CN106075602B - The preparation method of the hydrophilic lubrication coating solution of medical devices surface coating - Google Patents
The preparation method of the hydrophilic lubrication coating solution of medical devices surface coating 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 present invention provides a kind of preparation method of aqueous hydrophilic lubrication coating solution for medical devices, Hydrophilic lubrication polymer is firmly anchored at medical devices surface, resistance to wiping while reduces coefficient of friction and also produces super lubricating action.The present invention synthesizes the aqueous polyurethane with three-dimensional structure first, then by block copolymerization reaction bonding there is the polyvinylpyrrolidone class hydrophilic lubrication substance of cross-linked structure to obtain aqueous microgel dispersion, is eventually adding the hydrophilic lubrication coating solution that multifunctional assistant preparation is used for medical devices.The hydrophilic lubrication coating has the advantage that (1) coating is water dispersible, environmentally protective.(2) wet friction coefficient is low, and the resistance to excellent repeatable recycling of wiping is multiple.(3) dissolution rate is extremely low.(4) simple short time heat curing process can be coated in device surface, and adaptation is wide, and adhesiveness is strong.
Description
Technical field
The invention belongs to medical new material technology fields, are related to a kind of hydrophilic lubrication coating of medical devices surface coating
The preparation method of solution.
Background technique
With noninvasiveization of world today's medical technology, minimally invasiveization development trend, obtain interventional therapeutic technique extremely
It is widely applied and stable growth trend.Therefore, intervention medical devices have widely been answered as a kind of emerging diagnostic equipment
For clinical treatment every field.Intervening medical devices includes ultrasound guided probe, puncture needle, seal wire, conduit, catheter sheath, bracket, ball
Capsule, spring ring etc..Since intervention medical devices need to enter human body and proceed to along body lumen (such as blood vessel, tracheae, bile duct)
Diseased region directly carries out diagnosis and treatment, and cannot the tissues such as tube wall and haemocyte be caused with big damage when moving in lumen,
Movement of the intervention apparatus in lumen can neatly be operated by asking.Therefore, it carries out surface to intervention medical devices to be modified, significantly to change
The biocompatibility for being apt to material and human organ official jargon, the lubricity for increasing interposing catheter, the antibacterium adhesion energy for improving conduit
Power, the anti-hyperblastosis performance for improving bracket etc. just seem of crucial importance.
In order to realize these clinical demands, coating hydrophily lubricant coating in medical equipment is a kind of very important side
Method.Such as the insertion and replacement of catheter, vessel catheter, guide wire support, because of the presence of surface hydrophilic lubricating coating, to reduce
Friction between surface and vascular wall improves biocompatibility, is easier to operate to medical treatment.In clinical application,
Patient's pain drastically reduces, and greatly reduces the risk of vascular wall breakage.In addition, when conduit is used for and contacting blood
When, hydrophily lubricant coating helps to reduce the probability of thrombosis.
The hydrophilic lubrication coating for being able to satisfy clinical application must have following three features:
(1), good with medical devices surface adhesive, it is not easily to fall off.
(2), wet friction coefficient is low, and repeatedly resistance to wiping can be recycled.
(3), good biocompatibility, non-toxic by-products discharge in vivo.
Currently, the hydrophilic lubrication coating for medical devices surface of mainstream can be divided into two classes:
(1), by polyvinyl alcohol, matter acid, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, chitosan, polyoxy second
The Hydrophilic lubrications such as alkene ether polymer, polyurethane or acrylic adhesive, are complex as homogeneous solution, pass through the work of heat cure
Form one layer of coating used in medical devices surface, by Hydrophilic lubrication polymeric adhesion on medical device surface, resistance to wiping it is same
When reduce coefficient of friction and generate super lubricating action.
(2) the modification of molecular structure, is carried out to Hydrophilic lubrication polymer, while passing through 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, to make function
Energy property polymer is not easy to be desorbed from medical device surface, the hydrophilic lubrication effect played stably.
But these methods have different defects.The method that adhesive and hydrophilic lubrication polymer is compound is such as used,
Because of only simple physical mixed, it is easy to cause hydrophilic lubrication polymer to be soaked by water or body fluid de-, is destroyed entire coating,
Be only capable of using it is very few for several times, and have more substance dissolution in vivo and influence the health of patient.Or some coating products
In order to improve resistance to wiping, and more adhesive substance is used, but the effect for reducing lubrication by friction is had a greatly reduced quality,
Also the requirement of clinical use is not achieved.Moreover, more product has used a large amount of solvents, and not environmentally, processing environment is severe, danger
Evil property is high.If United States Patent (USP) US20090048537 has used Kollidon 90 as hydrophilic lubrication component, then
It is mixed after being dissolved with the NC Nitroncellulose as bonding agent with solvent and obtains coating, resistance to wiping properties can not be made to improve.
Meanwhile although hydrophilic profit is realized while meeting resistance to wiping requirement using the method that UV irradiates to a certain extent
Sliding effect, but usually this kind of product requires stringent pretreatment (such as the clean device surface of ultrasound, oxygen-free environment irradiation), complexity
Process equipment brings additional cost payout；The process is more complicated when coating medical equipment, higher cost.Such as Chinese patent
CN104177641A, the first method by pvc material ozone, ion sputtering and UV irradiation are pre-processed, then anaerobic feelings
Condition marry it is reversed answer 1-36h, finally also sufficiently to wash, this technique is cumbersome, and practicability is not high.
Therefore, how to solve the above problems, be those skilled in the art the content of important research.
Summary of the invention
To overcome the deficiencies in the prior art described above, it is an object of that present invention to provide a kind of coatings of medical devices surface
The preparation method of hydrophilic lubrication coating solution；The processing technology that coating solution is made in the preparation method is simple, can be in medical device
Surface formed it is resistance to wiping, hydrophilic lubrication effect coating outstanding, and can be recycled for multiple times, leachable is low, good biocompatibility.
In order to achieve the above objects and other related objects, the present invention provides a kind of hydrophilic profit of medical devices surface coating
The preparation method of sliding coating solution, includes the steps that following:
1000 parts of first step, preparation aqueous polyurethanes: by 105-182 parts of polyether Glycols and 50-120 parts of polyethers ternarys
The mixture of alcohol, in uniformly instilling the polyisocyanates containing 45-101 parts, 42-150 parts of solvent in 1-2h at 60-80 DEG C
In reaction vessel, adds 4-15 parts of ionic groups compounds and carry out ion reaction 1-2h；It is subsequently added into 0.5-2 parts of expansion
Chain agent carries out chain extending reaction 15-30min, and 6-25 parts of hydroxyl unsaturated monomer is then added and reacts 1-2h；Finally cool to
50 DEG C or less are neutralized with 3-8.5 parts of salt forming agents；This solution is added in 500-700 parts of water and carries out emulsification acquisition aqueous polyurethane；
Second step, preparation 1000 parts of three-dimensional-structure aqueous microgel dispersions: by 60-120 parts of vinyl pyrrolidone,
0.8-10 parts of crosslinking agent, 1.8-10 parts of reproducibility initiator and 20-80 parts of water are uniformly mixed and obtain the first mixed solution；
It is easy in addition, 1.8-10 parts of oxidative initiator and 20-45 parts of water are uniformly mixed and obtain the second mixing, then by described the
One mixed solution and second mixed solution are added dropwise in slowly uniform simultaneously in 2-4h in 94-442 part first at 60-80 DEG C
In the mixture of aqueous polyurethane and 450-800 part water prepared in step, rear insulation reaction 2h is added dropwise, obtains microgel
Aqueous dispersion；
Third step prepares hydrophilic lubrication coating solution: by aqueous microgel dispersion obtained in 100-500 parts of second steps,
50-150 parts of compatilizers, 0. 5-1.5 parts of wetting agent, 1-2 parts of pH adjusting agents and 340-800 parts of water are mixed evenly obtained
Then clear solution filters the clear solution with 5000 mesh filter screens, obtain hydrophilic lubrication coating solution.
In above-mentioned technical proposal, related content is explained as follows:
1, in above scheme, the polyisocyanates is 4,4 '-methyl diphenylene diisocyanates, isophorone two is different
The mixture of one or more of cyanate arbitrary proportion.
2, in above scheme, the polyether Glycols are that molecular weight is 1000g/mol, 2000g/mol, 3000g/mol
Polyoxypropyleneglycol, one or more of polytetrahydrofuran diol arbitrary proportion mixture；Preferential select is divided
The polyoxypropyleneglycol of 2000 g/mol of son amount and the polytetrahydrofuran diol of molecular weight 2000.Polyoxypropyleneglycol and poly-
Erythritan all has good biocompatibility and not facile hydrolysis.The polyether-tribasic alcohol is that molecular weight is 3000g/
The mixture of one or more of the polypropylene oxide triol of mol, 6000g/mol arbitrary proportion.
3, in above scheme, the ionic groups compound is 2,2- dihydromethyl propionic acid, 2,2- dihydroxymethyl fourth
The mixture of acid or both.
4, in above scheme, the hydroxyl unsaturated monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl-prop
The mixture of one or more of olefin(e) acid hydroxyl ethyl ester or hydroxy propyl methacrylate arbitrary proportion.
5, in above scheme, the crosslinking agent is N, N- methylene-bisacrylamide, glycol dimethacrylates
The mixture of one or more of ester arbitrary proportion.It is characterized in that water-soluble, low toxicity.
6, in above scheme, the reproducibility initiator is ascorbic acid, and the oxidative initiator is hydrogen peroxide.Its
Mass ratio is 1:0.75-1:1, and feature is after having reacted to human body totally nontoxic.
7, in above scheme, the compatilizer is one or both of acetone, butanone, diacetone alcohol or tetrahydrofuran
The mixture of any of the above ratio.
8, in above scheme, the wetting agent is sapn, tween, low-molecular-weight polyethylene glycol, lecithin, cholesterine or sea
The mixture of one or more of mosanom arbitrary proportion.
9, in above scheme, the pH adjusting agent is HEPES buffer solution, TES buffer solution or MOPS buffer solution
In any one or two or more arbitrary proportions mixture.
10, in above scheme, the number is mass parts.
11, in above scheme, the salt forming agent is triethylamine, trimethylamine, triethanolamine, tri-n-butylamine, mass concentration
One of sodium hydrate aqueous solution that potassium hydroxide aqueous solution or mass concentration for 50% are 50% and their mixture；
Preferentially select the sodium hydrate aqueous solution that potassium hydroxide aqueous solution, mass concentration that mass concentration is 50% are 50%.
12, in above scheme, the chain extender be 1,4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, 1,6- oneself
The mixture of one or more of glycol or cyclohexanedimethanol arbitrary proportion；Preferential selection 1,4- butanediol, second two
Alcohol.
13, in above scheme, the solvent is acetone, butanone, tetrahydrofuran, n,N-Dimethylformamide, N- methyl
Pyrrolidones etc. and their mixture；Preferential selection acetone and butanone.
14, in above scheme, the aqueous dispersion of the microgel is network semi-interpenetrating polymer aqueous dispersion.
Since above-mentioned technical proposal is used, the present invention has the advantage, that compared with prior art
1, the aqueous hydrophilic lubrication coating solution for medical devices prepared by the present invention only needs device surface letter first
Single clean dry, using the method for dip-coating, spraying, then 60 DEG C of heat cure 10-20min can be formed securely in device surface
Hydrophilic lubrication coating.It is had the advantage that in its performance
(1) coating is water dispersible, environmentally protective.
(2) wet friction coefficient is low, and the resistance to excellent repeatable recycling of wiping is multiple, wet friction coefficient < 0.1.
(3) dissolution rate is extremely low, after being impregnated 90 days in aqueous solution, mass loss rate < 0.5%.
(4) simple short time heat curing process can be coated in device surface, and adaptation is wide, and adhesiveness is strong, can be competent at poly-
The medical devices that vinyl chloride, polyurethane, silica gel, stainless steel material make.
2, present invention comprises the core components of aqueous hydrophilic lubrication coating --- and three-dimensional structure hydrophilic lubrication is micro- solidifying
The synthetic method of the aqueous dispersion of glue and method with multifunctional assistant composite coating preparation solution.
The core group of aqueous hydrophilic lubrication coating solution is divided into the active material for playing hydrophilic lubrication effect and by its anchor
Gu in the compound of device surface.Technical characteristic of the invention be that it is Promethean synthesized it is a kind of in three-dimensional structure,
The aqueous dispersion of hydrophilic lubrication microgel, then by the way that there is clinical practice application effect with compound prepared of multifunctional assistant
Hydrophilic lubrication coating solution.By bodily form cross-linked structure, by hydrophilic lubrication coating solution (hydrophilic polymer) firmly earth anchor
Gu reducing coefficient of friction in device surface, while resistance to wiping also produces super lubricating action.This tool with chemistry key connection
The aqueous dispersion of the hydrophilic lubrication microgel of three-dimensional-structure is different from simply mixing the physics such as hydrophilic lubrication polymer, adhesive
It closes；Due to becoming the molecular structure of an entirety, so more powerful effect can be played.The tool that the present invention designs and synthesizes
The aqueous dispersion of the hydrophilic lubrication microgel of three-dimensional structure is with the polyurethanes substance of aqueous cross-linked structure for anchoring
Then component by block copolymerization reaction bonding there is the polyvinylpyrrolidone class hydrophilic lubrication substance of cross-linked structure to obtain
?.Multifunctional assistant of the invention mainly includes wetting agent, pH adjusting agent and compatilizer.
3, the present invention has the aqueous dispersion of the hydrophilic lubrication microgel of three-dimensional structure by two-step reaction synthesis.It is first
The aqueous polyurethane substance with unsaturated group and micro- cross-linked structure in a kind of molecule segment is first synthesized, as anchoring
Component；Then, introducing vinylpyrrolidone monomer, unsaturated polyfunctionality crosslinking agent are copolymerized, and are obtained with polyethylene
Base pyrrolidones substance is the aqueous dispersion of the hydrophilic lubrication microgel with 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) molar ratio be NCO/OH=1.1-1.02.The mass concentration of aqueous polyurethane is 25%-40%.
In the aqueous dispersion of microgel, the matter of polyvinylpyrrolidone class solid matter and polyurethanes solid matter
Amount is than being 0.5-1.5.
When preparing the aqueous dispersion of microgel, in order to reduce influence of the residual initiators to human body, use safe and non-toxic
Ascorbic acid-hydrogen peroxide oxidation/reduction system cause polymerization, it is harmless.The aqueous dispersion concentration of microgel is
10%-25%。
In order to preferably adapt to medical devices basal plane, keep coating stronger with substrate adhesion, in hydrophilic lubrication coating formula
In, other than based on the aqueous dispersion with microgel, also use compatilizer, wetting agent, pH adjusting agent.Wherein wetting agent,
PH adjusting agent is biocompatibility.
In the present invention, the aqueous polyurethane of micro- crosslinking is prepared first, while introducing unsaturated group in segment end；The
The monomeric compound of two steps polyvinylpyrrolidone is copolymerized with it, and at the same time also carrying out micro- crosslinking Treatment.In this way, energy
It enough allows two kinds to form three-dimensional structure in the form of chemical bond in the molecule segment of the polymer of three-dimensional structure, has simultaneously
There is water dispersible.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily.
The main raw material(s) trade mark, abbreviation and manufacturer used in embodiment are as shown in table 1, remaining raw material is easy
The general chemistry product of purchase.
The 1 main raw material(s) trade mark of table, abbreviation and manufacturer
Embodiment one:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.08) are by 135 parts of DL-1000D and 70 part of MN-
The mixture of 3050DF, at 60 DEG C in uniformly instilled in 1h containing 75 parts of MDI, 80 parts of acetone reaction vessel in；It drips
10.5 parts of progress ion reaction 2h of 2,2- dimethylolpropionic acid are added after finishing；0.8 part of 1,4- butanediol is subsequently added into carry out
Then chain extending reaction 15min is added 6 parts of hydroxy-ethyl acrylates and reacts 1h.50 DEG C or less are finally cooled to 5.7 part 50% of hydrogen
Sodium hydroxide solution neutralizes, and 617 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end, matter
Measuring concentration is 30%.
Second step, (polyvinylpyrrolidone class is solid for the preparation of the aqueous dispersion of 1000 parts of three-dimensional structure microgels
0.5) mass ratio of body substance and aqueous polyurethane solid matter is: by 60 parts of vinyl pyrrolidones, 0.8 part of N, N- methylene
Base bisacrylamide, 1.8 parts of ascorbic acid, 20 parts of water are uniformly mixed；In addition 1.8 parts of hydrogen peroxide, 20 parts of water are mixed equal
It is even.Then this two kinds of mixed solutions have been prepared in 442 parts of first steps at 60 DEG C in uniform be added dropwise slow simultaneously in 2h
Aqueous polyurethane, 453.6 parts of water mixture in, rear insulation reaction 2h is added dropwise and obtains the Semi-IPN structural polymer of network
Aqueous dispersion (i.e. the aqueous dispersion of microgel).Aqueous dispersion mass concentration 20%.
Third step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: the network obtained in 250 parts of second steps is Semi-IPN poly-
Conjunction object aqueous dispersion, 100 parts of acetone, 1 part of sorbester p17,1 part of HEPES buffer solution, 648 parts of water are stirred for clear solution,
Then it is filtered with 5000 mesh filter screens and obtains coating solution.
Embodiment two:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.02) are by 182 parts of PolyTHF 1000 and 86
The mixture of part MN-3050DF, at 70 DEG C in uniformly instilled in 2h containing 101 parts of MDI, 42 parts of acetone reaction vessel in；
15 parts of progress ion reaction 1h of 2,2- dimethylolpropionic acid are added after being added dropwise；2 parts of ethylene glycol are subsequently added into be expanded
Then chain reaction 30min is added 10 parts of hydroxy-ethyl acrylates and reacts 2h.50 DEG C or less are finally cooled to 8 part 50% of hydroxide
Sodium solution neutralizes, and 554 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end, and quality is dense
Degree is 40%.
Second step, (polyvinylpyrrolidone class is solid for the preparation of the aqueous dispersion of 1000 parts of three-dimensional structure microgels
1) mass ratio of body substance and aqueous polyurethane solid matter is: by 120 parts of vinyl pyrrolidones, 2 parts of N, N- methylene
Bisacrylamide, 4 parts of ascorbic acid, 50 parts of water are uniformly mixed；In addition 5 parts of hydrogen peroxide, 30 parts of water are uniformly mixed.Then
By this two kinds of mixed solutions 60 DEG C in 2h simultaneously slowly it is uniform be added dropwise prepared in 314 parts first it is aqueous poly-
Urethane, 475 parts of water mixture in, rear insulation reaction 2h is added dropwise and obtains the Semi-IPN structural polymer aqueous dispersion of network.
Aqueous dispersion mass concentration 25%.
Third step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: the network obtained in 150 parts of second steps is Semi-IPN poly-
Conjunction object aqueous dispersion, 50 parts of butanone, 0.5 part of Tween 80,2 parts of TES buffer solutions, 797.5 parts of water are stirred for clear solution,
Then it is filtered with 5000 mesh filter screens and obtains coating solution.
Embodiment three:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.1) are by PolyTHF 2000 and 50 parts of 105 parts
The mixture of MN-3050DF, at 80 DEG C in uniformly instilled in 2h containing 60 parts of IPDI, 60 parts of butanone reaction vessel in；Drop
10 parts of progress ion reaction 2h of 2,2- dihydromethyl propionic acid are added after adding；It is subsequently added into 1 part of ethylene glycol and carries out chain extension
15min is reacted, 20 parts of hydroxypropyl acrylates are then added and react 2h.50 DEG C or less are finally cooled to 8.5 part 50% of hydroxide
Potassium solution neutralizes, and 685.5 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end, quality
Concentration is 25%.
Second step, preparation (the polyvinylpyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
1.5) mass ratio of matter and aqueous polyurethane solid matter is: by 100 parts of vinyl pyrrolidones, 5 parts of N, N- di-2-ethylhexylphosphine oxide
Acrylamide, 8 parts of ascorbic acid, 80 parts of water are uniformly mixed；In addition 9 parts of hydrogen peroxide, 40 parts of water are uniformly mixed.Then will
The aqueous poly- ammonia prepared in 225 parts of first steps is uniformly added dropwise in slow simultaneously in 3h at 70 DEG C in this two kinds of mixed solutions
Ester, 533 parts of water mixture in, rear insulation reaction 2h is added dropwise and obtains the Semi-IPN structural polymer aqueous dispersion of network.Water
Dispersion quality concentration 15%.
Third step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: the network obtained in 100 parts of second steps is Semi-IPN poly-
Conjunction object aqueous dispersion, 80 parts of diacetone alcohol, 1.5 parts of polyethylene glycol 400s, 1 part of MOPS buffer solution, 817.5 parts of water stir evenly
For clear solution, is then filtered with 5000 mesh filter screens and obtain coating solution.
Example IV:
The first step, the preparation of 1000 parts of aqueous polyurethanes: (NCO/OH=1.05) are by DL-2000D and 120 part of 170 parts
The mixture of VORANOL CP 6055 holds at 80 DEG C in uniformly instilling the reaction containing 45 parts of IPDI, 150 parts of butanone in 1h
In device；4 parts of progress ion reaction 2h of 2,2- dihydromethyl propionic acid are added after being added dropwise；Be subsequently added into 1 part of ethylene glycol into
Then row chain extending reaction 30min is added 8 parts of hydroxypropyl acrylates and reacts 1h.50 DEG C or less are finally cooled to 3 part 50% of hydrogen
Potassium oxide solution neutralizes, and 499 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end, matter
Measuring concentration is 35%.
Second step, preparation (the polyvinylpyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
1.5) mass ratio of matter and aqueous polyurethane solid matter is: by 60 parts of vinyl pyrrolidones, 3 parts of N, N- di-2-ethylhexylphosphine oxide third
Acrylamide, 3 parts of ascorbic acid, 20 parts of water are uniformly mixed；In addition 4 parts of hydrogen peroxide, 20 parts of water are uniformly mixed.Then by this
Two kinds of mixed solutions 80 DEG C in 4h simultaneously slowly be uniformly added dropwise the aqueous polyurethane prepared in 94 parts of first steps,
In the mixture of 796 parts of water, rear insulation reaction 1h is added dropwise and obtains the Semi-IPN structural polymer aqueous dispersion of network.Water dispersion
Weight concentration 10%.
Third step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: the network obtained in 500 parts of second steps is Semi-IPN poly-
Object aqueous dispersion is closed, 150 parts of tetrahydrofurans, 1 part of lecithin, 1 part of TES buffer solution, 348 parts of water are stirred for clarifying molten
Then liquid is filtered 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) are by DL-1000D and 72 part of 144 parts
The mixture of VORANOL CP 6055, in uniformly instilling the reaction vessel containing 94 parts of MDI, 80 parts of acetone in 2h at 60 DEG C
In；12 parts of progress ion reaction 2h of 2,2- dihydromethyl propionic acid are added after being added dropwise；Be subsequently added into 0.5 part of propylene glycol into
Then row chain extending reaction 15min is added 25 parts of hydroxypropyl acrylates and reacts 2h.50 DEG C or less are finally cooled to 7 part 50% of hydrogen
Sodium hydroxide solution neutralizes, and 565.5 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end,
Mass concentration is 35%.
Second step, preparation (the polyvinylpyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
1) mass ratio of matter and aqueous polyurethane solid matter is: by 80 parts of vinyl pyrrolidones, 10 parts of EGDMA-200,10 parts
Ascorbic acid, 30 parts of water are uniformly mixed；In addition 10 parts of hydrogen peroxide, 30 parts of water are uniformly mixed.Then this two kinds are mixed
Aqueous polyurethane, the 545 parts of water prepared in 285 parts of first steps are uniformly added dropwise in slow simultaneously in 4h at 80 DEG C in solution
Mixture in, rear insulation reaction 1h is added dropwise and obtains the Semi-IPN structural polymer aqueous dispersion of network.Aqueous dispersion quality
Concentration 20%.
Third step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: the network obtained in 350 parts of second steps is Semi-IPN poly-
Object aqueous dispersion is closed, 100 parts of tetrahydrofurans, 1.5 parts of cholesterine, 1.5 parts of HEPES buffer solutions, 547 parts of water are stirred for clear
Then clear solution is filtered 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) are by 133 parts of DL-3000D and 80 part of MN-
The mixture of 3050DF, at 70 DEG C in uniformly instilled in 1h containing 60 parts of MDI, 120 parts of acetone reaction vessel in；It drips
8 parts of progress ion reaction 1h of 2,2- dimethylolpropionic acid are added after finishing；It is subsequently added into 1.6 parts of butanediols and carries out chain extending reaction
Then 15min is added 15 parts of hydroxy-ethyl acrylates and reacts 1.5h.50 DEG C or less are finally cooled to 4.4 part 50% of sodium hydroxide
Solution neutralizes, and 578 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end, mass concentration
It is 35%.
Second step, preparation (the polyvinylpyrrolidone class solids of the aqueous dispersion of 1000 parts of three-dimensional-structure microgels
1.2) mass ratio of matter and aqueous polyurethane solid matter is: by 72 parts of vinyl pyrrolidones, 5 parts of EGDMA-200,5 parts
Ascorbic acid, 25 parts of water are uniformly mixed；In addition 6 parts of hydrogen peroxide, 45 parts of water are uniformly mixed.Then this two kinds mixing are molten
Liquid is at 60 DEG C in the aqueous polyurethane prepared in 227 parts of first steps, 615 parts of water is slowly uniformly added dropwise in 3h simultaneously
In mixture, rear insulation reaction 2h is added dropwise and obtains the Semi-IPN structural polymer aqueous dispersion of network.Aqueous dispersion quality is dense
Degree 15%.
Third step, the preparation of 1000 parts of hydrophilic lubrication coating solutions: the network obtained in 250 parts of second steps is Semi-IPN poly-
Conjunction object aqueous dispersion, 80 parts of diacetone alcohol, 1 part of sodium alginate, 2 parts of HEPES buffer solutions, 667 parts of water are stirred for clarifying
Then solution is filtered with 5000 mesh filter screens and obtains coating solution.
Comparative example:
In order to better illustrate the present invention the advantages of, has been respectively synthesized identical formula according to the method for embodiment one
Then the two is mixed with the method for physical mixed and is mixed by aqueous polyurethane and polyvinylpyrrolidonepolymers polymers
Solution.Finally hydrophilic lubrication coating solution is prepared by core of this mixed solution according to identical formula.It is aqueous poly- due to synthesizing
It is all separately synthesized when urethane and polyvinylpyrrolidone, so there is no form network blackboard, only simple nothing
Sequence admixture.
The preparation of aqueous polyurethane: (NCO/OH=1.08) are by the mixing of 135 parts of DL-1000D and 70 part of MN-3050DF
Object, at 60 DEG C in uniformly instilled in 1h containing 75 parts of MDI, 80 parts of acetone reaction vessel in；2 are added after being added dropwise,
10.5 parts of progress ion reaction 2h of 2- dimethylolpropionic acid；It is subsequently added into 0.8 part of 1,4- butanediol and carries out chain extending reaction
Then 15min is added 6 parts of hydroxy-ethyl acrylates and reacts 1h.Finally cool to 50 DEG C or less it is molten with 5.7 part 50% of sodium hydroxide
Liquid neutralizes, and 617 parts of water are added in this solution and carry out the aqueous polyurethane that emulsification obtains unsaturated monomer sealing end, and mass concentration is
30%。
The synthesis of polyvinylpyrrolidonepolymers polymers aqueous solution: by 60 parts of vinyl pyrrolidones, 0.8 part of N, N- is sub-
Bisacrylamide, 1.8 parts of ascorbic acid, 20 parts of water are uniformly mixed；In addition 1.8 parts of hydrogen peroxide, 20 parts of water are mixed
Uniformly.Then this two kinds of mixed solutions are added dropwise in 453.6 parts of water at 60 DEG C in slowly uniform simultaneously in 2h, are added dropwise
Insulation reaction 2h obtains the aqueous solution of polyvinylpyrrolidonepolymers polymers afterwards.
It is clear that 442 parts of aqueous polyurethanes and 558 parts of polyvinylpyrrolidonepolymers polymers aqueous solutions, which are stirred at room temperature,
Clear homogeneous solution (mass ratio of polyvinylpyrrolidone class solid matter and aqueous polyurethane solid matter is 0.5), this is mixed
Close concentration of polymer solution 20%.
The preparation of 1000 parts of hydrophilic lubrication coatings: the mixed solution for being 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 clear solution, are then filtered with 5000 mesh filter screens
Obtain coating solution.
Application example
The coating solution prepared in embodiment one to embodiment six and comparative example is coated in diameter as follows
For 0.46mm, 60cm long polyvinyl chloride catheter on.
Coating method: thoroughly dry after catheter surface ethyl alcohol and clean water are cleaned.Then conduit is on end complete
Immersion is loaded in the container of hydrophilic lubrication coating solution, and after being completely immersed in and keeping 10s, quick and complete drawing proposes liquid level.To
After dripless drippage, the dry 20min in 60 DEG C of convection ovens.
Test method: the conduit after applying coating is impregnated into different time in 37 DEG C of physiological saline environment.Then it cleans
Wet friction coefficient, the water contact angle of different soaking times are tested in conduit and drying.
Meanwhile by the method for the drying at room temperature after mold is cast, 0.5mm thickness, 5 × 5cm size is made in coating solution
Film.It is impregnated into different time in 37 DEG C of physiological saline environment, the quality of different soaking times is tested after dry after cleaning
Loss late.
The coating result that related data is shown in Table 2. visible embodiment 1-6 preparations is substantially better than comparative example, and hydrophilic lubrication
Effect and resistance to wiping are had excellent performance.
2. test comparison data of table
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of preparation method of the hydrophilic lubrication coating solution of medical devices surface coating, it is characterised in that including following
Step:
1000 parts of first step, preparation aqueous polyurethanes: by 105-182 parts of polyether Glycols and 50-120 parts of polyether-tribasic alcohols
Mixture, in the reaction for uniformly instilling the polyisocyanates containing 45-101 parts, 42-150 parts of solvent in 1-2h at 60-80 DEG C
In container, adds 4-15 parts of ionic groups compounds and carry out ion reaction 1-2h；It is subsequently added into 0.5-2 parts of chain extender
Chain extending reaction 15-30min is carried out, 6-25 parts of hydroxyl unsaturated monomer is then added and reacts 1-2h；Finally cool to 50 DEG C
It is neutralized below with 3-8.5 parts of salt forming agents；This solution is added in 500-700 parts of water and carries out emulsification acquisition aqueous polyurethane；
1000 parts of second step, preparation three-dimensional-structure aqueous microgel dispersions: by 60-120 parts of vinyl pyrrolidone, 0.8-10
The crosslinking agent, 1.8-10 parts of reproducibility initiator and 20-80 parts of water of part are uniformly mixed and obtain the first mixed solution；In addition,
1.8-10 parts of oxidative initiator and 20-45 parts of water are uniformly mixed and obtain the second mixed solution, is then mixed described first
It closes solution and second mixed solution and is added dropwise in the 94-442 parts of first steps at 60-80 DEG C in slowly uniform simultaneously in 2-4h
In the mixture of aqueous polyurethane and 450-800 part water prepared, rear insulation reaction 2h is added dropwise, obtains Microgel water
Granular media；
Third step prepares hydrophilic lubrication coating solution: by aqueous microgel dispersion obtained in 100-500 parts of second steps, 50-
Obtained clarification is mixed evenly in 150 parts of compatilizers, 0. 5-1.5 parts of wetting agent, 1-2 parts of pH adjusting agents and 340-800 parts of water
Then solution filters the clear solution with 5000 mesh filter screens, obtain hydrophilic lubrication coating solution.
2. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the polyisocyanates is one of 4,4 '-methyl diphenylene diisocyanates, isophorone diisocyanate
Or two kinds of mixture.
3. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the polyether Glycols be molecular weight be 1000g/mol polyoxypropyleneglycol, 2000 g/mol polyoxygenated
One or more of propylene glycol, the polyoxypropyleneglycol of 3000g/mol, polytetrahydrofuran diol arbitrary proportion
Mixture；The polyether-tribasic alcohol is one of the polypropylene oxide triol that molecular weight is 3000g/mol, 6000g/mol
Or two kinds of mixture.
4. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the ionic groups compound is the mixed of 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid or both
Close object.
5. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the hydroxyl unsaturated monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or first
The mixture of one or more of base hydroxypropyl acrylate arbitrary proportion.
6. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the crosslinking agent is one of N,N methylene bis acrylamide, polyethylene glycol dimethacrylate or two
The mixture of kind.
7. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the reproducibility initiator is ascorbic acid, and the oxidative initiator is hydrogen peroxide.
8. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the compatilizer is one or more of acetone, butanone, diacetone alcohol or tetrahydrofuran arbitrary proportion
Mixture.
9. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the wetting agent is that one or more of sapn, tween, lecithin, cholesterine or sodium alginate are any
The mixture of ratio.
10. the preparation method of the hydrophilic lubrication coating solution of medical devices surface according to claim 1 coating, special
Sign is: the pH adjusting agent be HEPES buffer solution, TES buffer solution or MOPS buffer solution in 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 |
| CN110507864B (en) * | 2019-09-29 | 2020-05-19 | 佛山市其右医疗科技有限公司 | Medical guide wire with excellent lubricating property |
| CN115054742A (en) * | 2020-01-07 | 2022-09-16 | 江苏百赛飞生物科技有限公司 | Curved surface modeling medical instrument with antibacterial coating and preparation method thereof |
| CN111286271A (en) * | 2020-03-16 | 2020-06-16 | 武汉思越化学技术有限公司 | Preparation method of hydrophilic agent for agricultural rock wool |
| CN115814158B (en) * | 2022-12-01 | 2024-02-23 | 中山大学 | Wear-resistant lubricating coating similar to articular cartilage and preparation method thereof |
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| CN101812265A (en) * | 2009-02-24 | 2010-08-25 | 赛诺医疗科学技术有限公司 | Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof |
| CN101934101A (en) * | 2010-08-24 | 2011-01-05 | 北京迪玛克医药科技有限公司 | Hydrophilic coating for surface of medical apparatus and preparation method thereof |
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| CN101812265A (en) * | 2009-02-24 | 2010-08-25 | 赛诺医疗科学技术有限公司 | Hydrophilic coat solution applied to surface of medicinal instrument and preparation method thereof |
| CN101934101A (en) * | 2010-08-24 | 2011-01-05 | 北京迪玛克医药科技有限公司 | Hydrophilic coating for surface of medical apparatus and preparation method thereof |
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