CN101712769A - Method for preparing polypropylene material with polylactic acid modified surface - Google Patents
Method for preparing polypropylene material with polylactic acid modified surface Download PDFInfo
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- CN101712769A CN101712769A CN200910212777A CN200910212777A CN101712769A CN 101712769 A CN101712769 A CN 101712769A CN 200910212777 A CN200910212777 A CN 200910212777A CN 200910212777 A CN200910212777 A CN 200910212777A CN 101712769 A CN101712769 A CN 101712769A
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Abstract
The invention aims to provide a simple practical method for modifying polypropylene surface to obtain required biocompatibility. The method comprises the following: step 1, pressing polypropylene raw material melted by a heating-melting method to be a thin slice with thickness of 0.33 mm; step 2, etching the polypropylene thin slice placed in an oxygen plasma cleaner; and step 3, placing the polypropylene thin slice treated with oxygen plasma in a 50mL round-bottom flask, adding 0.035 gram of 1,4-succinic anhydride and 0.06 gram of stannous chloride dihydrate (SnCl2.2H2O), adding 10 mL of lactic acid and then performing heating reaction for 10 hours under the protection of nitrogen. The method can solve the problem of combining polymer degradable material PLLA with polypropylene so as to form domestic novel herniorrhaphy composite material which is simple in process, economical and practical.
Description
Technical field
The present invention relates to the surface modification technology of polypropylene for medical article material, particularly relate to a kind of surface and utilize polylactic acid modified polypropylene film preparation methods.
Background technology
Polypropylene (polypropylene PP) is one of current five big class general-purpose plastics, because its raw material sources are abundant, low price is easy to machine-shaping, the product high comprehensive performance, and purposes is very extensive.Yet the low relatively surface energy of polypropylene and relative high chemical resistance have but hindered its application as functional materials, particularly when needs stick other compositions, as prepared Chinese ink, metal, mineral filler or other polymkeric substance etc.
Polypropylene is repaired as novel hernia and is begun to use clinically in the seventies in 20th century.The advantage of polypropylene sticking patch is that the net mesh of braiding is bigger, helps that surrounding tissue is grown into and the immersion of scavenger cell, is difficult in the twine hiding bacterium, so it not only has higher intensity, and anti-infection ability is also higher, at home and abroad most widely used.But such material is placed at intraperitoneal, can cause serious visceral surface adhesion.Aspect the starting material development of hernia sticking patch, China has possessed throughput.Shanghai Petrochemicals Company Ltd has succeeded in developing polypropylene for medical article, and other synthetic macromolecule base bio-absorbable fibers such as poly(lactic acid) and copolymer fibre thereof are used widely receiving medical field.The Sinopec Group that Donghua University accepts " synthetic method of poly(lactic acid) and fiber preparation process " project has been passed through technical evaluation in July, 2003.In vivo test shows, poly(lactic acid) (PLLA, polylactic acid) hydrolysis reaction can take place, the intermediate product of hydrolysis is a lactic acid, it is the eubolism product of sugar in the body, and the pathways metabolism that can follow according to lactic acid participates in biochemical metabolism in the body, finally generates harmless micromolecular water and carbonic acid gas, so can absorb in nontoxic, the nonirritant of this polymkeric substance, the body, have excellent biological compatibility.PLLA is obtaining application widely aspect surgical sutures, drug release carrier, tissue engineering bracket and the fixed repairing material.
In providing a kind of simple method, polypropylene surface is carried out modification, have the polypropylene material of resistance to blocking to become the technical problem that needs to be resolved hurrily in the art so that obtain the surface.
Summary of the invention
The purpose of this invention is to provide a kind of simple method, polypropylene surface is carried out modification, so that obtain specific biocompatibility, promptly surperficial resistance to blocking.A kind of polylactic acid modified polypropylene material, it is to produce with the method that may further comprise the steps:
A kind of surface utilizes the preparation method of polylactic acid modified polypropylene material, it is characterized in that, comprises following production stage:
Step 1: will be pressed into the thin slice of about 0.33mm after the method thawing of pp material with heating and melting;
Step 2: polypropylene sheet inserted carry out etching in the oxygen plasma cleanser;
Step 3: the polypropylene sheet that oxygen plasma treatment is crossed places in the 50mL round-bottomed flask, adds 0.035g 1,4 Succinic anhydried then, 0.06g two hydrated stannous chloride (SnCl
22H
2O), add lactic acid 10mL at last, under nitrogen protection, reacting by heating 10h.
Described pp material comprises isotatic polypropylene, syndiotactic polypropylene, Atactic Polypropelene, and the multipolymer of ethene and propylene, the molecular weight of described co-polymer from 10,000 to 4,000,000.
Operative temperature scope in the above-mentioned steps two is from 40 ℃ to 60 ℃.
The power range of the oxygen plasma cleanser in the above-mentioned steps two is from 50w to 150w.
Action time was from 1 second to 30 seconds in the above-mentioned steps two.
Temperature of reaction in the above-mentioned steps three is between 100 ℃ to 200 ℃.
Lactic acid in the above-mentioned steps three is selected from a kind of in L-lactic acid, D-lactic acid or the racemic lactic acid.
The concentration of the lactic acid aqueous solution in the above-mentioned steps three is between 85% to 100% (being pure lactic acid).
Beneficial effect of the present invention is:
Nonpolar polypropylene material is carried out finishing, can change its Surface Physical and chemical property, as put forward its character such as wetting ability, cementability, biocompatibility.In advance polypropylene is carried out surperficial carboxylated processing, carry out poly(lactic acid) (PLLA) grafting then on its surface, can solve high molecular degradable material PLLA and the polyacrylic problem that combines, thereby form simple, the economical and practical homemade novel hernia repairing composite material of technology.The PLLA material degraded and absorbed time in vivo is relevant with character, form and the volume of material, by changing the grafting condition, reaches the PLLA coating of different thickness, can explore suitable degradation time.Composite patch requires absorbable material degradation time in vivo more than 14 days, to such an extent as to there is time enough progressively to cover the skeleton (polypropylene layer) of sticking patch by the peritonaeum epithelial cell.
Consider from the health economics angle, consumption every year of global range entocele sticking patch is up to millions of, only the U.S. is used for the medical expense of hernia repairing every year up to 2.8 hundred million dollars, and perform the operation about about 20,000 examples in this class in China every year, surgery cost is about 100,000,000 yuans, the development of novel hernia sticking patch reduces the hernia medical expense and has important society and economic implications development China biomedical material.
Embodiment
Embodiment 1
Virgin pp preparation of sections and oxygen plasma surface etch:
Virgin pp preparation of sections: get one of polypropylene mesh, about 0.5cm * the 0.5cm of clip size, it is pressed into the essence polypropylene sheet of the about 0.8cm * 0.8cm of size under heating condition, with excessive propanone washed twice (magnetic stirring), each two hours, deionized water rinsing is clean, dry in loft drier (temperature＜85 ℃), preserve and called after PP dry back;
To place PDC-M type oxygen plasma cleanser etching 10s through virgin pp thin slice, specimen material called after PP-OH with the acetone rinsing;
The lip-deep lactic acid graft polymerization reaction of the polypropylene sheet that oxygen plasma treatment is crossed:
Get the polypropylene sheet PP-OH that 5 oxygen plasma treatment cross and put into two neck round-bottomed flasks;
Get 1,4-Succinic anhydried 0.018g puts into above flask;
Get two hydrated stannous chloride 0.030g and put into above flask;
Getting 85%L-lactic acid aqueous solution 5.0mL adds in the above flask;
140 ℃ of methyl-silicone oil oil bath temperatures are inserted magnetic stick and are stirred, and react reaction times 10h under the nitrogen protection.
Embodiment 2
Virgin pp preparation of sections and oxygen plasma surface etch
Virgin pp preparation of sections: get one of polypropylene mesh, about 0.5cm * the 0.5cm of clip size, it is pressed into the essence polypropylene sheet of the about 0.8cm * 0.8cm of size under heating condition, with excessive propanone washed twice (magnetic stirring), each two hours, deionized water rinsing is clean, dry in loft drier (temperature＜85 ℃), preserve and called after PP dry back;
To place PDC-M type oxygen plasma cleanser etching 30s through virgin pp thin slice, specimen material called after PP-OH with the acetone rinsing;
The lip-deep lactic acid graft polymerization reaction of the polypropylene sheet that oxygen plasma treatment is crossed:
Get the polypropylene sheet PP-OH that 5 oxygen plasma treatment cross and put into two neck round-bottomed flasks;
Get 1,4-Succinic anhydried 0.018g puts into above flask;
Get two hydrated stannous chloride 0.030g and put into above flask;
Getting 85%L-lactic acid aqueous solution 5.0mL adds in the above flask;
140 ℃ of methyl-silicone oil oil bath temperatures are inserted magnetic stick and are stirred, and react reaction times 10h under the nitrogen protection.
Embodiment 3
Virgin pp preparation of sections and oxygen plasma surface etch
Virgin pp preparation of sections: get one of polypropylene mesh, about 0.5cm * the 0.5cm of clip size, it is pressed into the essence polypropylene sheet of the about 0.8cm * 0.8cm of size under heating condition, with excessive propanone washed twice (magnetic stirring), each two hours, deionized water rinsing is clean, dry in loft drier (temperature＜85 ℃), preserve and called after PP dry back.
To place PDC-M type oxygen plasma cleanser etching 5s through virgin pp thin slice, specimen material called after PP-OH with the acetone rinsing;
The lip-deep lactic acid graft polymerization reaction of the polypropylene sheet that oxygen plasma treatment is crossed:
Get the polypropylene sheet PP-OH that 5 oxygen plasma treatment cross and put into two neck round-bottomed flasks;
Get 1,4-Succinic anhydried 0.018g puts into above flask;
Get two hydrated stannous chloride 0.030g and put into above flask;
Getting 85%L-lactic acid aqueous solution 5.0mL adds in the above flask;
160 ℃ of methyl-silicone oil oil bath temperatures are inserted magnetic stick and are stirred, and react reaction times 10h under the nitrogen protection.
Claims (8)
1. a surface utilizes the preparation method of polylactic acid modified polypropylene material, it is characterized in that, comprises following production stage:
Step 1: will be pressed into the thin slice of about 0.33mm after the method thawing of pp material with heating and melting;
Step 2: polypropylene sheet inserted carry out etching in the oxygen plasma cleanser;
Step 3: the polypropylene sheet that oxygen plasma treatment is crossed places in the 50mL round-bottomed flask, adds 0.035g 1,4 Succinic anhydried then, 0.06g two hydrated stannous chloride (SnCl
22H
2O), add lactic acid 10mL at last, under nitrogen protection, reacting by heating 10h.
2. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that described pp material comprises isotatic polypropylene, syndiotactic polypropylene, Atactic Polypropelene, and the multipolymer of ethene and propylene, the molecular weight of described co-polymer from 10,000 to 4,000,000.
3. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that the operative temperature scope in the described step 2 is from 40 ℃ to 60 ℃.
4. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that the power range of the oxygen plasma cleanser in the described step 2 is from 50w to 150w.
5. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that action time was from 1 second to 30 seconds in the described step 2.
6. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that the temperature of reaction in the described step 3 is between 100 ℃ to 200 ℃.
7. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that, the lactic acid in the described step 3 is selected from a kind of in L-lactic acid, D-lactic acid or the racemic lactic acid.
8. utilize the preparation method of polylactic acid modified polypropylene material as claim 1 described surface, it is characterized in that, the concentration of the lactic acid aqueous solution in the described step 3 is between 85% to 100% (being pure lactic acid).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910212777A CN101712769A (en) | 2009-11-09 | 2009-11-09 | Method for preparing polypropylene material with polylactic acid modified surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910212777A CN101712769A (en) | 2009-11-09 | 2009-11-09 | Method for preparing polypropylene material with polylactic acid modified surface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205151A (en) * | 2011-05-23 | 2011-10-05 | 中国医学科学院生物医学工程研究所 | Hernia patch solid-supported with antibiotic and preparation method |
| CN103028144A (en) * | 2011-09-30 | 2013-04-10 | 王明刚 | Tension-free hernia patch and preparation method thereof |
| CN103263693A (en) * | 2012-12-04 | 2013-08-28 | 中国医学科学院生物医学工程研究所 | Preparation method and use of immobilized antimicrobial drug hernia repair patch |
-
2009
- 2009-11-09 CN CN200910212777A patent/CN101712769A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205151A (en) * | 2011-05-23 | 2011-10-05 | 中国医学科学院生物医学工程研究所 | Hernia patch solid-supported with antibiotic and preparation method |
| CN103028144A (en) * | 2011-09-30 | 2013-04-10 | 王明刚 | Tension-free hernia patch and preparation method thereof |
| CN103028144B (en) * | 2011-09-30 | 2014-10-29 | 王明刚 | Tension-free hernia patch and preparation method thereof |
| CN103263693A (en) * | 2012-12-04 | 2013-08-28 | 中国医学科学院生物医学工程研究所 | Preparation method and use of immobilized antimicrobial drug hernia repair patch |
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Open date: 20100526 |