CN113337090B - Heat-resistant modified polylactic acid material and preparation method and application thereof - Google Patents
Heat-resistant modified polylactic acid material and preparation method and application thereof Download PDFInfo
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Abstract
A heat-resistant modified polylactic acid material and a preparation method and application thereof. The heat-resistant modified polylactic acid material has a repeating unit structure of a linear structure copolymerized by polylactic acid molecules and polyglycolide molecules, and the end group of the heat-resistant modified polylactic acid material is an unsaturated grease alcoholysis product; the heat-resistant modified polylactic acid material is formed by block copolymerization of polylactic acid molecular chains and polyglycolide molecular chains, wherein the mass fraction of the unsaturated oil is 0.8-2.3 wt%. The heat-resistant modified polylactic acid material has the advantages of strong brittleness resistance, high toughness, high temperature resistance, high biodegradation rate, low hygroscopicity and the like; the preparation method is simple and convenient to operate, does not discharge harmful substances, and is green and environment-friendly. Is especially suitable for manufacturing fast food boxes and flip-button beverage cup covers.
Description
Technical Field
The invention relates to a modified polylactic acid material, in particular to a heat-resistant modified polylactic acid material and a preparation method and application thereof.
Background
In recent years, people realize that white pollution has seriously influenced ecological balance, and the trend of adopting degradable plastics to replace non-degradable plastics is a development trend.
Currently, degradable plastics include PLA, PBAT, PBS. In particular, materials such as PLA and the like have good strength and rigidity, and are widely applied to the fields of disposable cup lids, lunch boxes and the like as ideal materials for replacing PP.
Because a lunch box (such as a hotel snack box) needs to have good high temperature resistance to avoid high temperature softening and water resistance, compared with a PP material, the PLA material commonly used at present has the defects of poor heat resistance temperature, poor toughness and the like.
N101602884A discloses a heat-resistant polylactic acid composite material and a preparation method thereof in 2009, on day 12 and 16, a nucleating agent is adopted to modify polylactic acid, so that the crystallization speed is increased, the crystallinity is increased, the heat resistance is improved, but the toughness of the material is reduced, and the situation with high requirement on the toughness cannot be met.
CN111875940A discloses a toughened heat-resistant polylactic acid 3D printing wire and a preparation method thereof in 11/3/2020, the polylactic acid is modified by adding cellulose and crosslinking, the heat resistance and toughness are greatly improved, but the cellulose absorbs moisture and is not suitable for manufacturing lunch boxes and other occasions with water, and the crosslinking also limits the re-processing and utilization of the material.
CN102906193A discloses a toughened polylactic acid containing polyhydroxyalkanoate in 2013, 1 month and 30 days, and the polylactic acid is subjected to blending or copolymerization modification by using polyhydroxyalkanoate to improve the toughness of the polylactic acid, but the introduction of polyhydroxyalkanoate reduces the heat-resistant temperature of the material and the rigidity of the material.
Therefore, how to provide a modified polylactic acid material with high toughness, high temperature resistance, high biodegradation rate, strong brittleness resistance and low hygroscopicity is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems that the modified polylactic acid material in the prior art is easy to be brittle, low in toughness, or not high in temperature resistance, or low in biodegradability, and is influenced by water absorption in a humid environment, and provides the heat-resistant modified polylactic acid material which is strong in brittleness resistance, high in toughness, high in temperature resistance and high in biodegradation rate.
The invention further aims to solve the technical problem of providing a preparation method of the heat-resistant modified polylactic acid material.
The technical scheme adopted for solving the technical problems is that the heat-resistant modified polylactic acid material has a repeating unit structure of a linear structure formed by copolymerizing polylactic acid resin molecules and polyglycolide molecules, and the end group is an unsaturated grease alcoholysis product;
the modified polylactic acid material is formed by block copolymerization of polylactic acid molecular chains and polyglycolide molecular chains, wherein the mass fraction of the unsaturated oil is 0.8-2.3 wt%.
Further, the content of the polyglycolide is 5 to 13 wt%.
Further, the content of the polyglycolide is 6 to 12 wt%.
Further, the content of the polyglycolide is 7 to 11 wt%.
Further, the content of the polyglycolide is 8 to 10 wt%.
Further, specifically, the upper limit of the content of the polyglycolide is selected from one of 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, and 13 wt%; the lower limit of the content of the polyglycolide is selected from one of 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 1 wt%.
Further, the mass fraction of the unsaturated oil is 0.5-1.3 wt%.
Further, the mass fraction of the unsaturated oil is 0.6-1.2 wt%.
Further, the mass fraction of the unsaturated oil is 0.7-1.1 wt%.
Further, the mass fraction of the unsaturated oil is 0.8-1.0 wt%.
Further, specifically, the upper limit of the mass fraction of the unsaturated oil-and-fat is selected from one of 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, and 1.3 wt%; the lower limit of the mass fraction of the unsaturated oil is selected from one of 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt% and 1.2 wt%.
Further, the molecular weight range of the heat-resistant modified polylactic acid material is 150000 to 200000.
Further, the molecular weight range of the heat-resistant modified polylactic acid material is 160000 to 190000.
Further, the molecular weight range of the heat-resistant modified polylactic acid material is 170000 to 180000.
Further, specifically, the upper limit of the molecular weight of the heat-resistant modified polylactic acid material is selected from 160000, 170000, 180000, 190000 and 200000; the lower limit of the molecular weight of the heat-resistant modified polylactic acid material is selected from 150000, 160000, 170000, 180000 and 190000.
Further, the melt index of the polylactic resin is 20-40g/min.
Further, the melt index of the polylactic resin is 25-35g/min.
Further, specifically, the upper limit of the melt index of the polylactic acid resin is selected from 25g/min, 30g/min, 35g/min and 40g/min; the lower limit of the melt index of the polylactic acid resin is selected from 20g/min, 25g/min, 30g/min and 35g/min.
Further, the relative molecular weight of the polyglycolide is 100000 to 300000.
Further, the polyglycolide has a relative molecular weight of 150000 to 250000.
Further, the relative molecular weight of the polyglycolide is 200000.
Further, the unsaturated oil is at least one selected from castor oil, linseed oil and tung oil.
The invention further solves the technical problems by adopting the technical scheme that the preparation method of the heat-resistant modified polylactic acid material adopts a mode of modifying polylactic acid by polyglycolide and unsaturated grease, is prepared from raw materials of polyglycolide, polyisocyanate, unsaturated grease, polyalcohol, polylactic acid resin and nucleating agent, and specifically comprises the following steps:
(1) Dividing polyisocyanate into two parts, uniformly mixing polyglycolide and one part of polyisocyanate, and reacting for 1-3h under the conditions that the temperature is 50-60 ℃ and the stirring speed is 50-100r/min to obtain a material A;
(2) Uniformly mixing unsaturated grease and polyol, reacting for 0.5-2h at the temperature of 240-250 ℃ and the stirring speed of 50-100r/min, adding another part of polyisocyanate after the reaction is finished, uniformly mixing, and reacting for 1-3h at the temperature of 50-60 ℃ and the stirring speed of 50-100r/min to obtain a material B;
(3) Uniformly mixing polylactic resin, a nucleating agent, a material A and a material B, then putting the mixture into an internal mixer, carrying out internal mixing treatment for 10-30min at the temperature of 230-240 ℃, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out grain cutting treatment in sequence to obtain the heat-resistant modified polylactic acid material.
Further, the preparation method of the heat-resistant modified polylactic acid material comprises the following raw materials in parts by weight:
100 parts of polylactic resin;
5-15 parts of polyglycolide;
0.5-1.5 parts of unsaturated oil;
0.15-0.25 part of polyol;
3-10 parts of polyisocyanate;
0.2 to 0.5 portion of nucleating agent.
Further, the polyhydric alcohol is at least one selected from the group consisting of ethylene glycol, butylene glycol, glycerol, and pentaerythritol.
Further, the polyisocyanate is selected from at least one of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.
Further, the nucleating agent is selected from at least one of an organic nucleating agent and an inorganic nucleating agent.
Preferably, the organic nucleating agent is selected from one or more of amide compounds, hydrazide compounds, metal phosphate compounds and organic carboxylic acid derivative compounds.
Preferably, the amide compound is at least one selected from the group consisting of Ethylene Bis Stearamide (EBS), ethylene Bis Hydroxystearamide (EBH), 1,3, 5-benzenetricarboxylamide.
Preferably, the hydrazide compound is selected from at least one of dibenzoylhydrazide malonate (N-4), TMC-300 and CHC-300.
Preferably, the metal phosphate compound is at least one selected from zinc phenylphosphate (PPZn), calcium phenylphosphate (PPCa), and barium phenylphosphate (PPBa).
Preferably, the organic carboxylic acid derivative is selected from at least one of sodium 2-chlorobenzoate, aluminum tert-butylbenzoate and aluminum hydroxy-tert-butylbenzoate.
Preferably, the inorganic nucleating agent is selected from at least one of talcum powder, montmorillonite, halloysite and attapulgite.
Preferably, the temperature of the mixing reaction is 230 to 240 ℃.
The heat-resistant modified polylactic acid material is particularly suitable for manufacturing disposable lunch boxes and flip-button beverage cup covers. The disposable lunch box and the flip-button beverage cup cover can resist the temperature of 110-130 ℃.
Compared with the prior art, the invention has the following advantages:
(1) The glycolide is introduced into the heat-resistant modified polylactic acid material, the ester bond density is increased in a molecular chain, the crystallization speed is accelerated, and the Tg is increased, so that the heat resistance of the polylactic acid material is improved.
(2) The heat-resistant modified polylactic acid material accelerates the oxidative degradation rate thereof by introducing unsaturated bonds into molecules, and can completely meet the biodegradation rate required by national standards.
(3) Due to the introduction of the polyglycolide and the alcoholysis product of the unsaturated fat, the polyglycolide and the alcoholysis product of the unsaturated fat have synergistic effect, so that the heat-resistant modified polylactic acid material disclosed by the invention has the advantages of high toughness, high temperature resistance, high biodegradation rate, low hygroscopicity and the like. Because of high toughness, the brittleness resistance is also strong.
(4) The preparation method of the heat-resistant modified polylactic acid material is simple and convenient to operate, green and environment-friendly, does not discharge harmful substances, and has high strength at the temperature of 110 ℃.
The heat-resistant modified polylactic acid material is particularly suitable for manufacturing disposable lunch boxes (such as hotel snack boxes, aviation snack boxes and the like) and flip-button beverage cup covers, wherein the food needs to be stored at high temperature.
Detailed Description
The present invention will be described in further detail with reference to examples.
The raw material materials in the examples of the present application are commercially available.
Example 1
The heat-resistant modified polylactic acid material of the embodiment is prepared from 5 kg of polyglycolide, 3.0 kg of toluene diisocyanate,
0.5 kg of castor oil, 0.15 kg of butanediol, 0.3 kg of toluene diisocyanate, 100 kg of polylactic resin and 0.5 kg of nucleating agent ethylene bis stearamide.
The preparation method comprises the following steps:
(1) Dividing toluene diisocyanate into 2.7 kg and 0.3 kg, uniformly mixing 5 kg of polyglycolide and 2.7 kg of toluene diisocyanate, and reacting for 3h at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material A;
(2) Uniformly mixing 0.5 kg of castor oil and 0.15 kg of butanediol, reacting for 2h at the temperature of 240 ℃ and the stirring speed of 80r/min, adding 0.3 kg of toluene diisocyanate after the reaction is finished, uniformly mixing, and reacting for 3h at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material B;
(3) Uniformly mixing 100 kg of polylactic acid resin, 0.5 kg of nucleating agent ethylene bis stearamide, the material A obtained in the step (1) and the material B obtained in the step (2), putting the mixture into an internal mixer, carrying out internal mixing treatment at 240 ℃ for 30min, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out grain-sized dicing treatment in sequence to obtain the modified polylactic acid material.
The melt index of the polylactic resin is 20g/10min.
The relative molecular weight of the polyglycolide was 150000.
Example 2
The heat-resistant modified polylactic acid material of the embodiment is prepared from 10 kg of polyglycolide, 6 kg of isophorone diisocyanate, 1 kg of linseed oil, 0.2 kg of glycerol, 100 kg of polylactic acid resin and 0.3 kg of nucleating agent, namely, dibenzoylhydrazide TMC-300.
The preparation method comprises the following steps:
(1) Dividing isophorone diisocyanate into 5.4 kg and 0.6 kg, uniformly mixing 10 kg of polyglycolide and 5.4 kg of isophorone diisocyanate, and reacting for 3 hours at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material A;
(2) Uniformly mixing 1 kg of linseed oil and 0.2 kg of glycerol, reacting for 2h at the temperature of 250 ℃ and the stirring speed of 80r/min, adding 0.6 kg of isophorone diisocyanate after the reaction is finished, uniformly mixing, and reacting for 3h at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material B;
(3) Uniformly mixing 100 kg of polylactic acid resin, 0.3 kg of nucleating agent dibenzoylhydrazine malonate TMC-300, the material A and the material B, then putting the mixture into an internal mixer, carrying out internal mixing treatment for 30min at the temperature of 240 ℃, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out granulation treatment in sequence to obtain the modified polylactic acid material.
The melt index of the polylactic resin is 30g/10min.
The relative molecular weight of the polyglycolide is 200000.
Example 3
The heat-resistant modified polylactic acid material of the embodiment is prepared from 15 kg of polyglycolide, 10 kg of diphenylmethane diisocyanate, 1.5 kg of tung oil, 0.25 kg of ethylene glycol, 100 kg of polylactic resin and 0.4 kg of nucleating agent talcum powder.
The preparation method comprises the following steps:
(1) Dividing diphenylmethane diisocyanate into 9 kg and 1 kg, uniformly mixing 15 kg of polyglycolide and 9 kg of diphenylmethane diisocyanate, and reacting for 3h at the conditions of 60 ℃ and 80r/min of stirring speed to obtain a material A;
(2) Uniformly mixing 1.5 kg of tung oil and 0.25 kg of ethylene glycol, reacting for 2h at the temperature of 250 ℃ and the stirring speed of 80r/min, adding 1 kg of diphenylmethane diisocyanate after the reaction is finished, uniformly mixing, and reacting for 3h at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material B;
(3) Uniformly mixing 100 kg of polylactic acid resin, 0.4 kg of nucleating agent talcum powder, material A and material B, then putting the mixture into an internal mixer, carrying out internal mixing treatment at 240 ℃ for 30min, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out grain cutting treatment in sequence to obtain the modified polylactic acid material.
The melt index of the polylactic resin is 40g/10min.
The polyglycolide has a relative molecular weight of 250000.
Comparative example 1
The difference from the starting material used in example 3 is that: the procedure of example 3 was followed, except that the amount of diphenylmethane diisocyanate used was reduced by 10% and that unsaturated oils, tung oil and polyhydric alcohol, ethylene glycol, were not used.
The preparation method comprises the following steps:
(1) Uniformly mixing 15 kg of polyglycolide and 9 kg of diphenylmethane diisocyanate, and reacting for 3h at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material A;
(2) Uniformly mixing 100 kg of polylactic acid resin, 0.4 kg of nucleating agent talcum powder and material A, then putting the mixture into an internal mixer, carrying out internal mixing treatment for 30min at the temperature of 240 ℃, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out grain cutting treatment in sequence to obtain the modified polylactic acid material.
The melt index of the polylactic resin is 40g/10min.
The polyglycolide has a relative molecular weight of 250000.
Comparative example 2
The difference from the starting material used in example 3 is that: the usage amount of the diphenylmethane diisocyanate is reduced by 90 percent, and polyglycolide is not used; the same as in example 3.
The preparation method comprises the following steps:
(1) Uniformly mixing 1.5 kg of tung oil and 0.25 kg of ethylene glycol, reacting for 2h at the temperature of 250 ℃ and the stirring speed of 80r/min, adding 1 kg of diphenylmethane diisocyanate after the reaction is finished, uniformly mixing, and reacting for 3h at the temperature of 60 ℃ and the stirring speed of 80r/min to obtain a material A;
(2) Uniformly mixing 100 kg of polylactic acid resin, 0.5 kg of nucleating agent and the material A, then putting the mixture into an internal mixer, carrying out internal mixing treatment for 30min at the temperature of 240 ℃, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out grain cutting treatment in sequence to obtain the modified polylactic acid material.
The melt index of the polylactic resin is 40g/10min.
Comparative example 3
The difference from the starting material used in example 3 is that: the same procedure as in example 3 was repeated except that polyglycolide, unsaturated oil tung oil, polyol ethylene glycol and polyisocyanate were not used.
The preparation method comprises the following steps:
uniformly mixing 100 parts of polylactic resin and 0.5 part of nucleating agent talcum powder, then putting the mixture into an internal mixer, carrying out internal mixing treatment for 30min at the temperature of 240 ℃, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then granulating treatment in sequence to obtain the modified polylactic acid material.
The melt index of the polylactic resin is 40g/10min.
The performance of the material products of examples 1 to 3 and the material products of comparative examples 1 to 3 is tested:
the thermal deformation temperature of the material product is detected according to a method specified in national standard GB/T1634.1-2004, the impact strength of a simply supported beam notch of the material product is detected according to a method specified in national standard GB/T1034-2008, the bending strength of the material product is detected according to a method specified in national standard GB/T9341-2008, and the biodegradation rate of the material product is detected according to a method specified in national standard GB/T20197-2006, and the result is shown in Table 1.
TABLE 1 Performance test data for the materials of examples 1-3 and comparative examples 1-3
As shown in Table 1, compared with the performances of comparative examples 2 and 3, the products of examples 1, 2 and 3 have greatly improved impact strength, obviously improved heat distortion temperature and greatly improved bending strength, which indicates that the introduction of polyglycolide greatly improves the brittleness resistance, toughness and high temperature resistance of the material.
Therefore, the heat-resistant modified polylactic acid material has high biodegradation rate, good toughness, high strength and greatly improved high-temperature resistance by introducing polyglycolide and an unsaturated oil alcoholysis product. Can be widely used for manufacturing food boxes (such as hotel snack boxes, aviation snack boxes and the like) of which the food needs to be stored at high temperature.
It should be understood that the above-mentioned embodiments are only illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the claims of the present application. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (16)
1. A heat-resistant modified polylactic acid material is characterized in that the structure of a repeating unit is a linear structure of polylactic acid resin molecules and polyglycolide molecules, and the end group is an unsaturated grease alcoholysis product;
the heat-resistant modified polylactic acid material is formed by block copolymerization of polylactic acid resin molecular chains and polyglycolide molecular chains, wherein the mass fraction of the unsaturated oil is 0.8-2.3 wt%;
the molecular weight is 150000 to 200000;
the melt index of the polylactic resin is 15-40g/min;
the unsaturated oil is at least one selected from castor oil, linseed oil and tung oil.
2. The preparation method of the heat-resistant modified polylactic acid material according to claim 1, wherein the polylactic acid resin is modified by polyglycolide and unsaturated fat, and is prepared from polyglycolide, polyisocyanate, unsaturated fat, polyol and polylactic acid resin as raw materials, and the preparation method specifically comprises the following steps:
(1) Dividing polyisocyanate into two parts, uniformly mixing polyglycolide and one part of polyisocyanate, and reacting for 1-3h under the conditions that the temperature is 50-60 ℃ and the stirring speed is 50-100r/min to obtain a material A;
(2) Uniformly mixing unsaturated oil and polyol, reacting for 0.5-2h at the temperature of 240-250 ℃ and at the stirring speed of 50-100r/min, adding another part of polyisocyanate after the reaction is finished, uniformly mixing, and reacting for 1-3h at the temperature of 50-60 ℃ and at the stirring speed of 50-100r/min to obtain a material B;
(3) Uniformly mixing polylactic acid resin, a nucleating agent, a material A and a material B, then putting the mixture into an internal mixer, carrying out internal mixing treatment for 10-30min at the temperature of 80-100 ℃, putting the mixture into a double-screw extruder after the internal mixing treatment, and carrying out mixing reaction, extrusion treatment, bracing treatment, cooling and then carrying out grain cutting treatment in sequence to obtain the modified polylactic acid material;
the temperature of the kneading reaction is preferably 200 to 210 ℃.
3. The preparation method of the heat-resistant modified polylactic acid material according to claim 2, wherein the weight parts of the raw materials are as follows:
100 parts of polylactic resin;
5-15 parts of polyglycolide;
0.5-1.5 parts of unsaturated oil;
0.15-0.25 part of polyol;
3-10 parts of polyisocyanate;
0.2 to 0.5 portion of nucleating agent.
4. The method for preparing a heat-resistant modified polylactic acid material according to claim 2 or 3, wherein the polyglycolide has a relative molecular weight of 10000 to 20000; the polyhydric alcohol is at least one selected from ethylene glycol, butanediol, glycerol and pentaerythritol.
5. The method for preparing the heat-resistant modified polylactic acid material according to claim 2 or 3, wherein the polyisocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
6. The method for preparing a heat-resistant modified polylactic acid material according to claim 4, wherein the polyisocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.
7. The method for preparing the heat-resistant modified polylactic acid material according to claim 2 or 3, wherein the nucleating agent is at least one selected from an organic nucleating agent and an inorganic nucleating agent.
8. The method for preparing the heat-resistant modified polylactic acid material according to claim 4, wherein the nucleating agent is at least one selected from the group consisting of organic nucleating agents and inorganic nucleating agents.
9. The method for preparing the heat-resistant modified polylactic acid material according to claim 5, wherein the nucleating agent is at least one selected from the group consisting of organic nucleating agents and inorganic nucleating agents.
10. The method for preparing the heat-resistant modified polylactic acid material according to claim 7, wherein the organic nucleating agent is one or more selected from amide compounds, hydrazide compounds, metal phosphate compounds and organic carboxylic acid derivatives.
11. The method for preparing a heat-resistant modified polylactic acid material according to claim 10, wherein the amide compound is at least one selected from the group consisting of ethylene bis stearamide, ethylene hydroxy bis stearamide, and 1,3, 5-benzenetricarboxylic acid amide.
12. The method for preparing the heat-resistant modified polylactic acid material according to claim 10, wherein the hydrazide compound is at least one selected from the group consisting of dibenzoylhydrazide malonate, TMC-300 and CHC-300.
13. The method for preparing a heat-resistant modified polylactic acid material according to claim 10, wherein the metal phosphate compound is at least one selected from zinc phenylphosphate, calcium phenylphosphate and barium phenylphosphate.
14. The method for preparing the heat-resistant modified polylactic acid material according to claim 10, wherein the organic carboxylic acid derivative is at least one selected from sodium 2-chlorobenzoate, aluminum tert-butylbenzoate, and aluminum hydroxy-p-tert-butylbenzoate.
15. The method for preparing the heat-resistant modified polylactic acid material according to claim 9, wherein the inorganic nucleating agent is at least one selected from the group consisting of talc, montmorillonite, halloysite and attapulgite.
16. The use of the heat-resistant modified polylactic acid material of claim 1 in the preparation of disposable lunch boxes and flip-top beverage cup lids.
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| JP2011089084A (en) * | 2009-10-26 | 2011-05-06 | Taiyo Kagaku Co Ltd | Polylactic acid-based resin composition and molding formed of the same |
| CN106751610A (en) * | 2016-12-08 | 2017-05-31 | 吉林中粮生化有限公司 | A kind of PLA porcelain imitation material and preparation method thereof |
| CN112080115A (en) * | 2020-09-25 | 2020-12-15 | 湖南钜亿新材料科技有限公司 | High-toughness polylactic acid composite material for environment-friendly tableware and preparation method thereof |
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2021
- 2021-05-28 CN CN202110593373.4A patent/CN113337090B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100505A (en) * | 2007-08-02 | 2008-01-09 | 同济大学 | Method for preparing polylactic acid-polycarbonate copolymers |
| JP2011089084A (en) * | 2009-10-26 | 2011-05-06 | Taiyo Kagaku Co Ltd | Polylactic acid-based resin composition and molding formed of the same |
| CN106751610A (en) * | 2016-12-08 | 2017-05-31 | 吉林中粮生化有限公司 | A kind of PLA porcelain imitation material and preparation method thereof |
| CN112080115A (en) * | 2020-09-25 | 2020-12-15 | 湖南钜亿新材料科技有限公司 | High-toughness polylactic acid composite material for environment-friendly tableware and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 杨惠 ; 刘文明 ; 黄小强 ; 李凤仪 ; .聚乳酸合成及改性研究进展.合成纤维.2008,(03),全文. * |
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