CN105985721B - A kind of coating and its preparation and application for forming catheter surface hydrophilic coating - Google Patents
A kind of coating and its preparation and application for forming catheter surface hydrophilic coating Download PDFInfo
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- CN105985721B CN105985721B CN201510073639.7A CN201510073639A CN105985721B CN 105985721 B CN105985721 B CN 105985721B CN 201510073639 A CN201510073639 A CN 201510073639A CN 105985721 B CN105985721 B CN 105985721B
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Abstract
The present invention relates to a kind of coating and its preparation and application for forming catheter surface hydrophilic coating, coating includes subbing and top coat paint, subbing includes aqueous polyurethane, polyfunctionality aziridine derivative and deionized water, top coat paint includes side carboxyl polyurethane, polymethyl vinyl ether maleic anhydride and organic solvent, each component forms cross-linked structure during solidification, combined closely between coating bottom and top by covalent bond, simultaneously with catheter surface firm attachment, make coating that there is excellent Hydrophilic lubrication and wearability, it is suitably applied the hydrophilic lubrication processing of the apparatus such as medical introducing duct in Endovascular Interventions technical field.
Description
Technical field
The present invention relates to medical instruments field, and in particular to a kind of coating for forming catheter surface hydrophilic coating and its preparation
And application method.
Background technology
Endovascular Interventions technology is widely used in clinical vascular radiography, angioplasty, Intravascular Thrombus or foreign matter
Removing etc., it is not only easy to operate compared with traditional medical technology, and because the wound of PCI is low, can subtract
The pain of hypopathia people, Operative risk is smaller, and medical expense is relatively low, therefore this technology has obtained extensively in medical domain
Popularization and utilization.Endovascular Interventions technology is to reach internal lesion farther out by vessel lumen by means of interposing catheter
Position, such as coronary artery vascular site, reinject diagnosis and treatment agent or insert apparatus, to reach to diagnosis is realized at position farther out in vivo
With the purpose of minimally-invasive treatment.Research of Intravascular Catheterization is one of main apparatus of endovascular temporary embolization, and its species can be made
Shadow interposing catheter, drug delivery interposing catheter, angioplasty interposing catheter etc., these interposing catheters typically can with excellent
For operability with security, it is necessary to which excellent blood compatibility, kink resistance and mechanical performance, no nuisance ooze out, good can
Processability, and there is good compatibility with X ray opacifying agent.
Lubricity is one of highly important performance of Research of Intravascular Catheterization.When conduit enter, exit blood vessel and
When being moved in blood vessel, high-lubricity can suppress macromolecular such as plasma protein, blood platelet etc. gluing in material surface in blood
It is attached, the damage to vascular wall and haemocyte is reduced, mitigates the disturbance to blood laminar flow, the generation of Coagulation test can be avoided.May be used also
Mitigate painful to caused by patient.Therefore, it is very necessary surface lubrication processing to be carried out to interposing catheter.Coat hydrophilic lubrication
Coating is the effective means for improving interposing catheter lubricity.Using containing a large amount of pyrrolidone groups, ethylene oxide group, carboxylic
The high-hydrophilic that base, the polymer of amide groups show in blood, high-efficiency lubricating can be reached as the film forming matter of coating
Purpose, such polymer include PVP (PVP), polyethylene glycol oxide (PEO), acrylamido copolymer,
Acrylic copolymer and maleic anhydride analog copolymer etc..
For the coating on hydrophilic lubrication interposing catheter, because conduit will be moved and be stopped a timing in human body
Between, therefore except meeting high hydrophilic lubrication performance, also need to focus on the firm of greasy property and stably, the hydrophilic segment of coating and painting
Layer integral part will not fallen off after being subjected to rubbing repeatedly, and maintain good combination property.It is particularly applied to seal wire, ball
On the intervention apparatus such as ductus bursae, guiding catheter.Using means such as covalent key connection or crosslinkings one can be played to hydrophilic compounds
Fixed fixation, such technology are also gradually widely used.Occur chemical reaction solidification coating system in, according to whether
Reaction is participated in, hydrophilic compounds can be divided into response type and non-reactive again, such as PVP, PEO are non-reactive, acrylic acid, horse
It is response type to carry out copolymer of anhydrides etc..
The hydrophilic coating system of early stage is in solidification mostly without using chemical reaction, such as United States Patent (USP) US
4589873rd, US 4835003, US 4875287, US 5331027, US 5509899, US 5620738 and US 6042876 are equal
Disclose the hydrophilic lubrication coating containing PVP, be the characteristics of this type coating, top layer is coated with PVP, but coating where PVP or its
Base coat does not all have introducing crosslinked structure, and PVP easily comes off after water swelling, and whole coating system can be made to lose hydrophilic profit
Sliding effect.
United States Patent (USP) US 8287890B2, US 6299980B1, US 5776611, US 5179174, the and of US 5160790
US 4666437 discloses the painting that the hydrophilic high mols such as PVP or PEO are coated using isocyanate crosslinking as base coat, top layer
Coating systems, it is that in top coat in addition to containing hydrophilic high mol, being also added into can be with bottom isocyanide the characteristics of this type coating
Acid esters crosslinking agent crosslinks the polyalcohol or polyamine of reaction, therefore serves certain fixation.But due to PVP or
PEO is simultaneously not involved in the cross-linking reaction in system, by friction after water swelling, is still easy to come off from coated substrate.
7696259 B2 of B2, US of United States Patent (USP) US 8039524, US7534495 B2, US 7052131 B2, US
8378011 B2, US 8512795 the B2 and B2 of US 8513320 disclose with hydrophilic high mols such as double bond compound and PVP
The UV curing system coating of composition.The characteristics of this type coating is that double bond compound is acrylic monomer, in the molten of solvent
Solution effect is lower mix with hydrophilic high mol, light trigger etc. after be coated, solidify to obtain the crosslinking knot of double bond by ultraviolet light
Structure.But the hydrophilic high mols such as the PVP using non-reactive still can have the problem of being come off after water suction rubs, and double bond chemical combination
Film fragility after thing crosslinking is larger, and mechanical property is poor, also poor to the tack of base material.In addition, with conventional curing mode
Compare, ultraviolet light solidifies requires higher to the coating processes and coating equipment of apparatus.
For response type hydrophilic compounds system, mainly contain DAAM-DMAA copolymer,
Acrylic acid-acrylamide copolymer, GMA-DMAA copolymer, methyl vinyl ether-
Copolymer-maleic anhydride etc..
The B1 of United States Patent (USP) US 6540698 are reported with homemade DAAM-DMAA copolymerization
Thing is dissolved in tetrahydrofuran as hydrophilic high mol and obtains solution, conduit is immersed in solution, immerses carbonic acid after drying again
In the aqueous solution of two hydrazides, pH value is adjusted to 3, is crosslinked using the reaction of carbonyl and hydrazides.But in this system, only with double
Acetone acrylamide-DMAA copolymer is as film forming matter, and its tack to base material is poor, under rubbing action
Easily come off.
United States Patent (USP) US 5804318 reports the homemade acrylamide copolymer containing primary amine or tertiary amine group, with containing
Epoxy radicals silicone coupling agents or aldehyde compound can first coat silicone coupling agents containing epoxy radicals, then apply as crosslinking agent
Copolymer, or copolymer is first applied, then immerse in aldehyde compound solution.But this coating only using the copolymer of crosslinking as into
Film thing, its adhesive force are still relatively low.
Method disclosed in the B2 of United States Patent (USP) US 6558798 is to mix aqueous polyurethane with aziridine crosslinker CX100
Be coated on equipment surfaces afterwards, it is to be coated it is half-dried after, coat acrylic acid-acrylamide copolymer, and then crosslinking knot is formed with bottom
Structure.Acrylic acid-acrylamide copolymer need to generally make acquisition by oneself, be using acrylic acid as raw material, acrylic acid be with corrosivity and
The compound of toxicity, harm can be also produced to human body even if a small amount of residual, while the monomer remained contains penetrating odor.The U.S.
Technology is similar with the B2 of US 6558798 disclosed in the B1 of patent US 6468649, and used primary raw material is also water-based poly- ammonia
Ester, aziridine crosslinker CX100 and acrylic acid-acrylamide copolymer, there is also similar defect.
The method of the B2 of the United States Patent (USP) US 8455094 and A of Chinese patent CN 102264403 reports is to use plasma
Body radiates and the method for high-temperature process, and mercaptan compound is grafted on conduit first, is coated with homemade methacrylic acid
Ethylene oxidic ester-DMAA copolymer, makes copolymer also graft on conduit after hot setting.The painting of this coating
Coating process condition is more harsh, because treatment temperature is higher the use of many conduit base materials is restricted, while need high
Expensive equipment.
Methyl vinyl ether-maleic acid copolymer has been widely used in medicine and the field such as food, its to human body without
Poison, there is hydrophilic carboxyl after esterification, be similarly applied to hydrophilic coating.
United States Patent (USP) US 5891109, which is reported, forms vinyl ether-maleic acid copolymer, polyurethane, MEK
Coating, coat after conduit through hot setting, then immerse open loop in ethanol or methylamine water solution, obtain the conduit of hydrophilic lubrication.But
What the anhydride group on this system medium vinyl ether-copolymer-maleic anhydride can only come out with minimal amount of polyurethane pyrolytic
Isocyanate groups react, and crosslinking degree is not high, therefore coating fastness is still poor, and the condition of hot setting makes it
Most polymeric catheter and apparatus are not suitable for.
United States Patent (USP) US 5229211 discloses a kind of interventional medical device, and equipment surfaces have maleic anhydride analog copolymer
The coating obtained with isocyanate prepolymer after covalent key connection, the ground of coating is polymer, selected from polyvinyl chloride, poly- ammonia
Ester, polyamide or polyester, it takes a single example in embodiment, i.e., by polyvinyl chloride, 4, the 4'- diphenylmethyls of micromolecular compound
Alkane diisocyanate, tetrahydrofuran composition solution, coat conduit, methyl vinyl ether-maleic acid copolymerization are coated with after drying
Thing, sodium salt solution and hot wash are immersed after solidification, obtains hydrophilic lubrication conduit.But in this system ground not with other groups
Part is connected by chemical reaction, thus coating fastness is still insufficient.In addition, isocyanate compound has toxicity, can be right
Health causes potential safety hazard.
It can be seen that relative to the hydrophilic high mol of non-reactive, the hydrophilic high mol of response type has more preferable coating
Fastness, but matched other components are not connected with each other closely in the coating, and conduit is lacked enough
Adhesive force, the problem of coating still has wearability deficiency, it is therefore desirable to build new coating architecture to realize that intervention is led
Manage not only hydrophilic lubrication but also wear-resisting purpose, it is still necessary to provide new technology to obtain the catheter coatings of higher performance.
The content of the invention
In view of the shortcomings of the prior art, the present invention provide it is a kind of formed catheter surface hydrophilic coating coating and its prepare and
Application method.Purpose is to confer to the excellent Hydrophilic lubrication of interposing catheter and wearability.
The present invention was both served by building two layer coating system, forming more component cross-linked structures using chemical key connection
Make coating outer surface that there is the effect of hydrophilic lubrication, in turn ensure that firm attachment and bottom and the top of coating bottom and conduit
Between combine closely, make crocking resistance excellent.
Further summary is exactly, because high Hydrophilic lubrication needs coating outer surface to possess substantial amounts of hydrophilic radical, and
Contradiction, if hydrophilic polymer too high levels in system, the fastness of this film forming matter is necessarily poor, solves in the present invention
Method certainly is exactly to build duplex coating, and applies the crosslinking of interlayer, i.e. top layer has the i.e. poly- first of the hydrophilic polymer of high content
Base vinyl ether-maleic acid and a small amount of polyurethane containing side carboxyl, bottom includes has the water-based of preferable adhesive force with conduit
Polyurethane and the intermediate medium i.e. polyfunctionality aziridine derivative that upper and lower two layers of coatings can be connected.In order that poly- methyl second
Alkene ether-maleic anhydride can react with aziridine group, using poly glycol monomethyl ether and partial maleic acid anhydride group
Esterification occurs for group, is grafted on the molecular skeleton of polymethyl vinyl ether-maleic anhydride, while acquisition can be with '-aziridino
The carboxyl that group reacts, and the Oxyerhylene on poly glycol monomethyl ether can also play hydrophilic effect.So, apply
Polyurethane and polymethyl vinyl ether-maleic anhydride in layer are formed tightly by the crosslinked action of polyfunctionality aziridine derivative
Close entirety, the fastness of hydrophilic coating greatly promote.
Above-mentioned purpose can be realized by technical scheme in detailed below：
A kind of coating for forming catheter surface hydrophilic coating, it is characterised in that coating includes subbing and top coat paint,
The subbing is made up of aqueous polyurethane, polyfunctionality aziridine derivative and deionized water, wherein polyfunctionality nitrogen
The quality of third piperidine derivatives is the 1%~10% of aqueous polyurethane quality, and the quality of deionized water is subbing gross mass
80%~99%, the top coat paint is by polyurethane containing side carboxyl, polymethyl vinyl ether-maleic anhydride, polyethyleneglycol
Methyl ether and organic solvent composition, wherein the mass ratio of polyurethane containing side carboxyl and polymethyl vinyl ether-maleic anhydride is 1:
(0.1~10), the quality of poly glycol monomethyl ether are 1%~20%, You Jirong of polymethyl vinyl ether-maleic anhydride quality
The quality of agent is the 80%~99% of top coat paint gross mass.
The coating of described formation catheter surface hydrophilic coating, it is characterised in that described polyfunctionality aziridine derives
Thing is trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, trimethylolpropane-three (3- '-aziridinos) propionic acid
One or more in ester, pentaerythrite-three (3- '-aziridinos) propionic ester.
The coating of described formation catheter surface hydrophilic coating, it is characterised in that point of the polyurethane containing side carboxyl
Subchain structure is anti-through addition by polyethers or polyester diol, diisocyanate, 2,2- dihydromethyl propionic acids and 1,4- butanediols
Should be connected, described polyethers or polyester diol be polyoxypropyleneglycol, polytetrahydrofuran diol, PCDL,
One kind in polycaprolactone glycol, for number-average molecular weight 1000~4000, described diisocyanate is 2,4- toluene diisocyanates
In acid esters, hexa-methylene 1,6- diisocyanate, 4,4'- methyl diphenylene diisocyanates, IPDI
It is a kind of.
The coating of described formation catheter surface hydrophilic coating, it is characterised in that described organic solvent is N, N- diformazans
Base formamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, N, N- dimethyl sulfoxide (DMSO)s, ethyl acetate, butyl acetate, two
One or more in chloromethanes, chloroform, acetone, butanone, tetrahydrofuran.
A kind of preparation method of the coating of described formation catheter surface hydrophilic coating, it is characterised in that including following step
Suddenly：
(1) preparation of the polyurethane containing side carboxyl：Polyurethane containing side carboxyl is synthesized using solvent method, by polyethers or polyester binary
Alcohol and diisocyanate are added in reactor, are warming up to 80 DEG C, and stirring reaction obtains performed polymer after 1 hour, add 2,2- dihydroxies
Methylpropanoic acid and BDO, after reacting 2 hours, DMF is added, after continuing reaction 1 hour, add two
Dibutyl tin laurate, then react 8 hours, room temperature is down to, solution in reactor is poured into the container equipped with deionized water, had
White depositions separate out, and collect sediment and are washed with deionized 3 times, are positioned in vacuum drying oven, true at 90 DEG C
Sky is dried 48 hours, obtains transparent cake product, the masterbatch of polyurethane containing side carboxyl is obtained after being granulated, wherein, described two is different
The molal quantity of cyanate is with the ratio between polyethers or the total mole number of polyester diol, 2,2- dihydromethyl propionic acids and 1,4- butanediols
(1.05~1.2):The ratio between molal quantity of 1,2,2- dihydromethyl propionic acid and BDO is 1:1, polyethers or polyester diol
The ratio between the gross mass of quality and diisocyanate, 2,2- dihydromethyl propionic acids and 1,4- butanediols be (1.5~1):1, N, N-
The ratio between the quality of dimethylformamide and the gross mass of other all raw materials are 4:1, the quality of dibutyl tin laurate is poly-
The 1% of ether or polyester diol quality, the quality of deionized water used and the mass ratio of DMF during precipitation
For 2:1, the quality of deionized water used and the mass ratio of DMF are 2 during washing every time:1；
(2) preparation of subbing：Aqueous polyurethane, polyfunctionality aziridine derivative, deionized water are added to appearance
In device, it is stirred at room temperature 30 minutes, obtains subbing, the wherein quality of polyfunctionality aziridine derivative is water-based poly- ammonia
The 1%~10% of ester quality, the quality of deionized water are the 80%~99% of subbing gross mass；
(3) preparation of top coat paint：Side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, polyethyleneglycol will be contained
Methyl ether, organic solvent are added into container, are stirred at room temperature 30 minutes, are obtained top coat paint, wherein polyurethane containing side carboxyl
Mass ratio with polymethyl vinyl ether-maleic anhydride is 1:(0.1~10), the quality of poly glycol monomethyl ether is poly- methyl second
The 1%~20% of alkene ether-maleic anhydride quality, the quality of organic solvent are the 80%~99% of top coat paint gross mass.
The preparation method of the coating of described formation catheter surface hydrophilic coating, it is characterised in that described in step (1)
Polyethers or polyester diol are in polyoxypropyleneglycol, polytetrahydrofuran diol, PCDL, polycaprolactone glycol
One kind, for number-average molecular weight 1000~4000, described diisocyanate is 2,4- toluene di-isocyanate(TDI)s, hexa-methylene 1,6-
One kind in diisocyanate, 4,4'- methyl diphenylene diisocyanates, IPDI.
The preparation method of the coating of described formation catheter surface hydrophilic coating, it is characterised in that described in step (2)
Polyfunctionality aziridine derivative be trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, trimethylolpropane-
One or more in three (3- '-aziridinos) propionic esters, pentaerythrite-three (3- '-aziridinos) propionic ester.
The preparation method of the coating of described formation catheter surface hydrophilic coating, it is characterised in that described in step (3)
Organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, N, N- dimethyl sulfoxide (DMSO)s, second
One or more in acetoacetic ester, butyl acetate, dichloromethane, chloroform, acetone, butanone, tetrahydrofuran.
A kind of application method of the coating of described formation catheter surface hydrophilic coating, it is characterised in that including following step
Suddenly：
(1) coating coating processing：Subbing is coated to the surface of conduit in a manner of dip-coating, spraying or brushing, in
Solidify 1 hour at 60 DEG C, top coat paint coated to having been coated with the conduit of subbing afterwards, solidified 1 hour at 80 DEG C,
Obtain conduit of the outer surface covered with cross-linked structure coating；
(2) coating hydrophilic is handled：The conduit that processing is completed in step (1) is immersed into concentrated ammonia liquor, soaks 1 at room temperature
Hour, dried 2 hours at 60 DEG C after taking-up, obtaining surface has the interposing catheter of hydrophilic cross-linking structure coating.
The beneficial effects of the invention are as follows：
(1) compared with prior art, the present invention solve thes problems, such as hydrophilic coating fastness deficiency, double by building
Layer coating system and chemical bond cross-linked structure, makes coating outer surface both hydrophilic lubrications, in turn ensure that the firm attached of bottom and conduit
And bottom and top between combine closely, make it have excellent wearability.The coating of the present invention is used for interposing catheter
Afterwards, conduit friction can be made to reduce by more than 90%.Hydrophilic coating retains complete after rubbing action repeatedly, is rubbed suffered by conduit
Wipe power increasing degree and be no more than 2%.
(2) present invention is by strictly controlling raw material type in the synthetic reaction of polyurethane containing side carboxyl, dosage, reaction temperature
With the condition such as time, reach and rising limit is made to molecular structure, NCO and hydroxyl mol ratio, soft and hard segments ratio, carboxyl-content
Fixed purpose, not tacky surface, high mechanical strength, the polyurethane containing side carboxyl of product yield high are obtained, meet this so as to obtain
Material needed for invention cross-linking reaction, it compensate for the deficiency of other high polymer material performances and function.
(3) subbing of the invention is water solution system, avoids corrosion of the organic solvent to interposing catheter, and more
Environmental protection.In addition, the paint solidification temperature of the present invention is relatively low, conduit will not be caused to damage.Therefore the scope of application is wider.It can be
Conduit provides firm hydrophilic lubrication performance, and be particularly suitable for use in Endovascular Interventions technical field, the medicine equipment that can be used for
Including seal wire, foley's tube, guiding catheter, thrombus suction catheter, peripheral central venous catheter, angiography catheter, expansion pipe and tear
Drive sheath etc..
Embodiment
Below by specific examples of the implementation, the present invention is described in detail.
Embodiment 1
The preparation of polyurethane containing side carboxyl (CPU)：Polyurethane containing side carboxyl is synthesized using solvent method, by polyethers or polyester two
First alcohol and diisocyanate are added in reactor, are warming up to 80 DEG C, and stirring reaction obtains performed polymer after 1 hour, add 2,2- bis-
Hydroxymethyl propionic acid and BDO, after reacting 2 hours, DMF is added, after continuing reaction 1 hour, added
Dibutyl tin laurate, then react 8 hours, room temperature is down to, solution in reactor is poured into the container equipped with deionized water,
There is white depositions precipitation, collect sediment and be washed with deionized 3 times, be positioned in vacuum drying oven, at 90 DEG C
Vacuum drying 48 hours, obtains transparent cake product, the masterbatch of polyurethane containing side carboxyl is obtained after being granulated.
Wherein, described polyethers or polyester diol are selected from polyoxypropyleneglycol (PPG), polytetrahydrofuran diol
(PTMG), one kind in PCDL (PCDL), polycaprolactone glycol (PCL), number-average molecular weight (Mn) 1000~
4000.Described diisocyanate be 2,4 toluene diisocyanate (TDI), hexa-methylene 1,6- diisocyanate (HDI), 4,
4'- methyl diphenylene diisocyanates (MDI), IPDI (IPDI).The molal quantity of the diisocyanate
F-a, polyethers or poly- are designated as with the ratio between polyethers or the total mole number of polyester diol, 2,2- dihydromethyl propionic acids and BDO
The ratio between the quality of ester dihydric alcohol and the gross mass of diisocyanate, 2,2- dihydromethyl propionic acids and BDO are designated as F-b, and 2,
The ratio between molal quantity of 2- dihydromethyl propionic acids and 1,4- butanediols is 1:1, the quality of DMF is all with other
The ratio between gross mass of raw material is 4:1, the quality of dibutyl tin laurate is the 1% of polyether Glycols quality, used during precipitation
The quality of deionized water and the mass ratio of N,N-dimethylformamide are 2:1, the quality of deionized water used when washing every time
Mass ratio with N,N-dimethylformamide is 2:1.
Respectively the code name of polyurethane product containing side carboxyl, raw material and proportioning are as shown in table 1.
Respectively melt polyurethane containing side carboxyl is processed into sheet material, tests its water contact angle, it can be found that its contact angle compared with
It is low, illustrate that material surface contains carboxyl.
The raw material and dosage of the polyurethane containing side carboxyl of table 1
Embodiment 2
By aqueous polyurethane, trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, deionized water add to
In container, it is stirred at room temperature 30 minutes, obtains subbing, wherein [3- (the 2- methylaziridines of trimethylolpropane-three
Base)] quality of propionic ester is the 1% of aqueous polyurethane quality, the quality of deionized water is the 80% of subbing gross mass.Will
The CPU-1 of polyurethane containing side carboxyl, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, N,N-dimethylformamide add
Enter into container, be stirred at room temperature 30 minutes, obtain top coat paint, wherein CPU-1 and polymethyl vinyl ether-maleic anhydride
Mass ratio be 1:0.1, the quality of poly glycol monomethyl ether is 1%, the N, N- bis- of polymethyl vinyl ether-maleic anhydride quality
The quality of NMF is the 80% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is in Sigma's Order
Strange company, the product that number-average molecular weight is 80000, aqueous polyurethane are the type products of Lubrizol Corp. Sancure 777, poly- second
The product that glycol monomethyl ether is Sigma-Aldrich, number-average molecular weight is 1000.Above-mentioned subbing is coated to Jie
Enter the surface of conduit, solidify 1 hour at 60 DEG C, afterwards coat top coat paint to having been coated with the conduit of subbing, in
Solidify 1 hour at 80 DEG C, obtain conduit of the outer surface covered with cross-linked structure coating, then be dipped in into concentrated ammonia liquor, in room
The lower immersion of temperature 1 hour, is dried 2 hours, obtaining surface has the interposing catheter of Hydrophilic lubrication after taking-up at 60 DEG C.
Interposing catheter lubricity method of testing is as follows：The conduit half length that length is 20cm is coated into above-mentioned coating, and
Coating layer, tube at one end are not vertically fixed in the lower clamp of stretching-machine second half length, and one is clamped certainly in catheter surface
Sliding block processed, the sliding block can be screwed on conduit and give the pressure of conduit fixation, and interlayer can carry certain volume inside sliding block
Deionized water, conduit can be implemented continuously infiltrate, with the upper clamp clamping slider that mechanics sensor is connected with stretching-machine,
Sliding block is pulled to conduit top from conduit bottom according to fixed speed, then the stress change of sensor embodies conduit on two kinds of surfaces
The frictional force being subject to, the difference of friction value reflect the Hydrophilic lubrication of conduit.Record two parts centre of surface position institute
Corresponding friction value, then the amplitude of water-wetted surface frictional force reduction is can obtain, is designated as fp-r, fp-r values are bigger, illustrate profit
Slip is better.
Interposing catheter abrasion resistance test method is as follows：The conduit for coating above-mentioned coating is loaded into lubricity method of testing
In described equipment, sliding block up-and-down movement 100 times under fixed displacement and speed are made by programme-control, recorded
Friction value when beginning and terminating, the difference of the friction value reflect the wear-resisting of the degree that coating abrasion comes off and conduit
Property.The amplitude of frictional force increase when terminating is designated as fp-i, fp-i values are smaller, illustrate that wearability is better.
Test result shows that it is 91.5% that conduit friction, which reduces degree fp-r values, in the present embodiment, and conduit is through rubbing
Friction increase degree fp-i values are 1.8% after wiping.
Embodiment 3
Aqueous polyurethane, trimethylolpropane-three (3- '-aziridinos) propionic ester, deionized water are added into container,
It is stirred at room temperature 30 minutes, obtains subbing, the quality of wherein trimethylolpropane-three (3- '-aziridinos) propionic ester is
The 2% of aqueous polyurethane quality, the quality of deionized water are the 83% of subbing gross mass.Side carboxyl polyurethane CPU- will be contained
2nd, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, DMA are added into container, in room temperature
Lower stirring 30 minutes, obtains top coat paint, and the mass ratio of wherein CPU-2 and polymethyl vinyl ether-maleic anhydride is 1:0.5,
The quality of poly glycol monomethyl ether is the 3% of polymethyl vinyl ether-maleic anhydride quality, the quality of DMA
For the 83% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight
For 80000 product, aqueous polyurethane is the type products of Lubrizol Corp. Sancure 777, and poly glycol monomethyl ether is western lattice
Agate aldrich company, the product that number-average molecular weight is 1000.Above-mentioned subbing is coated to the surface of interposing catheter, in 60
Solidify 1 hour at DEG C, top coat paint is coated to having been coated with the conduit of subbing afterwards, solidifies 1 hour at 80 DEG C, obtains
To conduit of the outer surface covered with cross-linked structure coating, then it is dipped in into concentrated ammonia liquor, soaks 1 hour at room temperature, takes out
Dried 2 hours at 60 DEG C afterwards, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 91.9% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.8% after conduit is rubbed.
Embodiment 4
Aqueous polyurethane, pentaerythrite-three (3- '-aziridinos) propionic ester, deionized water are added into container, in room
The lower stirring of temperature 30 minutes, obtains subbing, the wherein quality of pentaerythrite-three (3- '-aziridinos) propionic ester is water-based poly- ammonia
The 3% of ester quality, the quality of deionized water are the 85% of subbing gross mass.Side carboxyl polyurethane CPU-3, poly- methyl will be contained
Vinyl ether-maleic acid, poly glycol monomethyl ether, 1-METHYLPYRROLIDONE are added into container, are stirred at room temperature 30 points
Clock, obtains top coat paint, and the mass ratio of wherein CPU-3 and polymethyl vinyl ether-maleic anhydride is 1:1, polyethyleneglycol first
The quality of ether is the 5% of polymethyl vinyl ether-maleic anhydride quality, and the quality of 1-METHYLPYRROLIDONE is the total matter of top coat paint
The 85% of amount.The product that polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight is 80000,
Aqueous polyurethane is the type products of Lubrizol Corp. Sancure 777, poly glycol monomethyl ether be Sigma-Aldrich,
Number-average molecular weight is 1000 product.Above-mentioned subbing is coated to the surface of interposing catheter, solidified 1 hour at 60 DEG C,
Top coat paint is coated to having been coated with the conduit of subbing afterwards, solidified 1 hour at 80 DEG C, obtain outer surface covered with
The conduit of cross-linked structure coating, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, dry 2 after taking-up at 60 DEG C
Hour, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 92.2% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.9% after conduit is rubbed.
Embodiment 5
By aqueous polyurethane, trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, deionized water add to
In container, it is stirred at room temperature 30 minutes, obtains subbing, wherein [3- (the 2- methylaziridines of trimethylolpropane-three
Base)] quality of propionic ester is the 4% of aqueous polyurethane quality, the quality of deionized water is the 87% of subbing gross mass.Will
The CPU-4 of polyurethane containing side carboxyl, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, N, N- dimethyl sulfoxide (DMSO)s add
Into container, it is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-4 and polymethyl vinyl ether-maleic anhydride
Mass ratio is 1:2, the quality of poly glycol monomethyl ether is 7%, N of polymethyl vinyl ether-maleic anhydride quality, N- dimethyl
The quality of sulfoxide is the 87% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride be Sigma-Aldrich,
Number-average molecular weight is 80000 product, and aqueous polyurethane is the type products of Lubrizol Corp. Sancure 777, polyethyleneglycol
The product that methyl ether is Sigma-Aldrich, number-average molecular weight is 1000.Above-mentioned subbing is coated to interposing catheter
Surface, solidify 1 hour at 60 DEG C, afterwards coat top coat paint to having been coated with the conduit of subbing, at 80 DEG C
Solidification 1 hour, obtains conduit of the outer surface covered with cross-linked structure coating, then is dipped in into concentrated ammonia liquor, soaks at room temperature
Bubble 1 hour, dried 2 hours at 60 DEG C after taking-up, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 92.8% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.9% after conduit is rubbed.
Embodiment 6
Aqueous polyurethane, trimethylolpropane-three (3- '-aziridinos) propionic ester, deionized water are added into container,
It is stirred at room temperature 30 minutes, obtains subbing, the quality of wherein trimethylolpropane-three (3- '-aziridinos) propionic ester is
The 5% of aqueous polyurethane quality, the quality of deionized water are the 90% of subbing gross mass.Side carboxyl polyurethane CPU- will be contained
5th, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, ethyl acetate are added into container, are stirred at room temperature 30
Minute, obtain top coat paint, the mass ratio of wherein CPU-5 and polymethyl vinyl ether-maleic anhydride is 1:3, polyethyleneglycol
The quality of methyl ether is the 10% of polymethyl vinyl ether-maleic anhydride quality, and the quality of ethyl acetate is top coat paint gross mass
90%.The product that polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight is 80000, water
Property polyurethane be the type products of Lubrizol Corp. Sancure 777, poly glycol monomethyl ether be Sigma-Aldrich, number
Average molecular weight is 1000 product.Above-mentioned subbing is coated to the surface of interposing catheter, solidified 1 hour at 60 DEG C, it
Top coat paint is coated to having been coated with the conduit of subbing afterwards, solidifies 1 hour at 80 DEG C, obtains outer surface covered with friendship
Join the conduit of structure coating, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, drying 2 is small at 60 DEG C after taking-up
When, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 92.9% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.8% after conduit is rubbed.
Embodiment 7
Aqueous polyurethane, pentaerythrite-three (3- '-aziridinos) propionic ester, deionized water are added into container, in room
The lower stirring of temperature 30 minutes, obtains subbing, the wherein quality of pentaerythrite-three (3- '-aziridinos) propionic ester is water-based poly- ammonia
The 6% of ester quality, the quality of deionized water are the 92% of subbing gross mass.Side carboxyl polyurethane CPU-6, poly- methyl will be contained
Vinyl ether-maleic acid, poly glycol monomethyl ether, ethyl acetate are added into container, are stirred at room temperature 30 minutes, are obtained
The mass ratio of top coat paint, wherein CPU-6 and polymethyl vinyl ether-maleic anhydride is 1:4, the quality of poly glycol monomethyl ether
For the 12% of polymethyl vinyl ether-maleic anhydride quality, the quality of ethyl acetate is the 92% of top coat paint gross mass.Poly- first
The product that base vinyl ether-maleic acid is Sigma-Aldrich, number-average molecular weight is 80000, aqueous polyurethane are
The type products of Lubrizol Corp. Sancure 777, poly glycol monomethyl ether is Sigma-Aldrich, number-average molecular weight is
1000 product.Above-mentioned subbing is coated to the surface of interposing catheter, solidifies 1 hour at 60 DEG C, afterwards applies top layer
Material coating solidifies 1 hour at 80 DEG C, obtains outer surface covered with cross-linked structure coating to having been coated with the conduit of subbing
Conduit, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, dried 2 hours at 60 DEG C after taking-up, obtain table
Face has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 93.2% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.8% after conduit is rubbed.
Embodiment 8
By aqueous polyurethane, trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, deionized water add to
In container, it is stirred at room temperature 30 minutes, obtains subbing, wherein [3- (the 2- methylaziridines of trimethylolpropane-three
Base)] quality of propionic ester is the 7% of aqueous polyurethane quality, the quality of deionized water is the 94% of subbing gross mass.Will
The CPU-7 of polyurethane containing side carboxyl, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, butyl acetate are added to container
In, it is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-7 and polymethyl vinyl ether-maleic anhydride mass ratio
For 1:5, the quality of poly glycol monomethyl ether is the 14% of polymethyl vinyl ether-maleic anhydride quality, the quality of butyl acetate
For the 94% of top coat paint gross mass.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight
For 80000 product, aqueous polyurethane is the type products of Lubrizol Corp. Sancure 777, and poly glycol monomethyl ether is western lattice
Agate aldrich company, the product that number-average molecular weight is 1000.Above-mentioned subbing is coated to the surface of interposing catheter, in 60
Solidify 1 hour at DEG C, top coat paint is coated to having been coated with the conduit of subbing afterwards, solidifies 1 hour at 80 DEG C, obtains
To conduit of the outer surface covered with cross-linked structure coating, then it is dipped in into concentrated ammonia liquor, soaks 1 hour at room temperature, takes out
Dried 2 hours at 60 DEG C afterwards, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 93.5% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.9% after conduit is rubbed.
Embodiment 9
Aqueous polyurethane, trimethylolpropane-three (3- '-aziridinos) propionic ester, deionized water are added into container,
It is stirred at room temperature 30 minutes, obtains subbing, the quality of wherein trimethylolpropane-three (3- '-aziridinos) propionic ester is
The 8% of aqueous polyurethane quality, the quality of deionized water are the 96% of subbing gross mass.Side carboxyl polyurethane CPU- will be contained
8th, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, dichloromethane are added into container, are stirred at room temperature 30
Minute, obtain top coat paint, the mass ratio of wherein CPU-8 and polymethyl vinyl ether-maleic anhydride is 1:6, polyethyleneglycol
The quality of methyl ether is the 16% of polymethyl vinyl ether-maleic anhydride quality, and the quality of dichloromethane is top coat paint gross mass
96%.The product that polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight is 80000, water
Property polyurethane be the type products of Lubrizol Corp. Sancure 777, poly glycol monomethyl ether be Sigma-Aldrich, number
Average molecular weight is 1000 product.Above-mentioned subbing is coated to the surface of interposing catheter, solidified 1 hour at 60 DEG C, it
Top coat paint is coated to having been coated with the conduit of subbing afterwards, solidifies 1 hour at 80 DEG C, obtains outer surface covered with friendship
Join the conduit of structure coating, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, drying 2 is small at 60 DEG C after taking-up
When, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 93.6% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.9% after conduit is rubbed.
Embodiment 10
Aqueous polyurethane, pentaerythrite-three (3- '-aziridinos) propionic ester, deionized water are added into container, in room
The lower stirring of temperature 30 minutes, obtains subbing, the wherein quality of pentaerythrite-three (3- '-aziridinos) propionic ester is water-based poly- ammonia
The 9% of ester quality, the quality of deionized water are the 98% of subbing gross mass.Side carboxyl polyurethane CPU-6, poly- methyl will be contained
Vinyl ether-maleic acid, poly glycol monomethyl ether, chloroform are added into container, are stirred at room temperature 30 minutes, are obtained
The mass ratio of top coat paint, wherein CPU-6 and polymethyl vinyl ether-maleic anhydride is 1:7, the quality of poly glycol monomethyl ether
For the 18% of polymethyl vinyl ether-maleic anhydride quality, the quality of chloroform is the 98% of top coat paint gross mass.Poly- first
The product that base vinyl ether-maleic acid is Sigma-Aldrich, number-average molecular weight is 80000, aqueous polyurethane are
The type products of Lubrizol Corp. Sancure 777, poly glycol monomethyl ether is Sigma-Aldrich, number-average molecular weight is
1000 product.Above-mentioned subbing is coated to the surface of interposing catheter, solidifies 1 hour at 60 DEG C, afterwards applies top layer
Material coating solidifies 1 hour at 80 DEG C, obtains outer surface covered with cross-linked structure coating to having been coated with the conduit of subbing
Conduit, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, dried 2 hours at 60 DEG C after taking-up, obtain table
Face has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 93.8% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.9% after conduit is rubbed.
Embodiment 11
By aqueous polyurethane, trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, deionized water add to
In container, it is stirred at room temperature 30 minutes, obtains subbing, wherein [3- (the 2- methylaziridines of trimethylolpropane-three
Base)] quality of propionic ester is the 10% of aqueous polyurethane quality, the quality of deionized water is the 99% of subbing gross mass.
Side carboxyl polyurethane CPU-4, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, acetone will be contained to add to container
In, it is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-4 and polymethyl vinyl ether-maleic anhydride mass ratio
For 1:10, the quality of poly glycol monomethyl ether is the 20% of polymethyl vinyl ether-maleic anhydride quality, and the quality of acetone is top
The 99% of coating gross mass.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight is
80000 product, aqueous polyurethane are the type products of Lubrizol Corp. Sancure 777, and poly glycol monomethyl ether is Sigma
Aldrich company, the product that number-average molecular weight is 1000.Above-mentioned subbing is coated to the surface of interposing catheter, in 60 DEG C
Lower solidification 1 hour, top coat paint is coated to having been coated with the conduit of subbing, solidify 1 hour at 80 DEG C, obtain afterwards
Conduit of the outer surface covered with cross-linked structure coating, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, after taking-up
Dried 2 hours at 60 DEG C, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 94.0% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.9% after conduit is rubbed.
Embodiment 12
By aqueous polyurethane, trimethylolpropane-three (3- '-aziridinos) propionic ester, (the 3- aziridine of pentaerythrite-three
Base) propionic ester, deionized water add into container, be stirred at room temperature 30 minutes, obtain subbing, wherein trihydroxy methyl third
The quality of alkane-three (3- '-aziridinos) propionic ester is the 2% of aqueous polyurethane quality, pentaerythrite-three (3- '-aziridinos) third
The quality of acid esters is the 3% of aqueous polyurethane quality, and the quality of deionized water is the 90% of subbing gross mass.Side carboxylic will be contained
Based polyurethanes CPU-2, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, tetrahydrofuran are added into container,
Stir 30 minutes at room temperature, obtain top coat paint, the mass ratio of wherein CPU-2 and polymethyl vinyl ether-maleic anhydride is 1:
8, the quality of poly glycol monomethyl ether is the 8% of polymethyl vinyl ether-maleic anhydride quality, and the quality of tetrahydrofuran is top layer
The 95% of coating gross mass.Polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight is
80000 product, aqueous polyurethane are the type products of Lubrizol Corp. Sancure 777, and poly glycol monomethyl ether is Sigma
Aldrich company, the product that number-average molecular weight is 1000.Above-mentioned subbing is coated to the surface of interposing catheter, in 60 DEG C
Lower solidification 1 hour, top coat paint is coated to having been coated with the conduit of subbing, solidify 1 hour at 80 DEG C, obtain afterwards
Conduit of the outer surface covered with cross-linked structure coating, then be dipped in into concentrated ammonia liquor, soak 1 hour at room temperature, after taking-up
Dried 2 hours at 60 DEG C, obtaining surface has the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 93.6% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.8% after conduit is rubbed.
Embodiment 13
By aqueous polyurethane, trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, (3- of pentaerythrite-three
'-aziridino) propionic ester, deionized water add into container, be stirred at room temperature 30 minutes, obtain subbing, wherein three hydroxyls
The quality of methylpropane-three [3- (2- methylaziridines base)] propionic ester is the 4% of aqueous polyurethane quality, pentaerythrite-three
The quality of (3- '-aziridinos) propionic ester is the 2% of aqueous polyurethane quality, and the quality of deionized water is subbing gross mass
80%.Side carboxyl polyurethane CPU-1, polymethyl vinyl ether-maleic anhydride, poly glycol monomethyl ether, butanone, tetrahydrochysene will be contained
Furans is added into container, is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-1 and polymethyl vinyl ether-horse
The mass ratio for carrying out acid anhydrides is 1:9, the quality of poly glycol monomethyl ether is the 6% of polymethyl vinyl ether-maleic anhydride quality, fourth
The quality of ketone is the 40% of top coat paint gross mass, and the quality of tetrahydrofuran is the 50% of top coat paint gross mass.Poly- methyl second
The product that alkene ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight is 80000, aqueous polyurethane are won for road
The type products of profit company Sancure 777, poly glycol monomethyl ether are Sigma-Aldrich, number-average molecular weight 1000
Product.Above-mentioned subbing is coated to the surface of interposing catheter, solidifies 1 hour at 60 DEG C, afterwards applies top coat paint
Cover to having been coated with the conduit of subbing, solidify 1 hour at 80 DEG C, obtain outer surface leading covered with cross-linked structure coating
Pipe, then be dipped in into concentrated ammonia liquor, soak 1 hour, dried 2 hours at 60 DEG C after taking-up at room temperature, obtain surface tool
There is the interposing catheter of Hydrophilic lubrication.
Lubricity and abrasion resistance test method are same as Example 2, and test result shows, are rubbed in the present embodiment suffered by conduit
It is 93.1% to wipe power and reduce degree fp-r values, and friction increase degree fp-i values are 1.7% after conduit is rubbed.
Claims (9)
1. a kind of coating for forming catheter surface hydrophilic coating, it is characterised in that coating includes subbing and top coat paint, institute
State subbing to be made up of aqueous polyurethane, polyfunctionality aziridine derivative and deionized water, wherein polyfunctionality nitrogen third
The quality of piperidine derivatives is the 1%~10% of aqueous polyurethane quality, and the quality of deionized water is subbing gross mass
80%~99%, the top coat paint is by polyurethane containing side carboxyl, polymethyl vinyl ether-maleic anhydride, polyethyleneglycol
Methyl ether and organic solvent composition, wherein the mass ratio of polyurethane containing side carboxyl and polymethyl vinyl ether-maleic anhydride is 1:
(0.1~10), the quality of poly glycol monomethyl ether are 1%~20%, You Jirong of polymethyl vinyl ether-maleic anhydride quality
The quality of agent is the 80%~99% of top coat paint gross mass.
2. the coating according to claim 1 for forming catheter surface hydrophilic coating, it is characterised in that described polyfunctionality
Aziridine derivative is trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, (the 3- nitrogen of trimethylolpropane-three
Third piperidinyl) propionic ester, the one or more in pentaerythrite-three (3- '-aziridinos) propionic ester.
3. the coating according to claim 1 for forming catheter surface hydrophilic coating, it is characterised in that described contains side carboxyl
The molecular chain structure of polyurethane is by polyethers or polyester diol, diisocyanate, 2,2- dihydromethyl propionic acids and 1,4- fourths two
Alcohol is connected through addition reaction, and described polyethers or polyester diol are polyoxypropyleneglycol, polytetrahydrofuran diol, poly- carbon
One kind in acid esters glycol, polycaprolactone glycol, for number-average molecular weight 1000~4000, described diisocyanate is 2,4- first
Phenylene diisocyanate, hexa-methylene 1,6- diisocyanate, 4,4'- methyl diphenylene diisocyanates, the isocyanide of isophorone two
One kind in acid esters.
4. the coating according to claim 1 for forming catheter surface hydrophilic coating, it is characterised in that described organic solvent
For N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, N, N- dimethyl sulfoxide (DMSO)s, ethyl acetate, vinegar
One or more in acid butyl ester, dichloromethane, chloroform, acetone, butanone, tetrahydrofuran.
A kind of 5. preparation method of the coating according to claim 1 for forming catheter surface hydrophilic coating, it is characterised in that
Comprise the following steps：
(1) preparation of the polyurethane containing side carboxyl：Polyurethane containing side carboxyl is synthesized using solvent method, by polyethers or polyester diol with
Diisocyanate is added in reactor, is warming up to 80 DEG C, and stirring reaction obtains performed polymer after 1 hour, add 2,2- dihydroxymethyls
Propionic acid and BDO, after reacting 2 hours, DMF is added, after continuing reaction 1 hour, add two bays
Sour dibutyl tin, then react 8 hours, room temperature is down to, solution in reactor is poured into the container equipped with deionized water, there is white
Sediment separates out, and collects sediment and is washed with deionized 3 times, is positioned in vacuum drying oven, vacuum is done at 90 DEG C
Dry 48 hours, transparent cake product is obtained, the masterbatch of polyurethane containing side carboxyl is obtained after being granulated, wherein, two isocyanic acid
The molal quantity of ester is with the ratio between polyethers or the total mole number of polyester diol, 2,2- dihydromethyl propionic acids and 1,4- butanediols
(1.05~1.2):The ratio between molal quantity of 1,2,2- dihydromethyl propionic acid and BDO is 1:1, polyethers or polyester diol
The ratio between the gross mass of quality and diisocyanate, 2,2- dihydromethyl propionic acids and 1,4- butanediols be (1.5~1):1, N, N-
The ratio between the quality of dimethylformamide and the gross mass of other all raw materials are 4:1, the quality of dibutyl tin laurate is poly-
The 1% of ether or polyester diol quality, the quality of deionized water used and the mass ratio of DMF during precipitation
For 2:1, the quality of deionized water used and the mass ratio of DMF are 2 during washing every time:1；
(2) preparation of subbing：Aqueous polyurethane, polyfunctionality aziridine derivative, deionized water are added into container,
It is stirred at room temperature 30 minutes, obtains subbing, the wherein quality of polyfunctionality aziridine derivative is aqueous polyurethane matter
The 1%~10% of amount, the quality of deionized water are the 80%~99% of subbing gross mass；
(3) preparation of top coat paint：Side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, polyethyleneglycol first will be contained
Ether, organic solvent are added into container, are stirred at room temperature 30 minutes, are obtained top coat paint, wherein polyurethane containing side carboxyl with
The mass ratio of polymethyl vinyl ether-maleic anhydride is 1:(0.1~10), the quality of poly glycol monomethyl ether is poly- ethylene methacrylic
The 1%~20% of base ether-maleic anhydride quality, the quality of organic solvent are the 80%~99% of top coat paint gross mass.
6. the preparation method of the coating according to claim 5 for forming catheter surface hydrophilic coating, it is characterised in that step
(1) polyethers or polyester diol described in are polyoxypropyleneglycol, polytetrahydrofuran diol, PCDL, gather oneself
One kind in interior esterdiol, number-average molecular weight 1000~4000, described diisocyanate be 2,4- toluene di-isocyanate(TDI)s,
One kind in hexa-methylene 1,6- diisocyanate, 4,4'- methyl diphenylene diisocyanates, IPDI.
7. the preparation method of the coating according to claim 5 for forming catheter surface hydrophilic coating, it is characterised in that step
(2) the polyfunctionality aziridine derivative described in is trimethylolpropane-three [3- (2- methylaziridines base)] propionic ester, three
One or more in hydroxymethyl-propane-three (3- '-aziridinos) propionic ester, pentaerythrite-three (3- '-aziridinos) propionic ester.
8. the preparation method of the coating according to claim 5 for forming catheter surface hydrophilic coating, it is characterised in that step
(3) organic solvent described in is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, N, N- bis-
One kind or several in methyl sulfoxide, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, tetrahydrofuran
Kind.
A kind of 9. application method of the coating according to claim 1 for forming catheter surface hydrophilic coating, it is characterised in that
Comprise the following steps：
(1) coating coating processing：Subbing is coated to the surface of conduit in a manner of dip-coating, spraying or brushing, in 60 DEG C
Lower solidification 1 hour, top coat paint is coated to having been coated with the conduit of subbing, solidify 1 hour at 80 DEG C, obtain afterwards
Conduit of the outer surface covered with cross-linked structure coating；
(2) coating hydrophilic is handled：The conduit that processing is completed in step (1) is immersed into concentrated ammonia liquor, it is small to soak 1 at room temperature
When, dried 2 hours at 60 DEG C after taking-up, obtaining surface has the interposing catheter of hydrophilic cross-linking structure coating.
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| CN111514380B (en) * | 2019-02-02 | 2021-06-08 | 江苏百赛飞生物科技有限公司 | Ureteral stent and preparation method thereof |
| CN113634130B (en) * | 2020-05-11 | 2022-11-18 | 中国石油化工股份有限公司 | Pollution-resistant reverse osmosis membrane and preparation method and application thereof |
| CN111603618B (en) * | 2020-06-03 | 2021-04-20 | 江门市泰乐医疗科技有限公司 | Guide wire coating composition, guide wire coating and preparation method of guide wire coating |
| CN114276510B (en) * | 2022-02-09 | 2023-08-11 | 上海健倬生物科技有限公司 | Zero-free amine isocyanate modified aziridine crosslinking agent, and preparation method and application thereof |
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| CN104225687A (en) * | 2014-09-23 | 2014-12-24 | 北京迪玛克医药科技有限公司 | Paint for intervention duct and preparation method thereof, and intervention duct |
| CN104307051A (en) * | 2014-10-30 | 2015-01-28 | 北京迪玛克医药科技有限公司 | Hydrophilic coating layer and preparation method thereof as well as interventional device |
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