CN103865087A - Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone - Google Patents

Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone Download PDF

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Publication number
CN103865087A
CN103865087A CN201410083878.6A CN201410083878A CN103865087A CN 103865087 A CN103865087 A CN 103865087A CN 201410083878 A CN201410083878 A CN 201410083878A CN 103865087 A CN103865087 A CN 103865087A
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poly
peptide
ppdo
lactic acid
polylactic acid
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CN103865087B (en
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朱国全
王发刚
柳玉英
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Shandong University of Technology
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Shandong University of Technology
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Abstract

The invention discloses a method for improving the flexibility of a polypeptide membrane by polylactic acid and polydioxanone. The method comprises the following steps: (1) synthesizing polypeptide-polylactic acid grafted copolymer: adding polypeptide homopolymer, polylactic acid monododecyl ether, a solvent and a catalyst into a drying reactor, stirring to react for 2-3 days at 55-58 DEG C in the inert atmosphere, and filtering, dialyzing and drying to obtain a target product; (2) preparing a polylactic acid and polydioxanone modified polypeptide membrane: adding polypeptide-polylactic acid grafted copolymer, polydioxanone and a solvent into the drying reactor, stirring and mixing for 50-70 minutes at 40-50 DEG C in the inert atmosphere, forming a film by a tape casting method, and drying to obtain the target product. The preparation process is simple and easy to master, and the flexibility of the modified membrane is greatly improved.

Description

One is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness
Technical field
The present invention relates to one poly-peptide film kindliness is carried out to improved method, belong to field of polymer film preparing technology.
Background technology
Poly-peptide is a kind of have good biocompatibility and biomaterial of biodegradability, and poly-peptide film can be used as artificial skin etc., but poly-peptide is more stiff, and poly-peptide film lacks good kindliness, thereby has limited to a certain extent its application.Poly-(D, L) lactic acid and PPDO have good biocompatibility and biodegradability, soft and have each other a good blend.First polylactic acid chain segment is introduced to poly-peptide segment and formed poly-peptide-polylactic acid graft copolymer to improve the blend of poly-peptide, and then add poly-peptide-polylactic acid graft copolymer to form blend PPDO segment, make the poly-peptide film of modification, thereby greatly improved the kindliness of poly-peptide film.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate and effect preferably poly-peptide film kindliness to be carried out to improved method.Its technical scheme is:
One is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 60000~80000, the molecular weight of polylactic acid chain segment is 1000~2000, and the molecular weight of PPDO segment is 4000~5000; Its method of modifying adopts following steps:
1) poly-peptide-polylactic acid graft copolymer is synthetic: in dry reactor, add poly-peptide homopolymer, poly(lactic acid) monododecyl ether, solvent and catalyzer, under inert atmosphere, after 2~3 days, make target compound by filtering, dialyse, being dried in 55~58 DEG C of stirring reactions;
2) preparation of the poly-peptide film of poly(lactic acid) and PPDO modification: add poly-peptide-polylactic acid graft copolymer, PPDO and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50~70 minutes in 40~50 DEG C, by casting method film forming dry, obtain target compound.
Described one is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-Pidolidone ester) or poly-(r-methyl-Pidolidone ester), poly(lactic acid) monododecyl ether adopts poly-(D, L) lactic acid monododecyl ether, the mol ratio of poly(lactic acid) monododecyl ether and poly-peptide homopolymer is 15~25:1.
Described one is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, in step 1), catalyzer adopts tosic acid, the mol ratio of catalyzer and poly-peptide homopolymer is 25~45:1, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
Described one is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, step 2) in, the mass percent of PPDO in modified membrane is 1~3%, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1, described poly(lactic acid) and PPDO are improved the method for poly-peptide film kindliness, adopt graft copolymerization and two kinds of means of blend, simple to operate, be easy to grasp;
2, described poly-peptide modified membrane kindliness is greatly improved.
Embodiment
embodiment 1
1) poly-peptide-polylactic acid graft copolymer is synthetic:
In dry reactor, adding 12 gram molecular weights is poly(lactic acid) monododecyl ether, the 0.9 gram of tosic acid that 60000 poly-(r-phenmethyl-Pidolidone esters), 3.1 gram molecular weights are 1000, add again 260 milliliter 1,1,2-trichloroethane solvent, under inert atmosphere, in 55 DEG C of stirring reactions after 3 days, termination reaction, then by filtering, dialysis, the dry target compound that makes;
2) preparation of the poly-peptide film of poly(lactic acid) and PPDO modification:
In dry reactor, add 10 grams of poly-peptide-polylactic acid graft copolymers and 38 milliliter 1,1,2-trichloroethane solvent, separately add the PPDO (molecular weight is 4000) that accounts for modified membrane gross weight 1%, under inert atmosphere, be uniformly mixed after 50 minutes in 40 DEG C, use casting method film forming, the dry target compound that obtains in 50 DEG C of vacuum drying ovens.
After tested: the elongation at break of target compound of the present invention has improved 12.9% before than modification.
embodiment 2
1) poly-peptide-polylactic acid graft copolymer is synthetic:
In dry reactor, adding 12 gram molecular weights is poly(lactic acid) monododecyl ether, the 0.91 gram of tosic acid that 70000 poly-(r-ethyl-Pidolidone esters), 5.3 gram molecular weights are 1500, add again 230 milliliter 1,1,2-trichloroethane solvent, under inert atmosphere, in 56 DEG C of stirring reactions after 2 days, termination reaction, then by filtering, dialysis, the dry target compound that makes;
2) preparation of the poly-peptide film of poly(lactic acid) and PPDO modification:
In dry reactor, add 10 grams of poly-peptide-polylactic acid graft copolymers and 36 milliliter 1,1,2-trichloroethane solvent, separately add the PPDO (molecular weight is 4500) that accounts for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed after 60 minutes in 45 DEG C, use casting method film forming, the dry target compound that obtains in 50 DEG C of vacuum drying ovens.
After tested: the elongation at break of target compound of the present invention has improved 14.3% before than modification.
embodiment 3
1) poly-peptide-polylactic acid graft copolymer is synthetic:
In dry reactor, adding 12 gram molecular weights is poly(lactic acid) monododecyl ether, the 1.03 grams of tosic acid that 80000 poly-(r-methyl-Pidolidone esters), 7.2 gram molecular weights are 2000, add again 177 milliliters of dimethyl sulfoxide (DMSO), under inert atmosphere, in 58 DEG C of stirring reactions after 3 days, termination reaction, then make target compound by filtering, dialyse, being dried;
2) preparation of the poly-peptide film of poly(lactic acid) and PPDO modification:
In dry reactor, add 10 grams of poly-peptide-polylactic acid graft copolymers and 35.5 milliliters of dimethyl sulfoxide (DMSO), separately add the PPDO (molecular weight is 5000) that accounts for modified membrane gross weight 3%, under inert atmosphere, be uniformly mixed after 70 minutes in 50 DEG C, use casting method film forming, the dry target compound that obtains in 50 DEG C of vacuum drying ovens.
After tested: the elongation at break of target compound of the present invention has improved 15.6% before than modification.

Claims (4)

1. one kind is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 60000~80000, the molecular weight of polylactic acid chain segment is 1000~2000, and the molecular weight of PPDO segment is 4000~5000; Its method of modifying adopts following steps:
1) poly-peptide-polylactic acid graft copolymer is synthetic: in dry reactor, add poly-peptide homopolymer, poly(lactic acid) monododecyl ether, solvent and catalyzer, under inert atmosphere, after 2~3 days, make target compound by filtering, dialyse, being dried in 55~58 DEG C of stirring reactions;
2) preparation of the poly-peptide film of poly(lactic acid) and PPDO modification: add poly-peptide-polylactic acid graft copolymer, PPDO and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50~70 minutes in 40~50 DEG C, by casting method film forming dry, obtain target compound.
2. one according to claim 1 is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, it is characterized in that: in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-Pidolidone ester) or poly-(r-methyl-Pidolidone ester), poly(lactic acid) monododecyl ether adopts poly-(D, L) lactic acid monododecyl ether, the mol ratio of poly(lactic acid) monododecyl ether and poly-peptide homopolymer is 15~25:1.
3. one according to claim 1 is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, it is characterized in that: in step 1), catalyzer adopts tosic acid, the mol ratio of catalyzer and poly-peptide homopolymer is 25~45:1, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
4. one according to claim 1 is carried out improved method by poly(lactic acid) and PPDO to poly-peptide film kindliness, it is characterized in that: step 2) in, the mass percent of PPDO in modified membrane is 1~3%, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
CN201410083878.6A 2014-03-10 2014-03-10 A kind of method that poly-peptide film kindliness is improved by poly(lactic acid) and PPDO Expired - Fee Related CN103865087B (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN104497588A (en) * 2015-01-05 2015-04-08 山东理工大学 Method for improving hydrophilicity and flexibility of polydioxanone and polyacrylamide improved polypeptide film
CN104497591A (en) * 2015-01-05 2015-04-08 山东理工大学 Method for improving hydrophilicity and flexibility of polylactic acid and polyacrylamide improved polypeptide film
CN104559217A (en) * 2015-01-12 2015-04-29 山东理工大学 Method for improving hydrophilicity and flexibility of polypeptide film by polylactic acid and carboxymethyl chitosan
CN104559218A (en) * 2015-01-12 2015-04-29 山东理工大学 Method for improving hydrophilicity and flexibility of polypeptide film by poly(p-dioxanone) and carboxymethyl chitosan
CN104559211A (en) * 2015-01-06 2015-04-29 山东理工大学 Method for improving hydrophily and flexibility of polypeptide membrane by poly(p-dioxanone) and polyacrylic acid
CN105463623A (en) * 2015-12-08 2016-04-06 江苏苏博特新材料股份有限公司 POM (polyoxymethylene)-PLA (polylactic acid)-poly(p-dioxanone) ternary composite fibers and preparation method thereof
CN106977952A (en) * 2017-05-25 2017-07-25 山东理工大学 A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO
CN106977953A (en) * 2017-05-25 2017-07-25 山东理工大学 A kind of method that PLA is improved with PPDO to polypropylene sorrel water resistance and compliance
CN106987141A (en) * 2017-05-25 2017-07-28 山东理工大学 A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PPDO
CN107011677A (en) * 2017-05-25 2017-08-04 山东理工大学 A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PTMC

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* Cited by examiner, † Cited by third party
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CN107011669A (en) * 2017-05-22 2017-08-04 山东理工大学 A kind of method being improved with PPDO and PLA to polypropylene sorrel water resistance and compliance

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US6592847B1 (en) * 1998-05-14 2003-07-15 The General Hospital Corporation Intramolecularly-quenched near infrared flourescent probes

Patent Citations (1)

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US6592847B1 (en) * 1998-05-14 2003-07-15 The General Hospital Corporation Intramolecularly-quenched near infrared flourescent probes

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497588B (en) * 2015-01-05 2017-02-08 山东理工大学 Method for improving hydrophilicity and flexibility of polydioxanone and polyacrylamide improved polypeptide film
CN104497591A (en) * 2015-01-05 2015-04-08 山东理工大学 Method for improving hydrophilicity and flexibility of polylactic acid and polyacrylamide improved polypeptide film
CN104497588A (en) * 2015-01-05 2015-04-08 山东理工大学 Method for improving hydrophilicity and flexibility of polydioxanone and polyacrylamide improved polypeptide film
CN104559211B (en) * 2015-01-06 2017-03-08 山东理工大学 A kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid
CN104559211A (en) * 2015-01-06 2015-04-29 山东理工大学 Method for improving hydrophily and flexibility of polypeptide membrane by poly(p-dioxanone) and polyacrylic acid
CN104559218A (en) * 2015-01-12 2015-04-29 山东理工大学 Method for improving hydrophilicity and flexibility of polypeptide film by poly(p-dioxanone) and carboxymethyl chitosan
CN104559217A (en) * 2015-01-12 2015-04-29 山东理工大学 Method for improving hydrophilicity and flexibility of polypeptide film by polylactic acid and carboxymethyl chitosan
CN104559218B (en) * 2015-01-12 2017-06-16 山东理工大学 A kind of method that PPDO improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan
CN104559217B (en) * 2015-01-12 2017-06-30 山东理工大学 A kind of method that PLA improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan
CN105463623A (en) * 2015-12-08 2016-04-06 江苏苏博特新材料股份有限公司 POM (polyoxymethylene)-PLA (polylactic acid)-poly(p-dioxanone) ternary composite fibers and preparation method thereof
CN106977952A (en) * 2017-05-25 2017-07-25 山东理工大学 A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO
CN106977953A (en) * 2017-05-25 2017-07-25 山东理工大学 A kind of method that PLA is improved with PPDO to polypropylene sorrel water resistance and compliance
CN106987141A (en) * 2017-05-25 2017-07-28 山东理工大学 A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PPDO
CN107011677A (en) * 2017-05-25 2017-08-04 山东理工大学 A kind of method that PLA improves polypropylene sorrel water resistance and compliance with PTMC

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