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Polypeptide and polytetrahydrofuran graft copolymer and preparation method thereof

A technology of polytetrahydrofuran and graft copolymers, which is applied in the field of polymer material synthesis and preparation, can solve the problems of graft copolymers that have not been reported, increase the moisture resistance strength of copolymers, affect the efficiency of block copolymerization, etc., and achieve designable Strong resistance, moisture resistance, crystallization self-reinforcement, excellent biocompatibility

Active Publication Date: 2014-12-03
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Regarding block copolymers of polypeptide and polytetrahydrofuran, patent CN 1844191A discloses a preparation method for ring-opening polymerization of α-amino acid-N-carboxyl internal anhydride (NCA) by using amino-terminated polytetrahydrofuran as a macroinitiator. The copolymer The molecular weight of polytetrahydrofuran is 1800-50000. The introduction of polytetrahydrofuran segment can increase the moisture resistance of the copolymer, but the yield is usually lower than 80%, and the length of PTHF segment will obviously affect the efficiency of block copolymerization
[0006] However, there is no report about the graft copolymer of polytetrahydrofuran branched chain on the main chain of the polypeptide.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Poly(γ-benzyl-L-glutamate)-g-polytetrahydrofuran graft copolymer

[0029] A: Under nitrogen protection, dissolve 4.0g of γ-benzyl ester-L-glutamic acid (BLG) in 40mL of tetrahydrofuran (THF), add 2.0g of triphosgene, and react at 60°C for 2 hours to generate γ- Benzyl ester-L-glutamic acid-N-carboxyl internal anhydride (BLG-NCA) was precipitated with petroleum ether, filtered and dried to obtain the product with a yield of 33%. Dissolve 2.0 g of BLG-NCA in N, N-dimethylformamide, add 40 mg of triethylamine, react at 25 ° C for 6 hours, precipitate with methanol, and then dry in vacuo to obtain poly(γ-benzyl- L-glutamic acid ester), namely PBLG, the yield is 78%.

[0030] B: Under the protection of nitrogen, add 0.2mL methyl trifluoromethanesulfonate to 10mL solution containing THF and chloroform ([THF]=6.2mol / L), trigger THF to carry out living ring-opening polymerization at 20°C After 10 minutes, a single-ended polytetrahydrofuran active chain solution was obtained. ...

Embodiment 2

[0033] Poly(γ-benzyl-L-glutamate)-g-polytetrahydrofuran graft copolymer

[0034] A: Same as A in Example 1.

[0035] B: Same as B in Example 1, except that bulk polymerization is used.

[0036] C: Add 0.3 mL of the polytetrahydrofuran active chain solution of step B to 20 mL of the above PBLG in chloroform ([PBLG]=3.6 mmol / L) under stirring conditions, and react at 20° C. for 30 minutes. The obtained product was purified by chloroform and tetrahydrofuran solvents in sequence, and the purified product was vacuum-dried at a constant temperature of 40° C. for 18 hours to obtain 0.24 g of graft copolymer PBLG-g-PTHF. The grafting rate is 5%, and the M of the main chain PBLG n M of 2300, branched chain PTHF n for 1100.

Embodiment 3

[0038] Poly(γ-benzyl-L-glutamate)-g-polytetrahydrofuran graft copolymer

[0039] A: Same as A in Example 1.

[0040] B: Just change the addition amount of methyl trifluoromethanesulfonate to 0.3mL, and other conditions are the same as B in Example 1.

[0041] C: Under stirring conditions, add 4 mL of the polytetrahydrofuran living chain solution of step B to 20 mL of the above PBLG in chloroform ([PBLG]=3.6 mmol / L), and react at 20° C. for 30 minutes. The obtained product was purified by chloroform and tetrahydrofuran solvents in sequence, and the purified product was vacuum-dried at constant temperature at 40° C. for 18 hours to obtain 1.2 g of graft copolymer PBLG-g-PTHF. The grafting rate was 81%, and the M of the main chain PBLG n M of 2300, branched chain PTHF n for 700.

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Abstract

The invention relates to a polypeptide and polytetrahydrofuran graft copolymer and a preparation method thereof. A biodegradable polypeptide chain segment and a crystallizable weak-polarity polytetrahydrofuran chain segment form a graft copolymer, and excellent biocompatibility of the material is obtained. Certain anti-moisture strength of the material is obtained through the weak-polarity polytetrahydrofuran chain segment, and the crystallizable chain segment gives firmer physical crosslinking point and self-enhancement property to the material, thereby laying a good application foundation to the use of the material.

Description

Technical field: [0001] The invention relates to a graft copolymer with polypeptide as the main chain and polytetrahydrofuran as the branch chain and a preparation method thereof. It belongs to the field of polymer material synthesis and preparation. Background technique: [0002] Synthetic peptides have similar properties to natural peptides, can be degraded by enzymes in vivo, and release non-toxic small peptides or small molecule amino acids, which have good biodegradability and biocompatibility, and are used in tissue engineering and drug release carriers It has been widely used in materials, and can also be used in gene transfection vectors, macromolecular prodrugs, surface modification of biomaterials, and tissue engineering scaffolds after deprotection treatment. [0003] Polypeptide materials have many advantages, but their solubility varies greatly, making it difficult to control their degradation cycle and degradation rate, so their application is limited. The pr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G81/00C08G69/08C08G65/20
Inventor 吴一弦郭安儒俞瑞
Owner BEIJING UNIV OF CHEM TECH