CN103396516A - Preparation method of acrylate-modified polyvinyl chloride - Google Patents
Preparation method of acrylate-modified polyvinyl chloride Download PDFInfo
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- CN103396516A CN103396516A CN2013102781896A CN201310278189A CN103396516A CN 103396516 A CN103396516 A CN 103396516A CN 2013102781896 A CN2013102781896 A CN 2013102781896A CN 201310278189 A CN201310278189 A CN 201310278189A CN 103396516 A CN103396516 A CN 103396516A
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Abstract
The invention discloses a preparation method of acrylate-modified polyvinyl chloride. The method is characterized by comprising the following steps of: (1) pretreatment; (2) grafting reaction; and (3) removal of residue. The method disclosed by the invention has the advantages that (1) the use of compounds harmful to a human body is reduced, and the toxicity of the treated materials, caused by compound residue, is greatly reduced; (2) the influence of toxic pollutants generated in the intermediate steps on the environment is greatly reduced; (3) a one-step method is adopted to graft high-hydrophilicity HEMA (Hydroxyethyl Methacrylate) on the surface of medical PVC, and the process is simple and more controllable; and (4) the material prepared by adopting the method has good blood compatibility. The preparation method is simple and easy, has low equipment requirement and good controllability to the conditions and can be easily put into industrial production.
Description
Technical field
The invention belongs to the field of medical polymer material, be specifically related to a kind ofly for the preparation of high-end medical polymer material surfaces such as medical catheter, seal wire, heart valve and hemodialysis membranes, prepare method stable, high-hydrophilic HEMA coating.
Background technology
When the biomaterial material choice, polymkeric substance has good main nature, and characteristics such as mechanical property, thermostability, good solubility-resistence energy and easy preparation can be used as one of raw-material first-selection usually.Then, its surface properties does not reach best in biomedical applications.At biological device surface, surface modification can reduce thrombosis, control the adhesion of albumen and cell.One of them effective surface modifying method is on surface, to introduce hydrophilic composition, the main hydrophilic monomer with good biocompatibility or polymkeric substance comprises vinylformic acid (AA), methacrylic acid (MAA), hydroxyethyl methylacrylate (HEMA), Hydroxyethyl acrylate (HEA), acrylamide (MA), Methacrylamide at present, methyl-2-pyrrolidone (VP), polyoxyethylene glycol (PEG) or polyoxyethylene (PEO), and poly-methyl pyrrole alkane ketone (PVP) etc.
HEMA is typical hydroaropic substance.HEMA is as hydrophilic surface, because their easily polymerization and have hydroxyl.On the PVC surface of HEMA modification, white protein and Fibrinogen obviously reduce absorption, and to albuminised adhesion higher than Fibrinogen.Para-aminosalicylic acid (PAS) have hydroxyl and and hydroxy-acid group, the ionization of these groups can make polymer surfaces be more prone to aquation, spread coefficient when the polymer surfaces low water content shows and is not fixed on the PAS surface, water molecules has the movability of height, thereby obtains high blood compatibility.In order to improve the consistency of endotheliocyte, by the PVC surface graft HEMA in porous, improve surface hydrophilicity and water content, and pore structure has improved the activity of surperficial endotheliocyte.
PVC is the abbreviation of polyvinyl chloride, is a kind of polymeric material of vinyl in fact, and its material is a kind of amorphism material.PVC has that strength and modulus is higher, soft, rebound resilience is good, transparent and the plurality of advantages such as low price, be used to making the Dispoable medical transfusion instruments such as transfusion device, blood bag, catheter, peritoneal dialysis bag, hemodialysis pipeline and various medical catheters.The PVC material is owing to having the disposable medical articles such as resist chemical, wear-resisting, easy production, blood transfusion and infusion utensil and various flexible pipe for medical purpose, dialysis annex, surgical glove, breathing mask and membrane oxygenator, bring many convenience for the treatment nursing, and can prevent cross infection.The PVC material during as medical product, not only needs to meet the materialogy requirement, also needs to meet biological requirement.At present, the medical PVC material exist wetting ability poor, easily adsorb medicine and stick the biocompatibility issues such as bacterium, the blood compatibility problem during with the blood Long Term Contact, all limited its application and development.Carry out a large amount of study on the modification about the medical PVC material for this reason both at home and abroad, mainly comprised modification by copolymerization, the surface modification of PVC material or goods (as film and tubing etc.) etc.At the PVC surface graft, a large amount of research has been arranged.
The present invention adopts single step process, not only reduced the introducing of polyvinyl chloride hazardous and noxious substances, and cost is low, easily realize suitability for industrialized production, the material surface of preparation has improved the stability of coating, high-hydrophilic, extend the work-ing life of polymeric coating, enlarged the range of application of coating.
Summary of the invention
The novel method that the purpose of this invention is to provide a kind of acrylate modified polyvinyl chloride.This novel method adopts single step process, not only can reduce the introducing of objectionable impurities, and simplifies reaction process.This novel method has process simultaneously easily to be controlled, the characteristics such as the easy amplification of technique, and the modified surface that obtains has good blood compatibility.
Technical scheme provided by the invention is as follows: a kind of method of acrylate modified polyvinyl chloride comprises the following steps: 1) pre-treatment, 2) grafting reaction, 3) remove residual; It is characterized in that:
1), pre-treatment: get the medical PVC material surface and carry out activating pretreatment, make its surface active;
2), grafting reaction: pretreated polyvinyl chloride (PVC) material is inserted in the reaction soln system that contains hydroxyethyl methylacrylate (HEMA) and carried out grafting reaction formation reaction product, and HEMA fully disperses in reaction solvent;
3), removal is residual: by reaction product, fully clean, remove residual reactants, through vacuum-drying, be acrylate modified polyvinyl chloride.
Surface active pre-treatment in described step 1) is: select ozone, plasma body, radiation or ultraviolet lighting to carry out activating pretreatment to the medical PVC material surface;
The illumination of described UV-irradiation is that 100W～500W, time are 4～12 hours.
Described step 2) in, the medical PVC of surface active, reaction soln system direct and HEMA is reacted, and reaction system is the aqueous solution, and the catalyzer of use is ceric ammonium nitrate.
Described step 2) in, the reaction density of HEMA is 5%～10%, and temperature of reaction is 40～70 ℃, and the reaction times is 8～24 hours, and reaction is stirred and carried out under air or nitrogen atmosphere.
In described step 3), reaction product is by first using distilled water wash 10～24h under the condition of 50-80 ℃, then ultrasonic cleaning 0.2～1h in ethanol, finally in distilled water, wash, wash temperature is 50～80 ℃, at least change distilled water more than 10 times, vacuum-drying obtains to have hydrophilic acrylate modified polyvinyl chloride.
The advantage of technical scheme maximum provided by the invention mainly comprises: the toxicity that the material after the harmful compound of (1) minimizing uses, processes causes because compound is residual greatly reduces; (2) reduced in a large number the impact of the toxic pollutant of intermediate steps generation on environment; (3) adopt the HEMA of single stage method at medical PVC surface graft high-hydrophilic, process is simple, and is more controlled; (4) material that adopts this method to prepare has good blood compatibility.This preparation method is simple, and not high to equipment requirements, condition is easily controlled, and easily realizes suitability for industrialized production.
Embodiment
A kind of method of acrylate modified polyvinyl chloride comprises the following steps:
1, pre-treatment: medical polyvinyl material (can various forms, film for example, conduit, seal wire etc.) selects ozone, plasma body, radiation or ultraviolet lighting to carry out activating pretreatment to the medical PVC material surface; The illumination of described UV-irradiation is that 100W～500W, time are 4～12 hours.
2, grafting reaction: pretreated polyvinyl chloride (PVC) material is inserted in the reaction soln system that contains hydroxyethyl methylacrylate (HEMA) and carried out grafting reaction formation reaction product, the reaction density of HEMA is 5%～10%, temperature of reaction is 40～70 ℃, reaction times is 8～24 hours, in reaction solvent, fully disperses; Reaction is stirred and is carried out under air or nitrogen atmosphere.The medical PVC of surface active, reaction soln system direct and HEMA is reacted, and reaction system is the aqueous solution, and the catalyzer of use is ceric ammonium nitrate.
3), removal is residual: reaction product is by first using distilled water wash 10～24h under the condition of 50-80 ℃, then ultrasonic cleaning 0.2～1h in ethanol, finally in distilled water, wash, wash temperature is 50～80 ℃, at least change distilled water more than 10 times, vacuum-drying obtains to have hydrophilic acrylate modified polyvinyl chloride.
Embodiment 1:
Take HEMA as hydrophilic monomer, ozone oxidation is as surface preparation: under 50 ℃ of oil baths, nitrogen protection condition, magnetic agitation, preparation concentration is the aqueous solution of 5% HEMA in the there-necked flask of 50ml.Get clean PVC conduit, in the ozone of 25mg/L, activate 20min.The PVC material of surface active adds in reaction soln, and temperature of reaction is 70 ℃, and the reaction times is 8 hours.Get the PVC conduit of firm reaction, in the pure water of 80 ℃, clean 24h, change at least distilled water 10 times, and then ultrasonic cleaning 30min in ethanol, 60 ℃ of vacuum-dryings are preserved use to constant weight.The medical PVC material of preparation, surface hydrophilicity obviously improves, and water contact angle is lower than 55 °.Has good blood compatibility, substantially without platelet adhesion reaction.
Embodiment 2:
Take HEMA as hydrophilic monomer, ozone oxidation is as surface preparation: under 60 ℃ of oil baths, and the nitrogen protection condition, under magnetic agitation, preparation concentration is the aqueous solution solution of 5% HEMA in the there-necked flask of 50ml.Get clean PVC conduit, in the ozone of 20mg/L, activate 40min.The PVC material of surface active adds in reaction soln, and temperature of reaction is 60 ℃, and the reaction times is 24 hours.Get the PVC conduit of firm reaction, in the pure water of 80 ℃, clean 24h, change at least distilled water 10 times, and then ultrasonic cleaning 30min in ethanol, 60 ℃ of vacuum-dryings are preserved use to constant weight.The medical polyurethane material of preparation, surface hydrophilicity obviously improves, and water contact angle is lower than 50 °.Have good blood compatibility, surface is substantially without platelet adhesion reaction.
Embodiment 3:
Take HEMA as hydrophilic monomer, ultraviolet lighting is surface activation process: under 70 ℃ of oil baths, and the nitrogen protection condition, under magnetic agitation, preparation concentration is the aqueous solution of 10% HEMA in the there-necked flask of 50ml.Get clean PVC conduit, under the ultraviolet lighting of 300W, activate 15min.The PVC material of surface active adds in reaction soln, and temperature of reaction is 70 ℃, and the reaction times is 24 hours.Get the PVC conduit of firm reaction, in the pure water of 80 ℃, clean 24h, change at least distilled water 10 times, and then ultrasonic cleaning 30min in ethanol, 60 ℃ of vacuum-dryings are preserved use to constant weight.The medical polyurethane material of preparation, surface hydrophilicity obviously improves, and water contact angle is lower than 45 °.Have good blood compatibility, surface is substantially without platelet adhesion reaction.
The invention discloses a kind of novel method of acrylate modified polyvinyl chloride.With traditional method, compare the use that this novel method process is simple, greatly reduce the poisonous and harmful compound.This novel method mainly comprises the following steps: step 1: medical polyvinyl material surface activation treatment, surface active; Step 2: pretreated polyvinyl chloride material in step 1 is inserted in the reaction soln system that contains acrylate and carried out the grafting reaction; Step 3: fully clean, remove residual reactants by the reaction product of step 2, get final product by vacuum-drying.The method can be widely used all kinds of employing polyvinyl chloride as starting material medical material or field of medical appliances.
Claims (6)
1. the method for an acrylate modified polyvinyl chloride, comprise the following steps: 1) pre-treatment, 2) grafting reaction, 3) remove residual; It is characterized in that:
1), pre-treatment: get the medical PVC material surface and carry out activating pretreatment, make its surface active;
2), grafting reaction: pretreated polyvinyl chloride (PVC) material is inserted in the reaction soln system that contains hydroxyethyl methylacrylate (HEMA) and carried out grafting reaction formation reaction product, and HEMA fully disperses in reaction solvent;
3), removal is residual: by reaction product, fully clean, remove residual reactants, through vacuum-drying, be acrylate modified polyvinyl chloride.
2. the method for a kind of acrylate modified polyvinyl chloride according to claim 1, it is characterized in that: the surface active pre-treatment in described step 1) is: select ozone, plasma body, radiation or ultraviolet lighting to carry out activating pretreatment to the medical PVC material surface.
3. the method for a kind of acrylate modified polyvinyl chloride according to claim 2, it is characterized in that: the illumination of described UV-irradiation is that 100W～500W, time are 4～12 hours.
4. the method for a kind of acrylate modified polyvinyl chloride according to claim 1, it is characterized in that: the medical PVC of surface active described step 2), reaction soln system direct and HEMA is reacted, and reaction system is the aqueous solution, and the catalyzer of use is ceric ammonium nitrate.
5. the method for a kind of acrylate modified polyvinyl chloride according to claim 1, it is characterized in that: described step 2), the reaction density of HEMA is 5%～10%, temperature of reaction is 40～70 ℃, and the reaction times is 8～24 hours, and reaction is stirred and carried out under air or nitrogen atmosphere.
6. the method for a kind of acrylate modified polyvinyl chloride according to claim 1, it is characterized in that: in described step 3), reaction product is by first using distilled water wash 10～24h under the condition of 50-80 ℃, then ultrasonic cleaning 0.2～1h in ethanol, finally in distilled water, wash, wash temperature is 50～80 ℃, at least change distilled water more than 10 times, vacuum-drying obtains to have hydrophilic acrylate modified polyvinyl chloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177641A (en) * | 2014-08-12 | 2014-12-03 | 东南大学 | Method for preparing lubrication coating on surface of medical polyvinyl chloride (PVC) material |
| CN108192029A (en) * | 2018-01-04 | 2018-06-22 | 宜宾天原集团股份有限公司 | A kind of chloroethylene copolymer resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386684A (en) * | 2008-10-21 | 2009-03-18 | 东南大学 | Method for preparing high hydrophilic film on medical polyurethane material surface |
| CN101455861A (en) * | 2008-12-17 | 2009-06-17 | 东南大学 | Lubricity coatings preparation method on the medical catheter polymers surface |
-
2013
- 2013-07-02 CN CN2013102781896A patent/CN103396516A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386684A (en) * | 2008-10-21 | 2009-03-18 | 东南大学 | Method for preparing high hydrophilic film on medical polyurethane material surface |
| CN101455861A (en) * | 2008-12-17 | 2009-06-17 | 东南大学 | Lubricity coatings preparation method on the medical catheter polymers surface |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177641A (en) * | 2014-08-12 | 2014-12-03 | 东南大学 | Method for preparing lubrication coating on surface of medical polyvinyl chloride (PVC) material |
| CN104177641B (en) * | 2014-08-12 | 2017-04-05 | 东南大学 | A kind of method for preparing lubricating coating in medical polyvinyl material surface |
| CN108192029A (en) * | 2018-01-04 | 2018-06-22 | 宜宾天原集团股份有限公司 | A kind of chloroethylene copolymer resin and preparation method thereof |
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Application publication date: 20131120 |