CN1487007A - Injection molding process of preparing porous foamed polymer with medium porosity - Google Patents
Injection molding process of preparing porous foamed polymer with medium porosity Download PDFInfo
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- CN1487007A CN1487007A CNA031419682A CN03141968A CN1487007A CN 1487007 A CN1487007 A CN 1487007A CN A031419682 A CNA031419682 A CN A031419682A CN 03141968 A CN03141968 A CN 03141968A CN 1487007 A CN1487007 A CN 1487007A
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Abstract
The present invention relates to polymer material technology and biological material technology, and is especially injection molding proces of one kind of porous foamed polymer with medium porosity. The mixture of pore creating agent in 5-80 wt% and polymer is injection molded, and after demolding, the pore creating agent particle is leached out to obtain the porous foamed polymer with medium porosity. The porous foamed polymer has homogeneously distributed pores, and is suitable for tissue engineering and other application field.
Description
Technical field
The invention belongs to high polymer material technology and technical field of biological materials, be specifically related to a kind of high-molecular porous foamy injection moulding preparation method of medium porosity.
Technical background
Porous material is widely used in a plurality of technical fields such as chemical industry, pharmacy, biomedical engineering, as: tissue engineering bracket, cell culture vector, medicine sustained release carrier, wound dressings, separatory membrane and filtering material, chromatographic column filler, packing and insulating material etc.The problem that high-molecular porous foamy preparation mainly contains two aspects needs to solve i.e. pore and moulding.The pore method has particle pore, gas foaming, lyophilize etc. usually, and wherein, particle pore method is simple and practical, suitability is wide, the easy independent regulation of porosity and hole dimension, be one than method in common.Adopt suitable mould, through methods such as mold pressing or the injection moulding goods of plastic desired shape often.Gome etc. (Biomaterials, 2001,22:883-889) reported that a kind of foaming injection method prepares high-molecular porous foam, prepares the porous foam of surface compact, inner porous low porosity.We consider traditional injection moulding is combined with the particle pore, develop a kind of high-molecular porous foamy universal method for preparing medium porosity, are used for organizational project and other Application Areas.
Summary of the invention
The objective of the invention is to propose a kind of high-molecular porous foamy injection moulding preparation method of medium porosity.
The high-molecular porous foam of the medium porosity that the present invention relates to, porosity are 5-80%, and the porous foam endoporus is evenly distributed.
The high-molecular porous foam of the medium porosity that the present invention relates to, range of aperture size are 10-900 μ m, are generally 50-500 μ m.
The high-molecular porous foam of the medium porosity that the present invention relates to, its basic material are thermoplastic macromolecular material.Its molecular weight is 10,000～3,000,000, is generally 3～1,000,000.
The high-molecular porous foamy injection moulding preparation method of the medium porosity that the present invention proposes, concrete steps are as follows: will mix uniform high molecular polymer and pore-creating agent particles mixture after polymer melt, carry out injection moulding, cooling and demolding, leach the pore-creating agent particle then, promptly get the high-molecular porous foam of required different shape.
Among the present invention, preparation polymer-pore-creating agent particles mixture, can adopt following several method:
(1) polymeric foamed material is dissolved in solvent orange 2 A, forms high molecular strong solution, then the pore-creating agent particle is added in the solution, mixed evenly back drawout removes solvent, obtains uniform polymer-pore-creating agent particles mixture.
(2) macromolecular material is ground into the particle shape,, obtains uniform polymer-pore-creating agent particles mixture with the pore-creating agent mix particles.
(3) directly with polymer and pore-creating agent mix particles, obtain uniform polymer-pore-creating agent particles mixture.
Among the present invention, the injection moulding step is that gained polymer-pore-creating agent particles mixture is charged in the injection moulding machine hopper, charges into the die cavity of mould rapidly under the injection pressure effect, moulding.
Among the present invention, leach the pore-creating agent particle and can adopt following method, the goods that contain pore-creating agent after the demoulding are put into solvent B to leach the pore-creating agent particle; After treating that the pore-creating agent particle leaches fully, wet high-molecular porous foam is taken out from solvent B, vacuum-drying finally obtains required high-molecular porous foam to remove wherein residual solvent B then.
The solvent orange 2 A that the present invention is used requires the solubilized perforated foams, but can not change its structure and performance; The pore-creating agent particle is not dissolved, and do not change the character of pore-creating agent particle; Have suitable volatility, under vacuum condition, can remove fully.Solvent orange 2 A comprises any or its mixture in trichloromethane, methylene dichloride, tetrahydrofuran (THF), acetone, butanone, the dioxane.Used solvent B requires solubilized pore-creating agent particle, but does not dissolve foam materials, also can not change its character; Have suitable volatility, under vacuum condition, can remove fully.For water-soluble pore-creating agent particle, solvent B is generally tap water, pure water, deionized water etc., and better choice is a deionized water; For oil soluble pore-creating agent particle, solvent B is generally organic solvents such as pentane, hexane, heptane, octane, hexanaphthene.
The used pore-creating agent particle of the present invention can be the inorganics or the organism particle of crystallization or amorphous, and the pore-creating agent particle is dissolved in solvent B but is insoluble to solvent orange 2 A.The pore-creating agent particle not with used polymer generation chemical reaction, also be insoluble to solvent orange 2 A.The pore-creating agent particle is scattered in the macromolecular solution equably and keeps its shape and size, and after it was by solvent B dissolving, the occupied volume of pore-creating agent particle just became hole, formed porous foam.The pore structure of porous foam and size are determined by pore-creating agent particle shape, size and consumption.Used pore-creating agent particle comprises inorganic salt particle, polysaccharide, protein and other organic micromolecule compound, or the mixture of being made up of them.The preferential sodium salt particle of selecting comprises sodium-chlor, Trisodium Citrate, sodium tartrate.Particle sieves into different fractions with standard sieve, and the grain size scope is 10-900 μ m, and the stock size scope is 40-600 μ m.The porosity of porous foam depends on pore-creating agent particle consumption (based on polymer and pore-creating agent particle total weight, down together).Pore-creating agent particle amount ranges is 5wt%-80wt%; Corresponding polymer amount ranges is 95wt%-20wt%.
When carrying out injection moulding among the present invention, can adopt small injecting machine, also can adopt any equipment with shot capacity of design voluntarily.
When carrying out injection moulding among the present invention, injection temperature is higher than high molecular fusing point or yield temperature 10-100 ℃, usually above high molecular fusing point or yield temperature 20-80 ℃.
Among the present invention, during high-molecular porous foam vacuum-drying, temperature is no more than the fusing point or the second-order transition temperature of foam materials, generally is not higher than 50 ℃, is generally room temperature.
The present invention has following characteristics:
1, the injection moulding preparation method that proposes of the present invention is suitable for preparing the high-molecular porous foam of medium porosity.
2, the injection moulding preparation method that proposes of the present invention is suitable for preparing the high-molecular porous foam of complex contour.
3, the injection moulding preparation method that proposes of the present invention is suitable for preparing the high-molecular porous foam of even pore distribution.
When 4, carrying out injection moulding among the present invention, both can adopt general injection moulding machine, also can adopt small injecting machine or any equipment with shot capacity of design voluntarily.
5, simple and practical, the favorable reproducibility of high-molecular porous foamy injection moulding preparation method of the present invention's proposition helps scale operation.
6, the high-molecular porous foam injection moulding preparation method adaptability of the present invention's proposition is strong, be applicable to various thermal plastic high polymers and various pore-creating agent particle, be a general high-molecular porous foam preparation processes, can be used for organizational project and other multiple Application Areas.
Description of drawings
Fig. 1 is that 180-280 μ m, porosity are 65% PLGA85/15 porous foam electron scanning micrograph for the aperture.
Embodiment
The embodiment that the invention is further illustrated by the following examples, but be not limited to these embodiment.
Embodiment 1, with 0.9 gram molecular weight is that 33.6 ten thousand poly(lactic acid) is dissolved in 6 milliliters of chloroforms, getting 2.1 gram particles directly adds in the solution for 180-280 μ m sodium-chlor particle, stir the back uniform spreading in culture dish, make the solvent final vacuum that partly volatilizees remove residual solvent in the air, obtain polymer-pore-creating agent particles mixture; This mixture is charged in the small injecting machine hopper, install injection mold, mixture is in rapid mold filling after 180 ℃ of fusions, under injection pressure (manual control) effect; After the demoulding goods are put into deionized water to leach the pore-creating agent particle, changed water one time in per 4 hours, detect with silver nitrate aqueous solution after 72 hours, white precipitate do not occur, show that the pore-creating agent particle leaches fully; Wet porous foam is taken out from deionized water, with most of deionized water sucking-off, and then remove residual moisture under＞755mmHg the condition, finally obtain porous foam (seeing figure), porosity 65% in room temperature, vacuum tightness with thieving paper.
Embodiment 2, are that 33.6 ten thousand poly(lactic acid) is dissolved in 5 milliliters of chloroforms with 0.6 gram molecular weight, get 2.4 gram particles directly for 280-480 μ m sodium-chlor particle adds in the solution, and other is with embodiment 1, porosity 76%.
Embodiment 3, are that 300,000 PLGA85/15 is dissolved in 5 milliliters of chloroforms with 0.6 gram molecular weight, get 2.4 gram particles directly for 45-90 μ m sodium-chlor particle adds in the solution, and other is with embodiment 1, porosity 77%.
Embodiment 4, are that 300,000 PLGA85/15 is dissolved in 5 milliliters of chloroforms with 2.4 gram molecular weights, get 0.6 gram particle directly for 45-90 μ m sodium-chlor particle adds in the solution, and other is with embodiment 1, porosity 16%.
Claims (10)
1, a kind of high-molecular porous foamy preparation method of medium porosity is characterized in that the polymkeric substance-pore-creating agent particles mixture that will mix carries out injection moulding after polymer melt, and cooling and demolding leaches the pore-creating agent particle then.
2, preparation method according to claim 1, it is characterized in that polymeric foamed material is dissolved in solvent orange 2 A, form high molecular solution, the pore-creating agent particle that will be insoluble to solvent orange 2 A then adds in the solution, mixed evenly back drawout, remove solvent, obtain uniform polymer-pore-creating agent particles mixture; Solvent orange 2 A is any or its mixture in trichloromethane, methylene dichloride, tetrahydrofuran (THF), acetone, butanone, the dioxane.
3, preparation method according to claim 1 is characterized in that macromolecular material is ground into the particle shape, with the pore-creating agent mix particles, obtains uniform polymer-pore-creating agent particles mixture.
4, preparation method according to claim 1, the method that it is characterized in that leaching the pore-creating agent particle is as follows: the goods that contain pore-creating agent after the demoulding are put into solvent B to leach the pore-creating agent particle; After treating that the pore-creating agent particle leaches fully, wet high-molecular porous foam is taken out from solvent B, vacuum-drying finally obtains required high-molecular porous foam to remove wherein residual solvent B then; For water-soluble pore-creating agent particle, solvent B adopts tap water, pure water, deionized water; For oil soluble pore-creating agent particle, solvent B adopts a kind of of organic solvent pentane, hexane, heptane, hexanaphthene.
5, preparation method according to claim 1 is characterized in that the pore-creating agent particle is the inorganics or the organism particle of crystallization or amorphous.
6, preparation method according to claim 5 is characterized in that the pore particle adopts inorganic salt particle, polysaccharide, protein, or their mixture.
7, preparation method according to claim 1, the consumption that it is characterized in that the pore-creating agent particle is the 5wt%-80wt% of mixture total weight amount, and corresponding polymer amount ranges is 95wt%-20wt%, and the pore-creating agent size of particles is 10-900 μ m.
8, preparation method according to claim 1 is characterized in that used macromolecular material is a thermal plastic high polymer, and its molecular weight is 10,000-3,000,000.
9, preparation method according to claim 1 is characterized in that the injection moulding temperature is than the fusing point of macromolecular material or the high 10-100 of yield temperature ℃.
10, preparation method according to claim 4, when it is characterized in that high-molecular porous foam vacuum-drying, temperature is no more than the fusing point or the second-order transition temperature of foam materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141968 CN1253493C (en) | 2003-07-30 | 2003-07-30 | Injection molding process of preparing porous foamed polymer with medium porosity |
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| CN 03141968 CN1253493C (en) | 2003-07-30 | 2003-07-30 | Injection molding process of preparing porous foamed polymer with medium porosity |
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| CN1487007A true CN1487007A (en) | 2004-04-07 |
| CN1253493C CN1253493C (en) | 2006-04-26 |
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| CN 03141968 Expired - Fee Related CN1253493C (en) | 2003-07-30 | 2003-07-30 | Injection molding process of preparing porous foamed polymer with medium porosity |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291979B (en) * | 2005-10-05 | 2012-07-25 | 帝人工程有限公司 | Molded article and method of producing the same |
| CN105131327A (en) * | 2015-09-07 | 2015-12-09 | 广东工业大学 | Preparation method for porous film with controllable apertures |
| CN114057288A (en) * | 2020-08-03 | 2022-02-18 | 成都活水环能科技有限公司 | Novel MBBR filler and manufacturing process thereof |
-
2003
- 2003-07-30 CN CN 03141968 patent/CN1253493C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291979B (en) * | 2005-10-05 | 2012-07-25 | 帝人工程有限公司 | Molded article and method of producing the same |
| CN105131327A (en) * | 2015-09-07 | 2015-12-09 | 广东工业大学 | Preparation method for porous film with controllable apertures |
| CN114057288A (en) * | 2020-08-03 | 2022-02-18 | 成都活水环能科技有限公司 | Novel MBBR filler and manufacturing process thereof |
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| Publication number | Publication date |
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| CN1253493C (en) | 2006-04-26 |
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