CN111073239A - High-temperature-resistant polylactic acid injection-molded porcelain-like tableware and preparation method thereof - Google Patents
High-temperature-resistant polylactic acid injection-molded porcelain-like tableware and preparation method thereof Download PDFInfo
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Abstract
The invention relates to high-temperature-resistant polylactic acid injection molding porcelain-like tableware and a preparation method thereof, belonging to the field of high polymer materials. 70-90 parts of polylactic acid, 5-15 parts of a toughening agent, 0.05-0.20 part of a chain extender, 0.5-1 part of an organic nucleating agent, 5-20 parts of an inorganic nucleating agent, 0.05-1.0 part of an antioxidant and 0.5-2 parts of a hydrolysis resistant agent. The method has the advantages of simple process, high processing efficiency and easy operation, adopts the toughening agent and the nucleating agent to cooperatively modify the polylactic acid, improves the toughness of the polylactic acid, simultaneously has the heat resistance of the polylactic acid material, and can greatly improve the toughness and the heat resistance of the polylactic acid. The use of the organic nucleating agent and the inorganic nucleating agent can improve the crystallization speed of the polymer, change the size of spherulites, obviously improve the thermal deformation temperature of the polymer and meet the application of products when the polymer is melted and crystallized, the use of the in-mold crystallization in the injection molding process of the products improves the surface gloss of the products, and the use of the crystallization nucleating agent can further promote the perfect crystallization and ensure that the products have higher strength and surface gloss.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a polylactic acid toughening and heat-resisting composite material and a manufacturing method of a product thereof.
Background
The traditional porcelain-like tableware, also called melamine tableware, is made of amino molding plastic. The melamine formaldehyde resin is prepared by reacting melamine and formaldehyde under certain conditions, and then adding auxiliary materials such as a curing agent, cellulose, a coloring agent and the like. The material is molded and pressed to obtain the imitation tableware. The tableware product made of the porcelain-like tableware material is firm, has a flat surface, is resistant to high temperature and water impact, is not easy to break, has the characteristic of ceramic texture, becomes one of indispensable materials for manufacturing the tableware at present, is widely applied to restaurants, restaurants and student canteens in particular, and is a product with the advantages of export characteristics in China. In recent years, along with the improvement of the requirement of domestic and foreign environment protection technology on tableware, the porcelain-like tableware made of the material mainly has the following defects: firstly, the residual melamine and formaldehyde monomers of tableware affect the sanitation and health; secondly, the problem of toxicity released by melamine when the tableware is heated in a microwave oven is solved; thirdly, the tableware can not be degraded and thermoplastically processed and utilized after being discarded. The three problems restrict the development of porcelain-like tableware. Therefore, the development of a novel environment-friendly porcelain-like tableware material has practical significance in overcoming the defects of the technology applied to the existing porcelain-like tableware.
Polylactic acid is a biodegradable resin, which is prepared by polycondensation of lactic acid or ring-opening polymerization of lactic acid dimer-lactide, using lactic acid as a monomer. Polylactic acid is a polymer with excellent biocompatibility and biodegradability, is derived from renewable resource crops, has the most prominent advantages of biodegradability, can be completely decomposed by natural microorganisms, finally generates carbon dioxide and water, and does not pollute the environment. But the direct utilization of the alloy has the disadvantages of poor temperature resistance, and unsatisfactory strength and toughness. Because the common polylactic acid has the heat distortion temperature of below 60 ℃, the application of the polylactic acid in porcelain-like tableware is limited due to the defects of relatively low density and poor porcelain-like toughness.
Disclosure of Invention
The invention provides high-temperature-resistant polylactic acid injection molding porcelain-like tableware and a preparation method thereof, and aims to solve the problems of insecurity and environmental pollution of porcelain-like tableware.
The technical scheme adopted by the invention is as follows: the feed is prepared from the following raw materials in parts by mass:
70-90 parts of polylactic acid, 5-15 parts of a toughening agent, 0.05-0.20 part of a chain extender, 0.5-1 part of an organic nucleating agent, 5-20 parts of an inorganic nucleating agent, 0.05-1.0 part of an antioxidant and 0.5-2 parts of a hydrolysis resistant agent;
the polylactic acid is a mixed type polylactic acid, 95.75 percent of polylactic acid, 4.25 percent of polylactic acid, 10-20 ten thousand of polylactic acid number average molecular weight and 6g/10min of melt index.
The toughening agent is one or more of glycidyl methacrylate grafted ethylene-octene copolymer (POE-GMA), polybutylene adipate terephthalate (PBAT), thermoplastic polyurethane elastomer (TPU) and carbon dioxide based thermoplastic polyurethane elastomer (PPCU).
The chain extender is ADR-4370 of Bassfu company.
The organic nucleating agent is one or more of hydrazide nucleating Agent (ADH), polyamide (TMC), aromatic sulfonic acid ester derivative (LAK-301) and zinc phenyl phosphate (PPZn).
The inorganic nucleating agent is one or more of talcum powder, calcium carbonate, montmorillonite and silicon dioxide.
The antioxidant is one or two of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite.
The hydrolysis-resistant agent is polycarbodiimide.
A preparation method of high-temperature-resistant polylactic acid injection molding porcelain-like tableware comprises the following steps:
1) drying the raw materials, adding the dried raw materials into a high-speed mixer for mixing, and uniformly stirring;
2) extruding and granulating the raw materials in the mixer through a double-screw extruder;
3) drying and dehumidifying the polylactic acid modified material, and then performing injection molding on the polylactic acid modified material by using an injection molding machine mold.
The length-diameter ratio of screws of the double-screw-based extruder is 35-45: 1, the melt blending temperature is 150-190 ℃.
The method has the advantages of simple process, high processing efficiency and easy operation, adopts the toughening agent and the nucleating agent to cooperatively modify the polylactic acid, improves the toughness of the polylactic acid, simultaneously has the heat resistance of the polylactic acid material, and can greatly improve the toughness and the heat resistance of the polylactic acid. The use of the organic nucleating agent and the inorganic nucleating agent can improve the crystallization speed of the polymer, change the size of spherulites, obviously improve the thermal deformation temperature of the polymer and meet the application of products when the polymer is melted and crystallized, the use of the in-mold crystallization in the injection molding process of the products improves the surface gloss of the products, and the use of the crystallization nucleating agent can further promote the perfect crystallization and ensure that the products have higher strength and surface gloss.
The invention can partially replace the existing ceramic-like tableware in the market, in particular to heat-resistant tableware with the heat distortion temperature of more than 120 ℃. Because of the large use of non-renewable petroleum resources of the traditional high molecular materials, and the environmental pollution of the wastes is serious. The invention leads polylactic acid material products to enter the daily application field and replace most of the traditional petroleum-based plastic products.
Detailed Description
Example 1
Weighing the following raw materials in parts by weight:
70 parts of polylactic acid, 5 parts of toughening agent, 0.05 part of chain extender, 0.5 part of organic nucleating agent, 5 parts of inorganic nucleating agent, 0.05 part of antioxidant and 0.5 part of hydrolysis resistant agent; wherein:
the polylactic acid is mixed polylactic acid, the polylactic acid accounts for 95.75 percent, the polylactic acid accounts for 4.25 percent, the number average molecular weight of the polylactic acid is 10-20 ten thousand, and the melt index is 6g/10 min;
the toughening agent is glycidyl methacrylate grafted ethylene-octene copolymer (POE-GMA);
the chain extender is ADR-4370 of Basff company;
the organic nucleating agent is hydrazide nucleating Agent (ADH);
the inorganic nucleating agent is talcum powder;
the antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
the hydrolysis resistant agent is polycarbodiimide;
the raw materials are added into a high-speed mixer for mixing, the uniformly mixed materials are transferred to a double-screw extruder for immediately melting and blending, and the length-diameter ratio of screws of the screw extruder is 35: 1, sequentially heating each zone of the equipment at 150 ℃, 165 ℃, 172 ℃, 173 ℃, 185 ℃, 180 ℃ and 160 ℃, then extruding and bracing, water cooling, moisture absorption and grain cutting to obtain a granular composite material, drying and then hermetically storing to prevent moisture; and (5) injection molding of the injection molding machine.
Example 2
Weighing the following raw materials in parts by weight:
80 parts of polylactic acid, 10 parts of toughening agent, 0.12 part of chain extender, 0.8 part of organic nucleating agent, 12 parts of inorganic nucleating agent, 0.08 part of antioxidant and 1.2 parts of hydrolysis resistant agent;
the polylactic acid is mixed polylactic acid, the polylactic acid accounts for 95.75 percent, the polylactic acid accounts for 4.25 percent, the number average molecular weight of the polylactic acid is 10 to 20 ten thousand, the melt index is 6g/10min,
the toughening agent is polybutylene adipate terephthalate (PBAT) and a thermoplastic polyurethane elastomer (TPU);
the chain extender is ADR-4370 available from Basff.
The organic nucleating agent is polyamide (TMC), aromatic sulfonic acid ester derivative (LAK-301);
the inorganic nucleating agent is calcium carbonate and montmorillonite;
the antioxidant is phosphorous acid tri (2, 4-di-tert-butylphenyl) ester;
the hydrolysis-resistant agent is polycarbodiimide;
the raw materials are added into a high-speed mixer for mixing, the uniformly mixed materials are transferred to a double-screw extruder for immediately melting and blending, and the length-diameter ratio of screws of the screw extruder is 40: 1, sequentially heating the equipment zones at 150 ℃, 165 ℃, 172 ℃, 173 ℃, 185 ℃, 180 ℃ and 160 ℃, then extruding and bracing, water cooling, moisture absorption and grain cutting to obtain the granular composite material, drying, then hermetically storing to prevent from being affected with damp, and carrying out injection molding by using an injection molding machine.
Example 3
Weighing the following raw materials in parts by weight:
90 parts of polylactic acid, 15 parts of toughening agent, 0.20 part of chain extender, 1 part of organic nucleating agent, 20 parts of inorganic nucleating agent, 1.0 part of antioxidant and 2 parts of hydrolytic resistance agent;
the polylactic acid is mixed polylactic acid, the polylactic acid accounts for 95.75 percent, the polylactic acid accounts for 4.25 percent, the number average molecular weight of the polylactic acid is 10-20 ten thousand, and the melt index is 6g/10 min;
the toughening agent is glycidyl methacrylate grafted ethylene-octene copolymer, thermoplastic polyurethane elastomer and carbon dioxide-based thermoplastic polyurethane elastomer;
the chain extender is ADR-4370 of Basff company;
the organic nucleating agent is hydrazide nucleating Agent (ADH), polyamide (TMC) and zinc phenylphosphate (PPZn);
the inorganic nucleating agent is talcum powder, calcium carbonate and silicon dioxide;
the antioxidant is phosphorous acid tri (2, 4-di-tert-butylphenyl) ester;
the hydrolysis resistant agent is polycarbodiimide;
the raw materials are added into a high-speed mixer for mixing, the uniformly mixed materials are transferred to a double-screw extruder for immediately melting and blending, and the length-diameter ratio of screws of the screw extruder is 40: 1, sequentially heating the equipment zones at 150 ℃, 165 ℃, 172 ℃, 173 ℃, 185 ℃, 180 ℃ and 160 ℃, then extruding and bracing, water cooling, moisture absorption and grain cutting to obtain the granular composite material, drying, then hermetically storing to prevent from being affected with damp, and carrying out injection molding by using an injection molding machine.
Comparative example:
and drying to obtain the polylactic acid, namely Natureworks 4032D and LD mixed polylactic acid.
The preparation method of the polylactic acid porcelain-like tableware comprises the following steps: the polylactic acid modified material obtained in the examples 1 to 3 was injection molded in an injection mold, the temperature of the injection mold was 130 ℃, the crystallization time in the mold was 150 seconds, and the heating and temperature adjustment of the injection mold were performed using a heat-conductive oil type mold temperature controller.
Respectively adding the polylactic acid modified material obtained in the examples 1-3 and the polylactic acid raw material of the comparative example into an injection molding machine for injection molding to obtain a tensile sample strip and a bending sample strip, wherein the injection molding zone temperature is 180-190 ℃, the heat resistance, the tensile strength and the notch impact strength are tested according to GB/T1634.2-2004, GB1040-2006 and ISO180-06/2001, and the test results are shown in the following table:
| test index | Example 1 | Example 2 | Example 3 | Comparative example |
| Heat distortion temperature,. degree.C | 88.54 | 139.25 | 121.88 | 58 |
| Tensile strength, MPa | 49.84 | 62.28 | 55.46 | 65.5 |
| Impact strength, KJ/m | 31.28 | 9.23 | 3.77 | 3.65 |
| Melt index, g/10min | 8.68 | 16.52 | 12.49 | 4.95 |
As can be seen from the table, the polylactic acid porcelain imitating tableware has high temperature resistance, excellent shock resistance and excellent processing performance.
Claims (10)
1. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware is characterized by being prepared from the following raw materials in parts by mass: 70-90 parts of polylactic acid, 5-15 parts of a toughening agent, 0.05-0.20 part of a chain extender, 0.5-1 part of an organic nucleating agent, 5-20 parts of an inorganic nucleating agent, 0.05-1.0 part of an antioxidant and 0.5-2 parts of a hydrolysis resistant agent.
2. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 1, wherein: the polylactic acid is a mixed polylactic acid, the polylactic acid is 95.75 percent, the polylactic acid is 4.25 percent, the number average molecular weight of the polylactic acid is 10-20 ten thousand, and the melt index is 6g/10 min.
3. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 1, wherein: the toughening agent is one or more of glycidyl methacrylate grafted ethylene-octene copolymer (POE-GMA), polybutylene adipate terephthalate (PBAT), thermoplastic polyurethane elastomer (TPU) and carbon dioxide based thermoplastic polyurethane elastomer (PPCU).
4. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 1, wherein: the chain extender is ADR-4370 of Bassfu company.
5. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 1, wherein: the organic nucleating agent is one or more of hydrazide nucleating Agent (ADH), polyamide (TMC), aromatic sulfonic acid ester derivative (LAK-301) and zinc phenyl phosphate (PPZn).
6. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 1, wherein: the inorganic nucleating agent is one or more of talcum powder, calcium carbonate, montmorillonite and silicon dioxide.
7. The high temperature resistant polylactic acid injection molding porcelain imitating tableware according to claim 1, wherein the antioxidant is one or two of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite.
8. The high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 1, wherein: the hydrolysis-resistant agent is polycarbodiimide.
9. The preparation method of the high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claims 1 to 8, which comprises the following steps:
1) drying the raw materials, adding the dried raw materials into a high-speed mixer for mixing, and uniformly stirring;
2) extruding and granulating the raw materials in the mixer through a double-screw extruder;
3) drying and dehumidifying the polylactic acid modified material, and then performing injection molding on the polylactic acid modified material by using an injection molding machine mold.
10. The method for preparing the high-temperature-resistant polylactic acid injection-molded porcelain-like tableware according to claim 9, wherein the method comprises the following steps: the length-diameter ratio of a screw of the double-screw-based extruder is 35-45: 1, the melt blending temperature is 150-190 ℃.
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| CN111690240A (en) * | 2020-06-23 | 2020-09-22 | 南宁学院 | Polylactic acid/nano cellulose composite material and preparation method thereof |
| CN111978696A (en) * | 2020-08-17 | 2020-11-24 | 咖法科技(上海)有限公司 | Tea leaf residue polylactic acid and preparation method thereof |
| CN111995848A (en) * | 2020-08-13 | 2020-11-27 | 联泓(江苏)新材料研究院有限公司 | Degradable plastic composition and preparation method and application thereof |
| CN112852178A (en) * | 2020-12-23 | 2021-05-28 | 张文俊 | Noctilucent plastic injection molding part |
| CN113185820A (en) * | 2021-04-29 | 2021-07-30 | 赵若飞 | Degradable packaging material, packaging film bag and preparation method |
| CN113684557A (en) * | 2021-08-26 | 2021-11-23 | 海南赛诺实业有限公司 | Polylactic acid melt-spraying material and preparation method and application thereof |
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| CN111690240A (en) * | 2020-06-23 | 2020-09-22 | 南宁学院 | Polylactic acid/nano cellulose composite material and preparation method thereof |
| CN111995848A (en) * | 2020-08-13 | 2020-11-27 | 联泓(江苏)新材料研究院有限公司 | Degradable plastic composition and preparation method and application thereof |
| CN111978696A (en) * | 2020-08-17 | 2020-11-24 | 咖法科技(上海)有限公司 | Tea leaf residue polylactic acid and preparation method thereof |
| CN112852178A (en) * | 2020-12-23 | 2021-05-28 | 张文俊 | Noctilucent plastic injection molding part |
| CN113185820A (en) * | 2021-04-29 | 2021-07-30 | 赵若飞 | Degradable packaging material, packaging film bag and preparation method |
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Application publication date: 20200428 |