CN110105730B - Preparation method of composite high-strength polylactic acid gradient membrane material - Google Patents
Preparation method of composite high-strength polylactic acid gradient membrane material Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite high-strength polylactic acid gradient film material, belonging to the technical field of gradient materials. The technical scheme of the invention adopts xylitol and sebacic acid as raw materials to prepare an elastomer material as a modified material, and because a plurality of methylene groups exist in a sebacic acid chain segment, a crystalline structure is easy to form, so that the crystallinity is high, the strength of the elastomer is high, the crosslinking degree of the elastomer is high, and the tensile strength of the elastomer is high; the invention adopts compound amino acid to carry out modification treatment, the tensile strength of the amino acid biological elastomer is subjected to the combined action of crosslinking density and crystallinity, when the two reach a certain synergistic action, the material has higher mechanical strength, the elastomer is added in the casting film forming process, an effective network structure is formed in the casting film material, the bonding performance of the material is effectively improved through the configuration of a three-dimensional network structure, the casting film material is effectively penetrated and intertwined to form a better elastic structure, and the elastic strength of the material has excellent level.
Description
Technical Field
The invention relates to a preparation method of a composite high-strength polylactic acid gradient film material, belonging to the technical field of gradient materials.
Background
The gradient functional material is a new type composite material, it is generally compounded by two or more than two kinds of materials, in the course of preparation the composition, structure and porosity etc. elements are continuously changed in a certain direction of the material, so that the property and function of the material are also continuously changed, so that it can be adapted to different environments, and can implement a certain special function, and possesses more excellent physical, chemical and mechanical properties than traditional composite material. The material is characterized in that the organization structure of the material is continuously changed due to the continuous change of the material composition or other elements, and no obvious interface is arranged in the material.
In nature, many biological materials with gradient structures, such as non-uniform gradient structures of bones and teeth, shell structures of shells and the like, have excellent physicochemical properties and can better adapt to environmental changes. Polylactic acid (PLA), Polycaprolactone (PCL) and Natural Rubber (NR) are some of the most commonly used high molecular materials with good biodegradability in the medical field and the food packaging field at present. The polylactic acid material has good biocompatibility, excellent mechanical property and easy processing property, but the degradation period of the polylactic acid material is not easy to control, the polylactic acid material has crisp and hard texture, insufficient elasticity and flexibility and is not easy to process. The polycaprolactone material has excellent biocompatibility and flexibility and moderate degradation rate, but the application of the PCL material is limited due to the low melting point of the polycaprolactone material. The natural rubber has high solid content, good film forming property and good viscosity controllability, but has poor aging resistance and high temperature resistance. Therefore, the concept of gradient functionalization is introduced into a composite system of polylactic acid, and the gradient material is prepared by utilizing the complementarity of the performances of the two systems through the special design of the material structure and the proper operation process, so that the gradient material is undoubtedly better adapted to the external environment than a single homogeneous polylactic acid material, and is more beneficial to meeting the actual requirement.
Polylactic acid gradient materials have many specific and superior properties compared to homogeneous materials of the same composition. Wherein the polylactic acid gradient material has potential application in a drug controlled release system. For example, hydrophobic rapamycin is used as a model drug, and the prepared PLGA gradient material is used as a drug slow release material carrier. Medical materials are also one of the most widely used areas of polymer gradient materials. For example, the polylactic acid gradient material consisting of four compact layers of PLLA, PDLLA and TCP and one foamed layer of PDLLA and TCP can meet the requirements of the bone tissue engineering scaffold. The polylactic acid material with gradient property has a three-dimensional gradient structure, is beneficial to the growth of cells and the transmission of nutrients, and also discharges metabolites; the fusion performance and the degradability between organisms are strong, the degradation speed and the absorption speed are easy to control, and the method can be suitable for the growth of cells and tissues; the external compact layer provides certain mechanical properties, which can meet the requirements of the implant material. In addition, the polylactic acid is subjected to surface modification to form a collagen gradient and a gelatin gradient, so that the adhesion, proliferation and differentiation of cells can be promoted, and the polylactic acid can be used as a cartilage tissue engineering scaffold material. Also a tissue engineering scaffold for vascular transplantation and a Ti/PLLA gradient material of medical implant materials, etc.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem of poor biodegradability of the existing polylactic acid material, a preparation method of a composite high-strength polylactic acid gradient film material is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) adding phosphogypsum whiskers and talcum powder into a silane coupling agent, stirring and mixing the materials, stirring and blending the materials in a high-speed stirrer, standing the materials for 25-30 min after blending, cooling the materials to room temperature, filtering and collecting filter residues, drying the filter residues at 55-65 ℃ for 6-8 h, and grinding the filter residues through a 200-mesh sieve to obtain inorganic reinforced particles;
(2) respectively weighing xylitol, sebacic acid, glutamic acid and polycaprolactone, placing the materials in a three-neck flask, stirring, mixing, heating in an oil bath, introducing nitrogen to remove air after the materials are melted, carrying out heat preservation reaction for 3-5 hours, standing, cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 3-5 hours, and collecting the crosslinked elastomer material;
(3) respectively weighing 45-50 parts of epoxy silicone oil, 10-15 parts of toluene diisocyanate and 10-15 parts of cross-linked elastomer in parts by weight, placing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer in a three-neck flask, stirring, mixing, carrying out heat preservation reaction, collecting reaction liquid, filtering, washing and drying to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing, and sieving to obtain sieving powder;
(4) adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed matrix liquid, placing the mixed matrix liquid at 45-50 ℃ for heat preservation reaction for 25-30 min, standing for defoaming, and performing tape casting to form a membrane material;
(5) drying the matrix membrane material to obtain a dry matrix membrane material, adding the inorganic reinforced particles, the sieved powder and the polycaprolactone into dichloromethane, stirring and mixing to obtain a mixed casting solution, casting the mixed casting solution into the dry matrix membrane material, standing to form a membrane, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient membrane material.
The mixing ratio of the phosphogypsum whisker, the talcum powder and the silane coupling agent in the step (1) is 1: 5.
The blending treatment temperature in the step (1) is 115-120 ℃.
The particle size of the inorganic reinforced particles in the step (1) is 200 meshes.
And (3) introducing nitrogen at a speed of 25-30 mL/min in the step (2).
The crosslinking reaction temperature in the step (2) is 145-155 ℃.
The xylitol, the sebacic acid, the glutamic acid and the polycaprolactone are mixed according to the following mixing proportion in parts by weight: 45-50 parts of xylitol, 10-15 parts of sebacic acid, 6-8 parts of glutamic acid and 3-5 parts of polycaprolactone.
And (4) the thickness of the cast film in the step (4) is 0.5-0.8 mm.
The dryness of the dry substrate membrane material in the step (5) is 85%.
The mixing ratio of the inorganic reinforced particles, the sieved powder, the polycaprolactone and the dichloromethane in the step (5) is 1: 5: 20 by mass.
Compared with other methods, the method has the beneficial technical effects that:
(1) the technical scheme of the invention adopts xylitol and sebacic acid as raw materials to prepare an elastomer material as a modified material, and because a plurality of methylene groups exist in a sebacic acid chain segment, a crystalline structure is easy to form, so that the crystallinity is high, the strength of the elastomer is high, the crosslinking degree of the elastomer is high, and the tensile strength of the elastomer is high;
(2) according to the invention, composite amino acid is adopted for modification treatment, the tensile strength of the amino acid biological elastomer is subjected to the combined action of crosslinking density and crystallinity, when the two components achieve a certain synergistic effect, the material has higher mechanical strength, the elastomer is added in the casting film forming process, an effective network structure is formed in the casting film material, the bonding performance of the material is effectively improved through the configuration of a three-dimensional network structure, the casting film material is effectively communicated and intertwined to form a better elastic structure, and the elastic strength of the material has an excellent level;
(3) the technical scheme of the invention adopts the phosphogypsum whisker composite talcum powder for modification, because hydroxyl on the surface of the phosphogypsum whisker and a silane coupling agent are subjected to chemical reaction, oleophylic groups in the phosphogypsum whisker are increased, the hydrophobicity is increased, the wetting area is small, the surface free energy is reduced, the agglomeration of particles among powder is effectively reduced, the dispersibility of the phosphogypsum whisker in a gradient film material is improved, the uniformly dispersed phosphogypsum whisker can play a good reinforcing role, and the mechanical property of the gradient film material is improved, because the crystallinity is reduced after modification, the flexibility of a material chain is improved, the intermolecular force is reduced, the molecular structure is looser, the molecular chain segment motion is easier, after an impact load is applied to the material, the impact strength of the material is obviously enhanced, the toughness is improved, and meanwhile, the dispersibility and orientation of the filler in a matrix are improved by the compounded talcum powder material, further improves the dispersion degree and the structural performance of the material, and obviously and effectively improves the mechanical property of the material.
Detailed Description
Adding phosphogypsum whiskers and talcum powder into a silane coupling agent according to the mass ratio of 1: 5, stirring and mixing, placing into a high-speed stirrer, stirring and mixing, controlling the blending temperature to be 115-120 ℃, blending for 25-30 min, standing and cooling to room temperature, filtering, collecting filter residues, drying at 55-65 ℃ for 6-8 h, and grinding and sieving with a 200-mesh sieve to obtain inorganic reinforced particles; respectively weighing 45-50 parts by weight of xylitol, 10-15 parts by weight of sebacic acid, 6-8 parts by weight of glutamic acid and 3-5 parts by weight of polycaprolactone, placing the xylitol, the sebacic acid, the glutamic acid and the polycaprolactone into a three-neck flask, stirring, mixing, placing the mixture in an oil bath at 150-160 ℃, heating, introducing nitrogen into the three-neck flask to remove air after melting is completed, controlling the introduction rate of the nitrogen to be 25-30 mL/min, carrying out heat preservation reaction for 3-5 h in a nitrogen atmosphere, standing and cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 3-5 h at 145-155 ℃, and collecting a crosslinked elastomer material; respectively weighing 45-50 parts by weight of epoxy silicone oil, 10-15 parts by weight of toluene diisocyanate and 10-15 parts by weight of cross-linked elastomer, placing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer into a three-neck flask, stirring and mixing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer, reacting for 3-5 hours at 75-80 ℃, collecting reaction liquid, filtering the reaction liquid, washing the reaction liquid with acetone for 3-5 times, drying the reaction liquid for 6-8 hours at 45-50 ℃ to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing on the modified elastomer particles, and sieving; adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed matrix liquid, placing the mixed matrix liquid at 45-50 ℃ for heat preservation reaction for 25-30 min, standing and defoaming for 1-2 h, performing tape casting to form a film, controlling the thickness of the tape casting matrix film to be 0.5-0.8 mm to obtain a matrix film material, drying the matrix film material to 85% dryness to obtain a dried matrix film material, adding the inorganic reinforced particles, the sieved powder and polycaprolactone into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain a mixed casting liquid, pouring the mixed casting liquid into the dried matrix film material, standing to form a film, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient film material.
Example 1
Adding phosphogypsum whiskers and talcum powder into a silane coupling agent, stirring and mixing the materials, stirring and blending the materials in a high-speed stirrer, standing the materials for 25min after blending, cooling the materials to room temperature, filtering and collecting filter residues, drying the filter residues at 55 ℃ for 6h, and grinding the filter residues through a 200-mesh sieve to obtain inorganic reinforced particles; respectively weighing xylitol, sebacic acid, glutamic acid and polycaprolactone, placing the materials in a three-neck flask, stirring, mixing, heating in an oil bath, introducing nitrogen to remove air after the materials are melted, carrying out heat preservation reaction for 3 hours, standing and cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 3 hours, and collecting the crosslinked elastomer material; respectively weighing 45 parts of epoxy silicone oil, 10 parts of toluene diisocyanate and 10 parts of cross-linked elastomer in parts by weight, placing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer in a three-neck flask, stirring, mixing, keeping the temperature for reaction, collecting reaction liquid, filtering, washing and drying to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing, and sieving to obtain sieved powder; adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed base fluid, placing the mixed base fluid at 45 ℃ for heat preservation reaction for 25min, standing and defoaming, and performing tape casting to form a film, thus obtaining a base film material; drying the matrix membrane material to obtain a dry matrix membrane material, adding the inorganic reinforced particles, the sieved powder and the polycaprolactone into dichloromethane, stirring and mixing to obtain a mixed casting solution, casting the mixed casting solution into the dry matrix membrane material, standing to form a membrane, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient membrane material. The mixing ratio of the phosphogypsum whisker, the talcum powder and the silane coupling agent is 1: 5. The blending treatment temperature was 115 ℃. The particle size of the inorganic reinforcing particles is 200 meshes. The nitrogen gas was introduced at a rate of 25 mL/min. The crosslinking reaction temperature was 145 ℃. The xylitol, the sebacic acid, the glutamic acid and the polycaprolactone are mixed according to the mixing proportion of 45 parts by weight, 10 parts by weight, 6 parts by weight and 3 parts by weight of the polycaprolactone. The thickness of the cast film is 0.5 mm. The dryness of the dried base film material was 85%. The mixing ratio of the inorganic reinforced particles, the sieved powder, the polycaprolactone and the dichloromethane is 1: 5: 20 by mass.
Example 2
Adding phosphogypsum whiskers and talcum powder into a silane coupling agent, stirring and mixing the materials, stirring and blending the materials in a high-speed stirrer, standing the materials for 26min after blending, cooling the materials to room temperature, filtering and collecting filter residues, drying the filter residues at 57 ℃ for 7h, and grinding the filter residues through a 200-mesh sieve to obtain inorganic reinforced particles; respectively weighing xylitol, sebacic acid, glutamic acid and polycaprolactone, placing the materials in a three-neck flask, stirring, mixing, heating in an oil bath, introducing nitrogen to remove air after the materials are melted, carrying out heat preservation reaction for 4 hours, standing, cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 4 hours, and collecting the crosslinked elastomer material; respectively weighing 46 parts of epoxy silicone oil, 11 parts of toluene diisocyanate and 11 parts of cross-linked elastomer according to parts by weight, placing the epoxy silicone oil, 11 parts of toluene diisocyanate and 11 parts of cross-linked elastomer into a three-neck flask, stirring, mixing, keeping the temperature, reacting, collecting reaction liquid, filtering, washing and drying to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing, and sieving to obtain sieved powder; adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed base fluid, placing the mixed base fluid at 46 ℃ for heat preservation reaction for 26min, standing and defoaming, and performing tape casting to form a film, thus obtaining a base film material; drying the matrix membrane material to obtain a dry matrix membrane material, adding the inorganic reinforced particles, the sieved powder and the polycaprolactone into dichloromethane, stirring and mixing to obtain a mixed casting solution, casting the mixed casting solution into the dry matrix membrane material, standing to form a membrane, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient membrane material. The mixing ratio of the phosphogypsum whisker, the talcum powder and the silane coupling agent is 1: 5. The blending treatment temperature was 116 ℃. The particle size of the inorganic reinforcing particles is 200 meshes. The nitrogen gas was introduced at a rate of 26 mL/min. The crosslinking reaction temperature was 147 ℃. The xylitol, the sebacic acid, the glutamic acid and the polycaprolactone are mixed according to the mixing proportion of respectively weighing 46 parts of xylitol, 11 parts of sebacic acid, 7 parts of glutamic acid and 4 parts of polycaprolactone according to parts by weight. The thickness of the cast film is 0.6 mm. The dryness of the dried base film material was 85%. The mixing ratio of the inorganic reinforced particles, the sieved powder, the polycaprolactone and the dichloromethane is 1: 5: 20 by mass.
Example 3
Adding phosphogypsum whiskers and talcum powder into a silane coupling agent, stirring and mixing the materials, stirring and blending the materials in a high-speed stirrer, standing the materials after blending for 27min, cooling the materials to room temperature, filtering and collecting filter residues, drying the filter residues at 59 ℃ for 7h, and grinding the filter residues through a 200-mesh sieve to obtain inorganic reinforced particles; respectively weighing xylitol, sebacic acid, glutamic acid and polycaprolactone, placing the materials in a three-neck flask, stirring, mixing, heating in an oil bath, introducing nitrogen to remove air after the materials are melted, carrying out heat preservation reaction for 4 hours, standing, cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 4 hours, and collecting the crosslinked elastomer material; respectively weighing 47 parts of epoxy silicone oil, 12 parts of toluene diisocyanate and 12 parts of cross-linked elastomer according to parts by weight, placing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer into a three-neck flask, stirring, mixing, keeping the temperature for reaction, collecting reaction liquid, filtering, washing and drying to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing, and sieving to obtain sieved powder; adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed base fluid, placing the mixed base fluid at 47 ℃ for heat preservation reaction for 27min, standing and defoaming, and performing tape casting to form a film, thus obtaining a base film material; drying the matrix membrane material to obtain a dry matrix membrane material, adding the inorganic reinforced particles, the sieved powder and the polycaprolactone into dichloromethane, stirring and mixing to obtain a mixed casting solution, casting the mixed casting solution into the dry matrix membrane material, standing to form a membrane, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient membrane material. The mixing ratio of the phosphogypsum whisker, the talcum powder and the silane coupling agent is 1: 5. The blending treatment temperature was 117 ℃. The particle size of the inorganic reinforcing particles is 200 meshes. The nitrogen gas was introduced at a rate of 27 mL/min. The crosslinking reaction temperature was 149 ℃. The mixing proportion of the xylitol, the sebacic acid, the glutamic acid and the polycaprolactone is that 47 parts of the xylitol, 12 parts of the sebacic acid, 7 parts of the glutamic acid and 4 parts of the polycaprolactone are respectively weighed according to the parts by weight. The thickness of the cast film is 0.7 mm. The dryness of the dried base film material was 85%. The mixing ratio of the inorganic reinforced particles, the sieved powder, the polycaprolactone and the dichloromethane is 1: 5: 20 by mass.
Example 4
Adding phosphogypsum whiskers and talcum powder into a silane coupling agent, stirring and mixing the materials, stirring and blending the materials in a high-speed stirrer, standing the materials after blending for 30min, cooling the materials to room temperature, filtering and collecting filter residues, drying the filter residues at 65 ℃ for 8h, and grinding the filter residues through a 200-mesh sieve to obtain inorganic reinforced particles; respectively weighing xylitol, sebacic acid, glutamic acid and polycaprolactone, placing the materials in a three-neck flask, stirring, mixing, heating in an oil bath, introducing nitrogen to remove air after the materials are melted, carrying out heat preservation reaction for 5 hours, standing and cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 5 hours, and collecting the crosslinked elastomer material; respectively weighing 50 parts of epoxy silicone oil, 15 parts of toluene diisocyanate and 15 parts of cross-linked elastomer according to parts by weight, placing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer into a three-neck flask, stirring, mixing, keeping the temperature, reacting, collecting reaction liquid, filtering, washing and drying to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing, and sieving to obtain sieved powder; adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed base fluid, placing the mixed base fluid at 50 ℃ for heat preservation reaction for 30min, standing and defoaming, and performing tape casting to form a film to obtain a base film material; drying the matrix membrane material to obtain a dry matrix membrane material, adding the inorganic reinforced particles, the sieved powder and the polycaprolactone into dichloromethane, stirring and mixing to obtain a mixed casting solution, casting the mixed casting solution into the dry matrix membrane material, standing to form a membrane, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient membrane material. The mixing ratio of the phosphogypsum whisker, the talcum powder and the silane coupling agent is 1: 5. The blending treatment temperature was 120 ℃. The particle size of the inorganic reinforcing particles is 200 meshes. The nitrogen gas was introduced at a rate of 30 mL/min. The crosslinking reaction temperature was 155 ℃. The xylitol, the sebacic acid, the glutamic acid and the polycaprolactone are mixed according to the mixing proportion of 50 parts by weight of the xylitol, 15 parts by weight of the sebacic acid, 8 parts by weight of the glutamic acid and 5 parts by weight of the polycaprolactone. The thickness of the cast film is 0.8 mm. The dryness of the dried base film material was 85%. The mixing ratio of the inorganic reinforced particles, the sieved powder, the polycaprolactone and the dichloromethane is 1: 5: 20 by mass.
Comparative example: a composite high-strength polylactic acid gradient film material produced by Dongguan company.
The composite high-strength polylactic acid gradient membrane material prepared in the examples and the comparative examples is detected as follows:
thickness: the thickness characterization test was performed using a ModelYG41 fabric thickness gauge manufactured by Laizhou electronic devices, Inc., as specified by the national Standard of FZ/T01003.
Biodegradability: shearing a sample and a pure polylactic acid film into a size of 5cm multiplied by 5cm, drying, weighing, respectively spreading and immersing in PS phosphate buffer solution with pH =7.2, setting the test temperature to be 35 ℃, setting the gradient difference value of degradation time, drying and weighing at regular time, and calculating the degradation weight loss rate according to a formula.
Mechanical properties: mechanical properties of the samples were tested using an INSTRON model 5566 universal tester according to the specifications of GB 3022-91.
The specific test results are shown in table 1.
Table 1 comparative table of property characterization
As shown in Table 1, the composite high-strength polylactic acid gradient membrane material prepared by the invention has good biodegradability and mechanical properties.
Claims (10)
1. A preparation method of a composite high-strength polylactic acid gradient membrane material is characterized by comprising the following specific preparation steps:
(1) adding phosphogypsum whiskers and talcum powder into a silane coupling agent, stirring and mixing the materials, stirring and blending the materials in a high-speed stirrer, standing the materials for 25-30 min after blending, cooling the materials to room temperature, filtering and collecting filter residues, drying the filter residues at 55-65 ℃ for 6-8 h, and grinding the filter residues through a 200-mesh sieve to obtain inorganic reinforced particles;
(2) respectively weighing xylitol, sebacic acid, glutamic acid and polycaprolactone, placing the materials in a three-neck flask, stirring, mixing, heating in an oil bath, introducing nitrogen to remove air after the materials are melted, carrying out heat preservation reaction for 3-5 hours, standing, cooling to room temperature, collecting a polymer, pouring the polymer into a mold, carrying out crosslinking reaction for 3-5 hours, and collecting the crosslinked elastomer material;
(3) respectively weighing 45-50 parts of epoxy silicone oil, 10-15 parts of toluene diisocyanate and 10-15 parts of cross-linked elastomer in parts by weight, placing the epoxy silicone oil, the toluene diisocyanate and the cross-linked elastomer in a three-neck flask, stirring, mixing, carrying out heat preservation reaction, collecting reaction liquid, filtering, washing and drying to obtain modified elastomer particles, taking the modified elastomer particles, carrying out ball milling and crushing, and sieving to obtain sieving powder;
(4) adding the sieved powder and polylactic acid into dichloromethane according to the mass ratio of 1: 5: 20, stirring and mixing to obtain mixed matrix liquid, placing the mixed matrix liquid at 45-50 ℃ for heat preservation reaction for 25-30 min, standing for defoaming, and performing tape casting to form a membrane material;
(5) drying the matrix membrane material to obtain a dry matrix membrane material, adding the inorganic reinforced particles, the sieved powder and the polycaprolactone into dichloromethane, stirring and mixing to obtain a mixed casting solution, casting the mixed casting solution into the dry matrix membrane material, standing to form a membrane, naturally drying, and demolding to obtain the composite high-strength polylactic acid gradient membrane material.
2. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the mixing ratio of the phosphogypsum whisker, the talcum powder and the silane coupling agent in the step (1) is 1: 5.
3. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the blending treatment temperature in the step (1) is 115-120 ℃.
4. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the particle size of the inorganic reinforced particles in the step (1) is 200 meshes.
5. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: and (3) introducing nitrogen at a speed of 25-30 mL/min in the step (2).
6. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the crosslinking reaction temperature in the step (2) is 145-155 ℃.
7. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the xylitol, the sebacic acid, the glutamic acid and the polycaprolactone are mixed according to the following mixing proportion in parts by weight: 45-50 parts of xylitol, 10-15 parts of sebacic acid, 6-8 parts of glutamic acid and 3-5 parts of polycaprolactone.
8. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: and (4) the thickness of the cast film in the step (4) is 0.5-0.8 mm.
9. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the dryness of the dry substrate membrane material in the step (5) is 85%.
10. The preparation method of the composite high-strength polylactic acid gradient film material according to claim 1, which is characterized in that: the mixing ratio of the inorganic reinforced particles, the sieved powder, the polycaprolactone and the dichloromethane in the step (5) is 1: 5: 20 by mass.
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| CN101037512A (en) * | 2007-03-29 | 2007-09-19 | 浙江大学 | Method for preparing polymer material with gradient distributed surface biomacromolecule |
| WO2012136701A1 (en) * | 2011-04-05 | 2012-10-11 | Universitätsklinikum Freiburg | Biocompatible and biodegradable gradient layer system for regenerative medicine and for tissue support |
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| CN101037512A (en) * | 2007-03-29 | 2007-09-19 | 浙江大学 | Method for preparing polymer material with gradient distributed surface biomacromolecule |
| WO2012136701A1 (en) * | 2011-04-05 | 2012-10-11 | Universitätsklinikum Freiburg | Biocompatible and biodegradable gradient layer system for regenerative medicine and for tissue support |
| CN103342014A (en) * | 2013-07-12 | 2013-10-09 | 华东理工大学 | Controllably biodegradable poly(lactic-co-glycolic acid) (PLGA) bore gradient membrane and preparation process thereof |
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