WO2022032518A1 - 聚己内酯改性淀粉基生物降解树脂材料及其制备方法 - Google Patents

聚己内酯改性淀粉基生物降解树脂材料及其制备方法 Download PDF

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WO2022032518A1
WO2022032518A1 PCT/CN2020/108634 CN2020108634W WO2022032518A1 WO 2022032518 A1 WO2022032518 A1 WO 2022032518A1 CN 2020108634 W CN2020108634 W CN 2020108634W WO 2022032518 A1 WO2022032518 A1 WO 2022032518A1
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polycaprolactone
modified starch
parts
resin material
biodegradable resin
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PCT/CN2020/108634
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French (fr)
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陈昌平
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南京五瑞生物降解新材料研究院有限公司
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Priority to PCT/CN2020/108634 priority Critical patent/WO2022032518A1/zh
Priority to AU2020227123A priority patent/AU2020227123A1/en
Publication of WO2022032518A1 publication Critical patent/WO2022032518A1/zh

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    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • 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

Definitions

  • the invention relates to a polycaprolactone-modified starch-based biodegradable resin material and a preparation method thereof, belonging to the field of degradable plastics.
  • Biodegradable plastics are polymeric materials that can decompose into carbon dioxide and water in a relatively short period of time under normal environmental conditions.
  • biodegradable homopolyester such as PHA, PLA, PHB, PCL, PHBV, etc.
  • biodegradable copolyester such as PBS, PBSA, etc.
  • natural products with polysaccharide structure such as thermoplastic starch resin (TPS), Cellulose acetate, etc.
  • TPS thermoplastic starch resin
  • biodegradable membranes with high starch content have the disadvantages of decreased mechanical properties and poor water resistance.
  • PCL Polycaprolactone
  • metal organic compounds such as tetraphenyl tin
  • PCL has good biocompatibility, good organic polymer compatibility, and good biodegradability, and can be mutually compatible with a variety of conventional plastics, but when used alone, the melting point is low (about 60 ° C), and the Poor heat resistance.
  • the purpose of the present invention is to provide a polycaprolactone-modified starch-based biodegradable resin material with good mechanical properties and water resistance.
  • a polycaprolactone-modified starch-based biodegradable resin material is prepared from the following raw materials by weight:
  • the modified starch is one or a mixture of oxidized starch or hydroxypropyl starch.
  • the filler is talc, calcium carbonate or barium sulfate.
  • the plasticizer is glycerol or sorbitol.
  • the lubricant is calcium stearate or erucamide.
  • the invention also discloses a preparation method of the above-mentioned polycaprolactone-modified starch-based biodegradable resin material.
  • the modified starch, polycaprolactone, polysuccinic acid-adipic acid-butanediol copolyester are grafted Glycidyl methacrylate, fillers, plasticizers and lubricants are added to the high-speed mixer, and after high-speed stirring, blow molding.
  • the film blowing temperature is 150-178° C.
  • the inflation ratio is 3-5:1
  • the stirring speed is 600-1000 rpm
  • the stirring time is more than 30 minutes.
  • the invention adopts polycaprolactone and modified starch as the main body of the film, and adds plasticizer and polysuccinic acid-adipic acid-butanediol copolyester grafted glycidyl methacrylate, which can effectively improve starch and
  • the compatibility of polycaprolactone overcomes the disadvantage of low melting point of polycaprolactone.
  • the addition of lubricant improves the opening and surface finish of the film, and the filler can appropriately improve the strength and opening performance of the film.
  • the film prepared by the invention can be completely biodegraded, has good mechanical properties, water resistance and light transmittance, and has a wide range of uses.
  • Example 1 Weigh 100 parts of oxidized starch, 60 parts of polycaprolactone with a molecular weight of 80,000, 30 parts of polysuccinic acid-adipic acid-butanediol copolyester grafted glycidyl methacrylate, 10 parts of Talc, 20 parts of glycerol, and 5 parts of calcium stearate were added to a high-speed mixer, stirred at a high speed, the stirring speed was 800 rpm, and the stirring time was 1 h. 1.
  • Example 2 Weigh 100 parts of oxidized starch, 50 parts of polycaprolactone, 20 parts of polysuccinic acid-adipic acid-butanediol copolyester grafted glycidyl methacrylate, 5 parts of calcium carbonate, 10 parts of Add 1 part of glycerin and 1 part of calcium stearate into the high-speed mixer, stir at a high speed, the stirring speed is 600rpm, the stirring time is 30min, blow molding, the blowing temperature is 150 °C, and the inflation ratio is 3:1.
  • Example 3 Weigh 100 parts of oxidized starch, 70 parts of polycaprolactone, 40 parts of polysuccinic acid-adipic acid-butanediol copolyester grafted glycidyl methacrylate, 15 parts of barium sulfate, 25 parts of Parts of glycerin and 6 parts of calcium stearate were added to the high-speed mixer, stirred at a high speed, the stirring speed was 1000rpm, and the stirring time was 2h.
  • Example 4 Weigh 100 parts of hydroxypropyl starch, 60 parts of polycaprolactone, 25 parts of polysuccinic acid-adipic acid-butanediol copolyester grafted glycidyl methacrylate, 12 parts of barium sulfate , 25 parts of sorbitol and 4 parts of erucamide were added into the high-speed mixer, stirred at high speed, the stirring speed was 800 rpm, the stirring time was 2 hours, and the blow molding temperature was 160 °C, and the inflation ratio was 4:1.

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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)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种聚己内酯改性淀粉基生物降解树脂材料，由以下重量份的原料制备而成：改性淀粉100份、聚己内酯50-70份、聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯20-40份、填充剂5-15份、增塑剂10-25份、润滑剂1-6份。并公开了其制备方法。本发明采用聚己内酯与改性淀粉作为膜的主体，加入增塑剂和聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯，可有效提高淀粉与聚己内酯的相容性，克服聚己内酯熔点低的缺点。润滑剂的添加，提高了薄膜的开口性和表面光洁度，填充剂则可以适当提高薄膜强度和开口性能。本发明制得的薄膜可完全生物降解，且具有良好的力学性能、耐水性和透光性，具有广泛的用途。

Description

聚己内酯改性淀粉基生物降解树脂材料及其制备方法 技术领域
本发明涉及一种聚己内酯改性淀粉基生物降解树脂材料及其制备方法，属于可降解塑料领域。
背景技术
常规的塑料制品如聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)等其性状非常稳定，可在自然界长期稳定存在，难以降解，被称为白色垃圾，造成了严重的环境污染。为缓解环境压力，生物降解塑料成了目前的研发热点。
生物降解塑料是指能够在常规环境条件下在较短的时间内分解为二氧化碳和水的聚合物材料。目前常见的有：生物降解均聚酯，如PHA、PLA、PHB、PCL、PHBV等，生物降解共聚酯，如PBS、PBSA等；具有多糖结构的天然产物，如热塑性淀粉树脂(TPS)、醋酸纤维素等。其中淀粉含量较高的生物降解膜，会存在力学性能下降，耐水性能差的缺点。
聚己内酯(PCL)是由ε-己内酯在金属有机化合物(如四苯基锡)做催化剂，二羟基或三羟基做引发剂条件下开环聚合而成，属于聚合型聚酯。PCL具有良好的生物相容性，良好的有机高聚物相容性，以及良好的生物降解性，可与多种常规塑料互相兼容，但单独使用时熔点较低(60℃左右)，制品的耐热性差。
发明内容
本发明的目的在于提供一种聚己内酯改性淀粉基生物降解树脂材料，具有良好的力学性能和耐水性能。
本发明的目的通过以下技术方案实现：
一种聚己内酯改性淀粉基生物降解树脂材料，由以下重量份的原料制备而成：
Figure PCTCN2020108634-appb-000001
Figure PCTCN2020108634-appb-000002
优选的，所述改性淀粉为氧化淀粉或者羟丙基淀粉中的一种或混合物。
优选的，所述填充剂为滑石粉、碳酸钙或硫酸钡。
优选的，所述增塑剂为甘油或山梨醇。
优选的，所述润滑剂为硬脂酸钙或者芥酸酰胺。
本发明还公开了上述的聚己内酯改性淀粉基生物降解树脂材料的制备方法，将改性淀粉、聚己内酯、聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯、填充剂、增塑剂和润滑剂加入高速混料机中，高速搅拌后，吹塑成型。
优选的，吹膜温度为150-178℃，吹胀比为3-5：1，搅拌速度为600-1000rpm，搅拌时间在30min以上。
本发明采用聚己内酯与改性淀粉作为膜的主体，加入增塑剂和聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯，可有效提高淀粉与聚己内酯的相容性，克服聚己内酯熔点低的缺点。润滑剂的添加，提高了薄膜的开口性和表面光洁度，填充剂则可以适当提高薄膜强度和开口性能。本发明制得的薄膜可完全生物降解，且具有良好的力学性能、耐水性和透光性，具有广泛的用途。
具体实施方式
实施例1：称取100份氧化淀粉、60份分子量为80000的聚己内酯、30份聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯、10份滑石粉、20份甘油、5份硬脂酸钙加入高速混料机中，高速搅拌，搅拌速度为800rpm，搅拌时间为1h，吹塑成型，吹膜温度为160℃，吹胀比为4：1。
实施例2：称取100份氧化淀粉、50份聚己内酯、20份聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯、5份碳酸钙、10份甘油、1份硬脂酸钙加入高速混料机中，高速搅拌，搅拌速度为600rpm，搅拌时间在30min，吹塑成型，吹膜温度为150℃，吹胀比为3：1。
实施例3：称取100份氧化淀粉、70份聚己内酯、40份聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯、15份硫酸钡、25份甘油、6份硬脂酸钙加入高速混料机中，高速搅拌，搅拌速度为1000rpm，搅拌时间在2h，吹塑成型，吹膜温度为178℃，吹胀比为5：1。
实施例4：称取100份羟丙基淀粉、60份聚己内酯、25份聚丁二酸-己二酸- 丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯、12份硫酸钡、25份山梨醇、4份芥酸酰胺加入高速混料机中，高速搅拌，搅拌速度为800rpm，搅拌时间在2h，吹塑成型，吹膜温度为160℃，吹胀比为4：1。

Claims (8)

  1. 一种聚己内酯改性淀粉基生物降解树脂材料，由以下重量份的原料制备而成：
    Figure PCTCN2020108634-appb-100001
  2. 根据权利要求1所述的聚己内酯改性淀粉基生物降解树脂材料，其特征在于：所述改性淀粉为氧化淀粉或者羟丙基淀粉中的一种或混合物。
  3. 根据权利要求2所述的聚己内酯改性淀粉基生物降解树脂材料，其特征在于：所述填充剂为滑石粉、碳酸钙或硫酸钡。
  4. 根据权利要求3所述的聚己内酯改性淀粉基生物降解树脂材料，其特征在于：所述增塑剂为甘油或山梨醇。
  5. 根据权利要求4所述的聚己内酯改性淀粉基生物降解树脂材料，其特征在于：所述润滑剂为硬脂酸钙或者芥酸酰胺。
  6. 根据权利要求5所述的聚己内酯改性淀粉基生物降解树脂材料，其特征在于：
  7. 权利要求1-6中任一项所述的聚己内酯改性淀粉基生物降解树脂材料的制备方法，其特征在于：将改性淀粉、聚己内酯、聚丁二酸-己二酸-丁二醇共聚酯接枝甲基丙烯酸缩水甘油酯、填充剂、增塑剂和润滑剂加入高速混料机中，高速搅拌后，吹塑成型。
  8. 根据权利要求5所述的聚己内酯改性淀粉基生物降解树脂材料的制备方法，其特征在于：吹膜温度为150-178℃，吹胀比为3-5：1，搅拌速度为600-1000rpm，搅拌时间在30min以上。
PCT/CN2020/108634 2020-08-12 2020-08-12 聚己内酯改性淀粉基生物降解树脂材料及其制备方法 WO2022032518A1 (zh)

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CN117327388A (zh) * 2023-09-25 2024-01-02 上海宝柏新材料股份有限公司 一种淀粉改性可降解塑料及其制备方法
CN117327388B (zh) * 2023-09-25 2024-05-10 上海宝柏新材料股份有限公司 一种淀粉改性可降解塑料及其制备方法

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