WO2022252266A1 - Composite toughened and high-temperature-resistant polylactic acid modified material and preparation method therefor - Google Patents

Composite toughened and high-temperature-resistant polylactic acid modified material and preparation method therefor Download PDF

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WO2022252266A1
WO2022252266A1 PCT/CN2021/099077 CN2021099077W WO2022252266A1 WO 2022252266 A1 WO2022252266 A1 WO 2022252266A1 CN 2021099077 W CN2021099077 W CN 2021099077W WO 2022252266 A1 WO2022252266 A1 WO 2022252266A1
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polylactic acid
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mass
modified material
acid modified
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贾帅
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贾帅
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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
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

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  • the invention belongs to the technical field of biodegradable materials, and in particular relates to a compound toughened high temperature resistant polylactic acid modified material and a preparation method thereof.
  • Polylactic acid is polymerized from lactic acid, the product of microbial fermentation. It is a biodegradable aliphatic polyester polymer with low toxicity, low irritation and good biocompatibility. It can generate carbon dioxide and water, and the products can be recycled by nature. It is considered to be a promising biodegradable material, and it has been widely used in the fields of medicine, industry and agriculture, and life, and it has been increasingly researched by people. interest and attention.
  • polylactic acid also has disadvantages such as low melt strength, slow crystallization rate, low service temperature and heat distortion temperature, which hinder its application.
  • PLA is very brittle, and its low elongation at break and impact strength limit its applicable fields.
  • the performance advantages of many existing compounds can be combined, the components and composition of the blend can be changed to adjust its properties, and the properties of the copolymer can be modified compared to chemical copolymerization.
  • the reaction mechanism of the mixture is more clear, and it is convenient to modify its composition ratio to optimize the material performance.
  • biodegradable polymers are used for the toughening of PLA due to their biocompatibility, rapid and complete biodegradability, and high toughness (such as polybutylene succinate PBS, whose mechanical properties Excellent, with good biodegradability and processability, blending with PLA can improve the mechanical properties of the material while ensuring biodegradability); low cost of inorganic fillers, excellent mechanical properties, high thermal stability and workability Processability and other advantages can significantly improve the performance of the product under the condition of low production cost (for example, after adding white talc, the toughness of the product has been significantly improved).
  • the Chinese patent invention discloses a notification number: CN 103540111 B named "a high-strength, high-temperature-resistant fully degradable polylactic acid sheet and its manufacturing method".
  • the disclosed technical solution is: polylactic acid 50%- 78%; 10%-30% of toughening components; 10%-30% of inorganic fillers: 1%-3% of other additives; the polylactic acid is composed of L-polylactic acid with a weight average molecular weight of 100,000 to 200,000.
  • Its manufacturing methods include:
  • blended masterbatch Mechanically mix polylactic acid and toughening components according to the ratio, spray coupling agent, add inorganic fillers and other additives and mix again, so that plastic particles can be coated Layer inorganic filler, and then use the extruder to prepare the blended masterbatch, set the temperature of the extruder to 160°C-200°C, the speed of the feed screw to be 15-25rpm, the speed of the main screw to be 140-160rpm, and the cutting length to be 2 -4mm;
  • Composite material sheet preparation The prepared composite material blending masterbatch is prepared into a sheet through an extruder with a die mouth as a tablet, and the temperature of the extruder is set at 160°C-200°C, and the screw speed is 60rpm-100rpm .
  • the invention "a high-strength, high-temperature-resistant fully degradable polylactic acid sheet” has the following advantages:
  • the tensile strength of the polylactic acid sheet is greatly enhanced, which reaches above 80MPa, and the highest can reach 115MPa;
  • the Chinese patent invention discloses a notification number: CN 106084697 B named "a polylactic acid composite material with both heat resistance and mechanical properties".
  • the polylactic acid composite material is characterized in that, comprises polylactic acid, polybutylene succinate, filler and compatibilizer; Described filler is the mixture of one or both in talcum powder, calcium carbonate;
  • the compatibilizer is a mixture of polyvinyl acetate and polyvinyl acetate-ethylene copolymer, and the mixing ratio of polyvinyl acetate and polyvinyl acetate-ethylene copolymer is 1:1 to 2:1:
  • the parts by weight of each component are: 50-70 parts of polylactic acid, 20-50 parts of polybutylene succinate, 1-15 parts of compatibilizer, and 1-15 parts of filler.
  • Its preparation method mainly comprises the following steps:
  • step 2 After the resin extruded in step 2 is water-cooled, pelletized and dried, it is hot-pressed in a flat vulcanizer.
  • the hot-pressing temperature is 160-200°C
  • the pressure is 10-30MPa
  • the time is 5- 15 minutes, and then cold press at room temperature for 10 to 20 minutes.
  • the process flow is simple, the polylactic acid is modified by blending the heat-resistant biodegradable polybutylene succinate, and the composite use of inorganic fillers and compatibilizers, Achieve the improvement of heat resistance and tensile properties of biodegradable materials, especially the use of polyvinyl acetate and polyvinyl acetate-ethylene copolymer additives as compatibilizers for such materials, which effectively enhances the final prepared polylactic acid composite
  • the toughness of the material makes the polylactic acid composite material have more excellent thermal stability and mechanical properties, making it widely used in a wide range of fields, cost-effective: and large-scale production can be achieved with a small amount of conventional polymer processing equipment.
  • the Chinese patent invention discloses a kind of announcement number: CN 110804287 A named "a heat-resistant modified polylactic acid composite material", and its disclosed technical solution is: a heat-resistant modified polylactic acid composite material, its characteristic In, including the following raw material components: polylactic acid, polybutylene succinate, polybutylene adipate/terephthalate, erucamide, acetyl tributyl citrate, glycidyl methacrylate Graft ethyl methacrylate copolymer, antioxidant 10760, talcum powder; the mass fraction of the raw materials is as follows: polylactic acid: 45-60%, polybutylene succinate: 25-40%, poly Adipic acid/butylene terephthalate: 1020%, erucamide: 0.1-0.5%, acetyl tributyl citrate: 0.1-0.5%, glycidyl methacrylate grafted ethyl methacrylate Copolymer: 0.1w%, antioxidant 10760:
  • the invention has the beneficial effect: by introducing a fully biodegradable polybutylene succinate component with excellent temperature resistance, and adopting polybutylene adipate/terephthalate Toughening treatment and the use of ultra-fine talc powder to promote the crystallization behavior of the composite system are three ways to improve the heat resistance of the polylactic acid composite material, so as to adapt to the application of the polylactic acid composite material in the field of disposable products.
  • the straw extruded from the composite material can be used in the processing and preparation of hot drink packaging, expanding the application of fully biodegradable composite materials in the field of disposable products.
  • the Vicat softening temperature can only reach a maximum of 110°C, which cannot meet the heat resistance performance requirements in specific application scenarios; although the elongation at break in the above technical solutions can reach a maximum of 90%, But correspondingly, the modulus of elasticity of the modified material decreases.
  • the above modified materials have high production cost, low degree of degradation, small elastic modulus, low tensile strength, and cannot guarantee the comprehensive performance of the modified materials, making it difficult to promote and apply them on a large scale.
  • the object of the present invention is to provide a composite toughened high temperature resistant polylactic acid modified material and a preparation method thereof in order to overcome the shortcomings and deficiencies of the prior art.
  • the first aspect of the present invention is to provide a composite toughened high temperature resistant polylactic acid modified material
  • the technical solution is to include the following components in parts by mass: 30-60 parts by mass of polylactic acid, 20-50 parts by mass of butylene succinate, 5-12 parts by mass of inorganic filler, 0.5-1.2 parts by mass of chain extender, 1-10 parts by mass of plasticizer, 0.5-10 parts by mass of toughening agent, compatible 0.2 to 0.6 parts by mass of the agent, and 0.1 to 0.6 parts by mass of the temperature resistant agent.
  • the inorganic filler is one or more combinations of glass fiber, kaolin, calcium carbonate, calcium sulfate, talcum powder, mica, silicon dioxide, and carbon black.
  • the chain extender includes a mixture of one or more of peroxide compounds, isocyanate compounds, multifunctional epoxy compounds, and phosphate ester compounds.
  • the plasticizer includes butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate One or a mixture of esters and dimethyl phthalate.
  • the toughening agent includes styrene-butadiene thermoplastic elastomer, methyl methacrylate-butadiene-styrene terpolymer, ethylene-vinyl acetate copolymer, polybutadiene rubber one or a mixture of several.
  • the compatibilizer includes one or more of cyclic anhydride type, carboxylic acid type, epoxy type, oxazoline type, imide type, low molecular type, and isocyanate type.
  • the temperature resistant agent is one or more of polyethylene wax, erucamide and oleamide.
  • the second aspect of the present invention is to provide a method for preparing the composite toughened high temperature resistant polylactic acid modified material as described, comprising the following steps:
  • step S2 After uniformly mixing the formula weighed in step S1 according to the order of polylactic acid, polybutylene succinate, chain extender and compatibilizer, 1. Add the toughening agents in sequence and mix them evenly, and leave them in a closed place;
  • step S3 Add the mixed materials in step S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm;
  • step S4 drying the pellets obtained in step S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours;
  • step S5 Injecting the pellets obtained in step S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
  • the high-toughness and high-temperature-resistant polylactic acid-based composite material provided by the invention still maintains the degradable characteristics of polylactic acid, and the preparation method is simple and feasible, and the performance of polylactic acid can be changed by changing the content of toughening agent and the degree of crosslinking. For specific performance parameters, see the experimental data of the examples for details.
  • Figure 1 modified polylactic acid tensile strength diagram
  • Figure 6 Modified polylactic acid micro card softening point diagram
  • Fig. 7 modified polylactic acid infrared spectrogram
  • PLA PLA, PBS, chain extender, TBC, erucamide, white talc, toughener.
  • test sample obtained in S5 is subjected to a mechanical property test and a temperature resistance test.
  • the prepared modified material was named A1
  • the prepared modified material is named A2
  • the prepared modified material is named A4
  • the elastic modulus of the composite material tends to weaken, and when the loading of the toughening agent is 5%, the elastic modulus of A5 decreases by about 1000 MPa compared with A0, which shows that the toughening agent has an important effect on the material.
  • the elastic modulus has a more obvious weakening effect. Tougheners have less obvious effects on impact strength and tensile strength. See Figure 1, Figure 2, Figure 3, Figure 4, and Figure 5.
  • Figure 7 is the infrared spectra of A1, A2, and A3.
  • the CH stretching vibration peak on the saturated carbon at 2920cm -1 in the main chain of the PLA and PBS blend system and the CH stretching vibration peak at 1714cm -1
  • Figure 7 is the first cooling DSC curve
  • Figure 8 is the second heating DSC curve.
  • adding a nucleating agent can significantly increase the crystal nucleus density of PLA modified molecular fragments, rapidly increase the crystallization rate of PLA molecular chains, and increase the crystallinity, while the crystallinity and The heat resistance of the material is closely related. The higher the crystallinity, the higher the heat resistance, which greatly improves the heat resistance of PLA modified molecules.
  • thermogravimetric curve is shown in Figure 10.
  • Table 2 analyzes the temperature of the material at 5% weight loss (T 5% ) , at 10% weight loss (T 10% ) and at 50% weight loss (T 50% ).
  • T 5% weight loss
  • T 10% weight loss
  • T 50% 50% weight loss
  • Three processes of material mass loss can be observed in the thermogravimetric curve: the water loss of the modified polylactic acid, that is, A1 and A5, is basically the same, that is, the thermal decomposition curves basically overlap.
  • the modified PLA is relatively stable until 340 °C.
  • inorganic fillers significantly changed the morphology of pure PLA (Fig. A5), which significantly improved the tensile and impact properties of PLA, depending on the content of inorganic fillers (Fig. A0–A5). Morphological transitions due to increasing inorganic filler content were observed in binary blends. A0-a shows a typical “sea islands/water droplet in matrix” morphology, and A5-b shows a continuous morphology with a net-like texture. This structural change enhances the mechanical properties. It can be expected that with the increase of filler, the impact strength and hardness of the composite material will also increase, and the elongation at break of the composite material will be significantly improved. Through the electron microscopy analysis of the tensile and impact fracture sections , identifying the underlying toughening mechanism.

Abstract

A composite toughened and high-temperature-resistant polylactic acid modified material and a preparation method therefor. The polylactic acid modified material is prepared from the following raw materials in parts by mass: 30-60 parts of polylactic acid, 20-50 parts of polybutylene succinate, 5-12 parts of inorganic filler, 0.5-1.2 parts of chain extender, 1-10 parts of plasticizer, 0.5-10 parts of toughening agent, 0.2-0.6 parts of compatiblizing agent, and 0.1-0.6 parts of temperature-resistant agent. The composite toughened and high-temperature-resistant polylactic acid modified material still keeps the degradable characteristic of the polylactic acid; and the preparation method is simple and easy to implement, and can change the performance of the polylactic acid by changing the content of the toughening agent and the degree of crosslinking.

Description

一种复合增韧耐高温聚乳酸改性材料及其制备方法A composite toughened high temperature resistant polylactic acid modified material and its preparation method 技术领域technical field
本发明属于生物降解材料技术领域，具体涉及一种复合增韧耐高温聚乳酸改性材料及其制备方法。The invention belongs to the technical field of biodegradable materials, and in particular relates to a compound toughened high temperature resistant polylactic acid modified material and a preparation method thereof.
背景技术Background technique
聚乳酸(PLA)是以微生物发酵的产物乳酸为单体聚合而成的，一种毒性小、刺激性低、生物相容性好的生物可降解的脂肪族聚酯高分子聚合物，降解后可生成二氧化碳和水，产物可被自然界循环利用，被认为是一种具有发展前景的生物可降解材料，并且由于能够广泛的应用于医学领域、工农业领域以及生活领域，而日渐受到人们的研究兴趣和关注。Polylactic acid (PLA) is polymerized from lactic acid, the product of microbial fermentation. It is a biodegradable aliphatic polyester polymer with low toxicity, low irritation and good biocompatibility. It can generate carbon dioxide and water, and the products can be recycled by nature. It is considered to be a promising biodegradable material, and it has been widely used in the fields of medicine, industry and agriculture, and life, and it has been increasingly researched by people. interest and attention.
但聚乳酸也具有低熔体强度、慢的结晶速率、较低的使用温度和热变形温度等缺点，这些妨碍了其应用。另外，PLA很脆，它较低的断裂伸长率和冲击强度，使得其可应用的领域受到了很大的限制。However, polylactic acid also has disadvantages such as low melt strength, slow crystallization rate, low service temperature and heat distortion temperature, which hinder its application. In addition, PLA is very brittle, and its low elongation at break and impact strength limit its applicable fields.
通过聚合物、无机物等的共混，可以组合众多现有化合物的性能优势，改变共混物的组分和组成来调节其性质，且相比于化学共聚来改性共聚物的性能，共混的反应机理更明确，方便修改其组成比例以优化材料性能。其中，可生物降解的聚合物由于其生物相容性、快速而完全的生物降解性以及高韧性等优点而被用于PLA的增韧(例如聚丁二酸丁二醇酯PBS，其力学性能优异,具有良好的生物可降解性和可加工性,与PLA共混在提高材料力学性能的同时又能保证生物降解性)；无机填料的低成本、优异的机械性能、高的热稳定性和可加工性等优点，能在低生产成本的情况下显著提升产品的性能(如加入白滑石后，产品的韧性得到了明显的提升)。Through the blending of polymers, inorganic substances, etc., the performance advantages of many existing compounds can be combined, the components and composition of the blend can be changed to adjust its properties, and the properties of the copolymer can be modified compared to chemical copolymerization. The reaction mechanism of the mixture is more clear, and it is convenient to modify its composition ratio to optimize the material performance. Among them, biodegradable polymers are used for the toughening of PLA due to their biocompatibility, rapid and complete biodegradability, and high toughness (such as polybutylene succinate PBS, whose mechanical properties Excellent, with good biodegradability and processability, blending with PLA can improve the mechanical properties of the material while ensuring biodegradability); low cost of inorganic fillers, excellent mechanical properties, high thermal stability and workability Processability and other advantages can significantly improve the performance of the product under the condition of low production cost (for example, after adding white talc, the toughness of the product has been significantly improved).
但是，现有技术，还没有针对聚乳酸进行具有较好效果的增韧和耐高温性的技术方案，因此有必要对此进行改进。However, in the prior art, there is no technical solution for polylactic acid with better toughening and high temperature resistance, so it is necessary to improve this.
中国专利发明公开了一种公告号为：CN 103540111 B的名为“一种高强度、耐高温的全降解聚乳酸片材及其制造方法”，其公开的技术方案是：聚乳酸50％-78％；增韧组分10％-30％；无机填料10％-30％：其他助剂1％-3％；所述聚乳酸由重均分子量为10万至20万的左旋聚乳酸组成。其制造方法包括：The Chinese patent invention discloses a notification number: CN 103540111 B named "a high-strength, high-temperature-resistant fully degradable polylactic acid sheet and its manufacturing method". The disclosed technical solution is: polylactic acid 50%- 78%; 10%-30% of toughening components; 10%-30% of inorganic fillers: 1%-3% of other additives; the polylactic acid is composed of L-polylactic acid with a weight average molecular weight of 100,000 to 200,000. Its manufacturing methods include:
A、共混母粒的制备：将聚乳酸、增韧组分按配比先进行机械混合，喷上偶联剂后将无机填料和其他助剂加入后再次混合，使得塑料粒子都能包覆一层无机填料，然后使用挤出机制备共混母粒，设定挤出机温度为160℃-200℃，进料螺杆转速为15-25rpm，主螺杆转速为140-160rpm，切粒长度为2-4mm；A. Preparation of blended masterbatch: Mechanically mix polylactic acid and toughening components according to the ratio, spray coupling agent, add inorganic fillers and other additives and mix again, so that plastic particles can be coated Layer inorganic filler, and then use the extruder to prepare the blended masterbatch, set the temperature of the extruder to 160°C-200°C, the speed of the feed screw to be 15-25rpm, the speed of the main screw to be 140-160rpm, and the cutting length to be 2 -4mm;
B、复合材料片材制备：将制备的复合材料共混母粒通过模口为压片的挤出机制备片材，设定挤出机温度为160℃-200℃，螺杆转速为60rpm-100rpm。B. Composite material sheet preparation: The prepared composite material blending masterbatch is prepared into a sheet through an extruder with a die mouth as a tablet, and the temperature of the extruder is set at 160°C-200°C, and the screw speed is 60rpm-100rpm .
该发明“一种高强度、耐高温的全降解聚乳酸片材”具有以下优点：The invention "a high-strength, high-temperature-resistant fully degradable polylactic acid sheet" has the following advantages:
1、极大地增强了聚乳酸片材的拉伸强度，其达到了80MPa以上，最高可达到115MPa；1. The tensile strength of the polylactic acid sheet is greatly enhanced, which reaches above 80MPa, and the highest can reach 115MPa;
2、极大提高了其延伸率，其最高的延伸率达到90％；2. It greatly improves its elongation rate, and its highest elongation rate reaches 90%;
3、提高耐高温性能，其维卡软化温度可以达到110℃。3. Improve high temperature resistance, its Vicat softening temperature can reach 110°C.
中国专利发明公开了一种公告号为：CN 106084697 B的名为“一种兼具耐热和力学性能的聚乳酸复合材料”，其公开的技术方案是：一种兼具耐热和力学性能的聚乳酸复合材料，其特征在于，包括聚乳酸、聚丁二酸丁二醇酯、填充剂和增容剂；所述填充剂为滑石粉、碳酸钙中的一种或二者的混合物；所述增容剂为聚乙酸乙烯酯、聚乙酸乙烯酯-乙烯共聚物二者的混合物，聚乙酸乙烯酯与聚乙酸乙烯酯-乙烯共聚物的混合比例为1：1～2：1：以重量份数计，各组分的重量份数为：聚乳酸50～70份，聚丁二酸丁二醇酯20～50份，增容剂1～15份，填充剂1～15份。其制备方法主要包括以下步骤：The Chinese patent invention discloses a notification number: CN 106084697 B named "a polylactic acid composite material with both heat resistance and mechanical properties". The polylactic acid composite material is characterized in that, comprises polylactic acid, polybutylene succinate, filler and compatibilizer; Described filler is the mixture of one or both in talcum powder, calcium carbonate; The compatibilizer is a mixture of polyvinyl acetate and polyvinyl acetate-ethylene copolymer, and the mixing ratio of polyvinyl acetate and polyvinyl acetate-ethylene copolymer is 1:1 to 2:1: In terms of parts by weight, the parts by weight of each component are: 50-70 parts of polylactic acid, 20-50 parts of polybutylene succinate, 1-15 parts of compatibilizer, and 1-15 parts of filler. Its preparation method mainly comprises the following steps:
A、干燥预混过程：将聚乳酸、聚丁二酸丁二醇酯和填充剂干燥后混合均匀；A. Drying and premixing process: dry polylactic acid, polybutylene succinate and filler and mix them evenly;
B、熔融共混过程：将一定比例的增容剂和步骤1中的混合物通过双螺杆挤出机熔融共混挤出，混合挤出温度在140-200℃，螺杆转速为10-60rpm；B. Melt blending process: a certain proportion of the compatibilizer and the mixture in step 1 are melt blended and extruded through a twin-screw extruder, the mixed extrusion temperature is 140-200 ° C, and the screw speed is 10-60 rpm;
C、成型过程：步骤2中挤出后的树脂通过水冷、切粒和干燥后，在平板硫 化机中热压成型，热压温度在160～200℃，压力为10～30MPa，时间为5～15分钟，再常温冷压定型10～20分钟。C. Molding process: After the resin extruded in step 2 is water-cooled, pelletized and dried, it is hot-pressed in a flat vulcanizer. The hot-pressing temperature is 160-200°C, the pressure is 10-30MPa, and the time is 5- 15 minutes, and then cold press at room temperature for 10 to 20 minutes.
该发明的积极效果表现在：工艺流程简单，对聚乳酸的改性通过共混耐热性的生物降解材料聚丁二酸丁二醇酯，并采用无机填料和增容剂的复配使用，达到生物降解材料耐热和拉伸性能的提升，特别是采用聚乙酸乙烯酯、聚乙酸乙烯酯-乙烯共聚物类助剂作为此类材料的增容剂，有效增强了最终制备的聚乳酸复合材料的韧性，使聚乳酸复合材料具有更优异的热稳定性和力学性能，使其应用领域广泛，经济高效：且利用少量常规高分子加工设备即可实现规模化生产。The positive effects of the invention are as follows: the process flow is simple, the polylactic acid is modified by blending the heat-resistant biodegradable polybutylene succinate, and the composite use of inorganic fillers and compatibilizers, Achieve the improvement of heat resistance and tensile properties of biodegradable materials, especially the use of polyvinyl acetate and polyvinyl acetate-ethylene copolymer additives as compatibilizers for such materials, which effectively enhances the final prepared polylactic acid composite The toughness of the material makes the polylactic acid composite material have more excellent thermal stability and mechanical properties, making it widely used in a wide range of fields, cost-effective: and large-scale production can be achieved with a small amount of conventional polymer processing equipment.
中国专利发明公开了一种公告号为：CN 110804287 A的名为“一种耐热改性聚乳酸复合材料”，其公开的技术方案是：一种耐热改性聚乳酸复合材料，其特征在于，包括以下原材料组分：聚乳酸、聚丁二酸丁二醇酯、聚已二酸/对苯二甲酸丁二酯、芥酸酰胺、乙酰柠檬酸三丁酯、甲基丙烯酸缩水甘油酯接枝乙基甲基丙烯酸酯共聚物、抗氧剂10760、滑石粉；所述原材料的质量分数如下：聚乳酸：45-60％、聚丁二酸丁二醇酯：25-40％、聚已二酸/对苯二甲酸丁二酯：1020％、芥酸酰胺：0.1-0.5％、乙酰柠檬酸三丁酯：0.1-0.5％、甲基丙烯酸缩水甘油酯接枝乙基甲基丙烯酸酯共聚物：0.1w％、抗氧剂10760：1-0.5％、滑石粉：1-4％。The Chinese patent invention discloses a kind of announcement number: CN 110804287 A named "a heat-resistant modified polylactic acid composite material", and its disclosed technical solution is: a heat-resistant modified polylactic acid composite material, its characteristic In, including the following raw material components: polylactic acid, polybutylene succinate, polybutylene adipate/terephthalate, erucamide, acetyl tributyl citrate, glycidyl methacrylate Graft ethyl methacrylate copolymer, antioxidant 10760, talcum powder; the mass fraction of the raw materials is as follows: polylactic acid: 45-60%, polybutylene succinate: 25-40%, poly Adipic acid/butylene terephthalate: 1020%, erucamide: 0.1-0.5%, acetyl tributyl citrate: 0.1-0.5%, glycidyl methacrylate grafted ethyl methacrylate Copolymer: 0.1w%, antioxidant 10760: 1-0.5%, talcum powder: 1-4%.
与现有技术相比，该发明的有益效果：通过引入耐温性能优异的可全生物降解的聚丁二酸丁二醇酯组分、采用聚已二酸/对苯二甲酸丁二酯进行增韧处理、采用超细滑石粉促进复合体系的结晶行为三种方式来提升聚乳酸复合材料的耐热性能，以适应聚乳酸复合材料在一次用用品领域的应用。来用该复合材料挤出成型的吸管可以用于热饮包装的加工制备，拓展了可全生物质降解复合材料在一次性用品领域的应用。Compared with the prior art, the invention has the beneficial effect: by introducing a fully biodegradable polybutylene succinate component with excellent temperature resistance, and adopting polybutylene adipate/terephthalate Toughening treatment and the use of ultra-fine talc powder to promote the crystallization behavior of the composite system are three ways to improve the heat resistance of the polylactic acid composite material, so as to adapt to the application of the polylactic acid composite material in the field of disposable products. The straw extruded from the composite material can be used in the processing and preparation of hot drink packaging, expanding the application of fully biodegradable composite materials in the field of disposable products.
根据上述公开的三大技术方案，其维卡软化温度最高只能达到110℃，在特定应用场景下，达不到耐热性能要求；虽然以上技术方案中断裂伸长率最高可达到90％，但是相应的，其改性材料的弹性模量降低。以上的改性材料在实际 应用中，生产成本高，降解度小，弹性模量小，抗拉强度低下，且不能保证改性材料的综合性能的表现，难以规模化推广应用。According to the three major technical solutions disclosed above, the Vicat softening temperature can only reach a maximum of 110°C, which cannot meet the heat resistance performance requirements in specific application scenarios; although the elongation at break in the above technical solutions can reach a maximum of 90%, But correspondingly, the modulus of elasticity of the modified material decreases. In practical application, the above modified materials have high production cost, low degree of degradation, small elastic modulus, low tensile strength, and cannot guarantee the comprehensive performance of the modified materials, making it difficult to promote and apply them on a large scale.
发明内容Contents of the invention
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种复合增韧耐高温聚乳酸改性材料及其制备方法。The object of the present invention is to provide a composite toughened high temperature resistant polylactic acid modified material and a preparation method thereof in order to overcome the shortcomings and deficiencies of the prior art.
为实现上述目的，本发明的第一个方面是提供一种复合增韧耐高温聚乳酸改性材料，其技术方案是包括以下组分以质量份数计：聚乳酸30～60质量份、聚丁二酸丁二醇酯20～50质量份、无机填料5～12质量份、扩链剂0.5～1.2质量份、增塑剂1～10质量份、增韧剂0.5～10质量份、相容剂0.2～0.6质量份、耐温剂0.1～0.6质量份。In order to achieve the above object, the first aspect of the present invention is to provide a composite toughened high temperature resistant polylactic acid modified material, the technical solution is to include the following components in parts by mass: 30-60 parts by mass of polylactic acid, 20-50 parts by mass of butylene succinate, 5-12 parts by mass of inorganic filler, 0.5-1.2 parts by mass of chain extender, 1-10 parts by mass of plasticizer, 0.5-10 parts by mass of toughening agent, compatible 0.2 to 0.6 parts by mass of the agent, and 0.1 to 0.6 parts by mass of the temperature resistant agent.
进一步设置是所述无机填料为玻璃纤维、高岭土、碳酸钙、硫酸钙、滑石粉、云母、二氧化硅、炭黑中的一种或几种组合。It is further provided that the inorganic filler is one or more combinations of glass fiber, kaolin, calcium carbonate, calcium sulfate, talcum powder, mica, silicon dioxide, and carbon black.
进一步设置是所述扩链剂包括过氧化物类化合物、异氰酸酯类化合物、多官能团环氧化合物、磷酸酯类化合物中的一种或多种的混合物。It is further provided that the chain extender includes a mixture of one or more of peroxide compounds, isocyanate compounds, multifunctional epoxy compounds, and phosphate ester compounds.
进一步设置是所述增塑剂包括邻苯二甲酸丁苄酯、邻苯二甲酸二仲辛酯、邻苯二甲酸二环己酯、邻苯二甲酸二丁酯、邻苯二甲酸二异丁酯、邻苯二甲酸二甲酯中的一种或几种的混合物。It is further set that the plasticizer includes butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate One or a mixture of esters and dimethyl phthalate.
进一步设置是所述的增韧剂包括苯乙烯-丁二烯热塑性弹性体、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物、乙烯-醋酸乙烯酯共聚物、聚丁二烯橡胶中的一种或几种的混合物。It is further provided that the toughening agent includes styrene-butadiene thermoplastic elastomer, methyl methacrylate-butadiene-styrene terpolymer, ethylene-vinyl acetate copolymer, polybutadiene rubber one or a mixture of several.
进一步设置是所述的相容剂包括环状酸酐型、羧酸型、环氧型、恶唑啉型、酰亚胺型、低分子型、异氰酸酯型中的一种或多种的混合物。It is further provided that the compatibilizer includes one or more of cyclic anhydride type, carboxylic acid type, epoxy type, oxazoline type, imide type, low molecular type, and isocyanate type.
进一步设置是所述的耐温剂为聚乙烯蜡、芥酸酰胺和油酸酰胺中的一种或多种。It is further provided that the temperature resistant agent is one or more of polyethylene wax, erucamide and oleamide.
本发明的第二个方面是提供一种如所述的复合增韧耐高温聚乳酸改性材料的制备方法，包括以下步骤：The second aspect of the present invention is to provide a method for preparing the composite toughened high temperature resistant polylactic acid modified material as described, comprising the following steps:
S1、按照所述组分用量称取聚乳酸、聚丁二酸丁二醇酯、无机填料、扩链 剂、增塑剂、增韧剂、相容剂和耐温剂；S1. Weigh polylactic acid, polybutylene succinate, inorganic filler, chain extender, plasticizer, toughening agent, compatibilizer and temperature-resistant agent according to the amount of the components;
S2、将步骤S1所称取的配方按聚乳酸、聚丁二酸丁二醇酯、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐温剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置；S2. After uniformly mixing the formula weighed in step S1 according to the order of polylactic acid, polybutylene succinate, chain extender and compatibilizer, 1. Add the toughening agents in sequence and mix them evenly, and leave them in a closed place;
S3、将步骤S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分；S3. Add the mixed materials in step S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm;
S4、将步骤S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h；S4, drying the pellets obtained in step S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours;
S5、将步骤S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in step S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
本发明提供的高韧性耐高温聚乳酸基复合材料仍然保持聚乳酸可降解的特性，且制备方法简单易行，并可通过改变增韧剂含量以及交联度实现对聚乳酸性能的改变。具体性能参数，详细见实施例实验数据。The high-toughness and high-temperature-resistant polylactic acid-based composite material provided by the invention still maintains the degradable characteristics of polylactic acid, and the preparation method is simple and feasible, and the performance of polylactic acid can be changed by changing the content of toughening agent and the degree of crosslinking. For specific performance parameters, see the experimental data of the examples for details.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，根据这些附图获得其他的附图仍属于本发明的范畴。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, obtaining other drawings based on these drawings still belongs to the scope of the present invention without any creative effort.
图1改性聚乳酸抗拉强度关系图；Figure 1 modified polylactic acid tensile strength diagram;
图2改性聚乳酸弹性模量关系图；Figure 2 Modified polylactic acid modulus of elasticity diagram;
图3改性聚乳酸断裂延伸率关系图；Figure 3 Modified polylactic acid elongation at break diagram;
图4改性聚乳酸冲击强度关系图；Figure 4 Modified polylactic acid impact strength relationship diagram;
图5改性聚乳酸硬度关系图；Fig. 5 Modified polylactic acid hardness relationship diagram;
图6改性聚乳酸微卡软化点关系图；Figure 6 Modified polylactic acid micro card softening point diagram;
图7改性聚乳酸红外光谱图；Fig. 7 modified polylactic acid infrared spectrogram;
图8 DSC降温曲线图；Figure 8 DSC cooling curve;
图9 DSC升温曲线图；Figure 9 DSC heating curve;
图10热重曲线图；Figure 10 thermogravimetric curve;
图11热分解图；Figure 11 thermal decomposition diagram;
图12扫描电镜图。Figure 12 SEM image.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明作进一步地详细描述。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings.
下述具体实施例所述物料仅用于本发明的解释，但本发明所请求保护的物料并不受限于下述物料的型号。The materials described in the following specific examples are only used for explaining the present invention, but the materials claimed in the present invention are not limited to the models of the following materials.
所用物料：PLA、PBS、扩链剂、TBC、芥酸酰胺、白滑石、增韧剂。Materials used: PLA, PBS, chain extender, TBC, erucamide, white talc, toughener.
下面按照本申请所请求的保护方法进行高耐热性、高硬度的生物可降解PLA和PBS复合改性材料的制备，其步骤为：Carry out the preparation of high heat resistance, high hardness biodegradable PLA and PBS composite modified material according to the protection method requested by this application below, its steps are:
S1、按照配方用量称取PLA、PBS、无机填料、扩链剂、增塑剂、增韧剂、相容剂、耐温剂。S1. Weigh PLA, PBS, inorganic fillers, chain extenders, plasticizers, tougheners, compatibilizers, and temperature-resistant agents according to the dosage of the formula.
S2、将S1所称取的配方按PLA、PBS、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐温剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置一段时间。S2. After uniformly mixing the formula weighed in S1 in the order of PLA, PBS, chain extender, and compatibilizer, then add it in the order of temperature-resistant agent, inorganic filler, plasticizer, and toughening agent And mix evenly, airtight and stand for a period of time.
S3、将S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分。S3. Put the mixed materials in S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm.
S4、将S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h。S4. Dry the granules obtained in S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours.
S5、将S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
S6、将S5所得的测试样品进行力学性能测试和耐温性能测试。S6. The test sample obtained in S5 is subjected to a mechanical property test and a temperature resistance test.
实施例1(A1)Example 1 (A1)
S1、按照配方用量称取PLA 32质量份、PBS 54质量份、白滑石12质量份、扩链剂0.9质量份、增塑剂1质量份、相容剂0.3质量份、耐热剂0.1质量份。S1. Weigh 32 parts by mass of PLA, 54 parts by mass of PBS, 12 parts by mass of white talc, 0.9 parts by mass of chain extender, 1 part by mass of plasticizer, 0.3 parts by mass of compatibilizer, and 0.1 part by mass of heat-resistant agent according to the dosage of the formula .
S2、将S1所称取的配方按PLA、PBS、扩链剂、增塑剂、相容剂的先后顺序进行均匀混合后，再按无机填料、耐热剂的先后顺序加入其中并进行均匀混合，密闭静置一段时间。S2. After uniformly mixing the formula weighed in S1 according to the order of PLA, PBS, chain extender, plasticizer and compatibilizer, then add inorganic filler and heat resistant agent into it and mix uniformly , sealed for a period of time.
S3、将S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分。S3. Put the mixed materials in S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm.
S4、将S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h。S4. Dry the granules obtained in S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours.
S5、将S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
制得的改性材料命名为A1The prepared modified material was named A1
实施例2(A2)Example 2 (A2)
S1、按照配方用量称取PLA 32质量份、PBS 54质量份、白滑石12质量份、扩链剂0.9质量份、增塑剂1质量份、增韧剂0.5质量份、相容剂0.3质量份、耐热剂0.1质量份。S1. Weigh 32 parts by mass of PLA, 54 parts by mass of PBS, 12 parts by mass of white talc, 0.9 parts by mass of chain extender, 1 part by mass of plasticizer, 0.5 parts by mass of toughening agent, and 0.3 parts by mass of compatibilizer according to the dosage of the formula , 0.1 parts by mass of heat-resistant agent.
S2、将S1所称取的配方按PLA、PBS、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐热剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置一段时间。S2. After uniformly mixing the formula weighed in S1 according to the order of PLA, PBS, chain extender and compatibilizer, then add heat-resistant agent, inorganic filler, plasticizer and toughening agent in the order And mix evenly, airtight and stand for a period of time.
S3、将S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分。S3. Put the mixed materials in S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm.
S4、将S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h。S4. Dry the granules obtained in S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours.
S5、将S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
制得的改性材料命名为A2The prepared modified material is named A2
实施例3(A3)Example 3 (A3)
S1、按照配方用量称取PLA 32质量份、PBS 54质量份、白滑石12质量份、扩链剂0.9质量份、增塑剂1质量份、增韧剂1.5质量份、相容剂0.3质量份、耐热剂0.1质量份。S1. Weigh 32 parts by mass of PLA, 54 parts by mass of PBS, 12 parts by mass of white talc, 0.9 parts by mass of chain extender, 1 part by mass of plasticizer, 1.5 parts by mass of toughening agent, and 0.3 parts by mass of compatibilizer according to the dosage of the formula , 0.1 parts by mass of heat-resistant agent.
S2、将S1所称取的配方按PLA、PBS、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐热剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置一段时间。S2. After uniformly mixing the formula weighed in S1 according to the order of PLA, PBS, chain extender and compatibilizer, then add heat-resistant agent, inorganic filler, plasticizer and toughening agent in the order And mix evenly, airtight and stand for a period of time.
S3、将S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒， 挤出机转速100～500转/分。S3. Put the mixed material in S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the extruder rotates at 100-500 rpm.
S4、将S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h。S4. Dry the granules obtained in S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours.
S5、将S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
制得的改性材料命名为A3The obtained modified material is named A3
实施例4(A4)Example 4 (A4)
S1、按照配方用量称取PLA 32质量份、PBS 54质量份、白滑石12质量份、扩链剂0.9质量份、增塑剂1质量份、增韧剂3质量份、相容剂0.3质量份、耐热剂0.1质量份、玻璃纤。S1. Weigh 32 parts by mass of PLA, 54 parts by mass of PBS, 12 parts by mass of white talc, 0.9 parts by mass of chain extender, 1 part by mass of plasticizer, 3 parts by mass of toughening agent, and 0.3 parts by mass of compatibilizer according to the dosage of the formula , heat resistant agent 0.1 parts by mass, glass fiber.
S2、将S1所称取的配方按PLA、PBS、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐热剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置一段时间。S2. After uniformly mixing the formula weighed in S1 according to the order of PLA, PBS, chain extender and compatibilizer, then add heat-resistant agent, inorganic filler, plasticizer and toughening agent in the order And mix evenly, airtight and stand for a period of time.
S3、将S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分。S3. Put the mixed materials in S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm.
S4、将S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h。S4. Dry the granules obtained in S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours.
S5、将S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
制得的改性材料命名为A4The prepared modified material is named A4
实施例5(A5)Example 5 (A5)
S1、按照配方用量称取PLA 32质量份、PBS 54质量份、白滑石12质量份、扩链剂0.9质量份、增塑剂1质量份、增韧剂5质量份、相容剂0.3质量份、耐热剂0.1质量份。S1. Weigh 32 parts by mass of PLA, 54 parts by mass of PBS, 12 parts by mass of white talc, 0.9 parts by mass of chain extender, 1 part by mass of plasticizer, 5 parts by mass of toughening agent, and 0.3 parts by mass of compatibilizer according to the dosage of the formula , 0.1 parts by mass of heat-resistant agent.
S2、将S1所称取的配方按PLA、PBS、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐热剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置一段时间。S2. After uniformly mixing the formula weighed in S1 according to the order of PLA, PBS, chain extender and compatibilizer, then add heat-resistant agent, inorganic filler, plasticizer and toughening agent in the order And mix evenly, airtight and stand for a period of time.
S3、将S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分。S3. Put the mixed materials in S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm.
S4、将S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h。S4. Dry the granules obtained in S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours.
S5、将S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
制得的改性材料命名为A5The obtained modified material is named A5
在所有制备的改性材料中，经过力学性能测试后，发现随着增韧剂的含量增多，复合材料断裂生长率成增强趋势，且当增韧剂负载量为5％时，A5相比较于A0(纯PLA)拉伸强度提升20％左右，表明增韧剂对于材料的断裂伸长率有显著增强效果。但是随着增韧剂含量的增加，A5相较于A1、A2、A3、A4来说硬度略有下降，表明增韧剂对于材料的硬度有减弱效果。同时随着增韧剂的含量增多，复合材料弹性模量成减弱趋势，且当增韧剂负载量为5％时，A5相比较于A0的弹性模量降低1000MPa左右，表明增韧剂对于材料的弹性模量有较为明显减弱效果。增韧剂却对冲击强度和抗拉强度的影响不太明显。见图1、图2、图3、图4、图5。In all the prepared modified materials, after the mechanical performance test, it was found that with the increase of the content of the toughening agent, the fracture growth rate of the composite material tended to increase, and when the loading of the toughening agent was 5%, A5 compared with The tensile strength of A0 (pure PLA) is increased by about 20%, indicating that the toughening agent has a significant enhancement effect on the elongation at break of the material. However, as the content of the toughening agent increases, the hardness of A5 decreases slightly compared with A1, A2, A3, and A4, indicating that the toughening agent has a weakening effect on the hardness of the material. At the same time, as the content of the toughening agent increases, the elastic modulus of the composite material tends to weaken, and when the loading of the toughening agent is 5%, the elastic modulus of A5 decreases by about 1000 MPa compared with A0, which shows that the toughening agent has an important effect on the material. The elastic modulus has a more obvious weakening effect. Tougheners have less obvious effects on impact strength and tensile strength. See Figure 1, Figure 2, Figure 3, Figure 4, and Figure 5.
从图6可以明显看到改性后的聚乳酸其热变形温度有明显的上涨，由此可得出白滑石的加入对聚乳酸的热变形温度影响较大，提高了约50℃-60℃左右。It can be clearly seen from Figure 6 that the heat deflection temperature of the modified polylactic acid has increased significantly, and it can be concluded that the addition of white talc has a greater impact on the heat deflection temperature of polylactic acid, which has increased by about 50°C-60°C about.
图7为A1、A2、A3的红外光谱图，随着增韧剂含量的不断加入，PLA和PBS共混体系主链中2920cm -1处的饱和碳上的C-H伸缩振动峰、1714cm -1处C＝O伸缩振动峰、1334、1158和1017cm -1处的-O-C＝O-基团中的-C-O-伸缩振动峰以及669cm -1处的C-H面外弯曲振动峰均表现出峰强的增强或减弱，但这些峰的位置基本没有发生移动，说明在加入增韧剂后，PLA和PBS共混分子主链的结构保持基本不变，两者之间的相互作用力表现为物理相互作用。通过对比A1和A2的图谱，发现随着增韧剂含量的增多，1087cm -1处的-O-C＝O-基团中的-C-O-伸缩振动峰的吸收强度越来越小，推测这是因为在PLA和PBS共混体系中加入增韧剂，从而提高了主链分子之间的界面结合力，改善了PLA与其他物质之间的粘合增强。 Figure 7 is the infrared spectra of A1, A2, and A3. With the continuous addition of the toughening agent content, the CH stretching vibration peak on the saturated carbon at 2920cm -1 in the main chain of the PLA and PBS blend system, and the CH stretching vibration peak at 1714cm -1 The C=O stretching vibration peak, the -CO- stretching vibration peak in the -OC=O- group at 1334, 1158, and 1017 cm -1 , and the CH out-of-plane bending vibration peak at 669 cm - 1 all showed enhanced peak intensities or weakened, but the positions of these peaks basically did not move, indicating that after adding the toughening agent, the structure of the main chain of the PLA and PBS blend molecules remained basically unchanged, and the interaction force between the two showed physical interaction. By comparing the spectra of A1 and A2, it is found that as the content of the toughening agent increases, the absorption intensity of the -CO- stretching vibration peak in the -OC=O- group at 1087cm -1 becomes smaller and smaller, presumably because Adding a toughening agent to the PLA and PBS blend system increases the interfacial binding force between the main chain molecules and improves the adhesion enhancement between PLA and other substances.
通过对A1、A2、A3、A4、A5、A6进行DSC数据分析，得到图7为第一段降温DSC曲线，得到图8为第二段升温DSC曲线，表1给出了A0、A1、A2、 A5的结晶度(χ)。其中
Figure PCTCN2021099077-appb-000001
(△Hm为熔融焓，J/g；△Hcc为冷结晶焓，J/g；△H 0 m＝97.3J/g为纯PLA结晶焓) Through DSC data analysis of A1, A2, A3, A4, A5, and A6, Figure 7 is the first cooling DSC curve, and Figure 8 is the second heating DSC curve. Table 1 shows A0, A1, and A2 , A5 crystallinity (χ). in
Figure PCTCN2021099077-appb-000001
(△Hm is melting enthalpy, J/g; △Hcc is cold crystallization enthalpy, J/g; △H 0 m =97.3J/g is pure PLA crystallization enthalpy)
Figure PCTCN2021099077-appb-000002
Figure PCTCN2021099077-appb-000002
表1Table 1
从图8中可以看出A0、A1、A2、A5的结晶温度约在80℃左右；从图9中可以看出A0、A1、A2、A5的熔融温度约在113℃左右；但图9中出现了一小段凸出的峰，这是在熔融过程中出现了冷结晶的现象，这种现象是由于在降温过程中，PLA改性分子链末端还未排列规整就被冻结，再次升温时，分子链又开始运动，出现边升温、边结晶的现象，形成冷结晶峰，从而说明了PBS对于提高PLA结晶能力和结晶度有着一定的作用。It can be seen from Figure 8 that the crystallization temperature of A0, A1, A2, and A5 is about 80°C; it can be seen from Figure 9 that the melting temperature of A0, A1, A2, and A5 is about 113°C; but in Figure 9 A small section of protruding peaks appeared, which is the phenomenon of cold crystallization during the melting process. This phenomenon is due to the fact that during the cooling process, the ends of the PLA modified molecular chains are frozen before they are arranged in a regular manner. When the temperature is raised again, The molecular chains began to move again, and the phenomenon of heating and crystallization appeared, forming a cold crystallization peak, which showed that PBS had a certain effect on improving the crystallization ability and crystallinity of PLA.
从表1中可以看出在PLA中加入一定量的耐温剂与增韧剂，其结晶度相较于纯PLA提升了较多(2.4％左右)。A1相较于A0结晶度略有下降，说明增韧剂对结晶度有一定的影响，所以，这很可能是由于耐温剂与增韧剂共同作用影响PLA的结晶速率，可以使结晶速率跟得上注塑成型时的冷却速度，通过加入成核剂(无机填料)能使PLA改性分子片段明显增加晶核密度，能够快速增加PLA分子链结晶速率，使结晶度增大，而结晶度和物质耐热性有密切关系，结晶度越高，耐热性越高，也就使PLA改性分子的耐热性大大提高。It can be seen from Table 1 that adding a certain amount of temperature-resistant agent and toughening agent to PLA will increase its crystallinity more than that of pure PLA (about 2.4%). Compared with A0, the crystallinity of A1 is slightly lower, indicating that the toughening agent has a certain influence on the crystallinity. Therefore, this is likely to be due to the joint action of the temperature-resistant agent and the toughening agent on the crystallization rate of PLA, which can make the crystallization rate comparable to that of PLA. Based on the cooling rate during injection molding, adding a nucleating agent (inorganic filler) can significantly increase the crystal nucleus density of PLA modified molecular fragments, rapidly increase the crystallization rate of PLA molecular chains, and increase the crystallinity, while the crystallinity and The heat resistance of the material is closely related. The higher the crystallinity, the higher the heat resistance, which greatly improves the heat resistance of PLA modified molecules.
我们分析聚乳酸A0的热稳定性，并将其分别与改性后A1和A5复合材料进行了比较。热重曲线图如图10所示。表2分析了材料在5％失重(T 5％)下的温度、10％失重(T 10％)下的温度以及在50％失重(T 50％)下的温度。在热重曲线图中可以观察到三个材料质量损失的过程：改性后的聚乳酸即A1与A5的失水量基本相同，即热分解曲线图基本重叠。在聚合物加工过程中可发生多种化 学和物理反应，在图10中，改性后的聚乳酸在340℃之前相对稳定。在340～450℃左右的温度下所放样品开始分解，并且在图11中可以发现：在410℃之前，聚乳酸的分解速度更快，而且在420℃的时候，复合材料出现了第二个分解峰，这可能是由于添加的PBS分解的原因。在表2中也可以发现，A1和A5失重50％的温度比PLA要高，进一步表明改性后的聚乳酸出现第二个分解时产生的峰是由于PBS的分解造成。 We analyzed the thermal stability of PLA A0 and compared it with the modified A1 and A5 composites, respectively. The thermogravimetric curve is shown in Figure 10. Table 2 analyzes the temperature of the material at 5% weight loss (T 5% ) , at 10% weight loss (T 10% ) and at 50% weight loss (T 50% ). Three processes of material mass loss can be observed in the thermogravimetric curve: the water loss of the modified polylactic acid, that is, A1 and A5, is basically the same, that is, the thermal decomposition curves basically overlap. Various chemical and physical reactions can occur during polymer processing. In Figure 10, the modified PLA is relatively stable until 340 °C. The sample placed at a temperature of about 340-450°C begins to decompose, and it can be found in Figure 11: Before 410°C, the decomposition rate of polylactic acid is faster, and at 420°C, the composite material appears a second Decomposition peaks, which may be due to decomposition of the added PBS. It can also be found in Table 2 that the 50% weight loss temperature of A1 and A5 is higher than that of PLA, which further indicates that the second decomposition peak of the modified polylactic acid is caused by the decomposition of PBS.
Figure PCTCN2021099077-appb-000003
Figure PCTCN2021099077-appb-000003
表2Table 2
冲击试验后的A1和A5复合材料的断裂面截图SEM图如图12所示。可以看到，A1复合材料的断裂面整体光滑且平整，而添加增韧剂后改变了断裂面的外观，A5复合材料的断裂面出现了较多的细纹及小孔，由于微孔及细纹数量增多，说明其断裂时经过一定微裂纹的形成与增大，这能表明A4相比较于A1有更好的韧性，并且可以通过机械性能的分析证实。The SEM images of the fracture surfaces of A1 and A5 composites after the impact test are shown in Figure 12. It can be seen that the fracture surface of the A1 composite material is smooth and flat as a whole, but the appearance of the fracture surface is changed after adding the toughening agent, and there are more fine lines and small holes on the fracture surface of the A5 composite material. The increase in the number of cracks indicates that it undergoes the formation and growth of certain microcracks when it breaks, which can show that A4 has better toughness than A1, and it can be confirmed by the analysis of mechanical properties.
无机填料的加入明显改变了纯聚乳酸的形态(图A5)，这显著地改善了聚乳酸拉伸和冲击性能，具体取决于无机填料的含量(图A0-A5)。在二元共混物中观察到由于无机填料含量增加引起的形态转变。A0-a显示出典型的“海岛/基质中的水滴”形态，A5-b显示出具有网状纹理的连续形态。这种结构的改变增强了机械性能，可以预期随着填料的增加，复合材料的冲击强度和硬度同样会增强，且复合材料的断裂伸长率显著提升，通过拉伸和冲击断裂截面的电镜分析，确定了潜在的增韧机制。The addition of inorganic fillers significantly changed the morphology of pure PLA (Fig. A5), which significantly improved the tensile and impact properties of PLA, depending on the content of inorganic fillers (Fig. A0–A5). Morphological transitions due to increasing inorganic filler content were observed in binary blends. A0-a shows a typical “sea islands/water droplet in matrix” morphology, and A5-b shows a continuous morphology with a net-like texture. This structural change enhances the mechanical properties. It can be expected that with the increase of filler, the impact strength and hardness of the composite material will also increase, and the elongation at break of the composite material will be significantly improved. Through the electron microscopy analysis of the tensile and impact fracture sections , identifying the underlying toughening mechanism.
以上所揭露的仅为本发明较佳实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明权利要求所作的等同变化，仍属本发明所涵盖的范围。The above disclosures are only preferred embodiments of the present invention, and certainly cannot limit the scope of rights of the present invention. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope of the present invention.

Claims (8)

  1. 一种复合增韧耐高温聚乳酸改性材料，其特征在于包括以下组分，以质量份数计：聚乳酸30～60质量份、聚丁二酸丁二醇酯20～50质量份、无机填料5～12质量份、扩链剂0.5～1.2质量份、增塑剂1～10质量份、增韧剂0.5～10质量份、相容剂0.2～0.6质量份、耐温剂0.1～0.6质量份。A composite toughened high temperature resistant polylactic acid modified material, characterized in that it comprises the following components, in parts by mass: 30-60 parts by mass of polylactic acid, 20-50 parts by mass of polybutylene succinate, inorganic 5-12 parts by mass of filler, 0.5-1.2 parts by mass of chain extender, 1-10 parts by mass of plasticizer, 0.5-10 parts by mass of toughening agent, 0.2-0.6 parts by mass of compatibilizer, and 0.1-0.6 parts by mass of temperature-resistant agent share.
  2. 根据权利要求1所述的一种复合增韧耐高温聚乳酸改性材料，其特征在于：所述无机填料为玻璃纤维、高岭土、碳酸钙、硫酸钙、滑石粉、云母、二氧化硅、炭黑中的一种或几种组合。A composite toughened high temperature resistant polylactic acid modified material according to claim 1, characterized in that: the inorganic filler is glass fiber, kaolin, calcium carbonate, calcium sulfate, talcum powder, mica, silicon dioxide, carbon One or several combinations of black.
  3. 根据权利要求1所述的一种复合增韧耐高温聚乳酸改性材料，其特征在于：所述扩链剂包括过氧化物类化合物、异氰酸酯类化合物、多官能团环氧化合物、磷酸酯类化合物中的一种或多种的混合物。A composite toughened high temperature resistant polylactic acid modified material according to claim 1, characterized in that: the chain extender includes peroxide compounds, isocyanate compounds, multifunctional epoxy compounds, phosphate compounds A mixture of one or more of them.
  4. 根据权利要求1所述的一种复合增韧耐高温聚乳酸改性材料，其特征在于：所述增塑剂包括邻苯二甲酸丁苄酯、邻苯二甲酸二仲辛酯、邻苯二甲酸二环己酯、邻苯二甲酸二丁酯、邻苯二甲酸二异丁酯、邻苯二甲酸二甲酯中的一种或几种的混合物。A composite toughened high temperature resistant polylactic acid modified material according to claim 1, characterized in that: said plasticizer comprises butyl benzyl phthalate, di-sec-octyl phthalate, phthalate One or a mixture of dicyclohexyl formate, dibutyl phthalate, diisobutyl phthalate, and dimethyl phthalate.
  5. 根据权利要求1所述的一种复合增韧耐高温聚乳酸改性材料，其特征在于：所述的增韧剂包括苯乙烯-丁二烯热塑性弹性体、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物、乙烯-醋酸乙烯酯共聚物、聚丁二烯橡胶中的一种或几种的混合物。A composite toughened high temperature resistant polylactic acid modified material according to claim 1, characterized in that: said toughening agent comprises styrene-butadiene thermoplastic elastomer, methyl methacrylate-butadiene -One or more mixtures of styrene terpolymer, ethylene-vinyl acetate copolymer and polybutadiene rubber.
  6. 根据权利要求1所述的一种复合增韧耐高温聚乳酸改性材料，其特征在于：所述的相容剂包括环状酸酐型、羧酸型、环氧型、恶唑啉型、酰亚胺型、低分子型、异氰酸酯型中的一种或多种的混合物。A compound toughened high temperature resistant polylactic acid modified material according to claim 1, characterized in that: said compatibilizer includes cyclic anhydride type, carboxylic acid type, epoxy type, oxazoline type, acyl A mixture of one or more of imine type, low molecular weight type, and isocyanate type.
  7. 根据权利要求1所述的一种复合增韧耐高温聚乳酸改性材料，其特征在于：所述的耐温剂为聚乙烯蜡、芥酸酰胺和油酸酰胺中的一种或多种。A composite toughened high temperature resistant polylactic acid modified material according to claim 1, characterized in that: said temperature resistant agent is one or more of polyethylene wax, erucamide and oleamide.
  8. 一种如权利要求1所述的复合增韧耐高温聚乳酸改性材料的制备方法，其特征在于包括以下步骤：A method for preparing a composite toughened high temperature resistant polylactic acid modified material as claimed in claim 1, characterized in that it comprises the following steps:
    S1、按照所述组分用量称取聚乳酸、聚丁二酸丁二醇酯、无机填料、扩链剂、增塑剂、增韧剂、相容剂和耐温剂；S1. Weigh polylactic acid, polybutylene succinate, inorganic filler, chain extender, plasticizer, toughening agent, compatibilizer and temperature resistant agent according to the amount of the components;
    S2、将步骤S1所称取的配方按聚乳酸、聚丁二酸丁二醇酯、扩链剂、相容剂的先后顺序进行均匀混合后，再按耐温剂、无机填料、增塑剂、增韧剂的先后顺序加入其中并进行均匀混合，密闭静置；S2. After uniformly mixing the formula weighed in step S1 according to the order of polylactic acid, polybutylene succinate, chain extender and compatibilizer, 1. Add the toughening agents in sequence and mix them evenly, and leave them in a closed place;
    S3、将步骤S2所混合好的材料加入双螺杆挤出机，于170℃～190℃挤出造粒，挤出机转速100～500转/分；S3. Add the mixed materials in step S2 into a twin-screw extruder, extrude and granulate at 170°C-190°C, and the speed of the extruder is 100-500 rpm;
    S4、将步骤S3所得的料粒放于真空烘箱中干燥，烘箱温度设定为70～100℃，时间设定为8～12h；S4, drying the pellets obtained in step S3 in a vacuum oven, the temperature of the oven is set at 70-100° C., and the time is set at 8-12 hours;
    S5、将步骤S4所得的料粒于注塑机中注塑成制品，注塑温度170～200℃。S5. Injecting the pellets obtained in step S4 into a product in an injection molding machine at an injection temperature of 170-200°C.
PCT/CN2021/099077 2021-06-05 2021-06-09 Composite toughened and high-temperature-resistant polylactic acid modified material and preparation method therefor WO2022252266A1 (en)

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