CN1247697C - Polyurethane porous film and its preparing method - Google Patents
Polyurethane porous film and its preparing method Download PDFInfo
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- CN1247697C CN1247697C CN 200310109726 CN200310109726A CN1247697C CN 1247697 C CN1247697 C CN 1247697C CN 200310109726 CN200310109726 CN 200310109726 CN 200310109726 A CN200310109726 A CN 200310109726A CN 1247697 C CN1247697 C CN 1247697C
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Abstract
The thickness of a polyurethane porous film is from 80 to 120 mu m, the tensile strength of the film is from 10 to 20MPa, and the tensile yield is from 100 to 350%; the pore diameter of the outer surface where the film and a coagulator are contacted is from 5 to 20 mu m, and the pore diameter of the inner surface where the film and a mode are contacted is from 30 to 80 mu m; the humidity transmission rate of the film is from 900 to 1800 g/m per 24 h, the water absorption rate of weight is from 30 to 300 %, and the porosity is from 40 to 100%. A method of the film comprises the following steps: a polyurethane solution is synthesized by a two-step solution polymerization method; then proper solvents, pore creating agents, etc. are added in the polyurethane solution to dilute the polyurethane solution into a film forming liquid in a certain concentration; a film is prepared by a wet coating technique. The present invention has the advantages of simple technique and low cost, the outer surface of the polyurethane film is relatively compact, and the inner part is loose and porous.
Description
Technical field:
The invention belongs to a kind of urethane porous membrane and preparation method thereof, specifically is exactly the preparation method that a kind of pore size, water vapour permeability satisfy the urethane porous membrane of burn, wound covering requirement.
Background technology:
By covering sealing, semi-enclosed dressing in the wound or covering the tectum that surface of a wound place forms gel, for the surface of a wound is built one " wet union environment ", the advantage of this method obtains confirming existing a lot of years.People generally believe that desirable dressing should have following characteristics at present: can absorb a large amount of sepages and toxic substance; Allow a certain amount of water vapour and oxygen penetrating; Microorganism can not be penetrating, also should keep the enough humidity of wound simultaneously; More be difficult for causing the secondary wound during change dressings.Follow the principle of wound wet union, the dressing of the modern technologies manufacturing of newly-developed roughly has three kinds: hydrogel, foam, polyurethane film.Aerogel dressing is owing to bad mechanical strength, and toxic reaction in various degree appears in the hydrogel of some different component, and the synthesis technique complexity costs an arm and a leg, so popularize at clinical medicine as yet.The foamy advantage is to absorb a large amount of sepages, but owing to its thoroughly wet speed is excessive, therefore needs to be used with the saturating wet moderate dressing of speed.Polyurethane film has excellent biological compatibility, but its water vapour permeability can not satisfy the requirement of " wet union environment ", people just are being devoted to make polyurethane film have certain microvoid structure by physics or chemical process at present, to increase its water vapour permeability.
The preparation method of polyurethane film roughly has following several: industrial mainly by extruding or roll, but these methods are very high and film that made by this method is ventilative, water vapour permeability is poor slightly to the requirement of Polyurethane Thermoplastic Elastomer (TPU) micelle.The The DOW ChemicalCompany (Pub.No:US20020028877 A1) of the U.S. is that raw material is made polyurethane aqueous dispersion and then system film with the polyoxyethylene glycol, film wetting ability obtained by this method is better, but can only adopt dry method system film, the film that forms is dense, so water vapour permeability, ventilation property are relatively poor.The people such as Menachem Lewin of Israel HebrewUniversity of Jerusalem develop the polyurethane film through bromine water and ammonia treatment, the contact angle of this film drops to 20 ° (wetting ability increases) by 73 °, and in reaction, emit nitrogen and make the film that makes have certain microvoid structure, therefore speed ratio is undressed has increased by 30% for film saturating wet, reaches 900g/m
2.24h.The film of polyurethane solution has the branch of dry method and wet method: wherein the film that makes of dry method is dense, saturating wet, ventilation property is poor slightly; And adopt the wet-process coating technology can make prepared film have certain microvoid structure, can improve saturating wet, the permeability of film.But consider that from control and their influences wet thoroughly to final film, permeability thereof of the character of starting material itself, filming technology, pore size present research is less relatively.
Summary of the invention:
The invention provides that a kind of technology is simple, cost is low, pore size is moderate, water vapour permeability satisfies the preparation method that the surface of a wound covers the urethane porous membrane that requires.
Urethane porous membrane of the present invention, it is characterized in that thickness is at 80-120um, the tensile strength of film is at 10-20Mpa, tensile yield is at 100-350%, the aperture of the outside surface that film contacts with peptizer is at 5-20um, and the aperture of the internal surface that contacts with mould is at 30-80um, and the saturating wet speed of film is at 900-1800g/m2.24h, the weight water-intake rate is at 30-300%, and porosity is at 40-100%.
Preparation method of the present invention comprises the steps:
(1) polyether glycol that will dewater and vulcabond are under nitrogen protection, and 75-95 ℃ of reaction generated prepolymer in 2-3 hour; The solution that will be dissolved with chainextender under nitrogen protection adds in the performed polymer, and 75-95 ℃ of reaction made polyurethane solution in 1-2 hour, the add-on of solvent with the solid content of regulating final polyurethane solution at 25-50wt%; Adding the pore-creating agent of 3-20wt% in polyurethane solution, is that 10-30wt% makes film-casting liquid with solvent cut to solid content again;
(2) film-casting liquid is inclined on the mould, drawout is at room temperature placed 10-60 second, immerses in the precipitation bath to solidify 5-10 minute, gets membrane product through washing, oven dry demoulding again.
Peptizer in the precipitation bath is a water, in order to control the solidification rate of film-casting liquid, can add 3-30% solvent N in peptizer, and dinethylformamide (DMF) is regulated the solidification rate of polyurethane solution, and the temperature of precipitation bath is controlled in the 15-60 ℃ of scope.
Consisting of of each raw material wherein:
The mol ratio of raw material is a polyether glycol: vulcabond: chainextender=1: 2: 1-1: 6: 5, wherein optimum mole ratio was a polyether glycol: vulcabond: chainextender=1: 2.5: 1.5-1: 4: 3.
The best solid content of synthesis of polyurethane solution is at 25-40wt%
The best solid content of film-casting liquid is at 15-25wt%.
Aforesaid polyether glycol can be polyoxyethylene glycol (PEG), polypropylene glycol (PPG), PTMG (PTMG), polycaprolactone glycol (PCL) or their mixture.
Aforesaid vulcabond can be tolylene diisocyanate (TDI), ditan-4,4-vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or their mixture.
Aforesaid chainextender can be ethylene glycol, 1,4-butyleneglycol (BDO), hydroxy silicon oil or their mixture.
Aforesaid solvent can be N, dinethylformamide (DMF), tetrahydrofuran (THF) (THF), 1,4-dioxane (DO) or their mixture.
Pore-creating agent can be the polyoxyethylene glycol of 200-1000 for ethylene glycol or molecular weight.
Polymerization technique, filming technology that the present invention adopts are simple, and cost is lower.Prepared film internal structure is loose porous, can absorb a certain amount of sepage, plays the purpose of protecting liquid, and this microvoid structure can provide a suitable place for the structure of tissue; The more compact outer surface of film can stop the intrusion of bacterium, prevents that the transition of moisture content and inorganic salt is run off, but allows a certain amount of water vapour and gas permeation, and both are combined into wound surface and create one " wet union environment "; Can regulate the saturating wet speed of film by regulating raw-material kind and proportioning, pore size in addition, make it to satisfy the service requirements of the different surface of a wound; Can carry out hydrophilically modifiedly and organic-silicon-modified to material, improve the physiological compatibility of film etc.It is the very strong novel method of practicality of a kind of new pattern compress of preparation.
Embodiment:
Embodiment 1
Install agitator and thermometer additional with the 250ml four-hole bottle, add 30g PTMG-2000 (vacuum hydro-extraction), 13.125g MDI, 85 ± 2 ℃ were reacted 2 hours under nitrogen protection, made performed polymer; 3.375g BDO is dissolved among the 69.8g DMF, under nitrogen protection, this solution is added in the performed polymer, react down at 85 ± 2 ℃ and made polyurethane solution in 1.5 hours.In this solution, add 15g ethylene glycol, be diluted to 15wt% with DMF and make film-casting liquid; This film-casting liquid is inclined on the glass mold, and drawout was placed 30 seconds, immerse in the precipitation bath to solidify 8 minutes, and again through 60 ℃ of washings, 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 100um, and the outside surface aperture is at 5-10um, and the internal surface aperture is at 30-40um.The tensile strength of film is 20MPa, and tensile yield is 150%, and wet thoroughly speed is 1100g/m
2.24h, the weight water-intake rate is 70%, and porosity is 60%.
Embodiment 2
Install agitator and thermometer additional with the 250ml four-hole bottle, add 16g PTMG-1000 and 4gPEG-1000 (vacuum hydro-extraction), 12g MDI, performed polymer was made in 75 ± 2 ℃ of reactions in 3 hours under nitrogen protection; 2.52g BDO is dissolved among the 104g DMF, under nitrogen protection, this solution is added in the performed polymer, react down at 80 ± 2 ℃ and made polyurethane solution in 1.5 hours.With DMF this solution dilution is made film-casting liquid to 15wt%; This film-casting liquid is inclined on the glass mold, and drawout was placed 30 seconds, and enter and solidify 10 minutes in the precipitation bath, again through 60 ℃ of washings, 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 90um, and the outside surface aperture is at 5-10um, and the internal surface aperture is at 30-40um.The tensile strength of film is 13Mpa, and tensile yield is 300%, and wet thoroughly speed is 1500g/m
2.24h, the weight water-intake rate is 300%, and porosity is 50%.
Embodiment 3
Install agitator and thermometer additional with the 250ml four-hole bottle, add 30g PTMG-2000 (vacuum hydro-extraction), 12g MDI, 85 ± 2 ℃ were reacted 2 hours under nitrogen protection, made performed polymer; 1.4g BDO and 6.2g hydroxy silicon oil are dissolved among the 75g DMF, under nitrogen protection, this solution are added in the performed polymer, react down at 85 ± 2 ℃ and made polyurethane solution in 1.5 hours.This solution is diluted to 20wt% with DMF makes film-casting liquid; This film-casting liquid is inclined on the glass mold, and drawout was placed 30 seconds, immerse in the precipitation bath to solidify 8 minutes, and again through 60 ℃ of washings, 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 110um, and the outside surface aperture is at 5-10um, and the internal surface aperture is at 30-40um.The tensile strength of film is 17Mpa, and tensile yield is 150%, and wet thoroughly speed is 950g/m
2.24h, the weight water-intake rate is 30%, and porosity is 45%.
Embodiment 4
Install agitator and thermometer additional with the 250ml four-hole bottle, add 20g PTMG-1000 (vacuum hydro-extraction), 10g MDI, 80 ± 2 ℃ were reacted 2 hours under nitrogen protection, made performed polymer; 1.8g BDO is dissolved among the 74.2g DMF, under nitrogen protection, this solution is added in the performed polymer, react down at 80 ± 2 ℃ and made polyurethane solution in 1.5 hours.In this solution, add 10.6g ethylene glycol, be diluted to 15wt% with DMF and make film-casting liquid.This film-casting liquid is inclined on the glass mold, and drawout was placed 30 seconds, immersed in the precipitation bath to solidify 10 minutes, and the temperature of control precipitation bath is at 35 ℃, again through 60 ℃ of washings, and 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 80um, and the outside surface aperture is at 8-14um, and the internal surface aperture is at 40-65um.The tensile strength of film is 16Mpa, and tensile yield is 100%, and wet thoroughly speed is 1300g/m
2.24h, the weight water-intake rate is 55%, and porosity is 70%.
Embodiment 5
Install agitator and thermometer additional with the 250ml four-hole bottle, add 20g PCL-1000 (vacuum hydro-extraction), 10g MDI, 80 ± 2 ℃ were reacted 2 hours under nitrogen protection, made performed polymer; 1.8g BDO is dissolved among the 74.2g DMF, under nitrogen protection, this solution is added in the performed polymer, react down at 80 ± 2 ℃ and made polyurethane solution in 1.5 hours.In this solution, add 17.7g ethylene glycol, be diluted to 18wt% with DMF and make film-casting liquid.This film-casting liquid is inclined on the glass mold, and drawout was placed 30 seconds, immersed in the precipitation bath to solidify 6 minutes, and the concentration of control precipitation bath is 12%, again through 60 ℃ of washings, and 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 100um, and the outside surface aperture is at 8-14um, and the internal surface aperture is at 40-65um.The tensile strength of film is 16Mpa, and tensile yield is 100%, and wet thoroughly speed is 1350g/m
2.24h, the weight water-intake rate is 70%, and porosity is 70%.
Embodiment 6
Install agitator and thermometer additional with the 250ml four-hole bottle, add 30g PTMG-2000 (vacuum hydro-extraction), 15g MDI, 85 ± 2 ℃ were reacted 2 hours under nitrogen protection, made performed polymer; 4.05g BDO is dissolved among the 114.5g DMF, under nitrogen protection, this solution is added in the performed polymer, react down at 85 ± 2 ℃ and made polyurethane solution in 1.5 hours.Add 21.8g polyoxyethylene glycol-400 at this solution, be diluted to 18wt% with DMF and make film-casting liquid; This film-casting liquid is inclined on the glass mold, and drawout was placed 20 seconds, immerse in the precipitation bath to solidify 8 minutes, and again through 60 ℃ of washings, 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 100um, and the outside surface aperture is at 10-20um, and the internal surface aperture is at 50-75um.The tensile strength of film is 10Mpa, and tensile yield is 75%, and wet thoroughly speed is 1700mg/m
2.24h, the weight water-intake rate is 60%, and porosity is 90%.
Embodiment 7
Install agitator and thermometer additional with the 250ml four-hole bottle, add 30g PTMG-2000 (vacuum hydro-extraction), 13.14g MDI, 85 ± 2 ℃ were reacted 2 hours under nitrogen protection, made performed polymer; 3.38g BDO is dissolved among the 86.4g DMF, under nitrogen protection, this solution is added in the performed polymer, react down at 85 ± 2 ℃ and made polyurethane solution in 1.5 hours.Add 15g 1 at this solution, the 4-dioxane is diluted to 15wt% with DMF and makes film-casting liquid; This film-casting liquid is inclined on the glass mold, and drawout was placed 30 seconds, immerse in the precipitation bath to solidify 10 minutes, and again through 60 ℃ of washings, 90 ℃ of washings, oven dry, demoulding get membrane product at last.Film thickness obtained by this method is about 100um, and the outside surface aperture is at 6-10um, and the internal surface aperture is at 30-40um.The tensile strength of film is 19Mpa, and tensile yield is 100%, and wet thoroughly speed is 1250 g/m
2.24h, the weight water-intake rate is 60%, and porosity is 50%.
Claims (12)
1, a kind of urethane porous membrane, this urethane is by polyether glycol, vulcabond and chainextender reaction form, mol ratio is a polyether glycol: vulcabond: chainextender=1: 2: 1-1: 6: 5, it is characterized in that thickness is at 80-120um, the tensile strength of film is at 10-20Mpa, tensile yield is at 100-350%, the aperture of the outside surface that film contacts with peptizer is at 5-20um, the aperture of the internal surface that contacts with mould is at 30-80um, the saturating wet speed of film is at 900-1800g/m2.24h, the weight water-intake rate is at 30-300%, and porosity is at 40-100%.
2, the preparation method of a kind of urethane porous membrane as claimed in claim 1 is characterized in that comprising the steps:
(1) polyether glycol that will dewater and vulcabond are under nitrogen protection, and 75-95 ℃ of reaction generated prepolymer in 2-3 hour; The solution that will be dissolved with chainextender under nitrogen protection adds in the performed polymer, and 75-95 ℃ of reaction made polyurethane solution in 1-2 hour, the add-on of solvent with the solid content of regulating final polyurethane solution at 25-50wt%; Adding the pore-creating agent of 3-20wt% in polyurethane solution, is that 10-30wt% makes film-casting liquid with solvent cut to solid content again;
(2) film-casting liquid is inclined on the mould, drawout is at room temperature placed 10-60 second, immerses in the precipitation bath to solidify 5-10 minute, gets membrane product through washing, oven dry demoulding again; Wherein the mol ratio of each raw material consists of polyether glycol: vulcabond: chainextender=1: 2: 1-1: 6: 5,
3, the preparation method of a kind of urethane porous membrane as claimed in claim 2 is characterized in that the peptizer in the described precipitation bath is a water, and the temperature of precipitation bath is controlled in the 15-60 ℃ of scope
4, the preparation method of as claimed in claim 3 kind of urethane porous membrane is characterized in that adding in the described peptizer 3-30% solvent N, dinethylformamide.
5, the preparation method of a kind of urethane porous membrane as claimed in claim 2 is characterized in that the mol ratio of described each raw material consists of polyether glycol: vulcabond: chainextender=1: 2.5: 1.5-1: 4: 3.
6, the preparation method of a kind of urethane porous membrane as claimed in claim 2, the solid content that it is characterized in that described synthesis of polyurethane solution is at 25-40wt%
7, the preparation method of a kind of urethane porous membrane as claimed in claim 2, the solid content that it is characterized in that described film-casting liquid is at 15-25wt%.
8, the preparation method of a kind of urethane porous membrane as claimed in claim 2 is characterized in that described polyether glycol is polyoxyethylene glycol, polypropylene glycol, PTMG, polycaprolactone glycol or their mixture.
9, the preparation method of a kind of urethane porous membrane as claimed in claim 2, it is characterized in that described vulcabond is tolylene diisocyanate, ditan-4,4-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate or their mixture.
10, the preparation method of a kind of urethane porous membrane as claimed in claim 2 is characterized in that described chainextender is an ethylene glycol, 1,4-butyleneglycol, hydroxy silicon oil or their mixture.
11, the preparation method of a kind of urethane porous membrane as claimed in claim 2 is characterized in that described solvent is N, dinethylformamide, tetrahydrofuran (THF), 1,4-dioxane or their mixture.
12, the preparation method of a kind of urethane porous membrane as claimed in claim 2 is characterized in that described pore-creating agent is that ethylene glycol or molecular weight are the polyoxyethylene glycol of 200-1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109726 CN1247697C (en) | 2003-12-26 | 2003-12-26 | Polyurethane porous film and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109726 CN1247697C (en) | 2003-12-26 | 2003-12-26 | Polyurethane porous film and its preparing method |
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| CN1554705A CN1554705A (en) | 2004-12-15 |
| CN1247697C true CN1247697C (en) | 2006-03-29 |
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| CN 200310109726 Expired - Fee Related CN1247697C (en) | 2003-12-26 | 2003-12-26 | Polyurethane porous film and its preparing method |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270196B (en) * | 2007-12-29 | 2011-06-01 | 武汉科技学院 | Process for preparing hygroscopic vapor transmission polyurethane membrane |
| CN102773027A (en) * | 2012-08-10 | 2012-11-14 | 温州市登达化工有限公司 | Method for preparing high-performance polyurethane ultrafiltration/microfiltration separation membrane |
| CN103736134B (en) * | 2013-12-30 | 2015-04-29 | 深圳先进技术研究院 | Medical sponge dressing and preparation method thereof |
| CN104448788A (en) * | 2014-12-16 | 2015-03-25 | 江苏宏远新材料科技有限公司 | Waterproof and moisture permeable type thermoplastic polyurethane film and preparation method thereof |
| CN105111490B (en) * | 2015-08-06 | 2018-02-06 | 武汉纺织大学 | A kind of preparation method of high-strength and high-modulus highly-elastic urethane film |
| CN106084746A (en) * | 2016-06-08 | 2016-11-09 | 苏州市雄林新材料科技有限公司 | A kind of transparent high abrasion TPU film and preparation method thereof |
| EP3694909B1 (en) * | 2017-10-10 | 2024-06-12 | Basf Se | Elastic membrane |
| CN110872370B (en) * | 2019-12-05 | 2022-03-25 | 齐鲁工业大学 | Application of low-phosphorus cross-linking agent in preparation of polyurethane film |
| CN112341591B (en) * | 2020-10-27 | 2023-03-24 | 上海伊纯实业有限公司 | Polyurethane material and preparation method and application thereof |
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2003
- 2003-12-26 CN CN 200310109726 patent/CN1247697C/en not_active Expired - Fee Related
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