CN106075602A - The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated - Google Patents
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
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Abstract
The invention provides the preparation method of a kind of aqueous hydrophilic lubrication coating solution for medical devices, Hydrophilic lubrication polymer is anchored at firmly medical devices surface, reduce coefficient of friction while resistance to wiping and also create super lubrication.First the present invention synthesizes the aqueous polyurethane with three-dimensional three-dimensional-structure, then be there is by block copolymerization reaction bonding the polyvinyl pyrrolidone class hydrophilic lubrication material acquisition aqueous microgel dispersion of cross-linked structure, be eventually adding the multifunctional assistant preparation hydrophilic lubrication coating solution for medical devices.Described hydrophilic lubrication coating has the advantage that (1) coating is water dispersible, environmental protection.(2) wet friction coefficient is low, and the excellent repeatable recycling of resistance to wiping is repeatedly.(3) dissolution rate is extremely low.(4) simple short time heat curing process just can be coated in device surface, adapts to wide, and adhesiveness is strong.
Description
Technical field
The invention belongs to medical new material technology field, relate to the hydrophilic lubrication coating of a kind of medical devices surface-coated
The preparation method of solution.
Background technology
Along with noinvasive, Wicresoft's development trend of world today's medical skill, interventional therapeutic technique is made to obtain extremely
It is widely applied and stable growth trend.Therefore, get involved medical devices the most widely should as a kind of emerging diagnostic equipment
For clinical treatment every field.Get involved medical devices and include ultrasound guided probe, puncture needle, seal wire, conduit, catheter sheath, support, ball
Capsule, turn etc..Need enter human body and proceed to along body tube chamber (such as blood vessel, trachea, bile duct etc.) owing to getting involved medical devices
Diseased region directly carries out diagnosis and treatment, the tissue such as tube wall and hemocyte can not be caused big damage, when it moves in tube chamber
Ask and can operate intervention apparatus motion in tube chamber neatly.Therefore, intervention medical devices is carried out surface modification, significantly to change
Kind material and the biocompatibility of human organ official jargon, the lubricity of increase interposing catheter, the antibacterium adhesion energy of raising conduit
Power, the anti-hamartoplasia performance etc. of raising support just seem of crucial importance.
In order to realize these clinical demands, coating hydrophilic lubricant coating on medical device is a kind of very important side
Method.Such as catheter, vessel catheter, the insertion of guide wire support and replacing, because of the existence of surface hydrophilic lubricating coating, thus reduce
Friction between surface and blood vessel wall, improve biocompatibility, make the medical treatment be easier to operate to.When clinical practice,
Patient's pain drastically reduces, and greatly reduces the risk that blood vessel wall is damaged.Additionally, when conduit is used for and contacting blood
Time, hydrophilic lubricant coating contributes to reducing thrombotic probability.
The hydrophilic lubrication coating of clinical practice can be met and must possess three below feature:
(1) good with medical devices surface adhesive, difficult drop-off.
, wet friction coefficient low, and can recycle repeatedly, resistance to wiping.
(3), good biocompatibility, in vivo non-toxic by-products release.
At present, the hydrophilic lubrication coating for medical devices surface of main flow can be divided into two classes:
(1), by polyvinyl alcohol, matter acid, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, chitosan, polyoxyethylene ether
Deng Hydrophilic lubrication polymer, polyurethane-base or acrylic adhesive, it is complex as homogeneous solution, acting on by heat cure
Medical devices surface forms one layer of coating, is dropped by Hydrophilic lubrication polymeric adhesion while medical device surface, resistance to wiping
Low-friction coefficient produces super lubrication.
(2), Hydrophilic lubrication polymer is carried out the modification of molecular structure, simultaneously by pretreating process before coating, such as table
Facet etch, UV irradiation etc., make medical devices surface and Hydrophilic lubrication polymer generate the effect of chemical bond bridge, so that merit
Can be difficult to be desorbed from medical device surface by property polymer, the hydrophilic lubrication effect played stably.
But, these methods have different defects.As used method compound to adhesive and hydrophilic lubrication polymer,
Because of the simplest physical mixed, it is easily caused hydrophilic lubrication polymer and is soaked de-by water or body fluid, make whole coating be destroyed,
Be only capable of using very few for several times, and have more material dissolution in vivo and affect the health of patient.Or some coating product
In order to improve resistance to wiping, and employ more adhesive substance, but the effect but making lubrication reduce friction had a greatly reduced quality,
The requirement of Clinical practice is not reached yet.And, more product employs a large amount of solvent, and not environmentally, processing environment is severe, danger
Evil property is high.As United States Patent (USP) US20090048537 employs Kollidon 90 as hydrophilic lubrication component, then
Mix acquisition coating after dissolving with the NC Nitroncellulose solvent as bonding agent, resistance to wiping properties can not be made to improve.
Meanwhile, although the method using UV to irradiate realizes hydrophilic profit meeting while resistance to wiping requires to a certain extent
Sliding effect, but the pretreatment that usual this kind of product requirement is strict (as ultrasonic clean device surface, oxygen-free environment irradiate), complexity
Process equipment, brings extra cost payout；During coating medical equipment, technique is complex, relatively costly.Such as Chinese patent
CN104177641A, the method pretreatment first pvc material ozone, ion sputtering and UV irradiated, then anaerobic feelings
Under condition, grafting reaction 1-36h, the most fully to wash, and this technique is loaded down with trivial details, and practicality is the highest.
Therefore, how to solve the problems referred to above, be those skilled in the art's contents of important research.
Summary of the invention
For overcoming above-mentioned deficiency of the prior art, present invention aim at providing a kind of medical devices surface-coated
The preparation method of hydrophilic lubrication coating solution；The processing technique that this preparation method makes coating solution is simple, can be at medical device
Surface forms the coating that resistance to wiping, hydrophilic lubrication are remarkably productive, and can be recycled for multiple times, leachable is low, good biocompatibility.
For achieving the above object and other relevant purposes, the present invention provides the hydrophilic profit of a kind of medical devices surface-coated
The preparation method of sliding coating solution, the step including following:
The first step, 1000 parts of aqueous polyurethanes of preparation: by the polyether Glycols of 105-182 part and 50-120 part polyether-tribasic alcohol
Mixture, uniformly instills containing the polyisocyanates of 45-101 part, the reaction of 42-150 part solvent at 60-80 DEG C in 1-2h
In container, add 4-15 part ionic groups compound and carry out ion reaction 1-2h；It is subsequently added into the chain extender of 0.5-2 part
Carry out chain extending reaction 15-30min, be subsequently adding the hydroxyl unsaturated monomer reaction 1-2h of 6-25 part；Finally cool to 50 DEG C
Hereinafter neutralize with 3-8.5 part salt forming agent；500-700 part water is added this solution and carries out emulsifying acquisition aqueous polyurethane；
Second step, 1000 parts of three-dimensional-structure aqueous microgel dispersion of preparation: by vinyl pyrrolidone, the 0.8-10 of 60-120 part
Cross-linking agent, the reproducibility initiator of 1.8-10 part and 20-80 part water mix homogeneously of part obtain the first mixed solution；It addition,
Oxidative initiator and 20-45 part water mix homogeneously of 1.8-10 part are obtained the second mixing easily, then mixes described first
Close solution and described second mixed solution slowly to drip uniformly in 94-442 part first step in 2-4h at 60-80 DEG C simultaneously
In the aqueous polyurethane prepared and the mixture of 450-800 part water, insulation reaction 2h after dropping, it is thus achieved that Microgel water
A prose style free from parallelism；
3rd step, prepare hydrophilic lubrication coating solution: by the aqueous microgel dispersion prepared in 100-500 part second step, 50-
150 parts of compatilizers, 0. 5-1.5 part wetting agent, 1-2 part pH adjusting agent and 340-800 part water mixing and stirring prepare clarification
Solution, then filters described settled solution with 5000 mesh filter screens, it is thus achieved that hydrophilic lubrication coating solution.
In technique scheme, related content is explained as follows:
1, in such scheme, described polyisocyanates is 4,4 '-methyl diphenylene diisocyanate, isophorone diisocyanate
The mixture of one or more arbitrary proportions in ester.
2, in such scheme, described polyether Glycols be molecular weight be 1000g/mol, 2000g/mol, 3000g/mol
Polyoxypropyleneglycol, the mixture of one or more arbitrary proportions in polytetrahydrofuran diol；Preferential selection is divided
The polyoxypropyleneglycol of son amount 2000 g/mol and the polytetrahydrofuran diol of molecular weight 2000.Polyoxypropyleneglycol is with poly-
Erythritan is respectively provided with good biocompatibility and not facile hydrolysis.Described polyether-tribasic alcohol be molecular weight be 3000g/
The mixture of one or more arbitrary proportions in the polypropylene oxide triol of mol, 6000g/mol.
3, in such scheme, described ionic groups compound is 2,2-dihydromethyl propionic acid, 2,2-dihydroxymethyl fourth
Acid or both mixture.
4, in such scheme, described hydroxyl unsaturated monomer is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, methyl-prop
The mixture of one or more arbitrary proportions in olefin(e) acid hydroxyl ethyl ester or Hydroxypropyl methacrylate.
5, in such scheme, described cross-linking agent is N,N methylene bis acrylamide, glycol dimethacrylates
The mixture of one or more arbitrary proportions in ester.It is characterized in that water solublity, low toxicity.
6, in such scheme, described reproducibility initiator is ascorbic acid, and described oxidative initiator is hydrogen peroxide.Its
Mass ratio is 1:0.75-1:1, feature be reacted after to human body totally nontoxic.
7, in such scheme, described compatilizer is one or both in acetone, butanone, DAA or oxolane
The mixture of any of the above ratio.
8, in such scheme, described wetting agent is span, tween, low-molecular-weight polyethylene glycol, lecithin, cholesterol or sea
The mixture of one or more arbitrary proportions in sodium alginate.
9, in such scheme, described pH adjusting agent is HEPES buffer solution, TES buffer solution or MOPS buffer solution
In any one or the mixture of two or more arbitrary proportion.
10, in such scheme, described number is mass parts.
11, in such scheme, described salt forming agent is triethylamine, trimethylamine, triethanolamine, tri-n-butylamine, mass concentration
Be 50% potassium hydroxide aqueous solution or sodium hydrate aqueous solution that mass concentration is 50% in a kind of and their mixture；
Potassium hydroxide aqueous solution, the mass concentration of preferentially selecting mass concentration to be 50% are the sodium hydrate aqueous solution of 50%.
12, in such scheme, described chain extender be BDO, ethylene glycol, propylene glycol, diethylene glycol, 1,6-oneself
The mixture of one or more arbitrary proportions in glycol or cyclohexanedimethanol；Prioritizing selection 1,4-butanediol, second two
Alcohol.
13, in such scheme, described solvent is acetone, butanone, oxolane, DMF, N-methyl
Ketopyrrolidine etc., and their mixture；Prioritizing selection acetone and butanone.
14, in such scheme, the aqueous dispersion of described microgel is network semi-interpenetrating polymer aqueous dispersion.
Owing to technique scheme is used, the present invention compared with prior art has the advantage, that
1, the aqueous hydrophilic lubrication coating solution for medical devices prepared by the present invention, only needs first that device surface is simple
Clean dry, uses dip-coating, the method for spraying, and then 60 DEG C of heat cure 10-20min just can form firm parent at device surface
Water lubrication coating.Have the advantage that in its performance
(1) coating is water dispersible, environmental protection.
(2) wet friction coefficient is low, the excellent repeatable recycling of resistance to wiping repeatedly, wet friction coefficient < 0.1.
(3) dissolution rate is extremely low, after aqueous solution soaks 90 days, and mass loss rate < 0.5%.
(4) simple short time heat curing process just can be coated in device surface, adapts to wide, and adhesiveness is strong, can be competent at poly-
The medical devices that vinyl chloride, polyurethane, silica gel, stainless steel make.
2, the core component said three-dimensional body type structure hydrophilic lubrication that present invention comprises aqueous hydrophilic lubrication coating is micro-solidifying
The synthetic method of the aqueous dispersion of glue and the method with multifunctional assistant composite coating preparation solution.
The core group of aqueous hydrophilic lubrication coating solution is divided into the active substance of performance hydrophilic lubrication effect and by its anchor
Gu the compound at device surface.The technical characteristic of the present invention be that Promethean synthesized a kind of in three-dimensional three-dimensional-structure,
The aqueous dispersion of hydrophilic lubrication microgel, then has clinical practice application effect by prepared compound with multifunctional assistant
Hydrophilic lubrication coating solution.By bodily form cross-linked structure, by hydrophilic lubrication coating solution (hydrophilic polymer) firmly earth anchor
Gu at device surface, reduce coefficient of friction while resistance to wiping and also create super lubrication.This tool connected with chemical bond
The aqueous dispersion of the hydrophilic lubrication microgel of three-dimensional-structure is different from and is simply mixed by the physics such as hydrophilic lubrication polymer, adhesive
Close；Owing to becoming an overall molecular structure, it is possible to play more powerful effect.The tool that the present invention designs and synthesizes
Having the aqueous dispersion of the hydrophilic lubrication microgel of three-dimensional three-dimensional-structure is with the polyurethanes material of aqueous cross-linked structure for anchoring
Component, then has the polyvinyl pyrrolidone class hydrophilic lubrication material of cross-linked structure by block copolymerization reaction bonding and obtains
?.The multifunctional assistant of the present invention mainly includes wetting agent, pH adjusting agent and compatilizer.
3, the present invention synthesizes the aqueous dispersion of the hydrophilic lubrication microgel with three-dimensional three-dimensional-structure by two-step reaction.First
First synthesize the water-based polyurethane material of band unsaturated group and micro-cross-linked structure in a kind of molecule segment, as anchoring
Component；Then, introduce vinylpyrrolidone monomer, unsaturated polyfunctionality cross-linking agent carries out copolymerization, it is thus achieved that with polyethylene
Base pyrrolidinone compounds material is the aqueous dispersion of the hydrophilic lubrication microgel with three-dimensional three-dimensional-structure of hydrophilic lubrication component.
When preparing aqueous polyurethane, isocyanate groups and hydroxyl (include polyether polyol, chain extender, salt forming agent, band
Hydroxyl unsaturated monomer) mol ratio be NCO/OH=1.1-1.02.The mass concentration of aqueous polyurethane is 25%-40%.
In the aqueous dispersion of microgel, polyvinyl pyrrolidone class solid matter and the matter of polyurethanes solid matter
Amount ratio is 0.5-1.5.
When preparing the aqueous dispersion of microgel, in order to reduce the residual initiators impact on human body, employ safety non-toxic
Ascorbic acid-hydrogen peroxide oxidation/reduction system cause polymerization, harmless.The aqueous dispersion concentration of microgel is
10%-25%。
In order to preferably adapt to medical devices basal plane, make coating and substrate adhesion more firm, at hydrophilic lubrication coating formula
In, except, in addition to the aqueous dispersion of microgel, also using compatilizer, wetting agent, pH adjusting agent.Wherein wetting agent,
PH adjusting agent is biocompatibility.
In the present invention, first prepare the aqueous polyurethane of micro-crosslinking, introduce unsaturated group at segment end simultaneously；The
The monomeric compound of two step polyvinyl pyrrolidone and its copolymerization, and it is also carried out micro-crosslinking Treatment simultaneously.So, with regard to energy
Enough allow two kinds of molecule segments in the polymer of three-dimensional three-dimensional-structure form three-dimensional three-dimensional-structure with the form of chemical bond, have simultaneously
There is water dispersible.
Detailed description of the invention
By particular specific embodiment, embodiments of the present invention being described below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
The main raw material(s) trade mark, abbreviation and manufacturer used in embodiment is as shown in table 1, and remaining raw material is easy
The general chemistry product bought.
The table 1 main raw material(s) trade mark, abbreviation and manufacturer
Embodiment one:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.08) is by the DL-1000D and 70 parts of MN-of 135 parts
The mixture of 3050DF, uniformly instills in the reaction vessel containing 75 parts of MDI, 80 parts of acetone at 60 DEG C in 1h；Drip
Add 2,2-dimethylolpropionic acid 10.5 parts after Biing and carry out ion reaction 2h；It is subsequently added into 0.8 part of 1,4-butanediol to carry out
Chain extending reaction 15min, is subsequently adding 6 parts of 2-(Acryloyloxy)ethanol reaction 1h.Finally cool to the hydrogen that less than 50 DEG C with 5.7 part 50%
Sodium hydroxide solution neutralizes, and 617 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, matter
Amount concentration is 30%.
Second step, (polyvinyl pyrrolidone class is solid in the preparation of the aqueous dispersion of 1000 parts of three-dimensional three-dimensional-structure microgels
Body material is 0.5 with the mass ratio of aqueous polyurethane solid matter): by 60 parts of vinyl pyrrolidones, the N of 0.8 part, N-methylene
Base bisacrylamide, the ascorbic acid of 1.8 parts, 20 parts of water mix homogeneously；Additionally by the hydrogen peroxide of 1.8 parts, 20 parts of water mixing all
Even.Then these two kinds of mixed solutions are dripped at 60 DEG C in 2h the most uniformly and prepare in 442 parts of first steps
Aqueous polyurethane, 453.6 parts of water mixture in, after dropping insulation reaction 2h obtain the Semi-IPN structural polymer of network
Aqueous dispersion (i.e. the aqueous dispersion of microgel).Aqueous dispersion mass concentration 20%.
3rd step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: gather Semi-IPN for the network obtained in 250 parts of second steps
Compound aqueous dispersion, 100 parts of acetone, 1 part of sorbester p17,1 part of HEPES buffer solution, 648 parts of water are stirred for settled solution,
Then filter with 5000 mesh filter screens and obtain coating solution.
Embodiment two:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.02) is by the PolyTHF 1000 and 86 parts of MN-of 182 parts
The mixture of 3050DF, uniformly instills in the reaction vessel containing 101 parts of MDI, 42 parts of acetone at 70 DEG C in 2h；Drip
Add 2,2-dimethylolpropionic acid 15 parts after Biing and carry out ion reaction 1h；It is subsequently added into 2 parts of ethylene glycol and carries out chain extending reaction
30min, is subsequently adding 10 parts of 2-(Acryloyloxy)ethanol reaction 2h.Finally cool to the sodium hydroxide solution that less than 50 DEG C with 8 part 50%
Neutralizing, 554 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, mass concentration is
40%。
Second step, (polyvinyl pyrrolidone class is solid in the preparation of the aqueous dispersion of 1000 parts of three-dimensional three-dimensional-structure microgels
Body material is 1 with the mass ratio of aqueous polyurethane solid matter): by 120 parts of vinyl pyrrolidones, the N of 2 parts, N-methylene
Bisacrylamide, the ascorbic acid of 4 parts, 50 parts of water mix homogeneously；Additionally by hydrogen peroxide, 30 parts of water mix homogeneously of 5 parts.Then
The most slowly these two kinds of mixed solutions are dripped aqueous uniformly that prepared in 314 parts first at 60 DEG C in 2h gather
Urethane, 475 parts of water mixture in, after dropping insulation reaction 2h obtain network Semi-IPN structural polymer aqueous dispersion.
Aqueous dispersion mass concentration 25%.
3rd step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: gather Semi-IPN for the network obtained in 150 parts of second steps
Compound aqueous dispersion, 50 parts of butanone, 0.5 part of Tween 80,2 parts of TES buffer solution, 797.5 parts of water are stirred for settled solution,
Then filter with 5000 mesh filter screens and obtain coating solution.
Embodiment three:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.1) is by the PolyTHF 2000 and 50 parts of MN-of 105 parts
The mixture of 3050DF, uniformly instills in the reaction vessel containing 60 parts of IPDI, 60 parts of butanone at 80 DEG C in 2h；Drip
Add 2,2-dihydromethyl propionic acid 10 parts after Biing and carry out ion reaction 2h；It is subsequently added into 1 part of ethylene glycol and carries out chain extending reaction
15min, is subsequently adding 20 parts of Hydroxypropyl acrylate reaction 2h.Finally cool to less than 50 DEG C molten with the potassium hydroxide of 8.5 part 50%
Liquid neutralizes, and 685.5 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, mass concentration
It is 25%.
Second step, preparation (the polyvinyl pyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
Matter is 1.5 with the mass ratio of aqueous polyurethane solid matter): by 100 parts of vinyl pyrrolidones, the N of 5 parts, N-di-2-ethylhexylphosphine oxide
Acrylamide, the ascorbic acid of 8 parts, 80 parts of water mix homogeneously；Additionally by hydrogen peroxide, 40 parts of water mix homogeneously of 9 parts.Then will
These two kinds of mixed solutions slowly drip the poly-ammonia of the aqueous prepared in 225 parts of first steps at 70 DEG C in 3h simultaneously uniformly
Ester, 533 parts of water mixture in, after dropping insulation reaction 2h obtain network Semi-IPN structural polymer aqueous dispersion.Water
Dispersion quality concentration 15%.
3rd step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: gather Semi-IPN for the network obtained in 100 parts of second steps
Compound aqueous dispersion, 80 parts of DAAs, 1.5 parts of PEG400s, 1 part of MOPS buffer solution, 817.5 parts of water stir
For settled solution, then filter with 5000 mesh filter screens and obtain coating solution.
Embodiment four:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.05) is by the DL-2000D of 170 parts and 120 parts
The mixture of VORANOL CP 6055, uniformly instills the reaction containing 45 parts of IPDI, 150 parts of butanone at 80 DEG C in 1h and holds
In device；Add 2,2-dihydromethyl propionic acid 4 parts after dropping and carry out ion reaction 2h；It is subsequently added into 1 part of ethylene glycol to enter
Row chain extending reaction 30min, is subsequently adding 8 parts of Hydroxypropyl acrylate reaction 1h.Finally cool to the hydrogen that less than 50 DEG C with 3 part 50%
Potassium oxide solution neutralizes, and 499 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, matter
Amount concentration is 35%.
Second step, preparation (the polyvinyl pyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
Matter is 1.5 with the mass ratio of aqueous polyurethane solid matter): by 60 parts of vinyl pyrrolidones, the N of 3 parts, N-di-2-ethylhexylphosphine oxide third
Acrylamide, the ascorbic acid of 3 parts, 20 parts of water mix homogeneously；Additionally by hydrogen peroxide, 20 parts of water mix homogeneously of 4 parts.Then by this
Two kinds of mixed solutions 80 DEG C drip the most uniformly in 4h prepared in 94 parts of first steps aqueous polyurethane,
In the mixture of 796 parts of water, after dropping, insulation reaction 1h obtains network Semi-IPN structural polymer aqueous dispersion.Water-dispersible
Weight concentration 10%.
3rd step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: gather Semi-IPN for the network obtained in 500 parts of second steps
Compound aqueous dispersion, 150 parts of oxolanes, 1 part of lecithin, 1 part of TES buffer solution, 348 parts of water is stirred for clarifying molten
Liquid, then filters with 5000 mesh filter screens and obtains coating solution.
Embodiment five:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.06) is by the DL-1000D and 72 parts of VORANOL of 144 parts
The mixture of CP 6055, uniformly instills in the reaction vessel containing 94 parts of MDI, 80 parts of acetone at 60 DEG C in 2h；Drip
Add 2,2-dihydromethyl propionic acid 12 parts after Biing and carry out ion reaction 2h；Being subsequently added into 0.5 part of propylene glycol, to carry out chain extension anti-
Answer 15min, be subsequently adding 25 parts of Hydroxypropyl acrylate reaction 2h.Finally cool to less than 50 DEG C molten with the sodium hydroxide of 7 part 50%
Liquid neutralizes, and 565.5 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, mass concentration
It is 35%.
Second step, preparation (the polyvinyl pyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
The mass ratio of matter and aqueous polyurethane solid matter is 1): by 80 parts of vinyl pyrrolidones, the EGDMA-200 of 10 parts, 10 parts
Ascorbic acid, 30 parts of water mix homogeneously；Additionally by hydrogen peroxide, 30 parts of water mix homogeneously of 10 parts.Then by these two kinds mixing
Solution slowly drips the aqueous polyurethane prepared in 285 parts of first steps, 545 parts of water at 80 DEG C in 4h simultaneously uniformly
Mixture in, after dropping insulation reaction 1h obtain network Semi-IPN structural polymer aqueous dispersion.Aqueous dispersion quality
Concentration 20%.
3rd step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: gather Semi-IPN for the network obtained in 350 parts of second steps
Compound aqueous dispersion, 100 parts of oxolanes, 1.5 parts of cholesterol, 1.5 parts of HEPES buffer solution, 547 parts of water are stirred for clear
Clear solution, then filters with 5000 mesh filter screens and obtains coating solution.
Embodiment six:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.09) is by the DL-3000D and 80 parts of MN-of 133 parts
The mixture of 3050DF, uniformly instills in the reaction vessel containing 60 parts of MDI, 120 parts of acetone at 70 DEG C in 1h；Drip
Add 2,2-dimethylolpropionic acid 8 parts after Biing and carry out ion reaction 1h；It is subsequently added into 1.6 parts of butanediols and carries out chain extending reaction
15min, is subsequently adding 15 parts of 2-(Acryloyloxy)ethanol reaction 1.5h.Finally cool to the sodium hydroxide that less than 50 DEG C with 4.4 part 50%
Solution neutralizes, and 578 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, mass concentration
It is 35%.
Second step, preparation (the polyvinyl pyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
The mass ratio of matter and aqueous polyurethane solid matter is 1.2): by 72 parts of vinyl pyrrolidones, the EGDMA-200 of 5 parts, 5 parts
Ascorbic acid, 25 parts of water mix homogeneously；Additionally by hydrogen peroxide, 45 parts of water mix homogeneously of 6 parts.Then by molten for these two kinds mixing
Liquid drips the aqueous polyurethane prepared in 227 parts of first steps, 615 parts of water at 60 DEG C in 3h uniformly simultaneously slowly
In mixture, after dropping, insulation reaction 2h obtains network Semi-IPN structural polymer aqueous dispersion.Aqueous dispersion quality is dense
Degree 15%.
3rd step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: gather Semi-IPN for the network obtained in 250 parts of second steps
Compound aqueous dispersion, 80 parts of DAAs, 1 part of sodium alginate, 2 parts of HEPES buffer solution, 667 parts of water are stirred for clarification
Solution, then filters with 5000 mesh filter screens and obtains coating solution.
Comparative example:
In order to better illustrate advantages of the present invention, it is respectively synthesized the aqueous of identical formula according to the method for embodiment one
Then both are mixed acquisition by the method for physical mixed and mix molten by polyurethane and polyvinylpyrrolidonepolymers polymers
Liquid.Finally prepare hydrophilic lubrication coating solution with this mixed solution for core according to identical formula.Due to the synthesis poly-ammonia of aqueous
It is all separately synthesized when ester and polyvinyl pyrrolidone, so not forming network blackboard, the most unordered
Admixture.
The preparation of aqueous polyurethane: (NCO/OH=1.08) is by the DL-1000D of 135 parts and the mixing of 70 parts of MN-3050DF
Thing, uniformly instills in the reaction vessel containing 75 parts of MDI, 80 parts of acetone at 60 DEG C in 1h；2 are added after dropping,
2-dimethylolpropionic acid 10.5 parts carries out ion reaction 2h；It is subsequently added into 0.8 part of 1,4-butanediol and carries out chain extending reaction
15min, is subsequently adding 6 parts of 2-(Acryloyloxy)ethanol reaction 1h.Finally cool to less than 50 DEG C molten with the sodium hydroxide of 5.7 part 50%
Liquid neutralizes, and 617 parts of water add the aqueous polyurethane carrying out emulsifying acquisition unsaturated monomer end-blocking in this solution, and mass concentration is
30%。
The synthesis of polyvinylpyrrolidonepolymers polymers aqueous solution: by 60 parts of vinyl pyrrolidones, the N of 0.8 part, N-is sub-
Bisacrylamide, the ascorbic acid of 1.8 parts, 20 parts of water mix homogeneously；Additionally by hydrogen peroxide, 20 parts of water mixing of 1.8 parts
Uniformly.Then these two kinds of mixed solutions are slowly dripped in 453.6 parts of water at 60 DEG C in 2h uniformly simultaneously, drip complete
Rear insulation reaction 2h obtains the aqueous solution of polyvinylpyrrolidonepolymers polymers.
442 parts of aqueous polyurethanes and 558 parts of polyvinylpyrrolidonepolymers polymers aqueous solutions are stirred at room temperature as clear
Clear homogeneous solution (polyvinyl pyrrolidone class solid matter is 0.5 with the mass ratio of aqueous polyurethane solid matter), this mixes
Close concentration of polymer solution 20%..
The preparation of 1000 parts of hydrophilic lubrication coatings: be the mixed solution of 20% by 250 parts of above-mentioned mass concentrations, 100 part third
Ketone, 1 part of sorbester p17,1 part of HEPES buffer solution, 648 parts of water are stirred for settled solution, then filter with 5000 mesh filter screens
Obtain coating solution.
Application example
The coating solution of preparation in embodiment one to embodiment six and comparative example is coated in a diameter of as follows
On the polrvinyl chloride catheter of 0.46mm, 60cm length.
Painting method: be thoroughly dried after catheter surface ethanol and clean water are cleaned.Then conduit is the most complete
Immerse and become loaded with in the container of hydrophilic lubrication coating solution, after being completely immersed in and keeping 10s, quick and complete draw proposition liquid level.Treat
After dripless drippage, 60 DEG C of convection oven are dried 20min.
Method of testing: the conduit after applying coating is soaked in 37 DEG C of normal saline environment different time.Then clean
Conduit is also dried, test different the wet friction coefficient of soak time, water contact angle.
Meanwhile, by the method for drying at room temperature after mould is cast, coating solution is made 0.5mm thickness, 5 × 5cm size
Film.It is soaked in 37 DEG C of normal saline environment different time, the quality of the different soak time of dried test after cleaning
Loss rate.
Related data is shown in Table coating result prepared by embodiment 1-6 seen from 2. and is substantially better than comparative example, and hydrophilic lubrication
Effect and the excellent performance of resistance to wiping.
Table 2. test comparison data
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of technology.Therefore, lift
All art have what usually intellectual was completed under without departing from disclosed spirit and technological thought
All equivalences are modified or change, and must be contained by the claim of the present invention.
Claims (10)
1. the preparation method of the hydrophilic lubrication coating solution of a medical devices surface-coated, it is characterised in that include following
Step:
The first step, 1000 parts of aqueous polyurethanes of preparation: by the polyether Glycols of 105-182 part and 50-120 part polyether-tribasic alcohol
Mixture, uniformly instills containing the polyisocyanates of 45-101 part, the reaction of 42-150 part solvent at 60-80 DEG C in 1-2h
In container, add 4-15 part ionic groups compound and carry out ion reaction 1-2h；It is subsequently added into the chain extender of 0.5-2 part
Carry out chain extending reaction 15-30min, be subsequently adding the hydroxyl unsaturated monomer reaction 1-2h of 6-25 part；Finally cool to 50 DEG C
Hereinafter neutralize with 3-8.5 part salt forming agent；500-700 part water is added this solution and carries out emulsifying acquisition aqueous polyurethane；
Second step, 1000 parts of three-dimensional-structure aqueous microgel dispersion of preparation: by vinyl pyrrolidone, the 0.8-10 of 60-120 part
Cross-linking agent, the reproducibility initiator of 1.8-10 part and 20-80 part water mix homogeneously of part obtain the first mixed solution；It addition,
Oxidative initiator and 20-45 part water mix homogeneously of 1.8-10 part are obtained the second mixing easily, then mixes described first
Close solution and described second mixed solution slowly to drip uniformly in 94-442 part first step in 2-4h at 60-80 DEG C simultaneously
In the aqueous polyurethane prepared and the mixture of 450-800 part water, insulation reaction 2h after dropping, it is thus achieved that Microgel water
A prose style free from parallelism；
3rd step, prepare hydrophilic lubrication coating solution: by the aqueous microgel dispersion prepared in 100-500 part second step, 50-
150 parts of compatilizers, 0. 5-1.5 part wetting agent, 1-2 part pH adjusting agent and 340-800 part water mixing and stirring prepare clarification
Solution, then filters described settled solution with 5000 mesh filter screens, it is thus achieved that hydrophilic lubrication coating solution.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described polyisocyanates is the one in 4,4 '-methyl diphenylene diisocyanate, isophorone diisocyanate
Or the mixture of two or more arbitrary proportion.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described polyether Glycols be molecular weight be 1000g/mol, the polypropylene oxide two of 2000 g/mol, 3000g/mol
The mixture of one or more arbitrary proportions in alcohol, polytetrahydrofuran diol；Described polyether-tribasic alcohol is molecular weight
Mixture for one or more arbitrary proportions in the polypropylene oxide triol of 3000g/mol, 6000g/mol.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described ionic groups compound is 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid or both is mixed
Compound.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described hydroxyl unsaturated monomer is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methylacrylate or first
The mixture of one or more arbitrary proportions in base Hydroxypropyl acrylate.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described cross-linking agent is the one in N,N methylene bis acrylamide, polyethylene glycol dimethacrylate or two
Plant the mixture of any of the above ratio.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levying and be: described reproducibility initiator is ascorbic acid, described oxidative initiator is hydrogen peroxide.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described compatilizer is one or more arbitrary proportions in acetone, butanone, DAA or oxolane
Mixture.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described wetting agent is the one in span, tween, low-molecular-weight polyethylene glycol, lecithin, cholesterol or sodium alginate
Or the mixture of two or more arbitrary proportion.
The preparation method of the hydrophilic lubrication coating solution of medical devices surface-coated the most according to claim 1, it is special
Levy and be: described pH adjusting agent be in HEPES buffer solution, TES buffer solution or MOPS buffer solution any one or
The mixture of two or more arbitrary proportions.
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| CN110180753A (en) * | 2019-05-21 | 2019-08-30 | 宁波大学 | A kind of preparation method of hydrophilic coating |
| CN110507864A (en) * | 2019-09-29 | 2019-11-29 | 佛山市其右医疗科技有限公司 | A kind of medical guiding wire with fine lubrication function |
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| CN115814158A (en) * | 2022-12-01 | 2023-03-21 | 中山大学 | Articular cartilage-like wear-resistant lubricating coating and preparation method thereof |
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| CN115814158A (en) * | 2022-12-01 | 2023-03-21 | 中山大学 | Articular cartilage-like wear-resistant lubricating coating and preparation method thereof |
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