CN109535673B - Heat-resistant impact-resistant high-transparency polylactic acid composite material and preparation method thereof - Google Patents
Heat-resistant impact-resistant high-transparency polylactic acid composite material and preparation method thereof Download PDFInfo
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The invention relates to a heat-resistant, impact-resistant and high-transparency polylactic acid composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 100 parts of polylactic acid, 1-5 parts of a toughening agent, 0.1-0.5 part of a chain extender, 0.01-1 part of a crystallization nucleating agent, 0.01-0.05 part of a crystallization promoter and 0.1-3 parts of an antistatic agent, wherein the polylactic acid is multi-arm branched polylactic acid. Compared with the conventional linear chain polylactic acid resin, the branched polylactic acid has higher probability of winding the macromolecule long chains in a molten state, and higher strength of winding, and meanwhile, the toughening agent and the chain extender are matched with each other for use, so that the toughness of the polylactic acid is greatly increased, and the synergistic effect of the crystallization nucleating agent and the crystallization promoter ensures that the polylactic acid material has high temperature resistance and transparency, and the bis (beta-hydroxyethyl) cocoamine is used as the antistatic agent, so that the antistatic property of the polylactic acid is greatly improved, and the branched polylactic acid can be applied to take-out tableware.
Description
Technical Field
The invention relates to a heat-resistant, impact-resistant and high-transparency polylactic acid composite material and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
In recent years, with the rapid development of online catering take-out services, take-out foods bring great convenience to the life of people, and a large amount of take-out packages cause great pollution to the environment. At present, the main component of the main stream products of plastic lunch boxes and tableware is polypropylene, which has the advantages of low cost, simple and convenient production, good performance and the like, but the polypropylene is not degradable and becomes one of the main pollutants causing white pollution. In the face of increasing environmental pollution, environmentally friendly and completely biodegradable materials are required to be found to replace polypropylene.
The polylactic acid is thermoplastic resin derived from renewable plant resources such as corn, cassava, sugarcane and the like, is a completely biodegradable high polymer material, has excellent transparency, excellent processing formability and stable melt strength, can be processed into sheets, and then is subjected to plastic uptake to prepare products such as lunch boxes, trays, cup covers and the like, so that the polylactic acid is applied to the take-out industry. However, polylactic acid as a straight-chain aliphatic polyester has insufficient heat resistance, particularly insufficient toughness, high rigidity and high brittleness, is very easy to crack in the process of processing and forming, has a silver streak phenomenon, cannot stably and continuously produce products, and seriously restricts the application of the polylactic acid in the field of blister packaging products. Therefore, it is necessary to modify the polylactic acid resin to improve the insufficient molding problem thereof.
In order to improve the heat resistance and toughness of polylactic acid products and ensure high transparency of the products, researchers have conducted a great deal of research and development work on modified polylactic acid resins, such as the following:
the patent with the reference number of CN101983986B discloses a transparent and toughened polylactic resin and a preparation method thereof, the method adopts a blending granulation method of polylactic acid, a toughening agent, a plasticizer and an antioxidant to prepare the polylactic modified resin, improves the tensile elongation at break and the impact strength of the polylactic acid, keeps the transparency of the polylactic acid, but has insufficient heat resistance and can not meet the requirements of the field of packaging products;
the patent with the reference number of CN104312121B discloses a high-toughness transparent polylactic acid film and a preparation method thereof, wherein a self-synthesized network polyester multipolymer is used as a toughening agent of polylactic acid resin, and the assistance of a heat stabilizer is added, so that the polylactic acid modified resin has good toughness and excellent transparency, but the heat resistance of the polylactic acid modified resin is not improved;
the patent with the reference number of CN105062024A discloses a high-transparency high-temperature-resistance polylactic acid composite material and a preparation method thereof, wherein the transparency, the temperature resistance and the hydrolysis resistance stability of polylactic acid are improved by blending and granulating polylactic acid, a toughening agent, a crystallization nucleating agent, an hydrolysis resistance stabilizer and a lubricant, but the impact strength is not greatly improved, so that the polylactic acid composite material cannot be applied to blister lunch box products;
patent No. CN106633727A discloses a polylactic acid resin composition for blowing transparent heat-resistant bottles, which uses poly L-lactic acid, inorganic filler and elastomer toughening modifier with core-shell structure to realize high heat resistance of the product, so that the product can be applied to products of bottle blowing process, but the light transmittance of the modified polylactic acid material is only 80%, and the impact resistance is not well reflected.
The invention respectively improves and enhances the transparency, heat resistance and impact resistance of polylactic resin, but no modified polylactic resin simultaneously considers the transparency, heat resistance and impact resistance and can not meet the requirements of products in the field of packaging materials, and researches on preparing a heat-resistant impact-resistant high-transparency polylactic acid composite material are urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the technical problem that the existing modified polylactic acid resin can not simultaneously give consideration to transparency, heat resistance and impact resistance, a heat-resistant impact-resistant high-transparency polylactic acid composite material and a preparation method thereof are provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a heat-resistant impact-resistant high-transparency polylactic acid composite material comprises the following components in parts by weight: 100 parts of polylactic acid, 1-5 parts of toughening agent, 0.1-0.5 part of chain extender, 0.01-1 part of crystallization nucleating agent, 0.01-0.05 part of crystallization promoter and 0.1-3 parts of antistatic agent; the polylactic acid is multi-arm branched polylactic acid, the number average molecular weight of the polylactic acid is 5-20 ten thousand, and the number average molecular weight of each arm is 0.2-1 ten thousand.
Preferably, the polylactic acid is a three-arm branched polylactic acid, and the polylactic acid has the following structural formula, wherein n is 50-1000,
preferably, the melt index of the polylactic acid at the temperature of 190 ℃ and under the pressure of 2.16kg load is 2g/10min-50g/10min, and the melting point is 120 ℃ to 180 ℃.
Preferably, the toughening agent is one or more of polybutylene succinate, poly epsilon-caprolactone, ethylene vinyl acetate copolymer and oil-extended styrene-butadiene-styrene block copolymer.
Preferably, the oil-extended styrene-butadiene-styrene block copolymer is a blend of a styrene-butadiene-styrene block copolymer and white oil, and the weight ratio of the styrene-butadiene-styrene block copolymer to the white oil is 2: 3 to 3: 2.
Preferably, the chain extender is one or more of styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, ethylene glycol dimethacrylate and styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer.
Preferably, the crystallization nucleating agent is one or more of poly-D lactic acid, 4, 6-di-tert-butylphenyl phosphate and 1,3, 5-n-butylbenzene tricarballylamide, and the poly-D lactic acid is powder with the mesh number of 300-3000 meshes.
Preferably, the crystallization promoter is one or more of 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, tribenzylidene propyl ether hexanol and neopentyl glycol biphenyl ester.
Preferably, the antistatic agent is bis (β -hydroxyethyl) cocoamine.
The invention also provides a preparation method of the heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following preparation steps:
uniformly blending dried polylactic acid, a toughening agent, a chain extender, a crystallization nucleating agent, a crystallization promoter and an antistatic agent to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder for mixing, extruding and granulating, and drying the granules to obtain dried granules;
and adding the dried granules into an injection molding machine for injection molding.
Preferably, the drying method of the polylactic acid is as follows: putting the polylactic acid at 60-90 ℃ for vacuum drying for 6-10 h until the water content is less than 300 ppm; the drying method of the granules comprises the following steps: and (3) drying the granules in vacuum at 50-80 ℃ for 6-10 h until the water content is less than 300 ppm.
Preferably, the extrusion temperature of the double-screw extruder is 160-; the temperature of the charging barrel of the injection molding machine is 160-190 ℃, and the pressure is 40-55 MPa.
The invention has the beneficial effects that:
(1) the heat-resistant impact-resistant high-transparency polylactic acid composite material adopts multi-arm branched polylactic acid, compared with the conventional linear chain polylactic acid resin, the branched polylactic acid has higher probability of winding macromolecular long chains mutually in a molten state, and has higher strength of mutual winding, so that the polylactic acid resin has better impact strength, and provides good basic conditions for impact resistance, toughening and modification of the polylactic acid.
(2) The toughening agent adopted by the heat-resistant impact-resistant high-transparency polylactic acid composite material can provide a good toughening effect for polylactic acid resin, does not influence the high transparency of polylactic acid, and has the transmittance of over 90 percent; meanwhile, the toughening agent and the chain extender are matched with each other for use, so that the polylactic acid branched macromolecular chain and the toughening agent macromolecular chain are subjected to mutual crosslinking, the toughening effect of the toughening agent is better reflected, the interlayer phase separation phenomenon between the polylactic acid and the toughening agent can be reduced in the subsequent storage process, and the service life of the material is ensured.
(3) The crystallization nucleating agent and the crystallization accelerator adopted by the heat-resistant impact-resistant high-transparency polylactic acid composite material can greatly improve the crystallization speed of polylactic acid under the synergistic action, and simultaneously, the formed crystal structures are all 'small spherulites' with the spherulite size of nanometer, the crystals are small and many, so that the polylactic acid material can obtain high temperature resistance and simultaneously ensure the transparency of the polylactic acid material.
(4) The heat-resistant impact-resistant high-transparency polylactic acid composite material also adopts bis (beta-hydroxyethyl) cocoamine as an antistatic agent, so that the antistatic property of polylactic acid is greatly improved, and the polylactic acid composite material has dust absorption resistance in the application of packaging products.
(5) The heat-resistant impact-resistant high-transparency polylactic acid composite material is safe and environment-friendly, has low raw material cost, low requirement on required equipment and simple operation, can be applied to packaging products such as take-away lunch boxes, plastic trays, plastic suction cup covers and the like, perfectly replaces non-degradable plastics such as PP, PS and the like, can solve white pollution, promotes the development of novel environment-friendly material industry, and has wide market prospect.
Detailed Description
The present invention will now be described in further detail.
Example 1
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 5 ten thousand), 2 parts of toughening agent polybutylene succinate, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material comprises the following steps:
drying the three-arm branched polylactic acid at 60 ℃ for 10h in vacuum until the water content is less than 300 ppm;
uniformly blending the dried polylactic acid, a toughening agent, a chain extender, a crystallization nucleating agent, a crystallization promoter and an antistatic agent in a high-speed mixer to obtain a premixed raw material;
adding the obtained premixed raw materials into a double-screw extruder for mixing, extruding and granulating; the heating temperature of each area of the double-screw extruder from the feed inlet to the discharge outlet is set to be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, the rotating speed of a main machine is 300r/min, and the feeding frequency is 15r/min in sequence;
vacuum drying the obtained granules at 50 ℃ for 10h until the moisture content is less than 300 ppm;
and adding the obtained dried granules into a horizontal injection molding machine for injection molding, wherein the temperature of a charging barrel of the horizontal injection molding machine is set to be 160 ℃, 165 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃ and the pressure maintaining pressure to be 40-55 MPa from a feeding hole to a nozzle in sequence, and the pressure is maintained for 25s to obtain the corresponding sample strip.
Example 2
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of five-arm branched polylactic acid (the number average molecular weight is 20 ten thousand), 5 parts of toughening agent polybutylene succinate, 0.5 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 1 part of crystallization nucleating agent poly-D lactic acid powder, 0.01 part of crystallization accelerator tribenzyl diallyl ether diester hexanol and 1 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material comprises the following steps:
vacuum drying the three-arm branched polylactic acid at 90 ℃ for 6h until the water content is less than 300 ppm;
uniformly blending the dried polylactic acid, a toughening agent, a chain extender, a crystallization nucleating agent, a crystallization promoter and an antistatic agent in a high-speed mixer to obtain a premixed raw material;
adding the obtained premixed raw materials into a double-screw extruder for mixing, extruding and granulating; the heating temperature of each area of the double-screw extruder from the feed inlet to the discharge outlet is set to be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, the rotating speed of a main machine is 500r/min, and the feeding frequency is 7r/min in sequence;
vacuum drying the obtained granules at 80 ℃ for 6h until the moisture content is less than 300 ppm;
and adding the obtained dried granules into a horizontal injection molding machine for injection molding, wherein the temperature of a charging barrel of the horizontal injection molding machine is set to be 160 ℃, 165 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃ and the pressure maintaining pressure to be 40-55 MPa from a feeding hole to a nozzle in sequence, and the pressure is maintained for 25s to obtain the corresponding sample strip.
Example 3
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 1 part of toughening agent polybutylene succinate, 0.1 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.01 part of crystallization nucleating agent poly-D lactic acid powder, 0.05 part of crystallization accelerator neopentyl glycol diphenyl ester and 0.1 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material comprises the following steps:
vacuum drying the three-arm branched polylactic acid at 80 ℃ for 8h until the water content is less than 300 ppm;
uniformly blending the dried polylactic acid, a toughening agent, a chain extender, a crystallization nucleating agent, a crystallization promoter and an antistatic agent in a high-speed mixer to obtain a premixed raw material;
adding the obtained premixed raw materials into a double-screw extruder for mixing, extruding and granulating; the heating temperature of each area of the double-screw extruder from the feed inlet to the discharge outlet is set to be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 10r/min in sequence;
vacuum drying the obtained granules at 60 ℃ for 8h until the moisture content is less than 300 ppm;
and adding the obtained dried granules into a horizontal injection molding machine for injection molding, wherein the temperature of a charging barrel of the horizontal injection molding machine is set to be 160 ℃, 165 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃ and the pressure maintaining pressure to be 40-55 MPa from a feeding hole to a nozzle in sequence, and the pressure is maintained for 25s to obtain the corresponding sample strip.
Example 4
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of five-arm branched polylactic acid (the number average molecular weight is 15 ten thousand), 3 parts of toughening agent polybutylene succinate, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.6 part of crystallization nucleating agent 4, 6-di-tert-butyl phenyl sodium phosphate, 0.04 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.4 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 5
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 4 parts of toughening agent polybutylene succinate, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.8 part of crystallization nucleating agent 1,3, 5-n-butylbenzene tricarballylamide, 0.02 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.8 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 6
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of five-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 2 parts of toughening agent polybutylene succinate, 0.2 part of chain extender ethylene glycol dimethacrylate, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization promoter 1,3:2, 4-di (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 7
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 15 ten thousand), 2 parts of toughening agent polybutylene succinate, 0.2 part of chain extender styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 8
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 5 ten thousand), 2 parts of toughening agent poly epsilon-caprolactone, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-di (3, 4-dimethyl) benzylidene sorbitol acetal and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 9
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 20 ten thousand), 2 parts of toughening agent poly epsilon-caprolactone, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.1 part of crystallization nucleating agent 4, 6-di-tert-butyl phenyl sodium phosphate, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 10
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of five-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 2 parts of toughening agent poly epsilon-caprolactone, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 1 part of crystallization nucleating agent 1,3, 5-n-butylbenzene tricarballylamide, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 11
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 15 ten thousand), 4 parts of flexibilizer oil-filled styrene-butadiene-styrene block copolymer, 0.2 part of chain extender ethylene glycol dimethacrylate, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.05 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine; the oil-extended styrene-butadiene-styrene block copolymer is a blend of a styrene-butadiene-styrene block copolymer and white oil, and the weight ratio of the styrene-butadiene-styrene block copolymer to the white oil is 1: 1.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 12
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 3 parts of toughener oil-extended styrene-butadiene-styrene block copolymer, 0.4 part of chain extender styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine; the oil-extended styrene-butadiene-styrene block copolymer is a blend of a styrene-butadiene-styrene block copolymer and white oil, and the weight ratio of the styrene-butadiene-styrene block copolymer to the white oil is 3: 2.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 13
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 2 parts of a toughening agent ethylene vinyl acetate copolymer, 0.2 part of a chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of a crystallization nucleating agent poly-D lactic acid powder, 0.03 part of a crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 1.6 parts of an antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Example 14
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of three-arm branched polylactic acid (the number average molecular weight is 10 ten thousand), 2 parts of flexibilizer oil-filled styrene-butadiene-styrene block copolymer, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 3 parts of antistatic agent bis (beta-hydroxyethyl) cocoamine; the oil-extended styrene-butadiene-styrene block copolymer is a blend of a styrene-butadiene-styrene block copolymer and white oil, and the weight ratio of the styrene-butadiene-styrene block copolymer to the white oil is 2: 3.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Comparative example 1
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of linear polylactic acid (the number average molecular weight is 10 ten thousand), 2 parts of toughening agent polybutylene succinate, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Comparative example 2
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of linear polylactic acid (the number average molecular weight is 5 ten thousand), 2 parts of toughening agent poly epsilon-caprolactone, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Comparative example 3
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of linear polylactic acid (the number average molecular weight is 15 ten thousand), 2 parts of flexibilizer ethylene vinyl acetate copolymer, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
Comparative example 4
The embodiment provides a heat-resistant, impact-resistant and high-transparency polylactic acid composite material, which comprises the following components in parts by weight: 100 parts of linear polylactic acid (the number average molecular weight is 20 ten thousand), 2 parts of flexibilizer oil-filled styrene-butadiene-styrene block copolymer, 0.2 part of chain extender styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, 0.5 part of crystallization nucleating agent poly-D lactic acid powder, 0.03 part of crystallization accelerator 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, and 0.6 part of antistatic agent bis (beta-hydroxyethyl) cocoamine.
The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material sample strip is the same as that of example 3.
And (3) adopting a corresponding detailed specification flow in the ISO standard to carry out performance test on the test sample, wherein the specific performance is as shown in the table 1:
as can be seen from the above Table 1, the polylactic acid resin is limited to obtain a high-performance polylactic acid resin material with excellent comprehensive properties, and the high-performance polylactic acid resin material has the excellent characteristics of high impact resistance, high heat resistance and static resistance while maintaining the original high transparency, and has unexpected technical effects; the polylactic resin of the comparative example 1 adopts linear polylactic acid, so that the notch impact strength is obviously reduced, the brittleness is high, and the polylactic resin can not be applied to the field of packaging catering plastics.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. The heat-resistant impact-resistant high-transparency polylactic acid composite material is characterized by comprising the following components in parts by weight: 100 parts of polylactic acid, 1-5 parts of toughening agent, 0.1-0.5 part of chain extender, 0.01-1 part of crystallization nucleating agent, 0.01-0.05 part of crystallization promoter and 0.1-3 parts of antistatic agent; the polylactic acid is three-arm branched polylactic acid, the number average molecular weight of the polylactic acid is 5-20 ten thousand, the number average molecular weight of each arm is 0.2-1 ten thousand, the polylactic acid has the following structural formula, wherein n is 50-1000,
the crystallization nucleating agent is one or more of poly-D lactic acid, 4, 6-di-tert-butylphenyl phosphate and 1,3, 5-n-butylbenzene tricarballylamide, and the crystallization promoter is one or more of 1,3:2, 4-bis (3, 4-dimethyl) benzylidene sorbitol acetal, tribenzylidene propyl ether hexanol and neopentyl glycol biphenyl ester.
2. The heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 1, wherein the polylactic acid has a melt index of 2g/10min to 50g/10min and a melting point of 120 ℃ to 180 ℃ at a temperature of 190 ℃ and a pressure of 2.16kg under load.
3. The heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 1 or 2, wherein the toughening agent is one or more of polybutylene succinate, poly-epsilon-caprolactone, ethylene vinyl acetate copolymer and oil-extended styrene-butadiene-styrene block copolymer, the oil-extended styrene-butadiene-styrene block copolymer is a blend of styrene-butadiene-styrene block copolymer and white oil, and the weight ratio of the styrene-butadiene-styrene block copolymer to the white oil is 2: 3-3: 2.
4. The heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 1 or 2, wherein the chain extender is one or more of styrene-methyl methacrylate-glycidyl methacrylate ternary random copolymer, ethylene glycol dimethacrylate, and styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer.
5. The heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 1 or 2, wherein the poly-D lactic acid is a powder with a mesh number of 300-3000.
6. The heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 1 or 2, wherein the antistatic agent is bis (beta-hydroxyethyl) cocoamine.
7. The preparation method of the heat-resistant impact-resistant high-transparency polylactic acid composite material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
uniformly blending dried polylactic acid, a toughening agent, a chain extender, a crystallization nucleating agent, a crystallization promoter and an antistatic agent to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder for mixing, extruding and granulating, and drying the granules to obtain dried granules;
and adding the dried granules into an injection molding machine for injection molding.
8. The method for preparing the heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 7, wherein the drying method of the polylactic acid comprises the following steps: putting the polylactic acid at 60-90 ℃ for vacuum drying for 6-10 h until the water content is less than 300 ppm; the drying method of the granules comprises the following steps: and (3) drying the granules in vacuum at 50-80 ℃ for 6-10 h until the water content is less than 300 ppm.
9. The method for preparing the heat-resistant impact-resistant high-transparency polylactic acid composite material according to claim 7 or 8, wherein the extrusion temperature of the twin-screw extruder is 160-190 ℃, the rotation speed of the main machine is 300-500r/min, and the feeding frequency is 7-15 r/min; the temperature of the charging barrel of the injection molding machine is 160-190 ℃, and the pressure is 40-55 MPa.
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| CN111040401A (en) * | 2019-12-28 | 2020-04-21 | 诺思贝瑞新材料科技（苏州）有限公司 | High-performance modified polylactic acid composite material and preparation method thereof |
| CN114015216B (en) * | 2021-12-09 | 2022-12-30 | 海南赛诺实业有限公司 | Degradable modified antistatic agent and preparation method thereof |
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