CN114907680A - Recyclable water-soluble degradable foam material and preparation method thereof - Google Patents
Recyclable water-soluble degradable foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a recyclable water-soluble degradable foam material and a preparation method thereof, and the recyclable water-soluble degradable foam material comprises the following components in parts by mass: 100 parts of polylactic acid; 100 portions and 200 portions of modifier; 500 parts of a cosolvent; 10-30 parts of mixed cellulose; 7.5-24 parts of a foaming agent; 3-8 parts of a solubilizer; the modifier is polyvinyl alcohol which forms hydrogen bonds with carbon groups in polylactic acid molecules, and the mixed cellulose comprises the following components in parts by mass: modified starch: 30-60 parts; cellulose: 10-20 parts, the degradable foam material prepared by blending polylactic acid and polyvinyl alcohol has better waterproof performance than common polyvinyl alcohol material while ensuring the water solubility of the material, and has wider application range, and the swelling degree and the dissolving speed of the foam material can be improved by mixing cellulose to reinforce and fill the foam material.
Description
Technical Field
The invention relates to the technical field of high polymer foaming materials, in particular to a recyclable water-soluble degradable foaming material and a preparation method thereof.
Background
In the prior art, foam plastic has the advantages of light weight, heat insulation, shock absorption, high strength, low cost and the like, so that the foam plastic is widely applied to the fields of commodity packaging, goods transportation and the like. In recent years, with the development of economy and the improvement of living standard, online hot-tide mats come, the material consumption of people is more abundant, and meanwhile, the requirements on the foam plastic for packaging and transportation are increased. However, most foamed products such as polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyurethane and other foamed plastics have light weight and large volume, which brings great trouble to recycling and cannot be degraded, thereby causing great environmental pollution. The recyclable water-soluble degradable foam material prepared from the water-soluble polyvinyl alcohol material not only has the advantages of light weight and shock absorption of the traditional foam plastic, but also has unique properties such as water solubility, biodegradability and the like. Waste polyvinyl alcohol foamed plastic can be subjected to water-soluble treatment, and the obtained water solution can be used for preparing an adhesive for recycling and can also be used for curing garbage to reduce dust flying; due to the good degradation performance of the polyvinyl alcohol foam plastic, the waste foam plastic can be subjected to compost degradation or water degradation to relieve the environmental problem caused by white pollution. The polyvinyl alcohol contains a large amount of hydroxyl, is a general high polymer material with strong polarity and high water absorption, and the high water absorption can enable the surface of the polyvinyl alcohol foam to keep a humid environment for a long time, so that mold is bred, and the use of the polyvinyl alcohol foam in the environment with high humidity such as rainy days and marine transportation is limited.
The application numbers are: 201910098653.0 discloses a recyclable water-soluble degradable foam material and a preparation method thereof, wherein the recyclable water-soluble degradable foam material is prepared by mixing, melting, extruding, granulating and melting and foaming polyvinyl alcohol, cellulose, a water-soluble rate regulator, a composite foaming agent, a mildew preventive and a moisture-proof agent. However, the recyclable water-soluble degradable foaming material and the preparation method thereof are hydrophilic, are easy to dissolve in water, have limited application scenes, small application range and poor swelling degree, are not suitable for industrial production, have low economic benefit, cannot regulate and control the hydrophilic performance and the degradation performance of the foaming material within a certain range in the preparation process, and cannot regulate the molecular weight of a mixture and the proportion of a composite component to regulate the degradation speed of the foaming material.
Disclosure of Invention
The invention aims to provide a recyclable water-soluble degradable foam material and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
100 portions and 200 portions of modifier;
500 parts of a cosolvent;
10-30 parts of mixed cellulose;
7.5-24 parts of a foaming agent;
3-8 parts of a solubilizer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
the mixed cellulose comprises the following components in parts by mass:
modified starch: 30-60 parts;
cellulose: 10-20 parts.
The polylactic acid is prepared by taking a binary composite catalyst as a catalyst, the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of the polyvinyl alcohol is 500-1800, the molecular weight is 70000-75000, and the alcoholysis degree is 88-90.
The cosolvent is one or more of dimethyl sulfoxide solution, chloroform and tetrahydrofuran.
The mixed cellulose is a mixture formed by modified starch and cellulose, the modified starch is thermoplastic starch obtained by plasticizing and modifying by a plasticizer or modified starch obtained by melting and blending by glycerol, and the cellulose is one or two of fibrilia, corn stalk and wood chip plant fiber.
The foaming agent is one or more of carbon dioxide, n-butane, n-pentane, isopentane, diisopropyl azodicarboxylate, azodicarbonamide and p-toluenesulfonyl hydrazide.
The solubilizer is one or two of maleic anhydride-polylactic acid graft copolymer and polyvinyl alcohol-g-PLLA polylactic acid graft copolymer.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of mixed cellulose and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a chain extender and a nucleating agent into the screw extruder, outputting the melt, and carrying out foaming molding to obtain the foaming material.
In step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty air in a reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the mixed cellulose is less than 10 percent.
In the step 3), the chain extender is a composite chain extender composed of 1, 4-butanediol and 1, 4-butane diisocyanate, and the nucleating agent is one or more of carbon nano tubes, talcum powder, modified calcium carbonate, graphene or tetrafluoroethylene powder.
The invention has the beneficial effects that:
1. the water-soluble degradation foaming material of recoverable type can be used to goods packing, all kinds of foaming products such as transportation shock attenuation in this scheme, and the cost of manufacture is low, and the degradable foaming material who makes through polylactic acid and polyvinyl alcohol blending makes its waterproof performance better than ordinary polyvinyl alcohol material when guaranteeing material water-solubility itself, and application scope is wider to strengthen filling through mixed cellulose to foaming material, can effectively promote foaming material's swelling degree and dissolution rate.
2. The preparation method disclosed by the scheme is simple and direct, is suitable for industrial production, has high production efficiency and good economic benefit, the foaming material prepared by the preparation method integrates the characteristics of polylactic acid and polyvinyl alcohol, the hydrophilic performance and the degradation performance of the foaming material can be regulated and controlled within a certain range in the preparation process, the molecular weight of the polylactic acid can be regulated, and the degradation speed of the prepared foaming material can be regulated and controlled by regulating the molecular weight of the polylactic acid and the proportion of the composite components.
Drawings
FIG. 1 is a schematic diagram of the operation of the method for preparing the foamed material of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings,
the first embodiment is as follows:
a recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
100 parts of a modifier;
500 parts of dimethyl sulfoxide solution;
10 parts of mixed cellulose;
7.5 parts of carbon dioxide;
3 parts of maleic anhydride-polylactic acid graft copolymer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
wherein the mixed cellulose comprises the following components in parts by mass:
and (3) thermoplastic starch obtained by plasticizing and modifying a plasticizer: 30 parts of (1);
fibrilia: 10 parts.
The polylactic acid is prepared by taking a binary composite catalyst as a catalyst, wherein the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of polyvinyl alcohol is 500, the molecular weight is 75000, and the alcoholysis degree is 88.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of mixed cellulose and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a composite chain extender consisting of 1, 4-butanediol and 1, 4-butane diisocyanate and carbon nano tubes into the screw extruder, outputting the melt, and foaming and forming to obtain the foaming material.
The working principle diagram of the preparation method of the foaming material of the invention is shown in figure 1.
In the step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty the air in the reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the mixed cellulose is less than 10 percent.
Wherein, the preparation process of the polyvinyl alcohol comprises the following steps: weighing a certain mass of polyvinyl alcohol, slowly dispersing the polyvinyl alcohol, putting the polyvinyl alcohol into metered deionized water, soaking for about 1h, properly stirring to fully swell and disperse the polyvinyl alcohol, raising the temperature of fingers, continuously stirring at a stirring speed of 60-100r/min, raising the temperature at a speed of less than 3 ℃/min, keeping the dissolution temperature at 65-80 ℃, keeping the temperature for 1.0-1.5h, cooling while stirring after the polyvinyl alcohol is completely dissolved until the polyvinyl alcohol is at normal temperature, supplementing water to a metering value, and uniformly stirring.
Wherein the preparation process of the polyvinyl alcohol-dimethyl sulfoxide solution comprises the following steps: and slowly adding the metered polyvinyl alcohol into the dimethyl sulfoxide solution under stirring, heating to 80-120 ℃, and keeping the temperature until the polyvinyl alcohol is completely dissolved.
Among them, polyvinyl alcohol having an alcoholysis degree of 88% is selected because of its good water solubility.
Example two:
a recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
150 parts of a modifier;
500 parts of chloroform;
20 parts of mixed cellulose;
15 parts of n-butane;
5 parts of polyvinyl alcohol-g-PLLA polylactic acid graft copolymer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
wherein the mixed cellulose comprises the following components in parts by mass:
modified starch obtained by melt blending of glycerol: 45 parts of (1);
corn stalk fiber: 15 parts.
The polylactic acid is prepared by taking a binary composite catalyst as a catalyst, wherein the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of polyvinyl alcohol is 1150, the molecular weight is 72500, and the alcoholysis degree is 89.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of mixed cellulose and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a composite chain extender consisting of 1, 4-butanediol and 1, 4-butane diisocyanate as a chain extender and talcum powder into the screw extruder, outputting the melt, and carrying out foaming molding to obtain the foaming material.
In the step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty the air in the reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the mixed cellulose is less than 10 percent.
Example three:
a recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
200 parts of a modifier;
500 parts of tetrahydrofuran;
30 parts of mixed cellulose;
24 parts of n-pentane;
8 parts of polyvinyl alcohol-g-PLLA polylactic acid graft copolymer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
wherein the mixed cellulose comprises the following components in parts by mass:
and (3) thermoplastic starch obtained by plasticizing and modifying a plasticizer: 30-60 parts;
wood chip plant fiber: 10-20 parts.
The polylactic acid is prepared by taking a binary composite catalyst as a catalyst, wherein the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of polyvinyl alcohol is 1800, the molecular weight is 75000, and the alcoholysis degree is 90.
The mixed cellulose is a mixture formed by modified starch and cellulose, the modified starch is thermoplastic starch obtained by plasticizing and modifying by a plasticizer or modified starch obtained by melting and blending by glycerol, and the cellulose is one or two of fibrilia, corn stalk and wood chip plant fiber.
The foaming agent is one or more of carbon dioxide, n-butane, n-pentane, isopentane, diisopropyl azodicarboxylate, azodicarbonamide and p-toluenesulfonyl hydrazide.
The solubilizer is one or two of maleic anhydride-polylactic acid graft copolymer and polyvinyl alcohol-g-PLLA polylactic acid graft copolymer.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of mixed cellulose and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a composite chain extender consisting of 1, 4-butanediol and 1, 4-butane diisocyanate and modified calcium carbonate into the screw extruder, outputting the melt, foaming and molding to obtain the foaming material.
In step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty air in a reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the mixed cellulose is less than 10 percent.
In the step 3), the chain extender is a composite chain extender composed of 1, 4-butanediol and 1, 4-butane diisocyanate, and the nucleating agent is one or more of carbon nano tubes, talcum powder, modified calcium carbonate, graphene or tetrafluoroethylene powder.
Comparative example one:
to demonstrate the effect of the addition of co-solvent on the properties of the foams of the present invention, the dmso solution in example one was removed and a comparative sample was prepared in the same manner. The method comprises the following specific steps:
a recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
100 parts of a modifier;
10 parts of mixed cellulose;
7.5 parts of carbon dioxide;
3 parts of maleic anhydride-polylactic acid graft copolymer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
wherein the mixed cellulose comprises the following components in parts by mass:
and (3) thermoplastic starch obtained by plasticizing and modifying a plasticizer: 30 parts of (1);
fibrilia: 10 parts.
The polylactic acid is prepared by taking a binary composite catalyst as a catalyst, wherein the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of polyvinyl alcohol is 500, the molecular weight is 75000, and the alcoholysis degree is 88.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of mixed cellulose and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a composite chain extender consisting of 1, 4-butanediol and 1, 4-butane diisocyanate and carbon nano tubes into the screw extruder, outputting the melt, and foaming and forming to obtain the foaming material.
In step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty air in a reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the mixed cellulose is less than 10 percent.
Comparative example two:
the formulation of example 2 was different in that a comparative sample was prepared in the same process using only the thermoplastic starch obtained by plasticizing and modifying the plasticizer and the polylactic acid, without adding cellulose.
A recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
150 parts of a modifier;
500 parts of chloroform;
20 parts of modified starch obtained by melting and blending glycerol;
15 parts of n-butane;
5 parts of polyvinyl alcohol-g-PLLA polylactic acid graft copolymer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
the polylactic acid is prepared by taking a binary composite catalyst as a catalyst, wherein the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of polyvinyl alcohol is 1150, the molecular weight is 72500, and the alcoholysis degree is 89.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of modified starch obtained by melting and blending glycerol and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a composite chain extender consisting of 1, 4-butanediol and 1, 4-butane diisocyanate as a chain extender and talcum powder into the screw extruder, outputting the melt, and carrying out foaming molding to obtain the foaming material.
In step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty air in a reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, then precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the modified starch obtained by melting and blending the glycerol is less than 10 percent.
Comparative example three:
the difference from the formulation of example 2 is that a comparative sample was prepared in the same process using only corn stalk fiber as the cellulose blended with polylactic acid, without the addition of modified starch.
A recyclable water-soluble degradable foam material comprises the following raw materials in parts by mass:
100 parts of polylactic acid;
150 parts of a modifier;
500 parts of chloroform;
20 parts of corn stalk fiber;
15 parts of n-butane;
5 parts of polyvinyl alcohol-g-PLLA polylactic acid graft copolymer;
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
the polylactic acid is prepared by taking a binary composite catalyst as a catalyst, wherein the binary composite catalyst is stannous octoate and p-toluenic acid, the polymerization degree of polyvinyl alcohol is 1150, the molecular weight is 72500, and the alcoholysis degree is 89.
A preparation method of a recyclable water-soluble degradable foam material comprises the following steps:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of corn stalk fiber and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a composite chain extender consisting of 1, 4-butanediol and 1, 4-butane diisocyanate as a chain extender and talcum powder into the screw extruder, outputting the melt, and carrying out foaming molding to obtain the foaming material.
In step 1), the bulk melt polymerization of lactic acid comprises the following processes:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty air in a reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
In the step 2), the content of the corn stalk fiber is less than 10 percent.
In the preparation process, an intermittent stirring reactor and a double-screw extruder can be combined to carry out continuous melt polymerization experiments, so that polylactic acid with the molecular weight of 150000, which is prepared from lactic acid through continuous melt polycondensation, is obtained, a lactic acid prepolymer with low molar mass is further subjected to polycondensation on the extruder by using the double-screw extruder to prepare the polylactic acid with higher molar mass, when the reaction temperature is 150 ℃, the using amount of a catalyst is 0.5 percent, and the rotating speed of a screw is 75r/min, the molar mass of the polylactic acid can be quickly and effectively improved through a double-screw reaction extrusion polycondensation method, the dispersion coefficient of a reaction extrusion product is reduced, and the uniformity is improved.
Wherein, the corn stalk fiber is pure corn stalk cellulose obtained by removing lignin by sodium hydroxide treatment, and is filled into starch which is acetylated and has thermoplastic property for foaming.
Among them, the chain extender is used to increase the relative molecular mass of polylactic acid, thereby improving its viscoelasticity and making it more suitable for foaming.
Wherein, the nitrogen is introduced to be combined with the antioxidant to protect the reaction process of the polylactic acid, the inert gas can carry small molecular water, and the polycondensate is protected from being easily oxidized and degraded, and the color and luster of the product can be lightened.
The polylactic acid has good biocompatibility, degradability and excellent processability, the polyvinyl alcohol is a water-soluble synthetic polymer which is good in biocompatibility and degradable, and in the experimental process, the influence of factors such as polylactic acid and polyvinyl alcohol with different mass ratios, different types of catalysts, different types of co-solvents, different types of solubilizers, different types of cellulose, stirring speed and the like on the performance of the foaming material is recorded.
The following table shows the performance test results of the recyclable water-soluble degradable foam materials prepared in the test examples one to three and the comparative examples one to three, wherein the performance test samples are cut into cubes with the length, width and height of 2cm respectively, and the swelling rate, the degradation performance and the molecular weight of polylactic acid in the samples are observed.
Table 1: results of Performance testing
| Item | Example one | Example two | EXAMPLE III | Comparative example 1 | Comparative example No. two | Comparative example No. three |
| Water dissolving temperature (c)℃） | ≥5 | ≥5 | ≥5 | ≥5 | ≥5 | ≥5 |
| Water dissolution time (min) | ≥20 | ≥25 | ≥20 | ≥50 | ≤10 | ≤10 |
| Biodegradation Rate (%, 180 day) | ≥95 | ≥95 | ≥95 | ≤30 | ≥90 | ≥90 |
| Degree of swelling (%) | ≥80 | ≥85 | ≥80 | ≥20 | ≥50 | ≥50 |
| Hydrophilic Properties (%) | ≥10 | ≥8 | ≥10 | ≥18 | ≥15 | ≥15 |
The swelling degree and the dissolving speed of the foaming material corresponding to the polyvinyl alcohol with different contents and the polylactic acid with different molecular weights are measured, the solubility and the compatibility of the polyvinyl alcohol and the polylactic acid in a dimethyl sulfoxide solvent are optimal, the optimal compounding temperature is 60 ℃, the hydrophilic performance of the material is increased along with the increase of the content of the polyvinyl alcohol, the swelling degree and the dissolving speed of the composite material are improved, and the swelling degree and the dissolving speed of the composite film are reduced along with the increase of the molecular weight of the polylactic acid, so that the swelling degree and the dissolving speed of the composite material can be regulated and controlled through the molecular weight of the polylactic acid and the mass ratio of the polylactic acid to the polyvinyl alcohol.
Wherein, in the process of preparing the polylactic acid, the influence degree of each factor on the molecular weight of the polylactic acid is found after the influence of the reaction condition on the molecular weight of the polylactic acid is recorded as follows: the reaction temperature is higher than the reaction time and the dosage of the catalyst is higher than the type of the catalyst, and the optimal reaction conditions are as follows: stannous octoate and p-toluenecyclic acid are used as binary composite catalysts, the polymerization temperature is 170 ℃, the reaction is carried out for 12 hours under the vacuum degree of 0-300Pa, and the molecular weight of the prepared polylactic acid is 12400.
The working principle is as follows:
the preparation method of the foaming material disclosed by the scheme can be suitable for industrial production, and the molecular weight of the polylactic acid and the degradation speed of the prepared foaming material can be adjusted according to actual requirements in the preparation process.
The invention has the beneficial effects that 1, the recoverable water-soluble degradable foaming material in the scheme can be used for various foaming products such as goods packaging, transportation shock absorption and the like, the manufacturing cost is low, the water-solubility of the material is ensured, the waterproof performance of the degradable foaming material prepared by blending polylactic acid and polyvinyl alcohol is better than that of a common polyvinyl alcohol material, the application range is wider, and the swelling degree and the dissolving speed of the foaming material can be effectively improved by reinforcing and filling the foaming material by mixing cellulose; 2. the preparation method disclosed by the scheme is simple and direct, is suitable for industrial production, has high production efficiency and good economic benefit, the foamed material prepared by the preparation method integrates the property characteristics of polylactic acid and polyvinyl alcohol, the hydrophilic performance and the degradation performance of the foamed material can be regulated and controlled within a certain range in the preparation process, the molecular weight of the polylactic acid can be regulated, and the degradation speed of the prepared foamed material can be regulated by regulating the molecular weight of the polylactic acid and the proportion of the composite components.
While one embodiment of the present invention has been described in detail, the present invention is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The recyclable water-soluble degradable foam material is characterized by comprising the following raw materials in parts by mass:
wherein, the modifier is polyvinyl alcohol which can form hydrogen bonds with carbon groups in polylactic acid molecules;
the mixed cellulose comprises the following components in parts by mass:
modified starch: 30-60 parts;
cellulose: 10-20 parts.
2. The recyclable water-soluble degradable foam material as claimed in claim 1, wherein the polylactic acid is prepared by using a binary composite catalyst as a catalyst, the binary composite catalyst is stannous octoate and p-toluenic acid, the polyvinyl alcohol has a polymerization degree of 500-1800, a molecular weight of 70000-75000, and an alcoholysis degree of 88-90.
3. The recyclable water-soluble degradable foam material as claimed in claim 1, wherein the co-solvent is one or more of dimethylsulfoxide solution, chloroform and tetrahydrofuran.
4. The recyclable water-soluble degradable foam material as claimed in claim 1, wherein the mixed cellulose is a mixture of modified starch and cellulose, the modified starch is thermoplastic starch obtained by plasticizing and modifying with a plasticizer or modified starch obtained by melt blending with glycerol, and the cellulose is one or two of hemp fiber, corn stalk and wood chip plant fiber.
5. The recyclable water-soluble degradable foam material as claimed in claim 1, wherein the foaming agent is one or more of carbon dioxide, n-butane, n-pentane, isopentane, diisopropyl azodicarboxylate, azodicarbonamide and p-toluenesulfonyl hydrazide.
6. The recyclable water-soluble degradable foam material as set forth in claim 1, wherein the solubilizer is one or two of maleic anhydride-polylactic acid graft copolymer and polyvinyl alcohol-g-PLLA polylactic acid graft copolymer.
7. The method for preparing the recyclable water-soluble degradable foam material as described in any one of claims 1 to 6, comprising the steps of:
1) and preparing polylactic acid: melt polymerization is carried out on the body of the lactic acid, namely the polylactic acid is synthesized by a direct method;
2) blending modification of polylactic acid: adding a certain amount of polyvinyl alcohol aqueous solution and a cosolvent into a blending agent, stirring and heating to a blending temperature, weighing a certain amount of polylactic acid, dissolving the polylactic acid in a certain solvent under stirring, adding the polylactic acid solution into the polyvinyl alcohol solution under stirring at a certain temperature, and adding a certain amount of mixed cellulose and a solubilizer to obtain a blend;
3) and foaming and forming: adding the blend obtained in the step 2) into a screw extruder, adding a foaming agent, a chain extender and a nucleating agent into the screw extruder, outputting the melt, and carrying out foaming molding to obtain the foaming material.
8. The method for preparing the recyclable water-soluble degradable foam material as described in claim 7, wherein the bulk melt polymerization of lactic acid in step 1) comprises the following steps:
a) and primary dehydration: adding a certain amount of lactic acid into a reaction kettle, heating the reaction kettle to 60 ℃, and carrying out reduced pressure distillation on the lactic acid to remove 10-20% of water in the lactic acid;
b) and antioxidant protection: adding a certain amount of antioxidant into the reaction kettle, and introducing nitrogen into the reaction kettle before reaction to empty the air in the reaction system;
c) and secondary dehydration: heating the reaction kettle to 100-105 ℃, and dehydrating under reduced pressure for 2h, wherein the vacuum degree is 1480-1520 Pa;
d) and (3) catalytic reaction: cooling the reaction liquid, adding a certain amount of binary composite catalyst into the reaction kettle, pumping the reaction kettle to a vacuum degree of 300Pa, heating to 170 ℃, stirring the reaction liquid at a high speed, and reacting for 8-15h
e) And cooling: cooling the product, adding acetone with the amount 4 times that of the monomer after the product is cooled to room temperature, precipitating with water, filtering, decoloring and purifying the product, and drying in vacuum to obtain the polylactic acid.
9. The method for preparing the recyclable water-soluble degradable foam material as described in claim 8, wherein the content of the mixed cellulose in the step 2) is less than 10%.
10. The method for preparing the recyclable water-soluble degradable foam material as claimed in claim 9, wherein in the step 3), the chain extender is a composite chain extender composed of 1, 4-butanediol and 1, 4-butane diisocyanate, and the nucleating agent is one or more of carbon nanotubes, talcum powder, modified calcium carbonate, graphene or tetrafluoroethylene powder.
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