CN106146867A - A kind of preparation method of the PLLA/PGA composite membrane degrading controlled - Google Patents

A kind of preparation method of the PLLA/PGA composite membrane degrading controlled Download PDF

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Publication number
CN106146867A
CN106146867A CN201610638912.0A CN201610638912A CN106146867A CN 106146867 A CN106146867 A CN 106146867A CN 201610638912 A CN201610638912 A CN 201610638912A CN 106146867 A CN106146867 A CN 106146867A
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Prior art keywords
plla
pga
district
composite membrane
dried
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CN201610638912.0A
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刘淑强
吴改红
许安
高志刚
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Taiyuan University of Technology
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Taiyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The present invention relates to the PLLA/PGA composite membrane preparation method of controlled degradation time.The preparation method of a kind of PLLA/PGA composite membrane degrading controlled, according to required degradation time, weighs PLLA and PGA mix homogeneously with precision balance, is then warmed up to 65 ~ 70 DEG C and is dried 34 hours, carries out pre-crystallized, continues to be warmed up to 110 DEG C and is dried 12 hours；Extruded by double screw extruder, PLLA and the PGA mixture processed through step 2 is added in dichloromethane solution, makes PLLA and PGA mixture be completely dissolved；Use solvent evaporated method scraper film coating machine masking.The invention has the beneficial effects as follows: can make the degradation rate of composite membrane between bi-material.

Description

A kind of preparation method of the PLLA/PGA composite membrane degrading controlled
Technical field
The present invention relates to the PLLA/PGA composite membrane preparation method of controlled degradation time.
Background technology
PLLA, is a kind of abundant raw material source and reproducible polyphosphazene polymer ester material, is widely used in medical field, Particularly perform an operation stitching thread time, CO can drop in PLLA2And H2O, intermediate product lactic acid is also the normal products of internal metabolism, Need not take out stitches, it is to avoid the misery taken out stitches, be favored by a lot of people.But, PLLA is applied to during operation suture thread have one Individual problem, that is, the degradation cycle of PLLA does not mates with the healing rate of wound.When wound healing time in short-term, PLLA fails Degraded, can cause infection, and when wound healing time is long, PLLA has degraded, and strength declines, and also needs secondary to sew up.
Therefore need to prepare the controlled good biocompatibility of a kind of degradation cycle and biodegradable composite.
PGA, is another kind of polyphosphazene polymer ester material, good biocompatibility, and biodegradable, hydrophilic is higher than PLLA, because of This degradation rate is fast compared with PLLA.
Conventional patent application provides a lot of controlled composite of degrading, and provides one in patent 20880439.8 Plant Biodegradable mulch and the controlled mulch film of degraded of polyethylene integrative-structure, but this mulch film biocompatibility be bad, it is impossible to It is used as degradable material in human body.The direct solvent evaporated method also having prepares thin film, but the mixture for preparing of this method it Between the compatibility very poor.
Summary of the invention
The technical problem to be solved is: how to provide a kind of PLLA/PGA controlling degradation time to be combined Film.
PLLA/PGA composite membrane degradation time has relation with both mass ratios, and the degradation cycle of PLLA is usually six or seven Individual month, the degradation cycle of PGA was two or three months, if PLLA mass accounts for PLLA/PGA composite membrane gross mass in PLLA/PGA composite membrane A%(0 a 100), then the degradation cycle * of the degradation cycle+PGA film of the degradation cycle of PLLA/PGA composite membrane=PGA film The degradation cycle of a%, PGA film is relevant in the process conditions of itself with the degradation cycle of PGA film, uses these process conditions PGA film Degradation cycle is about 210 days, and the degradation cycle of PGA film is about 60 days, the PLLA/ therefore produced by these process conditions It is 60-210 days that PGA composite membrane can control degradation cycle, and error is less than 3 days.
Concrete technical scheme of the present invention is: the preparation method of a kind of PLLA/PGA composite membrane degrading controlled, According to required degradation time, weigh PLLA and PGA mix homogeneously with precision balance, be then warmed up to 65 ~ 70 DEG C of dry 3-4 little Time, carry out pre-crystallized, continue to be warmed up to 110 DEG C and be dried 12 hours；
Step 2, PLLA and PGA processed through step one is extruded by double screw extruder, double screw extruder 10 is set Individual heating-up temperature district is: 165 ~ 170 DEG C of 1-2 district, 171-174 DEG C of 3-4 district, 175-177 DEG C of 5-6 district, 178-182 DEG C of 7-8 district, 9- 10 185-190 DEG C of districts；
In step 3, PLLA and the PGA mixture addition dichloromethane solution that will process through step 2, shake under 25 DEG C of water-baths Swing after making PLLA and PG mixture A be completely dissolved and uniformly mixing, standing and defoaming, form bubble-free mixed solution, dichloromethane The amount of alkane solution meets makes PLLA and PGA mixture be completely dissolved；
Step 4, mixed solution step 3 prepared use and use solvent evaporated method scraper film coating machine masking.
The invention has the beneficial effects as follows: owing to raw material hydrophilic used is different, the degradation cycle of PLLA is usually six or seven Individual month, the degradation cycle of PGA was two or three months, the side evaporated by solvent by macromolecular materials different for both degradation cycles Method makes composite membrane, reaches different degradation rates by the mass percent changing two kinds of raw materials, can make composite membrane Degradation rate is between bi-material.The method evaporating solvent after using first melt blending during preparation, can solve directly to steam Sending out solvent and produce the problem of poor compatibility between mixture, this composite can be used for medical field, such as human organ, body Inner support and degradable operation suture thread.
Detailed description of the invention
Embodiment one:
(1) weigh 450gPLLA and 50gPGA section with precision balance, then section is blended in vacuum drum and is dried, use 2 stage seasonings, the most pre-crystallized before being dried.First risen to 65 ~ 70 DEG C of dry 3 ~ 4h by room temperature pre-crystallized, then be slowly ramped to 110 DEG C of dry 12h, so can make the moisture content of section reach less than 0.05%.
(2) dried section is prepared compound slice by double screw extruder.Arrange double screw extruder 10 to add Hot humidity province: 165 ~ 170 DEG C of 1-2 district, 171-174 DEG C of 3-4 district, 175-177 DEG C of 5-6 district, 178-182 DEG C of 7-8 district, 9-10 district 185-190℃。
(3) then compound slice is dissolved in equipped with in the conical flask of dichloromethane solution, water-bath constant temperature oscillator is modulated 25 DEG C, then putting in water-bath constant temperature oscillator by conical flask, PLLA and PGA can slowly be dissolved in dichloromethane solution, treats molten Liquid is completely dissolved and after mix homogeneously, standing and defoaming.
(4) mixed solution is poured on scraper film coating machine, owing to dichloromethane is particularly easy to volatilization, uses solvent evaporated method Masking, in film-forming process, uses the scraper of scraper film coating machine to scrape solution back and forth, and the composite film thickness so made is more equal Even.
(5) being immersed in the hanks buffer of simulated body fluid by prepared composite membrane, buffer is changed every day, fixed Phase measures strength and the mass loss rate of composite membrane.
(6) after result shows to degrade 24 weeks, the strength of composite membrane is reduced to original 50%, and after 30 weeks, quality becomes original 50%.
Embodiment two:
(1) weigh 250gPLLA and 250 PGA sections with precision balance, then section is blended in vacuum drum and is dried, adopt By 2 stage seasonings, the most pre-crystallized before being dried.First risen to 65 ~ 70 DEG C of dry 3 ~ 4h by room temperature pre-crystallized, more slowly heat up To 110 DEG C of dry 12h, the moisture content of section so can be made to reach less than 0.05%.
(2) dried section is prepared compound slice by double screw extruder.Arrange double screw extruder 10 to add Hot humidity province: 165 ~ 170 DEG C of 1-2 district, 171-174 DEG C of 3-4 district, 175-177 DEG C of 5-6 district, 178-182 DEG C of 7-8 district, 9-10 district 185-190℃。
(3) then compound slice is dissolved in equipped with in the conical flask of dichloromethane solution, water-bath constant temperature oscillator is modulated 25 DEG C, then putting in water-bath constant temperature oscillator by conical flask, PLLA and PGA can slowly be dissolved in dichloromethane solution, treats molten Liquid is completely dissolved and after mix homogeneously, standing and defoaming.
(4) mixed solution is poured on scraper film coating machine, owing to dichloromethane is particularly easy to volatilization, uses solvent evaporated method Masking, in film-forming process, uses the scraper of scraper film coating machine to scrape solution back and forth, and the composite film thickness so made is more equal Even.
(5) prepared composite membrane is immersed in the hanks buffer of simulated body fluid, periodic measurement composite membrane strong Power and mass loss rate.
(6) after result shows to degrade 16 weeks, composite membrane strength reduces to original 50%, and after 18 weeks, quality reduces to original 50%.
Embodiment three:
(1) weigh 50gPLLA and 450gPGA section with precision balance, then section is blended in vacuum drum and is dried, use 2 stage seasonings, the most pre-crystallized before being dried.First risen to 65 ~ 70 DEG C of dry 3 ~ 4h by room temperature pre-crystallized, then be slowly ramped to 110 DEG C of dry 12h, so can make the moisture content of section reach less than 0.05%.
(2) dried section is prepared compound slice by double screw extruder.Arrange double screw extruder 10 to add Hot humidity province: 165 ~ 170 DEG C of 1-2 district, 171-174 DEG C of 3-4 district, 175-177 DEG C of 5-6 district, 178-182 DEG C of 7-8 district, 9-10 district 185-190℃。
(3) then compound slice is dissolved in equipped with in the conical flask of dichloromethane solution, water-bath constant temperature oscillator is modulated 25 DEG C, then putting in water-bath constant temperature oscillator by conical flask, PLLA and PGA can slowly be dissolved in dichloromethane solution, treats molten Liquid is completely dissolved and after mix homogeneously, standing and defoaming.
(4) mixed solution is poured on scraper film coating machine, owing to dichloromethane is particularly easy to volatilization, uses solvent evaporated method Masking, in film-forming process, uses the scraper of scraper film coating machine to scrape solution back and forth, and the composite film thickness so made is more equal Even.
(5) prepared composite membrane is immersed in the hanks buffer of simulated body fluid, periodic measurement composite membrane strong Power and mass loss rate.
(6) when result shows to degrade 12 weeks, composite membrane strength reduces to original 50%, and when degrading 13 weeks, quality is original 50%.

Claims (1)

1. the preparation method of a controlled PLLA/PGA composite membrane of degrading, it is characterised in that carry out according to the steps:
Step one, according to required degradation time, weigh PLLA and PGA mix homogeneously with precision balance, be then warmed up to 65 ~ 70 DEG C It is dried 3-4 hour, carries out pre-crystallized, continue to be warmed up to 110 DEG C and be dried 12 hours；
Step 2, PLLA and PGA processed through step one is extruded by double screw extruder, double screw extruder 10 is set Individual heating-up temperature district is: 165 ~ 170 DEG C of 1-2 district, 171-174 DEG C of 3-4 district, 175-177 DEG C of 5-6 district, 178-182 DEG C of 7-8 district, 9- 10 185-190 DEG C of districts；
In step 3, PLLA and the PGA mixture addition dichloromethane solution that will process through step 2, shake under 25 DEG C of water-baths Swing after making PLLA and PG mixture A be completely dissolved and uniformly mixing, standing and defoaming, form bubble-free mixed solution, dichloromethane The amount of alkane solution meets makes PLLA and PGA mixture be completely dissolved；
Step 4, mixed solution step 3 prepared use and use solvent evaporated method scraper film coating machine masking.
CN201610638912.0A 2016-08-08 2016-08-08 A kind of preparation method of the PLLA/PGA composite membrane degrading controlled Pending CN106146867A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107962696A (en) * 2017-12-14 2018-04-27 陈逊 A kind of manufacturing process of polyglycolic acid resin laminated film
CN108822516A (en) * 2018-07-12 2018-11-16 安徽聚美生物科技有限公司 A kind of preparation method of disposable polylactic acid high temperature resistant cup lid
CN110025824A (en) * 2019-04-15 2019-07-19 太原科技大学 A kind of orientation tissue engineering bracket preparation method of core-shell structure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101240086A (en) * 2008-03-14 2008-08-13 上海悦仕生物材料有限公司 Total-biodegradation plastic film and preparation method thereof
CN101328308A (en) * 2008-07-29 2008-12-24 武汉理工大学 High tenacity biodegradable polylactic acid film and preparation thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101240086A (en) * 2008-03-14 2008-08-13 上海悦仕生物材料有限公司 Total-biodegradation plastic film and preparation method thereof
CN101328308A (en) * 2008-07-29 2008-12-24 武汉理工大学 High tenacity biodegradable polylactic acid film and preparation thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
寇士军 等: ""PLLA/PGA复合纤维的降解研究"", 《天津纺织科技》 *
赵婧 等: ""聚乳酸/聚己内酯共混膜的制备及其性能"", 《膜科学与技术》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107962696A (en) * 2017-12-14 2018-04-27 陈逊 A kind of manufacturing process of polyglycolic acid resin laminated film
CN108822516A (en) * 2018-07-12 2018-11-16 安徽聚美生物科技有限公司 A kind of preparation method of disposable polylactic acid high temperature resistant cup lid
CN108822516B (en) * 2018-07-12 2020-11-03 安徽聚美生物科技有限公司 Preparation method of disposable polylactic acid high-temperature-resistant cup cover
CN110025824A (en) * 2019-04-15 2019-07-19 太原科技大学 A kind of orientation tissue engineering bracket preparation method of core-shell structure

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Application publication date: 20161123