CN104877352A - Compatibilizer-containing fibroin/polylactic acid blended material and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of polymer materials. The invention discloses a blend material of silk protein and polylactic acid. In the blend, the mass content of silk protein is 0.1-99.9%, and the mass content of polylactic acid is 99.9-0.1%. Said blend is added with silk protein and polylactic acid copolymer (PSFLA) as a compatibilizer to improve the compatibility of silk protein and polylactic acid. The dosage of the compatibilizer is 0.01-100.0% of the total mass of the silk protein and the polylactic acid. Add silk protein, polylactic acid and PSFLA into hexafluoroisopropanol and dissolve at 20-60°C to prepare a blend solution. The blend liquid is dried under normal pressure or vacuum at 20-150 DEG C for 0.5-24 hours to obtain a blend material of silk protein and polylactic acid. The silk protein raw material can be in the form of fibers, powders, flakes and blocks, and the polylactic acid can be homopolymers, copolymers or blends thereof.

Description

A kind of fibroin/polylactic acid blend material containing compatibilizer and its preparation method

Technical field:

The invention belongs to the technical field of polymer materials, and in particular relates to a blend material of silk protein and polylactic acid, a preparation method and application thereof.

Background technique:

Polylactic acid (PLA) is a biodegradable aliphatic polyester material. It has good biocompatibility, the degradation products are water and carbon dioxide, and has no pollution to the environment. It is widely used in tissue engineering and other biomedical fields. Polylactic acid is hydrophobic, and its cell adhesion is poor. It may cause inflammation after being implanted into the organism as a tissue engineering material. In addition, pure PLA resin has the disadvantages of slow crystallization rate, large shrinkage rate of molded products, poor dimensional stability, poor processing thermal stability, and poor durability of products, which limit the application of polylactic acid. Therefore, polylactic acid materials must be modified, and commonly used modification methods include copolymerization modification and blending modification. Among them, using other polymer materials to modify polylactic acid by blending is one of the simple and effective methods to improve the performance of polylactic acid. The copolymerization modification of polylactic acid is to change the hydrophilicity and crystallinity of the material through the copolymerization of polylactic acid and other monomers or oligomers. The degradation rate of the polymer can be determined according to the molecular weight of the copolymer and the comonomer or low The type and ratio of polymers can be controlled, so as to realize the wide application of polylactic acid materials in tissue engineering. The copolymerization modification process route of polylactic acid includes ring-opening polymerization of lactide/comonomer and co-condensation polymerization of lactic acid/comonomer. Lactide or lactic acid is copolymerized with hydrophilic monomers or polymers such as polyethylene glycol, amino acids, polypeptides and polysaccharides, and hydrophilic polymer segments are introduced into hydrophobic polylactic acid segments, which can Improve the biocompatibility of the material and regulate its degradation rate.

Silk fibroin (SF) is a natural amino acid copolymer with excellent mechanical properties and biocompatibility. Silk fibroin contains 18 kinds of amino acids, among which glycine (36%), alanine (28%), serine (14%) and tyrosine (10%) are more abundant. Some amino acids of silk protein widely exist in human and vertebrate tissues, and have affinity for human cells. Silk protein can be made into various forms such as fiber, powder, gel, silk peptide powder and silk film according to different purposes, and can be used as a cosmetic base material, food additive and pharmaceutical raw material. In recent years, silk fibroin gels and porous materials have been developed as drug release carriers, three-dimensional cell culture media, artificial skin, anticoagulant materials and dialysis membranes, etc., but the regenerated silk protein materials still have mechanical properties and degradation speed. Unmanageable problems. Moreover, the pure silk film has a high dissolution rate and cannot be used directly. After insolubilization treatment, the strength is relatively high, but the elongation is small. Therefore, regenerated silk protein materials need to be modified to meet the requirements of practical applications.

Research on polylactic acid modified by silk protein has attracted increasing attention. Gao Qinwei and others used silk protein as a hydrophilic group to copolymerize with polylactic acid to form a block copolymer to improve the hydrophilicity and biocompatibility of polylactic acid materials (ZL200810242819.3, ZL200810242818.9, ZL200910232602.9 , ZL200910232601.4, ZL200810242817.4). In addition, there are also research reports on the preparation of biomedical materials with excellent cell adhesion and good degradation performance by mixing silk protein and polylactic acid. Chen Jianyong and Zhang Jiazhong modified silk fibroin film with poly-L-lactic acid, and the mechanical properties of the blended film were significantly improved, and the vapor permeability was also improved, but the moisture permeability was slightly decreased (Acta Chemical Society, 2008, 3(59): 773～777; Functional Materials, 2007, 12(38): 2048～2051). Zhou Yan, Liu Yang, etc. made a blend film by fully mixing silk fibroin solution and polylactic acid solution, changing the structure and properties of silk fibroin, and preparing biodegradable films (Silk Monthly, 2007, 4: 16-18). Zhang Youzhu, Wu Jialin and others carried out research on the blending of polylactic acid and silk fibroin, electrospinning to prepare blended nanofibers or bioengineering scaffolds, and analyzed the biocompatibility and mechanical properties of the blends (Synthetic Fiber Industry, 2008, 31(3): 1～3; Journal of Applied Polymer Science, 2009, 113: 2675～2682; Journal of Materials Science, 2010, 93A: 158～163). Zhang Feng, Zuo Baoqi, etc. reported the preparation of silk fibroin/polylactic acid blended nanofibers by electrospinning, but the blending of SF and PLA could not form a compatible system, and there were two separate crystals in the blended SF/PLA nanofibers. Area (Polymer Materials Science and Engineering, 2009, 25(5): 75～78). At present, in the silk fibroin/polylactic acid blend materials prepared by the solution blending method, there are problems such as poor compatibility between silk fibroin and polylactic acid components, uneven mixing, and interface defects, which lead to difficulties in the performance of the blend materials. Meet the use requirements.

The severe shortage of oil resources in our country has restricted the development of economy, and our country has rich biological resources of lactic acid, which can replace petrochemical products. At the same time, my country is a big silk country in the world, and silk protein peptide chains can be prepared from waste silk and waste cocoons in production. Fibroin/polylactic acid modified materials have broad application prospects in the fields of biomedical materials, textile materials, plastics and coatings.

Invention content:

The purpose of the present invention is to overcome the problems existing in the preparation method and performance of the above-mentioned existing silk protein/polylactic acid blends, to prepare polylactic acid/silk protein blend materials by using silk protein and polylactic acid as raw materials, and to provide a The preparation method of the silk protein/polylactic acid blend material, the obtained blend has good processability, mechanical properties and other properties.

The technical scheme adopted to realize the object of the present invention is as follows:

A preparation method of a silk protein poly/lactic acid blend, the invention uses hexafluoroisopropanol as a solvent, silk protein (SF) and polylactic acid (PLA) as raw materials, and a copolymer (PSFLA) of silk protein and polylactic acid ) is a compatibilizer, and a solution blending method is adopted to prepare a PLA/SF blend material, and the obtained blend component includes 0.1 to 99.9% by weight of silk protein and 99.9 to 0.1% by weight of polylactic acid, and the compatibilizer ( The amount of PSFLA) is 0.01-100.0% of the total mass of polylactic acid and silk protein in the blend system.

The preparation process of the blend of silk protein and polylactic acid comprises: adding the silk protein into hexafluoroisopropanol, and stirring at a constant temperature of 20-60° C. until the silk protein is completely dissolved. Add polylactic acid with a mass fraction of 0.1-99.9% of the silk protein/polylactic acid blend into the solution, and stir at a constant temperature of 20-60°C until the polylactic acid is completely dissolved. Finally, add silk protein and polylactic acid copolymer (PSFLA), the amount of which is 0.01-100.0% of the total mass of polylactic acid and silk protein in the blend system, and stir at a constant temperature at 20-60°C until PSFLA is completely dissolved to obtain PSFLA-containing Silk protein/polylactic acid blend solution. The mass concentration of the hexafluoroisopropanol solution of the silk protein and polylactic acid blend is 0.1-40%. The blended solution is dried under normal pressure or vacuum at 20-150° C. for 0.5-24 hours, and hexafluoroisopropanol is recovered to obtain a blend of polylactic acid and silk fibroin. After the obtained blend is granulated and vacuum-dried, a silk protein/polylactic acid blend material is obtained.

Further, the mixed solution of silk protein and polylactic acid can also be prepared by the following steps: add silk protein, polylactic acid, and compatibilizer (PSFLA) to hexafluoroisopropanol in proportion at the same time, heat to a certain temperature, and then keep the temperature constant , until the dissolution is complete, to obtain the fibroin/polylactic acid blend solution.

Further, the mixed solution of silk protein and polylactic acid can also be prepared by the following steps: respectively dissolve silk protein, polylactic acid, and a compatibilizer (PSFLA) in hexafluoroisopropanol, and then dissolve the obtained silk protein solution 1. The polylactic acid solution is mixed with the hexafluoroisopropanol solution of the compatibilizer PSFLA to obtain the silk protein/polylactic acid blend solution.

Further, the mixed solution of silk protein and polylactic acid can also be prepared by the following steps: adding silk protein powder and PSFLA to hexafluoroisopropanol at the same time, heating at constant temperature to swell for a certain period of time or after dissolving, then adding polylactic acid, and constant temperature to The fibroin, polylactic acid and PSFLA are completely dissolved to obtain a fibroin/polylactic acid blend solution.

Further, the mixed solution of silk protein and polylactic acid can also be prepared by the following steps: adding silk protein powder and polylactic acid to hexafluoroisopropanol at the same time, heating at constant temperature to swell for a certain period of time or after dissolving, then adding PSFLA, constant temperature Until the fibroin, polylactic acid and PSFLA are completely dissolved to obtain a fibroin/polylactic acid blend solution.

Further, the mixed solution of silk protein and polylactic acid can also be prepared by the following steps: add polylactic acid and PSFLA to hexafluoroisopropanol at the same time, heat at constant temperature to swell for a certain period of time or dissolve, then add silk protein, and keep the temperature until The fibroin, polylactic acid and PSFLA are completely dissolved to obtain a fibroin/polylactic acid blend solution.

Further, the compatibilizer of the blend of silk protein and polylactic acid is a copolymer of silk protein and polylactic acid (PSFLA). The copolymer can be prepared by the following process: lactide and silk fibroin are used as raw materials, a stannous octoate/naphthalene disulfonic acid system is used as a catalyst, and the silk protein/polylactic acid copolymer (PSFLA) is obtained by ring-opening polymerization. PSFLA molecular chain contains silk fibroin segment and polylactic acid segment, which can improve the compatibility between the two components of silk protein and polylactic acid, and improve the performance of the blend.

Further, the polylactic acid is a homopolymer or copolymer of L-lactic acid and D-lactic acid, or a blend of any ratio between polylactic acid homopolymers, polylactic acid homopolymers and copolymers .

Further, the silk protein can be in different forms such as fibrous, powder, flake, block, etc., and the relative molecular mass of the silk protein is 1,000-300,000.

Further, the blended solution of silk protein and polylactic acid can be formed by methods such as coating, tape casting, extrusion and the like.

Furthermore, the hexafluoroisopropanol waste liquid generated in the production process can be recycled and regenerated, thereby reducing production costs and environmental pollution.

The invention adopts the method of solution blending to prepare the blend of silk protein and polylactic acid, the process is simple, the raw material source of silk protein is rich, and the forming method is simple. The silk protein and polylactic acid blend material of the present invention has the characteristics of uniform structure, low cost, high mechanical strength, good formability, little environmental pollution, degradable environment and the like.

Detailed ways:

The technical solutions of the present invention will be further described below in conjunction with specific embodiments. The present invention can be better understood from the following examples. However, the specific material ratios, process conditions and results described in the examples are only used to illustrate the present invention, and the examples are not intended to limit the scope of the present invention.

Example 1:

Add 5 parts of silk protein powder into 50 parts of hexafluoroisopropanol, heat up to 50°C and dissolve for 10 hours until the silk protein is completely dissolved, then add 15 parts of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 80,000 , 0.02 parts of polylactic acid and silk protein copolymer compatibilizer (PSFLA), continue to stir until PLLA, silk protein, and PSFLA are completely dissolved to obtain a blend. The blend solution was scraped on a constant temperature hot glass plate to form a film, evaporated to a gel at room temperature and pressure, and the resulting blend film was vacuum-dried at 50°C for 10 hours to obtain a silk protein/poly-L-lactic acid blend Material.

Example 2:

Add 1 part of silk protein powder to 50 parts of hexafluoroisopropanol, heat up to 50°C and dissolve for 5 hours until the silk protein is completely dissolved, then add 1 part of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 80,000 , 0.02 parts of compatibilizer (PSFLA), and continue to stir until PLLA, silk protein, and PSFLA are completely dissolved to obtain a blend. The blend was scraped on a constant temperature hot glass plate to form a film, and evaporated to a gel at normal temperature and pressure. The resulting blend film was vacuum-dried at 60° C. for 10 hours to obtain a silk protein/poly-L-lactic acid blend.

Example 3:

Add 19 parts of silk protein powder into 50 parts of hexafluoroisopropanol, heat up to 30°C and dissolve for 100 hours until the silk protein is completely dissolved, then add 1 part of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 80,000 , 0.2 parts of polylactic acid and silk protein copolymer compatibilizer (PSFLA), continue to stir until PLLA, silk protein, and PSFLA are completely dissolved to obtain a blend. The blend was scraped on a constant temperature hot glass plate to form a film, and evaporated to a gel at normal temperature and pressure. The resulting blend film was vacuum-dried at 50° C. for 24 hours to obtain a silk protein/poly-L-lactic acid blend material.

Example 4:

Add 2 parts of silk protein powder to 100 parts of hexafluoroisopropanol, heat up to 50°C and dissolve for 5 hours until the silk protein is completely dissolved, then add 38 parts of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 80,000 , 0.004 parts of polylactic acid and silk protein copolymer compatibilizer (PSFLA), continue to stir until PLLA, silk protein, and PSFLA are completely dissolved to obtain a blend. The blend was evaporated to gel at normal temperature and pressure. The resulting blend film was vacuum-dried at 60° C. for 10 hours to obtain a silk protein/poly-L-lactic acid blend material.

Example 5:

Add 1 part of silk protein powder to 50 parts of hexafluoroisopropanol, heat up to 50°C under stirring and swell for 5 hours until the silk protein is completely dissolved, then heat up to 60°C, and then add 1 part of Wan’s poly-L-lactic acid (PLLA), continue stirring at constant temperature until PLLA is completely dissolved, then add 0.1 part of compatibilizer PSFLA, continue stirring until PLLA, silk protein and PSFLA are completely dissolved, and obtain a PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, extruded, and the extruded product was vacuum-dried at 50° C. for 10 hours to obtain a silk protein/polylactic acid blend material.

Embodiment 6:

Add 19 parts of silk protein powder into 50 parts of hexafluoroisopropanol, heat up to 60°C under stirring and swell for 20 hours until the silk protein is completely dissolved, then heat up to 60°C, and then add 1 part of Wan's poly-L-lactic acid (PLLA), continue stirring at constant temperature until PLLA is completely dissolved, then add 8 parts of compatibilizer PSFLA, continue stirring until PLLA, silk protein and PSFLA are completely dissolved, and obtain PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, extruded, and the extruded product was vacuum-dried at 50° C. for 10 hours to obtain a silk protein/polylactic acid blend material.

Embodiment 7:

Add 10 parts of silk protein powder into 50 parts of hexafluoroisopropanol, heat up to 55°C under stirring and swell for 9 hours until the silk protein is completely dissolved, then add 10 parts of poly-L-lactic acid with a relative number average molecular weight of 30,000 (PLLA), continue stirring at constant temperature until PLLA is completely dissolved, then add 1 part of compatibilizer PSFLA, continue stirring until PLLA, silk protein and PSFLA are completely dissolved, and obtain PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, and then vacuum-dried at 50° C. for 10 hours to obtain a silk protein/polylactic acid blend material.

Embodiment 8:

Add 1 part of silk protein powder into 20 parts of hexafluoroisopropanol, and raise the temperature to 45°C under stirring until the silk protein is completely dissolved. Add 1 part of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 100,000 to 20 parts of hexafluoroisopropanol, and raise the temperature to 50°C under stirring until PLLA is completely dissolved. Add 0.1 part of compatibilizer PSFLA into 10 parts of hexafluoroisopropanol, and raise the temperature to 50°C under stirring until PSFLA is completely dissolved. The obtained fibroin solution, PLLA solution and PSFLA are mixed together to obtain a PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, and then vacuum-dried at 150° C. for 0.5 hour to obtain a silk protein/polylactic acid blend material.

Embodiment 9:

Add 10 parts of silk protein powder into 30 parts of hexafluoroisopropanol, and heat up to 50°C under stirring until the silk protein is completely dissolved. Add 10 parts of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 100,000 to 15 parts of hexafluoroisopropanol, and raise the temperature to 50°C under stirring until PLLA is completely dissolved. Add 1 part of compatibilizer PSFLA into 5 parts of hexafluoroisopropanol, and raise the temperature to 50°C under stirring until PSFLA is completely dissolved. The obtained fibroin solution, PLLA solution and PSFLA are mixed together to obtain a PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, and then vacuum-dried at 150° C. for 0.5 hour to obtain a silk protein/polylactic acid blend material.

Example 10:

Add 2 parts of silk protein powder into 20 parts of hexafluoroisopropanol, and raise the temperature to 50°C under stirring until the silk protein is completely dissolved. Add 2 parts of poly-L-lactic acid (PLLA) with a relative number-average molecular mass of 100,000 to 10 parts of hexafluoroisopropanol, and raise the temperature to 50°C under stirring until PLLA is completely dissolved. Add 4 parts of compatibilizer PSFLA into 20 parts of hexafluoroisopropanol, and raise the temperature to 55°C under stirring until PSFLA is completely dissolved. The obtained fibroin solution, PLLA solution and PSFLA are mixed together to obtain a PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, and then vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 11:

Add 1 part of silk protein powder, 1 part of poly-L-lactic acid (PLLA) with a relative number-average molecular weight of 100,000, and 0.1 part of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, and heat up to 50°C under stirring Until the fibroin, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The blended solution was evaporated to gel at normal temperature and pressure, the PLLA/SF blend was extruded, and the extrudate was vacuum-dried at 50°C for 10 hours to obtain a silk protein/polylactic acid blend material.

Example 12:

Add 10 parts of silk protein powder, 10 parts of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 100,000, and 1 part of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, and heat up to 55°C under stirring Until the fibroin, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The blended solution was evaporated to a gel state at normal temperature and pressure, and then vacuum-dried at 100° C. for 3 hours to obtain a silk protein/polylactic acid blend material.

Example 13:

Add 2 parts of silk protein powder, 2 parts of poly-L-lactic acid (PLLA) with a relative number-average molecular weight of 200,000, and 4 parts of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, and heat up to 55°C under stirring Until the fibroin, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 14:

Add 1 part of silk protein powder and 1 part of poly-L-lactic acid (PLLA) with a relative number average molecular mass of 100,000 to 50 parts of hexafluoroisopropanol at the same time, heat up to 50°C under stirring, and dissolve at a constant temperature for 3 hours. Then add 0.1 part of compatibilizer PSFLA, and keep the temperature at 50°C until the silk protein powder, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 50° C. for 15 hours to obtain a silk protein/polylactic acid blend material.

Example 15:

Add 10 parts of silk protein powder and 10 parts of poly-L-lactic acid (PLLA) with a relative number average molecular weight of 100,000 to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, and dissolve at a constant temperature for 10 hours. Then add 1 part of compatibilizer PSFLA, and keep the temperature at 50°C until the silk protein powder, PLLA and PSFLA are completely dissolved to obtain the PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 100° C. for 3 hours to obtain a silk protein/polylactic acid blend material.

Example 16:

Add 2 parts of silk protein powder and 2 parts of poly-L-lactic acid (PLLA) with a relative number average molecular mass of 100,000 to 50 parts of hexafluoroisopropanol at the same time, heat up to 50°C under stirring, and dissolve at constant temperature for 6 hours. Then add 4 parts of compatibilizer PSFLA, and keep the temperature at 55°C until the silk protein powder, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 17:

Add 1 part of silk protein powder and 0.1 part of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, and dissolve at constant temperature for 3 hours, then add 1 part of relative number average molecular weight of 100,000 The poly-L-lactic acid (PLLA) was kept at 50°C until the silk protein powder, PLLA, and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 50° C. for 15 hours to obtain a silk protein/polylactic acid blend material.

Example 18:

Add 10 parts of silk protein powder and 1 part of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, and dissolve at constant temperature for 10 hours, then add 10 parts with a relative number average molecular weight of 100,000 The poly-L-lactic acid (PLLA) was kept at 55°C until the silk protein powder, PLLA, and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 100° C. for 3 hours to obtain a silk protein/polylactic acid blend material.

Example 19:

Add 2 parts of silk protein powder and 4 parts of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 54°C under stirring, and dissolve at constant temperature for 8 hours, then add 2 parts with a relative number average molecular weight of 100,000 The poly-L-lactic acid is kept at 50°C until the silk protein powder, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 20:

Add 1 part of poly-L-lactic acid with a relative number average molecular weight of 100,000 and 0.1 part of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, dissolve at constant temperature for 3 hours, and then add 1 part of silk protein powder was kept at 50°C until the silk protein powder, PLLA, and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 50° C. for 24 hours to obtain a silk protein/polylactic acid blend material.

Example 21:

Add 10 parts of poly-L-lactic acid with a relative number average molecular weight of 100,000 and 1 part of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, dissolve at constant temperature for 10 hours, and then add 10 parts of silk protein powder were kept at a constant temperature of 55°C until the silk protein powder, PLLA, and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 100° C. for 3 hours to obtain a silk protein/polylactic acid blend material.

Example 22:

Add 2 parts of poly-L-lactic acid with a relative number average molecular weight of 100,000 and 4 parts of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, dissolve at constant temperature for 8 hours, and then add 2 parts of silk protein powder were kept at a constant temperature of 50°C until the silk protein powder, PLLA and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 23:

Add 1 part of purified waste silk, 1 part of poly-L-lactic acid with a relative number average molecular mass of 100,000, and 0.1 part of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, and heat up to 50 °C under stirring. Keep the temperature until the silk, PLLA and PSFLA are completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 50° C. for 15 hours to obtain a silk protein/polylactic acid blend material.

Example 24:

Add 10 parts of purified waste silk and 1 part of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 50°C under stirring, and dissolve at constant temperature for 10 hours, then add 10 parts with a relative number average molecular weight of 100,000 poly D, L-lactic acid, at a constant temperature of 55 ° C until the silk protein powder, PLLA, and PSFLA are completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 100° C. for 1 hour to obtain a silk protein/polylactic acid blend material.

Example 25:

Add 2 parts of purified waste silk and 4 parts of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, raise the temperature to 54 °C under stirring, and dissolve at constant temperature for 8 hours, then add 2 parts of poly-L-lactic acid and 2 Parts of poly D, L-lactic acid were kept at 50°C until the silk protein powder, PLLA, and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 26

Add 10 parts of poly-L-lactic acid, 5 parts of flaky silk protein, and 5 parts of compatibilizer PSFLA into 50 parts of hexafluoroisopropanol at the same time, heat up to 50°C under stirring, and dissolve at a constant temperature. Silk protein powder, PLLA, PSFLA Completely dissolved to obtain PLLA/SF blend. The PLLA/SF blend liquid was extruded, and the PLLA/SF blend was vacuum-dried at 95° C. for 6 hours to obtain a silk protein/polylactic acid blend material.

Example 27:

Add 1 part of purified waste silk, 1 part of poly-L-lactic acid with a relative number average molecular weight of 100,000, and 0.1 part of compatibilizer PSFLA to 50 parts of hexafluoroisopropanol at the same time, and stir at 20 ° C for 40 hours , and then raised the temperature to 50°C, and kept the temperature until the silk, PLLA, and PSFLA were completely dissolved to obtain a PLLA/SF blend. The PLLA/SF blend was vacuum-dried at 50° C. for 24 hours to obtain a silk protein/polylactic acid blend material.

Claims (10)

1. a blend for fibroin and poly (l-lactic acid), is characterized in that: in described blend, and the mass content of fibroin is 0.1 ~ 99.9%, and the mass content of poly(lactic acid) is 99.9 ~ 0.1%.

2. fibroin according to claim 1 and polylactic acid blend, is characterized in that: in fibroin and polylactic acid blend, with the addition of expanding material.This expanding material is the multipolymer (PSFLA) of fibroin and poly(lactic acid), containing silk fibroin segment and polylactic acid chain segment in its molecular chain.In fibroin and polylactic acid blend, add PSFLA, the fibroin in increase blend and the consistency between poly(lactic acid), improve the performance of fibroin and polylactic acid blend material.

3. the expanding material of fibroin according to claim 2 and polylactic acid blend, it is characterized in that: this expanding material is the multipolymer (PSFLA) of fibroin and poly(lactic acid), following technique is adopted to prepare: with rac-Lactide, silk fibroin for raw material, with stannous octoate/naphthalene disulfonic acid system for catalyzer, ring-opening polymerization obtains fibroin/copolymer of poly lactic acid (PSFLA).

4. fibroin according to claim 1 and polylactic acid blend, is characterized in that: the consumption of expanding material (PSFLA) is 0.01 ~ 100.0% of poly(lactic acid) and fibroin total mass in blend.

5. fibroin according to claim 1 and polylactic acid blend, is characterized in that: realize with the following step: first add in hexafluoroisopropanol by fibroin, is heated to 20 ~ 60 DEG C, and constant temperature is stirred to fibroin dissolves completely; Then add poly(lactic acid), constant temperature is stirred to poly(lactic acid) and dissolves completely; Finally add fibroin and copolymer of poly lactic acid (PSFLA), constant temperature is stirred to PSFLA and dissolves completely, finally obtains the fibroin/polylactic acid blend solution containing expanding material PSFLA.By this blend solution 20 ~ 150 DEG C of normal pressures or vacuum-drying 0.5 ~ 24 hour, obtain the blend of poly(lactic acid) and silk fibroin.The blend of gained is through granulation and after vacuum-drying, obtain fibroin/polylactic acid coblended matter material.

6. fibroin according to claim 1 and polylactic acid blend, it is characterized in that: described fibroin and poly(lactic acid) mixing solutions also can adopt following five kinds of modes to prepare: 1) add in hexafluoroisopropanol solution by fibroin, poly(lactic acid), fibroin and copolymer of poly lactic acid (PSFLA) simultaneously, constant temperature after being heated to 20 ~ 60 DEG C, dissolve completely to fibroin, poly(lactic acid), PSFLA, obtain blend solution.2) or by fibroin, poly(lactic acid), PSFLA be dissolved in hexafluoroisopropanol respectively, then the hexafluoroisopropanol solution of the hexafluoroisopropanol solution of the hexafluoroisopropanol solution of the fibroin of gained, poly(lactic acid), PSFLA is mixed, obtain blend solution.3) or by fibroin powder, PSFLA add in hexafluoroisopropanol simultaneously, after being heated to 20 ~ 60 DEG C, after swelling certain hour or completely dissolving, then add poly(lactic acid), constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.4) or by fibroin powder, poly(lactic acid) add in hexafluoroisopropanol simultaneously, after being heated to 20 ~ 60 DEG C, the swelling certain hour of constant temperature or after dissolving, then adds PSFLA, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.5) or by poly(lactic acid), PSFLA add in hexafluoroisopropanol simultaneously, after being heated to 20 ~ 60 DEG C, the swelling certain hour of constant temperature or after dissolving, then adds fibroin, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.

7. fibroin according to claim 1 and polylactic acid blend, is characterized in that: described fibroin can be the forms such as fiber, powder, thin slice or bulk, and its relative molecular mass is 1000 ~ 300000.

8. fibroin according to claim 1 and polylactic acid blend, is characterized in that: poly(lactic acid) be the homopolymer of Pfansteihl and D-ALPHA-Hydroxypropionic acid, multipolymer or these they between blend.

9. claim 5 and described fibroin and polylactic acid blend solution, is characterized in that: the concentration of the fibroin of gained and the hexafluoroisopropanol blend solution of poly(lactic acid) is 0.1 ~ 40%.

10. fibroin according to claim 1 and polylactic acid blend, is characterized in that: described fibroin and polylactic acid blend solution can be taked to extrude, curtain coating, coating process carry out shaping.Mold compound can be prepared into fibroin and polylactic acid blend pellet further.