comparative examples

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

本发明公开了一种可生物降解的聚酯组合物，其特征在于，按重量份计，包括如下组分: i)58重量份～80重量份的脂肪族-芳香族共聚酯； ii)20重量份～32重量份的淀粉； iii)0～10重量份的加工助剂。本发明通过研究意外的发现，以芳香族羧酸占二酸的总量为44摩尔％～48摩尔％的脂肪族-芳香族共聚酯为基体树脂，且所述脂肪族-芳香族共聚酯结晶峰宽度D为5℃～16℃，以粒径D(50)为2μm～12μm的淀粉作为另外一相，同时，添加特定含量的加工助剂，制备得到的聚酯组合物具有优异的横纵向撕裂强度，并且所述聚酯组合物满足工业堆肥，在12周的降解测试过程中，生物降解率达到90％以上。

Description

一种可生物降解聚合物组合物及其应用 技术领域
本发明属于高分子材料改性技术领域，具体涉及一种可生物降解聚合物组合物及其应用。
背景技术
可生物降解聚酯是以生物资源为原料的一类高分子材料，相对于以石化资源为原料的石油基高分子，可生物降解聚酯能够在生物或生物化学作用过程中或生物环境中发生降解，是目前生物降解塑料研究中非常活跃和市场应用最好的降解材料之一。
目前以脂肪族聚酯或脂肪族-芳香族共聚酯为基础树脂的聚酯组合物，广泛应用于购物袋、厨余垃圾袋等领域。而薄膜的纵横向撕裂性能则是评估所制备的购物袋、厨余垃圾袋等产品性能优劣的重要指标。如中国专利CN 101522797 B所述，市场上目前存在的基于淀粉的可生物降解的袋子的一个缺陷在于缺乏机械性能的均一性，特别是在横向和纵向的撕裂强度。由基于淀粉的可生物降解聚酯组合物制备的薄膜在厚度18μm～20μm的情况下，所述的膜仍过于柔顺或者过于脆性，以致不能经受住一定极限重量。这些性能方面的局限性在低湿度条件下，由于组合物中水分的缺失而尤为明显。
中国专利CN 101522797 B通过选用平均尺寸小于0.3μm的淀粉作为分散相，以模量大于1000MPa的刚性且脆性的聚合物作为另外的分散相；同时，通过将所述组合物在这种减小的温度和剪切条件的挤出机或其他机器中加工，而获得小颗粒尺寸的淀粉分散相和典型层状结构的刚性且脆性的聚合物的分散相。上述方法虽然很好的提升了材料纵横向撕裂性能的均一性，但存在如下问题，以纳米淀粉作为分散相，一方面由于淀粉颗粒小而易发生团聚，为了解决尺寸稳定性问题，需要特定的加工设备和加工工艺，不具有普适性；另一方面，纳米淀粉较普通尺寸的淀粉价格更高，导致产品性价比偏低。
中国专利CN 102639594 B采用芳族酸的含量为二羧酸总摩尔含量的48至70摩尔％的脂族-芳族共聚酯为基础树脂，以平均尺寸为1μm的淀粉作为分散相，也在一定程度上提升了聚酯组合物的机械性能。
中国专利CN 102597105 B报道了，目前市售的聚酯通常具有小于48摩尔％的芳香族羧酸的量，因为在该阈值以上，这类聚酯的生物降解百分比会显著降低，在工业堆肥或家庭堆肥的条件下，难以有效的降解。
Muller等人(Angew.Chem.，Int.Ed(1999)，38,1438-1441)中报道了对苯二甲酸的 摩尔分数为42％的聚丁二酸己二酸酯—共聚—对苯二甲酸酯类型的共聚物在堆肥中在12周内完全生物降解，而具有51％的对苯二甲酸酯摩尔分数的产物具有低于40％的生物降解百分比。
中国专利CN02804139.9报道了为了遵循CEN 13432方法的可生物降解的特性，对于可生物降解的脂肪族-芳香族聚合物，含有对苯二甲酸的量(基于总酸的摩尔数)必须不超过55％，优选不超过50％。
本发明通过研究意外的发现，以芳香族羧酸占二酸的总量为44摩尔％～48摩尔％的脂肪族-芳香族共聚酯为基体树脂，且所述脂肪族-芳香族共聚酯结晶峰宽度D为5℃～16℃，以粒径D(50)为2μm～12μm的淀粉作为另外一相，同时，添加特定含量的加工助剂，制备得到的聚酯组合物具有优异的横纵向撕裂强度，并且所述聚酯组合物满足工业堆肥，在12周的降解测试过程中，生物降解率达到90％以上。
发明内容
为了克服现有技术的缺陷或不足，本发明的首要目的旨在提供一种可生物降解的聚酯组合物，该聚酯组合物具有优异的横纵向撕裂强度，并且所述聚酯组合物满足工业堆肥，在12周的降解测试过程中，生物降解率达到90％以上。
本发明是通过以下技术方案实现的：
一种可生物降解的聚酯组合物，按重量份数计，包括如下组分：
i)58重量份～80重量份的脂肪族-芳香族共聚酯；
ii)20重量份～32重量份的淀粉；
iii)0～10重量份的加工助剂。
优选地，所述可生物降解的聚酯组合物，按重量份数计，包括如下组分：
i)62重量份～80重量份的脂肪族-芳香族共聚酯；
ii)20重量份～30重量份的淀粉；
iii)0～8重量份的加工助剂。
其中，组分i)中，所述脂肪族-芳香族共聚酯中，芳香族羧酸占二酸的总量为44摩尔％～48摩尔％，且所述脂肪族-芳香族共聚酯结晶峰宽度D为5℃～16℃，优选为8℃～12℃。
本发明通过选择芳香族羧酸含量为二酸总摩尔含量的44摩尔％—48摩尔％的脂肪族-芳香族共聚酯作为基体树脂，既不会因为对苯二甲酸含量过低导致聚酯组合物机械性能变差，也不会因为对苯二甲酸含量过高，而较大程度的影响聚酯组合物的生物降解性能。另外，通过选择脂肪族-芳香族共聚酯结晶峰宽度D为5℃～16℃，制备得到的聚酯组合物具有较好的 结晶性能，同时，本发明根据不同应用领域对材料机械性能要求的不同，对脂肪族-芳香族共聚酯的添加量进行了筛选。
本发明所述的组分i)中，所述脂肪族-芳香族共聚酯选自聚己二酸对苯二甲酸丁二醇酯PBAT、聚癸二酸对苯二甲酸丁二醇酯PBSeT中的一种或其混合物。
本发明采用淀粉作为聚酯组合物的组分ii)，考虑的是淀粉作为天然来源的聚合物，成本低，毒性小的特点，以淀粉与脂肪族-芳香族共聚酯共混，不仅能提升聚酯组合物的机械性能，而且可以极大地降低组合物的成本；同时，淀粉作为天然来源的聚合物，有助于改善所述聚酯组合物的生物降解性能。
本发明所述的组分ii)中，所述淀粉的粒径D(50)为2μm～12μm，优选为3μm～11μm，更优选为5μm～10μm；淀粉的粒径越大，越不易团聚，有利于在聚酯组合物的分散；但当淀粉粒径D(50)超过12μm时，由于淀粉颗粒过大，影响薄膜产品的表面特性(粗糙)，导致聚酯组合物在加工过程中需要更高的加工温度来实现材料的塑化，而过高的加工温度会导致脂肪族-芳香族共聚酯的降解，而影响了材料的性能；同时，过高的加工温度，也会导致过高的能耗和加工成本。
所述加工助剂选自水、甘油、聚甘油、环氧大豆油、柠檬酸酯、乙酰柠檬酸酯、乙二醇、聚乙二醇中的一种或几种的混合，优选水、甘油或聚甘油中的一种或几种的混合。
所述的一种可生物降解聚合物组合物，按重量份数计，所述可生物降解聚合物组合物还包括0至20重量份的有机或无机填料。
所述有机填料选自天然纤维、秸秆、木粉中的一种或几种的混合；所述无机填料选自滑石粉、蒙脱土、高岭土、白垩、碳酸钙、石墨、石膏、导电炭黑、氯化钙、氧化铁、白云石、二氧化硅、硅灰石、二氧化钛、硅酸盐、云母、玻璃纤维或矿物纤维中的一种或几种的混合。
根据实际性能需要，本发明所述的一种可生物降解的聚合物组合物，按重量份数计，还包括0至4重量份的下述其他助剂：脱模剂、表面活性剂、蜡、防静电剂、染料、抗UV助剂或其他塑料添加剂。
所述脱模剂为：硅酮母粒、蒙坦蜡、芥酸酰胺、油酸酰胺；
所述表面活性剂为聚山梨醇酯、棕榈酸酯或月桂酸酯中的一种或者两种及以上的混合物；
所述蜡为硬脂酰胺、山嵛酸酰胺、蜂蜡或蜂蜡酯中的一种或者两种及以上的混合物；
所述防静电剂为永久性抗静电剂，具体可以列举出PELESTAT-230、PELESTAT-6500、SUNNICO ASA-2500中的一种或者两种及以上的混合物；
所述染料为炭黑、黑种、钛白粉、硫化锌、酞青蓝、荧光橙中的一种或者两种及以上的混合物。
抗UV助剂包括UV吸收剂和UV稳定剂；
所述UV吸收剂为UV-944、UV-234、UV531、UV326中的一种或几种；
所述UV稳定剂为UV-123、UV-3896、UV-328中的一种或几种；
所述其他塑料添加剂可以为成核剂、防雾剂、润滑剂(如硬脂酸钙)、主抗氧剂、辅抗氧剂、增塑剂等。
本发明所述的聚酯组合物制备的12μm±1μm薄膜，根据标准ASTM D-882/88测试，具有优异的横纵向撕裂强度，纵向撕裂强度≥1000mN；优选≥1100mN，更优选≥1200mN；横向撕裂强度≥2400mN；优选≥2600mN，更优选≥2800mN；
本发明所述的聚酯组合物制备的12μm±1μm薄膜，根据标准ISO 16929(2013)测试，12周后的生物降解率大于90％。
本发明所述的聚酯组合物根据标准EN 13432在工业堆肥中是可生物降解的。
本发明还公开了上述可生物降解的聚酯组合物在制备购物袋、堆肥袋、地膜、保护性覆盖膜、筒仓膜、薄膜带、织物、非织物、纺织品、渔网、承重袋或垃圾袋中的应用。
本发明与现有技术相比，具有如下有益效果：
本发明通过研究意外的发现，以芳香族羧酸占二酸的总量为44摩尔％～48摩尔％的脂肪族-芳香族共聚酯为基体树脂，且所述脂肪族-芳香族共聚酯结晶峰宽度D为5℃～16℃，以粒径D(50)为2μm～12μm的淀粉作为另外一相，同时，添加特定含量的加工助剂，制备得到的聚酯组合物具有优异的横纵向撕裂强度，并且所述聚酯组合物满足工业堆肥，在12周的降解测试过程中，生物降解率达到90％以上。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明实施例和对比例采用的原料如下：
组分i)选用PBAT-1：芳香族羧酸占二酸的总量46摩尔％，结晶峰宽度D为11℃；
PBAT-2：芳香族羧酸占二酸的总量44摩尔％，结晶峰宽度D为8℃；
PBAT-3：芳香族羧酸占二酸的总量48摩尔％，结晶峰宽度D为15℃；
PBAT-4：芳香族羧酸占二酸的总量38摩尔％，结晶峰宽度D为11℃；
PBAT-5：芳香族羧酸占二酸的总量58摩尔％，结晶峰宽度D为11℃；
PBAT-6：芳香族羧酸占二酸的总量46摩尔％，结晶峰宽度D为4℃；
PBAT-7：芳香族羧酸占二酸的总量46摩尔％，结晶峰宽度D为25℃；
PBAT-8：芳香族羧酸占二酸的总量58摩尔％，结晶峰宽度D为25℃；
PBSeT：芳香族羧酸占二酸的总量46摩尔％，结晶峰宽度D为11℃；
组分ii)选用淀粉-1，粒径D(50)4μm；
淀粉-2，粒径D(50)8μm；
淀粉-3，粒径D(50)12μm；
淀粉-4，粒径D(50)16μm；
淀粉-5，粒径D(50)1μm；
组分iii)选用加工助剂：水、甘油；
填料选用：滑石粉、碳酸钙；
其他助剂：增塑剂选用柠檬酸酯；表面活性剂选用棕榈酸酯；
其它组分均来源于市购产品。
各性能指标的评价方法：
脂肪族-芳香族共聚酯的结晶峰宽度D的测试方法：
通过差示扫描量热仪(DSC)测定，具体测试方法如下：采用高纯度标准物(铟)校准差示扫描量热仪，将5～10mg脂肪族-芳香族共聚酯放入铝制坩埚中，以10℃/min的速度(第一次扫描)加热到220℃，恒温5min，然后以10℃/min的速度冷却到-30℃，从第一次扫描的差示热分析图降温曲线上获得脂肪族-芳香族共聚酯的结晶峰。取结晶峰起始端和终止端做切线，两切线端点的温差即结晶峰宽度。
淀粉的粒径D(50)的测试方法：
本发明所述淀粉的粒径D(50)测试方法参照GB/T 19077.1《粒度分析激光衍射法》方法测定。
聚酯组合物的纵向和横向撕裂强度：将所述聚酯组合物制备成12μm±1μm薄膜，根据标准ASTM D-882/88测试得到；
聚酯组合物的12周后的生物降解率：将所述聚酯组合物制备成12μm±1μm薄膜，根据标准ISO 16929(2013)测试得到。
实施例1-11及对比例1-4:
按照表1所述的重量份配比，将脂肪族-芳香族共聚酯、淀粉、加工助剂、填料、其他助 剂混匀后投入单螺杆挤出机中，于140℃-240℃挤出、造粒，得到可生物降解的聚酯组合物。所得聚酯组合物的各项性能测试数据如表1所示。
表1实施例和对比例中各组分配比及性能测试结果(重量份)
Figure PCTCN2019088370-appb-000001
续表1
Figure PCTCN2019088370-appb-000002

Claims (11)

  1. 一种可生物降解的聚酯组合物，其特征在于，按重量份计，包括如下组分:
    i)58重量份～80重量份的脂肪族-芳香族共聚酯；
    ii)20重量份～32重量份的淀粉；
    iii)0～10重量份的加工助剂。
  2. 根据权利要求1所述的可生物降解的聚酯组合物，其特征在于，按重量份计，包括如下组分：
    i)62重量份～80重量份的脂肪族-芳香族共聚酯；
    ii)20重量份～30重量份的淀粉；
    iii)0～8重量份的加工助剂。
  3. 根据权利要求1或2所述的可生物降解的聚酯组合物，其特征在于，组分i)中，所述脂肪族-芳香族共聚酯中，芳香族羧酸占二酸的总量为44摩尔％～48摩尔％，且所述脂肪族-芳香族共聚酯结晶峰宽度D为5℃～16℃，优选为8℃～12℃。
  4. 根据权利要求1或2所述的可生物降解的聚酯组合物，其特征在于，组分ii)中，所述淀粉的粒径D(50)为2μm～12μm，优选为3μm～11μm，更优选为5μm～10μm。
  5. 根据权利要求1或2所述的可生物降解的聚酯组合物，其特征在于，所述聚酯组合物制备的12μm±1μm薄膜根据标准ASTM D-882/88测试的纵向撕裂强度≥1000mN；优选≥1100mN，更优选≥1200mN；所述聚酯组合物制备的12μm±1μm薄膜根据标准ASTM D-882/88测试的横向撕裂强度≥2400mN；优选≥2600mN，更优选≥2800mN；所述聚酯组合物制备的12±1μm薄膜根据标准ISO 16929(2013)测试的12周后的生物降解率大于90％。
  6. 根据权利要求1或2所述的可生物降解的聚酯组合物，其特征在于，组分i)中，所述脂肪族-芳香族共聚酯选自聚己二酸对苯二甲酸丁二醇酯PBAT、聚癸二酸对苯二甲酸丁二醇酯PBSeT中的一种或其混合物。
  7. 根据权利要求1-2任一项所述的可生物降解的聚酯组合物，其特征在于，所述加工助剂选自水、甘油、聚甘油、环氧大豆油、柠檬酸酯、乙酰柠檬酸酯、乙二醇、聚乙二醇中的一种或几种的混合，优选水、甘油或聚甘油中的一种或几种的混合。
  8. 根据权利要求1-2任一项所述的可生物降解的聚酯组合物，其特征在于，按重量份数计，所述可生物降解的聚酯组合物还包括0至20重量份的有机或无机填料。
  9. 根据权利要求8所述的一种可生物降解的聚酯组合物，其特征在于，所述有机填料选自天然纤维、秸秆、木粉中的一种或几种的混合；所述无机填料选自滑石粉、蒙脱土、高岭土、 白垩、碳酸钙、石墨、石膏、导电炭黑、氯化钙、氧化铁、白云石、二氧化硅、硅灰石、二氧化钛、硅酸盐、云母、玻璃纤维或矿物纤维中的一种或几种的混合。
  10. 根据权利要求1-2任一项所述的可生物降解的聚酯组合物，其特征在于，按重量份数计，所述聚合物组合物还包括0至4重量份的下述其他助剂：脱模剂、表面活性剂、蜡、防静电剂、染料、抗UV助剂或其他塑料添加剂。
  11. 如权利要求1-10任一项所述的可生物降解的聚酯组合物在制备购物袋、堆肥袋、地膜、保护性覆盖膜、筒仓膜、薄膜带、织物、非织物、纺织品、渔网、承重袋或垃圾袋中的应用。
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