技术领域technical field
本发明涉及一种对聚肽膜柔顺性进行改进的方法，属于聚合物薄膜制备技术领域。The invention relates to a method for improving the flexibility of a polypeptide film, belonging to the technical field of polymer film preparation.
背景技术Background technique
聚肽是一种具有良好的生物相容性和生物可降解性的生物材料，聚肽膜可用作人造皮肤等，但聚肽比较僵硬，聚肽膜缺乏较好的柔顺性，从而一定程度上限制了其应用。聚丙二醇与聚三亚甲基碳酸酯具有较好的生物相容性和生物可降解性，比较柔软且相互间具有较好的共混性。先将聚丙二醇链段引入聚肽链段形成聚肽-聚丙二醇接枝共聚物以提高聚肽的共混性，然后再将聚三亚甲基碳酸酯链段加入聚肽-聚丙二醇二嵌段共聚物形成共混物，制得改性聚肽膜，从而极大地提高了聚肽膜的柔顺性。Polypeptide is a biomaterial with good biocompatibility and biodegradability. Polypeptide film can be used as artificial skin, etc., but the polypeptide is relatively stiff and lacks good flexibility, so to a certain extent limits its application. Polypropylene glycol and polytrimethylene carbonate have better biocompatibility and biodegradability, are relatively soft and have better blendability with each other. First, the polypropylene glycol segment is introduced into the polypeptide segment to form a polypeptide-polypropylene glycol graft copolymer to improve the blendability of the polypeptide, and then the polytrimethylene carbonate segment is added to the polypeptide-polypropylene glycol diblock The copolymer forms a blend to prepare a modified polypeptide film, which greatly improves the flexibility of the polypeptide film.
发明内容Contents of the invention
本发明的目的在于提供一种操作简单及效果较好的对聚肽膜柔顺性进行改进的方法。其技术方案为：The purpose of the present invention is to provide a method for improving the flexibility of the polypeptide film with simple operation and good effect. Its technical solution is:
一种用聚丙二醇与聚三亚甲基碳酸酯对聚肽膜柔顺性进行改进的方法，其特征在于：改性膜中聚肽链段的分子量为60000～80000，聚丙二醇链段的分子量为1000～2000，聚三亚甲基碳酸酯链段的分子量为4000～6000；其改性方法采用以下步骤：A method for improving the flexibility of a polypeptide film by using polypropylene glycol and polytrimethylene carbonate, characterized in that: the molecular weight of the polypeptide segment in the modified film is 60,000 to 80,000, and the molecular weight of the polypropylene glycol segment is 1000 ~2000, the molecular weight of the polytrimethylene carbonate segment is 4000~6000; the modification method adopts the following steps:
1）聚肽-聚丙二醇接枝共聚物的合成：在干燥反应器内加入聚肽均聚物、聚丙二醇单丁醚、溶剂和催化剂，惰性气氛下，于55～57℃搅拌反应2～3天后，通过过滤、透析、干燥制得目标物；1) Synthesis of polypeptide-polypropylene glycol graft copolymer: Add polypeptide homopolymer, polypropylene glycol monobutyl ether, solvent and catalyst into a dry reactor, and stir at 55-57°C for 2-3 hours under an inert atmosphere. Days later, the target object was obtained by filtration, dialysis, and drying;
2）聚丙二醇与聚三亚甲基碳酸酯改性的聚肽膜的制备：在干燥反应器内加入聚肽-聚丙二醇接枝共聚物、聚三亚甲基碳酸酯和溶剂，惰性气氛下，于45～50℃搅拌混合40～60分钟后，用流延法成膜并干燥，得到目标物。2) Preparation of polypropylene glycol and polytrimethylene carbonate-modified polypeptide film: Add polypeptide-polypropylene glycol graft copolymer, polytrimethylene carbonate and solvent in a drying reactor, and in an inert atmosphere, in Stir and mix at 45-50°C for 40-60 minutes, then form a film by casting method and dry to obtain the target product.
所述的一种用聚丙二醇与聚三亚甲基碳酸酯对聚肽膜柔顺性进行改进的方法，步骤1）中，聚肽均聚物采用聚（γ-苯甲基-L-谷氨酸酯）、聚（γ-乙基-L-谷氨酸酯）或聚（γ-甲基-L-谷氨酸酯），聚丙二醇单丁醚与聚肽均聚物的摩尔比为15～25:1。In the method for improving the flexibility of a polypeptide film by using polypropylene glycol and polytrimethylene carbonate, in step 1), the homopolymer of the polypeptide is poly(γ-benzyl-L-glutamic acid ester), poly(γ-ethyl-L-glutamate) or poly(γ-methyl-L-glutamate), the molar ratio of polypropylene glycol monobutyl ether to polypeptide homopolymer is 15～ 25:1.
所述的一种用聚丙二醇与聚三亚甲基碳酸酯对聚肽膜柔顺性进行改进的方法，步骤1）中，催化剂采用对甲苯磺酸，催化剂与聚肽均聚物的摩尔比为25～45:1，溶剂采用1,2-二氯乙烷或1,1,2-三氯乙烷，反应物溶液浓度为5～15g:100mL。In the method for improving the flexibility of the polypeptide film by using polypropylene glycol and polytrimethylene carbonate, in step 1), the catalyst uses p-toluenesulfonic acid, and the molar ratio of the catalyst to the homopolymer of the polypeptide is 25 ～45:1, the solvent is 1,2-dichloroethane or 1,1,2-trichloroethane, and the concentration of the reactant solution is 5～15g:100mL.
所述的一种用聚丙二醇与聚三亚甲基碳酸酯对聚肽膜柔顺性进行改进的方法，步骤2）中，聚三亚甲基碳酸酯在改性膜中的质量百分比为2～4%，溶剂采用1,2-二氯乙烷或1,1,2-三氯乙烷，混合物溶液浓度为25～30g:100mL。In the method for improving the flexibility of the polypeptide film by using polypropylene glycol and polytrimethylene carbonate, in step 2), the mass percentage of polytrimethylene carbonate in the modified film is 2-4% , the solvent is 1,2-dichloroethane or 1,1,2-trichloroethane, and the concentration of the mixture solution is 25-30g:100mL.
本发明与现有技术相比，其优点为：Compared with the prior art, the present invention has the advantages of:
1、所述的聚丙二醇与聚三亚甲基碳酸酯改进聚肽膜柔顺性的方法，采用接枝共聚和共混两种手段，操作简单、易于掌握；1. The method for improving the flexibility of the polypeptide film with polypropylene glycol and polytrimethylene carbonate adopts two methods of graft copolymerization and blending, which are simple to operate and easy to master;
2、所述的聚肽改性膜柔顺性有了很大的提高。2. The flexibility of the polypeptide modified membrane has been greatly improved.
具体实施方式detailed description
实施例1Example 1
1）聚肽-聚丙二醇接枝共聚物的合成：1) Synthesis of polypeptide-polypropylene glycol graft copolymer:
在干燥反应器内加入12克分子量为60000聚（γ-苯甲基-L-谷氨酸酯）、3.1克分子量为1000的聚丙二醇单丁醚、0.9克对甲苯磺酸，再加入260毫升1,1,2-三氯乙烷溶剂，惰性气氛下，于55℃搅拌反应2天后，终止反应，再通过过滤、透析、干燥制得目标物；Add 12 grams of poly(γ-benzyl-L-glutamate) with a molecular weight of 60,000, 3.1 grams of polypropylene glycol monobutyl ether with a molecular weight of 1000, and 0.9 grams of p-toluenesulfonic acid into the dry reactor, and then add 260 ml 1,1,2-Trichloroethane solvent, under an inert atmosphere, stirred and reacted at 55°C for 2 days, terminated the reaction, and then obtained the target product by filtration, dialysis, and drying;
2）聚丙二醇与聚三亚甲基碳酸酯改性的聚肽膜的制备：2) Preparation of Polypropylene Glycol and Polytrimethylene Carbonate Modified Polypeptide Film:
在干燥反应器内加入10克聚肽-聚丙二醇接枝共聚物和38.2毫升1,1,2-三氯乙烷溶剂，另加入占改性膜总重量2%的聚三亚甲基碳酸酯（分子量为4000），惰性气氛下，于45℃搅拌混合40分钟后，用流延法成膜，在50℃真空干燥箱中干燥得到目标物。Add 10 grams of polypeptide-polypropylene glycol graft copolymer and 38.2 milliliters of 1,1,2-trichloroethane solvent in the drying reactor, and add polytrimethylene carbonate (polytrimethylene carbonate) accounting for 2% of the total weight of the modified membrane in addition. The molecular weight is 4000), under an inert atmosphere, stirred and mixed at 45°C for 40 minutes, then formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.
经测试：本发明目标物的断裂伸长率比改性前提高了12.7%。After testing: the elongation at break of the object of the present invention is 12.7% higher than that before modification.
实施例2Example 2
1）聚肽-聚丙二醇接枝共聚物的合成：1) Synthesis of polypeptide-polypropylene glycol graft copolymer:
在干燥反应器内加入12克分子量为70000聚（γ-乙基-L-谷氨酸酯）、5.3克分子量为1500的聚丙二醇单丁醚、0.91克对甲苯磺酸，再加入216毫升1,1,2-三氯乙烷溶剂，惰性气氛下，于56℃搅拌反应3天后，终止反应，再通过过滤、透析、干燥制得目标物；Add 12 grams of poly(γ-ethyl-L-glutamate) with a molecular weight of 70,000, 5.3 grams of polypropylene glycol monobutyl ether with a molecular weight of 1500, and 0.91 grams of p-toluenesulfonic acid in the dry reactor, and then add 216 milliliters of 1 , 1,2-trichloroethane solvent, under an inert atmosphere, stirred and reacted at 56 ° C for 3 days, terminated the reaction, and then obtained the target product by filtration, dialysis, and drying;
2）聚丙二醇与聚三亚甲基碳酸酯改性的聚肽膜的制备：2) Preparation of Polypropylene Glycol and Polytrimethylene Carbonate Modified Polypeptide Film:
在干燥反应器内加入10克聚肽-聚丙二醇接枝共聚物和36.5毫升1,1,2-三氯乙烷溶剂，另加入占改性膜总重量3%的聚三亚甲基碳酸酯（分子量为5000），惰性气氛下，于47℃搅拌混合50分钟后，用流延法成膜，在50℃真空干燥箱中干燥得到目标物。Add 10 grams of polypeptide-polypropylene glycol graft copolymer and 36.5 milliliters of 1,1,2-trichloroethane solvent in the dry reactor, add the polytrimethylene carbonate ( The molecular weight is 5000), under an inert atmosphere, stirred and mixed at 47°C for 50 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.
经测试：本发明目标物的断裂伸长率比改性前提高了16.6%。After testing: the elongation at break of the object of the present invention is 16.6% higher than that before modification.
实施例3Example 3
1）聚肽-聚丙二醇接枝共聚物的合成：1) Synthesis of polypeptide-polypropylene glycol graft copolymer:
在干燥反应器内加入12克分子量为80000聚（γ-甲基-L-谷氨酸酯）、7.2克分子量为2000的聚丙二醇单丁醚、1.03克对甲苯磺酸，再加入177毫升1,2-二氯乙烷，惰性气氛下，于57℃搅拌反应3天后，终止反应，再通过过滤、透析、干燥制得目标物；Add 12 grams of poly(γ-methyl-L-glutamate) with a molecular weight of 80,000, 7.2 grams of polypropylene glycol monobutyl ether with a molecular weight of 2000, and 1.03 grams of p-toluenesulfonic acid in the dry reactor, and then add 177 milliliters of 1 , 2-dichloroethane, under an inert atmosphere, stirred and reacted at 57 ° C for 3 days, terminated the reaction, and then obtained the target product by filtration, dialysis, and drying;
2）聚丙二醇与聚三亚甲基碳酸酯改性的聚肽膜的制备：2) Preparation of Polypropylene Glycol and Polytrimethylene Carbonate Modified Polypeptide Film:
在干燥反应器内加入10克聚肽-聚丙二醇接枝共聚物和35.8毫升1,2-二氯乙烷，另加入占改性膜总重量4%的聚三亚甲基碳酸酯（分子量为6000），惰性气氛下，于50℃搅拌混合60分钟后，用流延法成膜，在50℃真空干燥箱中干燥得到目标物。Add 10 grams of polypeptide-polypropylene glycol graft copolymer and 35.8 milliliters of 1,2-dichloroethane into the dry reactor, and add polytrimethylene carbonate (molecular weight 6000) accounting for 4% of the total weight of the modified membrane ), under an inert atmosphere, stirred and mixed at 50°C for 60 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.
经测试：本发明目标物的断裂伸长率比改性前提高了18.5%。After testing: the elongation at break of the object of the present invention is increased by 18.5% compared with that before modification.
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| CN201410084337.5ACN103819906B (en) | 2014-03-10 | 2014-03-10 | A kind of method that polypropylene glycol and PTMC are improved poly-peptide film kindliness |
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