CN113088055A - High-performance polyvinyl alcohol-based composite material and preparation method thereof - Google Patents
High-performance polyvinyl alcohol-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance polyvinyl alcohol-based composite material and a preparation method thereof, belonging to the technical field of polymer processing. According to the invention, by adding the compatilizer, the interfacial interaction force between the polyglycolic acid matrix and the degradable polyester B is obviously improved, and the toughening effect of the degradable polyester B is further obviously improved by matching with a specific blending process; in addition, the functional filler is added to react with the polyglycolic acid matrix in situ to promote dispersion, so that the crystallization effect is provided, and the heat resistance of the composite material is improved better. The polyglycolic acid composite material has good toughness, high strength and good heat resistance, and can be applied to the field of equipment manufacturing and packaging of high-performance degradable materials.
Description
Technical Field
The invention relates to a high-performance polyvinyl alcohol-based composite material and a preparation method thereof, belonging to the technical field of polymer processing.
Background
With the increasing living standard of people, plastic products have penetrated into various fields of national economy. Traditional plastic products such as polyethylene, polypropylene and the like have strong stability and are difficult to degrade when being discarded in nature, and the generated garbage brings huge negative effects on ecological environment, water resources and the like. The development of fully biodegradable polymers to replace conventional plastic products is one of the effective approaches to solve the above problems, and a great deal of research has been conducted in recent years.
The main biodegradable plastics in the market at present comprise polylactic acid (PLA), poly (butylene adipate terephthalate) (PBAT), poly (butylene succinate) (PBS), poly (butylene succinate-adipate-succinate) (PBSA), polycaprolactone and the like, but the materials have poor barrier properties to oxygen and water vapor due to the self-structure of the materials. Polyglycolic acid is a green high polymer material with good biocompatibility, processability and mechanical property and excellent barrier property, the cost is greatly reduced along with the breakthrough of synthesis technology in recent years, and the polyglycolic acid is a preferred material for preparing biodegradable high-barrier products.
The polyglycolic acid has short molecular chain structural unit and poor chain flexibility, so that the brittleness is high, and meanwhile, due to the low glass transition temperature of the polyglycolic acid, the polyglycolic acid also has the problems of low crystallinity, poor heat resistance of products and the like during the preparation of products such as films and the like, so that the application field of the polyglycolic acid is limited to a great extent. In CN1768114A, a small amount of aromatic polyester resin is added into polyglycolic acid resin to improve the moisture resistance and toughness of polyglycolic acid, in CN109575536A, polyglycolic acid and polybutylene succinate-co-butylene terephthalate are blended, and mesoporous silica is added to improve the mechanical property and the heat preservation and moisture preservation performance of the material. However, the known modification systems have a limited toughening effect because the interfacial force between the two phases is weak, and the prior art has focused only on improving the toughness of polyglycolic acid and has not solved the heat resistance problem of polyglycolic acid at the same time. CN107903599A adopts nano inorganic filler and reinforcing fiber to improve the mechanical properties of polyglycolic acid, but does not mention the improvement of toughness and heat resistance at the same time.
Disclosure of Invention
Aiming at the defects of the existing preparation method of the high-barrier biodegradable material and the modification method of the polyglycolic acid, the invention provides a completely degradable polyglycolic acid-based composite material which has simple process, easy control and high heat resistance and high barrier. The compatibility between polyglycolic acid and degradable polyester is greatly improved by adding the compatilizer, the flexibility of polyglycolic acid is obviously improved, meanwhile, the toughening modification and the heat-resistant modification of polyglycolic acid are synchronously carried out by adding the tough degradable polyester and the inorganic filler, the mechanical property of the material is improved, the crystallization rate of the composite material is improved, the heat-resistant property of the material is further improved, and the high-performance polyglycolic acid-based composite material is prepared.
The basic principle of the invention is as follows: generally, a toughness component elastomer is required to be added for toughening modification of the material, but due to poor compatibility of the elastomer and a matrix, elastomer particles are easy to be separated from the matrix phase, stress concentration points are generated, the toughening effect is poor, the strength is greatly reduced, and due to the low glass transition temperature of the toughness component, the heat resistance of the composite material is generally reduced. The inorganic filler is added in the heat-resistant modification, but the dispersion of the inorganic filler in a matrix is a difficult problem, particularly the inorganic filler is easy to agglomerate in the processing process when the addition amount of the filler is large, the heat-resistant performance of the material is improved, the mechanical performance is negatively affected, and the toughening effect cannot be achieved generally. According to the invention, firstly, the mutual acting force of the toughness component and the matrix is improved by adding the compatilizer, and for the compatilizer based on in-situ reaction (such as a vinyl acetate copolymer containing a glycidyl methacrylate structural unit), according to the difference of the reactivity of the groups on the compatilizer with the toughness component and the matrix, the degradable polyester B and the compatilizer are preferably firstly melted and blended to prepare a master batch, and the groups on the compatilizer can react with the terminal carboxyl or the terminal hydroxyl on the polyglycolic acid to generate the comb graft copolymer. By controlling the reaction temperature and the reaction time, the reaction groups of the compatilizer are only partially reacted, and the reaction with the end groups of the polyglycolic acid is continued in the subsequent process of melt blending the master batch and the polyglycolic acid matrix. Meanwhile, the heat resistance of the polyglycolic acid-based material is obviously improved by adding the inorganic filler, and the inorganic filler is preferably subjected to activation treatment to achieve a more excellent heat-resistant modification effect.
Specifically, based on the above principle, the present invention provides a method for preparing a high-performance polyvinyl alcohol-based composite material, comprising the following steps:
the preparation method comprises the following steps of: 50-95 parts of polyglycolic acid, 5-50 parts of tough degradable polyester, 0.5-30 parts of functional filler, 0.01-10 parts of compatilizer, 0-3 parts of antioxidant, 0-1 part of lubricant and 0-1 part of chain extender;
preparation by the first method: firstly, mixing the degradable polyester A and the compatilizer according to the weight part ratio, and carrying out melt blending to obtain a blending master batch; then uniformly premixing polyglycolic acid, blending master batch, functional filler, antioxidant, lubricant and chain extender, and then melting and blending through a double-screw extruder to obtain a polyglycolic acid-based composite material;
alternatively, prepared by mode two:
uniformly mixing polyglycolic acid, degradable polyester A, functional filler, compatilizer, antioxidant, lubricant and chain extender according to the weight part ratio to obtain a premix, and then carrying out melt blending on the premix to obtain the polyglycolic acid-based composite material.
In one embodiment of the present invention, the polyglycolic acid is a homopolymer of glycolic acid or a glycolic acid-based copolymer. The glycolic acid-based copolymer is a copolymer mainly composed of a glycolic acid segment and containing an aliphatic polymer, an aromatic polymer or a combination thereof.
In one embodiment of the present invention, the degradable polyester a is at least one of polylactic acid, adipic acid/butylene terephthalate copolymer, polycaprolactone, polybutylene succinate, polyhydroxyalkanoate, polybutylene succinate/adipate copolymer, and carbon dioxide-based copolymer.
In one embodiment of the present invention, the functional filler is at least one of talc powder, graphene, wollastonite, boron nitride and montmorillonite which are not modified or are subjected to surface modification. The surface modification refers to modification by using a silane coupling agent or fatty acid; wherein, the mass ratio of the silane coupling agent or fatty acid to the functional filler is (3-5): 100.
in one embodiment of the invention, the compatibilizing agent is at least one of a compound or polymer containing a plurality of epoxy groups, isocyanate groups, glycolic acid segments, wherein the molecular weight of the compound is no greater than 10 kDa.
In one embodiment of the present invention, the compatibilizing agent comprises: at least one of a methacrylate-based copolymer, a vinyl acetate-based copolymer and an ethanol-based copolymer, wherein the methacrylate-based copolymer and the vinyl acetate-based copolymer further contain a glycidyl methacrylate structural unit, and the mass percentage content of the glycidyl methacrylate is 0.1-20%; the glycolic acid-based copolymer contains glycolic acid units and degradable polyester A constituent units at the same time.
In one embodiment of the present invention, the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
In one embodiment of the present invention, the lubricant is at least one of paraffin wax, liquid paraffin wax, polyethylene wax, stearic acid amide, methylene bis stearic acid amide, N-ethylene bis stearic acid amide, and pentaerythritol stearate;
in an embodiment of the present invention, the chain extender may specifically be selected from the group consisting of chain extenders ADR, SAG, HDI, IPDI, MDI, TDI.
In one embodiment of the present invention, the composition may be added with at least one of 0 to 5 parts of nucleating agent, 0 to 3 parts of antibacterial agent, 0 to 3 parts of plasticizer, 0 to 3 parts of ultraviolet absorber, 0 to 3 parts of antistatic agent, and 0 to 3 parts of melt reinforcing agent.
In one embodiment of the invention, the nucleating agent is an organic nucleating agent and at least one of magnesium stearate, sodium benzoate, Surlyn 8920.
In one embodiment of the invention, in the first embodiment, the temperature of the melt blending of the degradable polyester A and the compatibilizer is 1 to 150 ℃ above the melting point of the degradable polymer A, and the blending time is 1 to 15 minutes. Alternatively, the melt blending may be performed by melt blending in an internal mixer or by melt blending in a twin-screw extruder.
In one embodiment of the present invention, in the first embodiment, the temperature of the polyglycolic acid, the blending masterbatch, the functional filler, the antioxidant, the lubricant, and the chain extender after premixing is 1 to 50 ℃ above the melting point of the polyglycolic acid. Alternatively, melt blending may be melt blended in a twin screw extruder.
In one embodiment of the present invention, in the second embodiment, the temperature of melt blending the premixture is 1 to 50 ℃ above the melting point of polyglycolic acid. Alternatively, the premixes are melt blended by an internal mixer or twin screw extruder.
The invention provides a polyvinyl alcohol-based composite material prepared by the method.
The invention also provides the application of the polyvinyl alcohol-based composite material in the field of equipment manufacturing and packaging.
Compared with the prior art for preparing the polyvinyl alcohol-based composite material, the invention mainly has the following outstanding advantages:
(1) according to the invention, by adding the compatilizer, the interfacial interaction force between the polyglycolic acid matrix and the degradable polyester B is obviously improved, so that the degradable polyester B has a better toughening effect, and the toughening effect of the degradable polyester B can be further improved by preferably using a two-step method according to the compatilizer and the difference of the reaction activities of the two components; the heat resistance of the composite material is improved by adding the functional filler, and preferably, the functional filler and the polyglycolic acid matrix are subjected to in-situ reaction through activation modification of the inorganic filler, so that the functional filler is better dispersed in the matrix, a better crystallization promoting effect is achieved, and the heat resistance of the composite material is better improved.
(2) The toughness and the heat resistance of the polyglycolic acid are improved by adding the tough degradable polyester and the inorganic filler. When 20 parts of tough polyester and 20 parts of inorganic filler are added, the elongation at break of the polyglycolic acid composite material can reach more than 56, the tensile strength is kept at 78MPa, the heat distortion temperature can reach 82 ℃, and the cost of the polyglycolic acid-based composite material can be greatly reduced by adding the inorganic filler.
(3) The polyglycolic acid material prepared by the invention keeps high barrier property and is a completely biodegradable material.
(4) The method provided by the invention does not relate to any solvent, has the characteristics of no toxicity and no pollution, and related equipment is simple and easy to obtain and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of a brittle cross section of a polyglycolic acid composite material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples and comparative examples, but the examples should not be construed as limiting the scope of the present invention.
The following examples relate to polybutylene adipate/terephthalate: basf, C1200.
Polyglycolic acid: the number average molecular weight is 15 ten thousand, and the molecular weight distribution is 1.3.
Poly (butylene adipate/terephthalate): basf, C1200
Example 1
20 parts of poly (butylene adipate/terephthalate) and 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) are uniformly premixed at room temperature, and then added into an internal mixer to be mixed for 4 minutes (the mixing temperature is 190 ℃) to obtain a mixed master batch;
80 parts of polyglycolic acid, 23 parts of the blending master batch, 43700.1 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the related silane coupling agent KH550 activated talcum powder comprises the following steps: firstly, adding KH550 into a 95% ethanol aqueous solution, stirring overnight, and hydrolyzing to obtain a silane coupling agent solution; adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution (the weight ratio of the talcum powder to the coupling agent is 100: 3) while stirring, continuing stirring for 10 minutes, and drying for 24 hours at 80 ℃.
Example 2
20 parts of poly (butylene adipate/terephthalate) and 1 part of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) are uniformly premixed at room temperature, and then added into an internal mixer to be mixed for 4 minutes (the mixing temperature is 190 ℃) to obtain a mixed master batch;
80 parts of polyglycolic acid, 23 parts of the blending master batch, 43700.1 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the related silane coupling agent KH550 activated talcum powder comprises the following steps: firstly, adding KH550 into a 95% ethanol aqueous solution, stirring overnight, and hydrolyzing to obtain a silane coupling agent solution; adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution (the weight ratio of the talcum powder to the coupling agent is 100: 3) while stirring, continuing stirring for 10 minutes, and drying for 24 hours at 80 ℃.
Example 3
Uniformly premixing 20 parts of poly (butylene adipate/terephthalate) and 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) at room temperature, and adding the mixture into an internal mixer for mixing for 6 minutes (the mixing temperature is 190 ℃) to obtain a blending master batch;
80 parts of polyglycolic acid, 23 parts of the blending master batch, 43700.1 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the related silane coupling agent KH550 activated talcum powder comprises the following steps: firstly, adding KH550 into a 95% ethanol aqueous solution, stirring overnight, and hydrolyzing to obtain a silane coupling agent solution; adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution (the weight ratio of the talcum powder to the coupling agent is 100: 3) while stirring, continuing stirring for 10 minutes, and drying for 24 hours at 80 ℃.
Example 4
20 parts of poly (butylene adipate/terephthalate) and 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) are uniformly premixed at room temperature, and then added into an internal mixer to be mixed for 4 minutes (the mixing temperature is 170 ℃) to obtain a mixed master batch;
80 parts of polyglycolic acid, 23 parts of the blending master batch, 43700.1 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the related silane coupling agent KH550 activated talcum powder comprises the following steps: firstly, adding KH550 into a 95% ethanol aqueous solution, stirring overnight, and hydrolyzing to obtain a silane coupling agent solution; adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution (the weight ratio of the talcum powder to the coupling agent is 100: 3) while stirring, continuing stirring for 10 minutes, and drying for 24 hours at 80 ℃.
Example 5
80 parts of polyglycolic acid, 20 parts of polybutylene adipate/terephthalate, 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%), 44680.1 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol base composite material.
The preparation process of the related silane coupling agent KH550 activated talcum powder comprises the following steps: firstly, adding KH550 into a 95% ethanol aqueous solution, stirring overnight, and hydrolyzing to obtain a silane coupling agent solution; adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution (the weight ratio of the talcum powder to the coupling agent is 100: 3) while stirring, continuing stirring for 10 minutes, and drying for 24 hours at 80 ℃.
Example 6
80 parts of polyglycolic acid, 20 parts of polybutylene adipate/terephthalate, 0.3 part of hexamethylene diisocyanate, 20 parts of talcum powder, 44680.3 parts of chain extender ADR, 1 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 225 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol based composite material.
Example 7
60 parts of polyglycolic acid, 40 parts of poly (butylene adipate/terephthalate), 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of the glycidyl methacrylate is 5%), 43700.2 parts of chain extender, 25 parts of talcum powder, 0.5 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.5 part of polyethylene wax are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 220 ℃, the screw rotating speed is 150rpm) to obtain the high-performance polyvinyl alcohol based composite material.
Example 8
40 parts of poly (butylene adipate/terephthalate) and 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of the glycidyl methacrylate is 5%) are uniformly premixed at room temperature, and then added into an internal mixer to be mixed for 4 minutes (the mixing temperature is 190 ℃) to obtain a mixed master batch;
60 parts of polyglycolic acid, 43 parts of the blending master batch, 44680.2 parts of chain extender, 25 parts of talcum powder, 0.5 part of polyethylene wax, 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.5 part of polyethylene wax are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 220 ℃, the screw rotating speed is 150rpm) to obtain the high-performance polyglycolic acid-based composite material.
Example 9
80 parts of polyglycolic acid, 20 parts of polybutylene adipate/terephthalate, 0.3 part of hexamethylene diisocyanate, 43700.2 parts of chain extender ADR, 15 parts of boron nitride activated by silane coupling agent KH560 and 0.3 part of tris [2, 4-di-tert-butylphenyl ] phosphite are premixed uniformly at room temperature, and then the premix is added into a double-screw extruder from a main feeding port, and is subjected to continuous melt extrusion and granulation (the screw temperature is 230 ℃ and the screw rotation speed is 150rpm) to obtain the high-performance polyvinyl alcohol based composite material.
The preparation process of the related boron nitride activated by the silane coupling agent KH560 comprises the following steps: firstly, adding KH560 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding boron nitride into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the boron nitride to the coupling agent is 100: 5.
example 10
85 parts of polyglycolic acid, 15 parts of polybutylene succinate (with the molecular weight of 13 ten thousand), 0.3 part of hexamethylene diisocyanate, 10 parts of boron nitride activated by a silane coupling agent KH560 and 0.3 part of tris [2, 4-di-tert-butylphenyl ] phosphite are premixed uniformly at room temperature, and then the premix is added into a double-screw extruder from a main feeding port and is subjected to continuous melt extrusion and granulation (the screw temperature is 225 ℃, the screw rotating speed is 220rpm) to obtain the high-performance polyvinyl alcohol acid based composite material.
The preparation process of the related boron nitride activated by the silane coupling agent KH560 comprises the following steps: firstly, adding KH560 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding boron nitride into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the boron nitride to the coupling agent is 100: 3.
example 11
90 parts of polyglycolic acid, 10 parts of polybutylene succinate/adipate (with the molecular weight of 8 ten thousand), 44680.5 parts of chain extender ADR, 15 parts of talcum powder and calcium carbonate activated by silane coupling agent KH550, 1 part of liquid paraffin and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, and then the premix is added into a double-screw extruder from a main feeding port and subjected to continuous melt extrusion and granulation (the screw temperature is 230 ℃, the screw rotating speed is 180rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the silane coupling agent KH550 activated talcum powder and calcium carbonate comprises the following steps: firstly, adding KH550 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding talcum powder and calcium carbonate into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the talcum powder to the calcium carbonate to the coupling agent is 50:50: 4.
Example 12
85 parts of polyglycolic acid, 15 parts of polybutylene succinate (with the molecular weight of 13 ten thousand), 43702 parts of chain extender ADR, 2 parts of polyglycolic acid-butylene succinate copolymer, 20 parts of KH550 modified talcum powder and montmorillonite, 1 part of liquid paraffin and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 180rpm) to obtain the high-performance polyvinyl alcohol base composite material.
The preparation process of the talcum powder and the montmorillonite activated by the silane coupling agent KH550 comprises the following steps: firstly, adding KH550 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding talcum powder and montmorillonite into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the talcum powder to the montmorillonite to the coupling agent is 50:50: 4.
Comparative example 1
And adding 100 parts of dried polyglycolic acid into an internal mixer for melt blending for 5 minutes (the blending temperature is 230 ℃), and hot-pressing the obtained blend at the temperature of 240 ℃ to obtain the polyglycolic acid material.
Comparative example 2
And (3) uniformly premixing 80 parts of dried polyglycolic acid and 20 parts of polybutylene adipate/terephthalate at room temperature, adding the premix into a double-screw extruder from a main feeding port, and carrying out continuous melt extrusion and granulation (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the toughness degradable polyglycolic acid composite material.
Comparative example 3
And (2) uniformly premixing 80 parts of dried polyglycolic acid, 20 parts of polybutylene adipate/terephthalate and 20 parts of talcum powder at room temperature, adding the premix into a double-screw extruder from a main feeding port, and carrying out continuous melt extrusion and granulation (the screw temperature is 230 ℃ and the screw rotating speed is 200rpm) to obtain the heat-resistant toughness degradable polyglycolic acid composite material.
Comparative example 4
And (2) uniformly premixing 80 parts of dried polyglycolic acid, 20 parts of polybutylene adipate/terephthalate and 20 parts of silane coupling agent KH550 activated talcum powder at room temperature, adding the premix into a double-screw extruder from a main feeding port, and carrying out continuous melt extrusion and granulation (the screw temperature is 230 ℃, and the screw rotating speed is 200rpm) to obtain the high-heat-resistance degradable polyglycolic acid composite material.
The preparation process of the silane coupling agent KH550 activated talcum powder and calcium carbonate comprises the following steps: firstly, adding KH550 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the talcum powder to the calcium carbonate to the coupling agent is 100: 3.
comparative example 5
Uniformly premixing 20 parts of poly (butylene adipate/terephthalate) and 15 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) at room temperature, and adding the mixture into an internal mixer for mixing for 4 minutes (the mixing temperature is 190 ℃) to obtain a blending master batch;
80 parts of polyglycolic acid, 35 parts of the blending master batch, 43700.3 parts of chain extender, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol based composite material.
The preparation process of the silane coupling agent KH550 activated talcum powder and calcium carbonate comprises the following steps: firstly, adding KH550 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the talcum powder to the coupling agent is 100: 3.
comparative example 6
Uniformly premixing 20 parts of poly (butylene adipate/terephthalate) and 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) at room temperature, and adding the mixture into an internal mixer for mixing for 15 minutes (the mixing temperature is 190 ℃) to obtain a blending master batch;
80 parts of polyglycolic acid, 23 parts of the blending master batch, 43700.3 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the silane coupling agent KH550 activated talcum powder and calcium carbonate comprises the following steps: firstly, adding KH550 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the talcum powder to the coupling agent is 100: 3.
comparative example 7
20 parts of poly (butylene adipate/terephthalate) and 3 parts of ethylene-vinyl acetate-glycidyl methacrylate copolymer (the mass content of glycidyl methacrylate is 8%) are uniformly premixed at room temperature, and then added into an internal mixer to be mixed for 4 minutes (the mixing temperature is 230 ℃) to obtain a mixed master batch;
80 parts of polyglycolic acid, 23 parts of the blending master batch, 43700.3 parts of chain extender ADR, 20 parts of talcum powder activated by silane coupling agent KH550, 0.5 part of polyethylene wax and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are premixed uniformly at room temperature, then the premix is added into a double-screw extruder from a main feeding port, and continuous melt extrusion and granulation are carried out (the screw temperature is 230 ℃, the screw rotating speed is 200rpm) to obtain the high-performance polyvinyl alcohol-based composite material.
The preparation process of the silane coupling agent KH550 activated talcum powder and calcium carbonate comprises the following steps: firstly, adding KH550 into 95% ethanol water solution, stirring overnight for hydrolysis to obtain silane coupling agent solution, adding talcum powder into a high-speed stirrer, adding the silane coupling agent solution while stirring, continuing to stir for 10 minutes, and drying at 80 ℃ for 24 hours. The weight ratio of the talcum powder to the coupling agent is 100: 3.
the materials obtained in the examples and comparative examples were dried sufficiently and then used in an injection molding machine to prepare standard sample bars. And testing the tensile property of the material at normal temperature according to the GB/T1040-2006 standard method. The stretching rate was set at 10mm/min and the same sample was tested for at least 6 bars and averaged. The crystallinity is measured by DSC, and the heating rate is 10 ℃/min; the heat distortion temperature is tested according to the GB/T1634.2-2004 standard, and the test condition is 1.80 MPa. The test results are shown in table one.
Table 1 performance results of the polyglycolic acid-based composites prepared in example 1 and comparative example
As can be seen from fig. 1, the spherical PBAT particles in the blend prepared in example 1 were uniformly dispersed in the PGA matrix, with a diameter of about 1 μm, and the phase interface of the two phases was blurred, indicating good compatibility between PGA and PBAT.
As can be seen from table 1, pure polyglycolic acid (comparative example 1) has very high strength, but its elongation at break and notched impact strength are very low, and it is a very brittle material, and its crystallinity, though not low, is not high in heat distortion temperature due to low glass transition temperature. After the polyglycolic acid is blended with the tough degradable polyester poly (butylene adipate-terephthalate) (comparative example 2), the strength is obviously reduced, the toughness is improved to a certain extent but still at a lower level, and meanwhile, the heat distortion temperature is reduced due to the addition of the tough degradable polyester. After 20 parts of functional filler is continuously added (comparative example 3), the heat distortion temperature of the composite material is improved, but the toughness is slightly reduced. This is due to the poor compatibility of the tough polyester with the matrix, poor toughening effect with a substantial reduction in strength. The invention (as example 5) discloses a high-performance polyvinyl alcohol-based composite material, which is characterized in that a compatilizer methacrylate-based copolymer is added to compatibilize and modify tough polyester, so that the interfacial interaction force between the high-performance polyvinyl alcohol-based composite material and a polyglycolic acid matrix is remarkably improved, and the size of a dispersed phase is reduced; the functional filler is activated and modified, so that the agglomeration of the functional filler in the material is obviously reduced, and the dispersion is more uniform. Preferably, the composite material prepared by the two-step method (such as example 1) can further improve the compatibilization efficiency, the groups in the compatibilizer are different from the reactivity between the polyglycolic acid matrix and the polybutylene adipate-terephthalate, and the compatibilizer can be better dispersed in a phase interface selectively by the two-step method, so that the interface acting force is further improved. The two modification methods act together, so that the toughness and the heat resistance of the composite material are improved (the elongation at break reaches 66%, the notch impact strength reaches 15.7MPa, and the thermal deformation temperature reaches 82 ℃), and the tensile strength of the composite material is improved (the tensile strength is 78MPa) compared with that of an unmodified composite material, so that the high-performance polyvinyl alcohol base composite material is obtained. The two-step reaction uses different blending temperatures and blending times within the appropriate range to affect the compatibilization effect and thus the final properties of the composite (e.g., examples 1-4, example 8), but the properties are consistently higher than those of the samples prepared by one-step blending under the same conditions (examples 5 and 7). However, if the reaction temperature, time control or charge ratio control during the preparation of blend A is not proper, the desired compatibilization effect cannot be achieved, and the overall performance is poor (as in comparative examples 6-7). In addition, the composite prepared according to the invention (as in example 1) is also significantly inferior in the overall performance by compatibilization modification of only one of the functional fillers (comparative example 4). The preparation method disclosed by the invention is simple and practical, is easy for industrial production, and the obtained high-performance polyvinyl alcohol-based composite material has excellent strength, toughness and heat resistance, can be formed by a plastic forming process and is applied to the fields of plastic packaging and plastic products.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for preparing a high-performance polyvinyl alcohol-based composite material is characterized by comprising the following steps:
the preparation method comprises the following steps of: 50-95 parts of polyglycolic acid, 5-50 parts of tough degradable polyester, 0.5-30 parts of functional filler, 0.01-10 parts of compatilizer, 0-3 parts of antioxidant, 0-1 part of lubricant and 0-1 part of chain extender;
preparation by the first method: firstly, mixing the degradable polyester A and the compatilizer according to the weight part ratio, and carrying out melt blending to obtain a blending master batch; then uniformly premixing polyglycolic acid, blending master batch, functional filler, antioxidant, lubricant and chain extender, and then melting and blending through a double-screw extruder to obtain a polyglycolic acid-based composite material;
alternatively, prepared by mode two:
uniformly mixing polyglycolic acid, degradable polyester A, functional filler, compatilizer, antioxidant, lubricant and chain extender according to the weight part ratio to obtain a premix, and then carrying out melt blending on the premix to obtain a polyglycolic acid-based composite material;
the degradable polyester A is at least one of polylactic acid, adipic acid/butylene terephthalate copolymer, polycaprolactone, polybutylene succinate, polyhydroxyalkanoate, polybutylene succinate/adipate copolymer and carbon dioxide-based copolymer.
2. The method of claim 1, wherein the polyglycolic acid is a homopolymer of glycolic acid or a glycolic acid-based copolymer.
3. The method of claim 1, wherein the functional filler is at least one of talc, graphene, wollastonite, boron nitride, and montmorillonite which are unmodified or surface-modified; the surface modification refers to modification using a silane coupling agent or a fatty acid.
4. The method of claim 1, wherein the compatibilizing agent comprises: at least one of the methacrylate-based copolymer, the vinyl acetate-based copolymer and the glycolic acid-based copolymer also contains a glycidyl methacrylate structural unit; wherein the mass percentage content of the glycidyl methacrylate is 0.1-20%; the glycolic acid-based copolymer contains glycolic acid units and degradable polyester A constituent units at the same time.
5. The method according to claim 1, wherein in the first mode, the temperature for melt blending the degradable polyester A and the compatibilizer is 1 to 150 ℃ above the melting point of the degradable polymer A, and the blending time is 1 to 15 minutes.
6. The method according to claim 1, wherein in the first mode, the temperature of the polyglycolic acid, the blending master batch, the functional filler, the antioxidant, the lubricant and the chain extender is 1 to 50 ℃ above the melting point of the polyglycolic acid when the polyglycolic acid, the blending master batch, the functional filler, the antioxidant, the lubricant and the chain extender are premixed and then melt-blended.
7. The method according to claim 1, wherein in the second mode, the temperature for melt blending the premixture is 1 to 50 ℃ above the melting point of polyglycolic acid.
8. The method according to any one of claims 1 to 7, wherein the components may be added with at least one of 0 to 3 parts of an antibacterial agent, 0 to 3 parts of a plasticizer, 0 to 3 parts of an ultraviolet absorber, 0 to 3 parts of an antistatic agent, and 0 to 3 parts of a melt reinforcing agent.
9. A polyglycolic acid-based composite material prepared by the method of any one of claims 1 to 8.
10. Use of a polyglycolic acid-based composite material according to claim 9 in the field of equipment manufacturing and packaging.
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