CN114479198A - Starch-based degradable plastic film and preparation method thereof - Google Patents
Starch-based degradable plastic film and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
Abstract
The application relates to the technical field of biodegradable materials, and particularly discloses a starch-based degradable plastic film and a preparation method thereof, wherein the starch-based degradable plastic film comprises the following raw materials: polyhydroxy fatty acid ester, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer; the technical scheme effectively ensures the mechanical property, the chemical property and the water resistance of the finally prepared plastic film by utilizing the synergistic effect among the raw materials. The application also provides a preparation method of the starch-based degradable plastic film, which comprises the steps of reacting dehydrated lactic acid, a cross-linking agent and a reaction solvent, and adding corn starch and allophanate to react to obtain a reactant; mixing polyhydroxy fatty acid ester, 3-chloropropyl methyl dichlorosilane and reactants, adding a filler and a compatilizer, uniformly mixing, and finally blow molding to obtain a plastic film; the technical scheme has the advantages of simple preparation method, mild preparation conditions and excellent comprehensive performance of the plastic film.
Description
Technical Field
The application relates to the technical field of biodegradable materials, in particular to a starch-based degradable plastic film and a preparation method thereof.
Background
The plastic product has the characteristics of high strength, light weight, corrosion resistance, low price and the like, and is widely applied to production and life of people. The application of plastic products brings great convenience to people and brings serious negative effects, most of waste plastic products can be degraded under special conditions, the light and biological degradation speed of the waste plastic products in the natural environment is very slow, the waste plastic products can completely disappear after about hundreds of years, and although the waste plastic products can be treated by burying, burning and other methods, the methods have great defects. The waste plastics after being used in large quantity can not be automatically degraded, and can cause serious environmental pollution after being remained in the natural environment for a long time, thereby not only influencing the ecological balance, but also threatening the health of human beings. In order to solve this problem, research and development of degradable plastics have become an ideal way to solve white pollution, and the degradable plastics can be automatically and completely decomposed under natural conditions after being discarded, and have little pollution to the environment, however, the production cost thereof is high, so that the practical application thereof is limited.
The starch-based plastic is a biomass material prepared by taking starch as a raw material, and can be rapidly and completely degraded in a natural environment. Compared with chemical or biological degradable bioplastics such as poly (dehydrated lactic acid) (PLA), polyvinyl alcohol (PVA), poly (butylene succinate) (PBS) and the like, the starch-based plastic has rich raw material sources and obvious price advantage, so the research and application proportion of the starch-based degradable material accounts for more than 70 percent of that of degradable plastics in China. However, the using performance of the starch-based degradable plastic still has obvious disadvantages, and the starch-based degradable plastic is difficult to achieve the using performance of the traditional plastic products in the aspect of mechanical property; in addition, because starch macromolecules have very strong water absorption, the starch-based degradable plastic has poor water resistance, is sensitive to humidity change and easy to absorb water, the mechanical property of a product after water absorption is obviously reduced, and the precipitation of an auxiliary agent can be seriously caused, so that the application range is limited.
Disclosure of Invention
In order to obtain the starch-based degradable plastic with excellent mechanical property and good water resistance, the application provides the starch-based degradable plastic film and the preparation method thereof, reasonable raw material collocation is adopted, and process parameters in the preparation process are controlled.
In a first aspect, the application provides a starch-based degradable plastic film, which adopts the following technical scheme:
a starch-based degradable plastic film comprises the following raw materials in parts by weight: 10-18 parts of polyhydroxy fatty acid ester, 50-70 parts of corn starch, 20-30 parts of dehydrated lactic acid, 0.4-1.2 parts of cross-linking agent, 120 parts of reaction solvent, 2-4 parts of ethyl allophanate, 0.5-1.5 parts of 3-chloropropyl methyl dichlorosilane, 18-25 parts of filler and 0.5-1.5 parts of compatilizer.
Preferably, the starch-based degradable plastic film comprises the following raw materials in parts by weight: 12-16 parts of polyhydroxyalkanoate, 55-65 parts of corn starch, 22-28 parts of dehydrated lactic acid, 0.6-1 part of cross-linking agent, 140 parts of reaction solvent 130, 2.5-3.5 parts of ethyl allophanate, 0.8-1.2 parts of 3-chloropropylmethyldichlorosilane, 20-24 parts of filler and 0.8-1.2 parts of compatilizer.
Preferably, the starch-based degradable plastic film comprises the following raw materials in parts by weight: 14 parts of polyhydroxy fatty acid ester, 60 parts of corn starch, 25 parts of dehydrated lactic acid, 0.8 part of cross-linking agent, 135 parts of reaction solvent, 3 parts of allophanate, 1 part of 3-chloropropyl methyl dichlorosilane, 22 parts of filler and 1 part of compatilizer.
By adopting the technical scheme, the polyhydroxyalkanoate has physical and chemical properties similar to those of synthetic plastics and a plurality of excellent performances such as biodegradability, biocompatibility, optical activity, piezoelectricity, gas separation property and the like which are not possessed by the synthetic plastics; according to the method, corn starch and dehydrated lactic acid are used as main raw materials, the dehydrated lactic acid is subjected to self-polycondensation in the presence of a cross-linking agent and then is subjected to cross-linking reaction with the corn starch, the degree of the cross-linking reaction is high, and a network structure polymer with high compactness is obtained through the reaction; the addition of the allophanate can obviously improve the activity and the number of reactive groups in a reaction system, reduce the number of hydrophilic groups and improve the water resistance, so that water is difficult to enter the inside of the network polymer; the reticular polymer is blended and reinforced with polyhydroxy fatty acid ester in the presence of 3-chloropropyl methyl dichlorosilane, and finally, the filler and the compatilizer are added and uniformly mixed, so that the prepared plastic film has excellent mechanical property and good water resistance.
Preferably, the reaction solvent is a compound agent of polyvinyl alcohol, polyhydric alcohol and water in a mass ratio of 4-5:1-2: 3-5.
Preferably, the polyhydric alcohol is one or more of pentaerythritol, diethylene glycol, dipropylene glycol or neopentyl glycol.
By adopting the technical scheme, the polyvinyl alcohol has better gas barrier property, thermal stability and biocompatibility, and the reaction solvent is formed after the polyvinyl alcohol is mutually dissolved with the polyhydric alcohol and the water, so that a good reaction environment for the dehydrated lactic acid can be provided.
Preferably, the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6-8: 1.
By adopting the technical scheme, the compound agent of the p-toluenesulfonic acid and the dicumyl peroxide is used as the reaction crosslinking agent of the dehydrated lactic acid, the corn starch and the allophanate, so that the polycondensation of the lactic acid can be effectively catalyzed, the crosslinking reaction of the polycondensate and other raw materials can be promoted, and the reaction efficiency is high.
Preferably, the filler is prepared by mixing and crushing plant fibers and calcium carbonate in a mass ratio of 4-7:2-11 into particles with the particle size of 0.1-50 mu m.
By adopting the technical scheme, the plant fiber and the calcium carbonate are mixed to be used as the filler for the plastic film, so that the toughness, the tensile strength and the strength of the plastic film can be obviously improved.
Preferably, the compatibilizer includes at least one of maleic anhydride, bismaleimide, glycidyl methacrylate, vinyl silane, and a maleic anhydride-acrylic acid copolymer.
By adopting the technical scheme, the compatilizer is added, so that the dispersity and the compatibility of a formula system are improved, the full dispersion and combination among the raw materials are ensured, the finally prepared plastic film has strong intermolecular binding force, and the physical and chemical properties are obviously improved.
In a second aspect, the application provides a preparation method of a starch-based degradable plastic film, which adopts the following technical scheme:
a preparation method of a starch-based degradable plastic film comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, adding corn starch and ethyl allophanate after pre-reaction treatment, and further stirring for reaction for 1-2 hours to obtain a reactant;
s3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyldichlorosilane together into the reactant in the step S2, stirring and mixing for 15-25min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding at a processing temperature of 168-176 ℃ by using a single-screw extrusion film blowing machine to form a plastic film, and finally cutting, splitting and packaging.
By adopting the technical scheme.
Preferably, the pre-reaction treatment in step S2 is specifically as follows: controlling the temperature of the reaction kettle to be 90-98 ℃ and the pressure to be 2.4-3.2kPa, fully reacting for 30-50min, heating to 155-165 ℃, carrying out heat preservation treatment for 1-3h, and then cooling to 80-88 ℃ to finish the pre-reaction treatment.
By adopting the technical scheme.
In summary, the present application has the following beneficial effects:
1. the method adopts the polyhydroxyalkanoate with good biodegradability, the corn starch and the dehydrated lactic acid as main raw materials, controls the selection proportion and the reaction mode among the raw materials, and utilizes the synergistic effect among the raw materials to effectively ensure the mechanical property, the chemical property and the water resistance of the finally prepared plastic film; the obtained plastic film has good degradation performance and short degradation period, and can be completely degraded within 3-6 months.
2. According to the method, dehydrated lactic acid is subjected to self-polycondensation in the presence of a cross-linking agent, then is subjected to cross-linking reaction with corn starch in the presence of allophanate, and after the reaction is completed, is subjected to blending reinforcement with polyhydroxyalkanoate in the presence of 3-chloropropylmethyldichlorosilane, and finally is added with a filler and a compatilizer and is uniformly mixed to obtain the required plastic film; the preparation method is simple, the preparation conditions are mild, and the obtained plastic film is excellent in comprehensive performance and can be widely applied to packaging in the fields of food, industry, agriculture and the like.
Detailed Description
The present application is further illustrated with reference to specific examples.
Example one
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 10 parts of polyhydroxy fatty acid ester, 50 parts of corn starch, 20 parts of dehydrated lactic acid, 0.4 part of cross-linking agent, 120 parts of reaction solvent, 2 parts of allophanate, 0.5 part of 3-chloropropyl methyl dichlorosilane, 18 parts of filler and 0.5 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol, polyalcohol and water in a mass ratio of 4:1:3, and the polyalcohol is pentaerythritol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6: 1;
the filler is prepared by mixing plant fiber and calcium carbonate at a mass ratio of 2:1, and pulverizing to particle size of 0.1 μm
The compatilizer is maleic anhydride.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 90 ℃ and the pressure at 2.4kPa, fully reacting for 30min, heating to 155 ℃, carrying out heat preservation treatment for 1h, then cooling to 80 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring and reacting for 1h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 15min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 168 ℃, and finally cutting, splitting and packaging.
Example two
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 12 parts of polyhydroxy fatty acid ester, 55 parts of corn starch, 22 parts of dehydrated lactic acid, 0.6 part of cross-linking agent, 130 parts of reaction solvent, 2.5 parts of ethyl allophanate, 0.8 part of 3-chloropropyl methyl dichlorosilane, 20 parts of filler and 0.8 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol, polyhydric alcohol and water in a mass ratio of 4:2:3, and the polyhydric alcohol is diethylene glycol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6.5: 1;
the filler is prepared by mixing and crushing plant fiber and calcium carbonate with the mass ratio of 5:4 into 10 mu m
The compatilizer is bismaleimide.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle, controlling the temperature of the reaction kettle at 92 ℃ and the pressure at 2.6kPa, fully reacting for 35min, heating to 158 ℃, carrying out heat preservation treatment for 1.5h, then cooling to 82 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring for reaction for 1.2h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 18min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 170 ℃, and finally cutting, splitting and packaging.
EXAMPLE III
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 14 parts of polyhydroxy fatty acid ester, 60 parts of corn starch, 25 parts of dehydrated lactic acid, 0.8 part of cross-linking agent, 135 parts of reaction solvent, 3 parts of allophanate, 1 part of 3-chloropropyl methyl dichlorosilane, 22 parts of filler and 1 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol, polyhydric alcohol and water in a mass ratio of 4.5:1.2:4, and the polyhydric alcohol is dipropylene glycol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 7: 1;
the filler is prepared by mixing and crushing plant fibers and calcium carbonate in a mass ratio of 5.5:6 into particles with the particle size of 25 mu m, and the compatilizer is glycidyl methacrylate.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 94 ℃ and the pressure at 2.8kPa, fully reacting for 40min, heating to 160 ℃, carrying out heat preservation treatment for 2h, then cooling to 84 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring for reaction for 1.5h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 20min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 172 ℃, and finally cutting, splitting and packaging.
Example four
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 16 parts of polyhydroxy fatty acid ester, 65 parts of corn starch, 28 parts of dehydrated lactic acid, 1 part of cross-linking agent, 140 parts of reaction solvent, 3.5 parts of allophanate, 1.2 parts of 3-chloropropyl methyl dichlorosilane, 24 parts of filler and 1.2 parts of compatilizer;
wherein the reaction solvent is a compound agent of polyvinyl alcohol, polyalcohol and water in a mass ratio of 5:1:3, and the polyalcohol is neopentyl glycol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 7.5: 1;
the filler is prepared by mixing and crushing plant fiber and calcium carbonate with the mass ratio of 2:3 into particles with the particle size of 40 mu m
The compatilizer is vinyl silane.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle, controlling the temperature of the reaction kettle at 96 ℃ and the pressure at 3kPa, fully reacting for 45min, heating to 162 ℃, carrying out heat preservation treatment for 2.5h, then cooling to 86 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring for reaction for 1.8h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2, stirring and mixing for 22min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 174 ℃, and finally cutting, splitting and packaging.
EXAMPLE five
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 18 parts of polyhydroxy fatty acid ester, 70 parts of corn starch, 30 parts of dehydrated lactic acid, 1.2 parts of a cross-linking agent, 150 parts of a reaction solvent, 4 parts of allophanate, 1.5 parts of 3-chloropropyl methyl dichlorosilane, 25 parts of a filler and 1.5 parts of a compatilizer;
wherein the reaction solvent is a compound agent of polyvinyl alcohol, polyalcohol and water in a mass ratio of 5:2:5, and the polyalcohol is pentaerythritol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 8: 1;
the filler is prepared by mixing plant fiber and calcium carbonate at a mass ratio of 7:11 and pulverizing into particles with a particle size of 50 μm
The compatilizer is maleic anhydride-acrylic acid copolymer.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 98 ℃ and the pressure at 3.2kPa, fully reacting for 50min, heating to 165 ℃, carrying out heat preservation treatment for 3h, then cooling to 88 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring for reaction for 2h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 25min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding at the processing temperature of 176 ℃ by using a single-screw extrusion film blowing machine to form a plastic film, and finally cutting, splitting and packaging.
Comparative example 1
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 10 parts of polyhydroxy fatty acid ester, 50 parts of corn starch, 20 parts of dehydrated lactic acid, 0.4 part of cross-linking agent, 120 parts of reaction solvent, 2 parts of allophanate, 0.5 part of 3-chloropropyl methyl dichlorosilane, 18 parts of filler and 0.5 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol and water in a mass ratio of 4: 3;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6: 1;
the filler is prepared by mixing plant fiber and calcium carbonate at a mass ratio of 2:1, and pulverizing to particle size of 0.1 μm
The compatilizer is maleic anhydride.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 90 ℃ and the pressure at 2.4kPa, fully reacting for 30min, heating to 155 ℃, carrying out heat preservation treatment for 1h, then cooling to 80 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring and reacting for 1h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 15min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 168 ℃, and finally cutting, splitting and packaging.
Comparative example No. two
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 10 parts of polyhydroxy fatty acid ester, 50 parts of corn starch, 20 parts of dehydrated lactic acid, 0.4 part of cross-linking agent, 120 parts of reaction solvent, 2 parts of allophanate, 0.5 part of 3-chloropropyl methyl dichlorosilane, 18 parts of filler and 0.5 part of compatilizer;
wherein the reaction solvent is a compound agent of polyalcohol and water in a mass ratio of 1:3, and the polyalcohol is pentaerythritol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6: 1;
the filler is prepared by mixing and crushing plant fiber and calcium carbonate in a mass ratio of 2:1 into particles with the particle size of 0.1 mu m, and the compatilizer is maleic anhydride.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 90 ℃ and the pressure at 2.4kPa, fully reacting for 30min, heating to 155 ℃, carrying out heat preservation treatment for 1h, then cooling to 80 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring and reacting for 1h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 15min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 168 ℃, and finally cutting, splitting and packaging.
Comparative example No. three
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 10 parts of polyhydroxy fatty acid ester, 50 parts of corn starch, 20 parts of dehydrated lactic acid, 0.4 part of cross-linking agent, 120 parts of reaction solvent, 2 parts of allophanate, 0.5 part of 3-chloropropyl methyl dichlorosilane, 18 parts of filler and 0.5 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol, polyalcohol and water in a mass ratio of 4:1:3, and the polyalcohol is pentaerythritol;
the cross-linking agent is p-toluenesulfonic acid;
the filler is prepared by mixing plant fiber and calcium carbonate at a mass ratio of 2:1, and pulverizing to particle size of 0.1 μm
The compatilizer is maleic anhydride.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle, controlling the temperature of the reaction kettle at 90 ℃ and the pressure at 2.4kPa, fully reacting for 30min, heating to 155 ℃, carrying out heat preservation treatment for 1h, then cooling to 80 ℃, completing pre-reaction treatment, adding corn starch and allophanate, and further stirring and reacting for 1h to obtain a reactant;
s3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyldichlorosilane together into the reactant obtained in the step S2, stirring and mixing for 15min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding at a processing temperature of 168 ℃ by using a single-screw extrusion film blowing machine to obtain a plastic film, and finally cutting, splitting and packaging.
Comparative example No. four
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 10 parts of polyhydroxy fatty acid ester, 50 parts of corn starch, 20 parts of dehydrated lactic acid, 0.4 part of cross-linking agent, 120 parts of reaction solvent, 2 parts of allophanate, 0.5 part of 3-chloropropyl methyl dichlorosilane, 18 parts of filler and 0.5 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol, polyalcohol and water in a mass ratio of 4:1:3, and the polyalcohol is pentaerythritol;
the cross-linking agent is dicumyl peroxide;
the filler is prepared by mixing plant fiber and calcium carbonate at a mass ratio of 2:1, and pulverizing to particle size of 0.1 μm
The compatilizer is maleic anhydride.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 90 ℃ and the pressure at 2.4kPa, fully reacting for 30min, heating to 155 ℃, carrying out heat preservation treatment for 1h, then cooling to 80 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring and reacting for 1h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 15min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 168 ℃, and finally cutting, splitting and packaging.
Comparative example five
The application provides a starch-based degradable plastic film, which comprises the following raw materials in parts by weight: 10 parts of polyhydroxy fatty acid ester, 50 parts of corn starch, 20 parts of dehydrated lactic acid, 0.4 part of cross-linking agent, 120 parts of reaction solvent, 2 parts of allophanate, 0.5 part of 3-chloropropyl methyl dichlorosilane, 18 parts of filler and 0.5 part of compatilizer;
wherein the reaction solvent is a mixture of polyvinyl alcohol, polyalcohol and water in a mass ratio of 4:1:3, and the polyalcohol is pentaerythritol;
the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6: 1;
the filler is prepared by mixing plant fiber and calcium carbonate at a mass ratio of 2:1, and pulverizing to particle size of 0.1 μm
The compatilizer is maleic anhydride.
The application also provides a preparation method of the starch-based degradable plastic film, which comprises the following steps:
s1, weighing raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropylmethyldichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, controlling the temperature of the reaction kettle at 90 ℃ and the pressure at 2.4kPa, fully reacting for 30min, heating to 155 ℃, carrying out heat preservation treatment for 1h, then cooling to 80 ℃, completing pre-reaction treatment, adding corn starch and ethyl allophanate, and further stirring and reacting for 1h to obtain a reactant;
and S3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyl dichlorosilane into the reactant in the step S2 together, stirring and mixing for 15min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding to form a plastic film through a single-screw extrusion film blowing machine at the processing temperature of 168 ℃, and finally cutting, splitting and packaging.
The properties of the starch-based degradable plastic films prepared in the first to fifth examples and the first to fifth comparative examples are respectively tested according to national standards of ASTM-D638, GB/T1034-2008 and GB/T20197-2006, and the following results are obtained:
table 1:
| elongation at break/% | Tensile strength/MPa | Water absorption/%) | Degradability (buried in soil) | |
| Example one | 183.7 | 58.6 | 5.1 | 307d complete degradation |
| Example two | 189.1 | 59.0 | 4.7 | 275d complete degradation |
| EXAMPLE III | 192.5 | 60.7 | 4.1 | 258d is completely degraded |
| Example four | 187.9 | 59.4 | 4.5 | 283d is completely degraded |
| EXAMPLE five | 185.0 | 59.2 | 4.9 | 342d is completely degraded |
| Comparative example 1 | 145.1 | 47.9 | 16.8 | 313d complete degradation |
| Comparative example No. two | 124.8 | 43.4 | 14.9 | 354d complete degradation |
| Comparative example No. three | 106.3 | 42.0 | 39.5 | 311d complete degradation |
| Comparative example No. four | 133.2 | 44.8 | 27.7 | 317d is completely degraded |
| Comparative example five | 174.7 | 56.5 | 45.3 | 308d is completely degraded |
As can be seen from Table 1: the degradation performance of the starch-based degradable plastic films prepared in the first to fifth embodiments of the application is similar to that of the starch-based degradable plastic films prepared in the first to fifth embodiments of the application, and the plastic films can be completely degraded within 6 months; from the first example and the first and second comparative examples, it can be seen that: the compound agent of polyvinyl alcohol, polyalcohol and water is used as a reaction solvent, so that the elongation at break, tensile strength and water absorption of the plastic film can be comprehensively improved; from the first example and the third and fourth comparative examples, it can be seen that: the compound agent of the p-toluenesulfonic acid and the dicumyl peroxide is used as the cross-linking agent for reaction, so that the elongation at break, tensile strength and water absorption of the plastic film can be comprehensively improved; from example one and comparative example five it can be seen that: the addition of the allophanate can further improve the water resistance of the prepared plastic film.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The starch-based degradable plastic film is characterized by comprising the following raw materials in parts by weight: 10-18 parts of polyhydroxy fatty acid ester, 50-70 parts of corn starch, 20-30 parts of dehydrated lactic acid, 0.4-1.2 parts of cross-linking agent, 120 parts of reaction solvent, 2-4 parts of ethyl allophanate, 0.5-1.5 parts of 3-chloropropyl methyl dichlorosilane, 18-25 parts of filler and 0.5-1.5 parts of compatilizer.
2. The starch-based degradable plastic film according to claim 1, characterized by comprising the following raw materials in parts by weight: 12-16 parts of polyhydroxyalkanoate, 55-65 parts of corn starch, 22-28 parts of dehydrated lactic acid, 0.6-1 part of cross-linking agent, 140 parts of reaction solvent 130, 2.5-3.5 parts of ethyl allophanate, 0.8-1.2 parts of 3-chloropropylmethyldichlorosilane, 20-24 parts of filler and 0.8-1.2 parts of compatilizer.
3. The starch-based degradable plastic film according to claim 1, characterized by comprising the following raw materials in parts by weight: 14 parts of polyhydroxy fatty acid ester, 60 parts of corn starch, 25 parts of dehydrated lactic acid, 0.8 part of cross-linking agent, 135 parts of reaction solvent, 3 parts of allophanate, 1 part of 3-chloropropyl methyl dichlorosilane, 22 parts of filler and 1 part of compatilizer.
4. The starch-based degradable plastic film as claimed in claim 1, wherein the reaction solvent is a mixture of polyvinyl alcohol, polyhydric alcohol and water in a mass ratio of 4-5:1-2: 3-5.
5. The starch-based degradable plastic film according to claim 4, wherein the polyol is one or more of pentaerythritol, diethylene glycol, dipropylene glycol or neopentyl glycol.
6. The starch-based degradable plastic film as claimed in claim 1, wherein the cross-linking agent is a compound agent of p-toluenesulfonic acid and dicumyl peroxide in a mass ratio of 6-8: 1.
7. The starch-based degradable plastic film according to claim 1, wherein the filler is obtained by mixing and crushing plant fibers and calcium carbonate in a mass ratio of 4-7:2-11 to a particle size of 0.1-50 μm.
8. The starch-based degradable plastic film according to claim 1, wherein the compatibilizer comprises at least one of maleic anhydride, bismaleimide, glycidyl methacrylate, vinyl silane, and maleic anhydride-acrylic acid copolymer.
9. The method for preparing a starch-based degradable plastic film according to any one of claims 1 to 8, characterized by comprising the steps of:
s1, weighing the raw materials of polyhydroxyalkanoate, corn starch, dehydrated lactic acid, a cross-linking agent, a reaction solvent, allophanate, 3-chloropropyl methyl dichlorosilane, a filler and a compatilizer in parts by weight for later use;
s2, adding dehydrated lactic acid, a cross-linking agent and a reaction solvent into a reaction kettle together, adding corn starch and ethyl allophanate after pre-reaction treatment, and further stirring for reaction for 1-2 hours to obtain a reactant;
s3, adding the polyhydroxyalkanoate and the 3-chloropropylmethyldichlorosilane together into the reactant in the step S2, stirring and mixing for 15-25min, adding the filler and the compatilizer, stirring and mixing uniformly, performing hot melt extrusion blow molding at a processing temperature of 168-176 ℃ by using a single-screw extrusion film blowing machine to form a plastic film, and finally cutting, splitting and packaging.
10. The method for preparing a starch-based degradable plastic film according to claim 8, wherein the pre-reaction treatment in the step S2 is as follows: controlling the temperature of the reaction kettle to be 90-98 ℃ and the pressure to be 2.4-3.2kPa, fully reacting for 30-50min, heating to 155-165 ℃, carrying out heat preservation treatment for 1-3h, and then cooling to 80-88 ℃ to finish the pre-reaction treatment.
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