CN105983140A - Coating for hydrophilic lubrication interventional catheter and preparation and application methods of coating - Google Patents

Abstract

The invention relates to a coating for a hydrophilic lubrication interventional catheter and preparation and application methods of the coating. The coating comprises a bottom layer coating body and a top layer coating body, the bottom layer coating body is prepared from side carboxyl polyurethane, a polyisocyanate curing agent and an organic solvent, and the top layer coating body is prepared from side carboxyl polyurethane, poly vinyl methyl ether-maleic anhydride and an organic solvent; when curing is conducted, all components form a cross-linked structure, the bottom of the coating is closely connected with the top of the coating through a covalent bond, the coating is firmly attached to the surface of the catheter, the coating has hydrophilic lubrication and excellent abrasion resistance and is suitable for hydrophilic lubrication treatment of instruments of the hydrophilic lubrication and the like for traditional Chinese medical science in the technical field of intravascular interventional treatment.

Description

A kind of coating for hydrophilic lubrication interposing catheter and preparation and application thereof

Endovascular Interventions technology is widely used in clinical vascular radiography, angioplasty, Intravascular Thrombus or foreign body The aspects such as removing, compared with tradition medical skill, the most easy to operate, and owing to the wound of interventional therapy is low, it is possible to Alleviating the misery of patient, Operative risk is less, and medical expense is relatively low, and therefore this technology obtains at medical domain Promote widely and use.Endovascular Interventions technology be by mean of interposing catheter by vessel lumen arrive internal relatively Remote diseased region, such as vascular sites such as coronary artery, reinjects diagnosis and treatment agent or inserts apparatus, with reach to internal farther out Position realizes the purpose of diagnosis and minimally-invasive treatment.Research of Intravascular Catheterization is one of main apparatus of endovascular temporary embolization, Its kind can have radiography interposing catheter, medicine to carry interposing catheter, angioplasty interposing catheter etc., and these interventions are led Pipe should have excellent operability and safety, it is generally required to the blood compatibility of excellence, certain blood property of softening, Ooze out without nuisance, excellent kink resistance, excellent mechanical performance, good machinability opaque with X-ray Agent has the performances such as the good compatibility.

Lubricity is one of highly important performance of Research of Intravascular Catheterization.When conduit is entering, exiting blood vessel and at blood In pipe during motion, high-lubricity can suppress gluing at material surface such as the macromole in blood such as plasma protein, platelet etc. Attached, reduce blood vessel wall and the damage of hemocyte, alleviate the disturbance to blood laminar flow, the generation of Coagulation test can be avoided. Also can alleviate the misery that patient is caused.Therefore, it is the most necessary for interposing catheter carries out surface lubrication processing.Coating Hydrophilic lubrication coating is to improve the effective means of interposing catheter lubricity.Utilize containing a large amount of pyrrolidone groups, oxidation second The high-hydrophilic that thiazolinyl group, carboxyl, the polymer of amide groups show in blood, the film forming matter as coating is permissible Reach the purpose of high-efficiency lubricating, this base polymer include polyvinyl pyrrolidone (PVP), polyethylene glycol oxide (PEO), Acrylamido copolymer, acrylic copolymer and maleic anhydride analog copolymer etc..

For the coating on hydrophilic lubrication interposing catheter, owing to conduit to carry out moving and stop a timing in human body Between, therefore except meeting high hydrophilic lubrication performance, also need to focus on the firm and stable of greasy property, the hydrophilic segment of coating Will not fall off after standing repeatedly to rub with coating integral part, and maintain good combination property.It is particularly applied to On the intervention apparatus such as seal wire, foley's tube, guiding catheter.Utilize covalent bond to connect or the means such as crosslinking can be to hydrophiling Compound plays certain fixation, and this type of technology is the most gradually widely used.At the coating body that chemical reaction solidification occurs In system, according to whether participating in reaction, hydrophilic compounds can be divided into again response type and non-reactive, such as PVP, PEO For non-reactive, acrylic acid, the copolymer etc. of maleic acid anhydride are response type.

Hydrophilic coating system in early days does not the most use chemical reaction when solidification, such as United States Patent (USP) US 4589873, US 4835003, US 4875287, US 5331027, US 5509899, US 5620738 and US 6042876 are the most public Having opened the hydrophilic lubrication coating containing PVP, the feature of this type coating is, top layer is coated with PVP, but PVP place is coated with Layer or its base coat the most do not introduce cross-linked structure, and PVP easily comes off after imbibition, can make whole coating system Lose the effect of hydrophilic lubrication.

United States Patent (USP) US 8287890 B2, US 6299980 B1, US 5776611, US 5179174, US 5160790 All disclose with isocyanate crosslinking as base coat with US 4666437, top layer coats the hydrophilic height such as PVP or PEO The coating system of molecule, the feature of this type coating is, in top coat in addition to containing hydrophilic high mol, being also added into can To crosslink polyhydric alcohol or the polyamine of reaction with bottom isocyanate crosslinking, thereby serve to certain fixing work With.But due to PVP or PEO the cross-linking reaction that is not involved in system, through friction after imbibition, the most very Easily come off from coated substrate.

United States Patent (USP) US 8039524 B2, US 7696259 B2, US7534495 B2, US 7052131 B2, US 8378011 B2, US 8512795 B2 and US 8513320 B2 all disclose with the hydrophilic height such as double bond compound and PVP The UV curing system coating of molecular composition.The feature of this type coating is, double bond compound is acrylic monomer, It is coated after mixing with hydrophilic high mol, light trigger etc. under the dissolution of solvent, is obtained by ultraviolet light polymerization double The cross-linked structure of key.But what the hydrophilic high mols such as the PVP of employing non-reactive came off after still there is water suction friction asks Thin film fragility after topic, and double bond compound crosslinking is relatively big, and mechanical property is poor, the most poor to the tack of base material. Additionally, compared with conventional curing mode, coating processes and the coating equipment of apparatus are required higher by ultraviolet light polymerization.

For response type hydrophilic compounds system, mainly contain N-[2-(2-methyl-4-oxopentyl)-DMAA copolymer, Acrylic acid-acrylamide copolymer, glycidyl methacrylate-DMAA copolymer, methyl ethylene Ether-copolymer-maleic anhydride etc..

United States Patent (USP) US 6540698 B1 reports with homemade N-[2-(2-methyl-4-oxopentyl)-DMAA copolymer As hydrophilic high mol, being dissolved in oxolane obtaining solution, conduit immerses in solution, immerses carbon after drying again In the aqueous solution of acid dihydrazide, pH value is adjusted to 3, utilizes the reaction of carbonyl and hydrazides to cross-link.But in this individual system, Only using N-[2-(2-methyl-4-oxopentyl)-DMAA copolymer as film forming matter, it is poor to the tack of base material, Easily come off under rubbing action.

United States Patent (USP) US 5804318 reports homemade containing primary amine or the acrylamide copolymer of tertiary amine group, to contain Epoxy radicals silicone coupling agents or aldehyde compound, as cross-linking agent, can first coat containing epoxy radicals silicone coupling agents, then It is coated with copolymer, or is first coated with copolymer, then immerse in aldehyde compound solution.But this coating is only with the copolymer of crosslinking As film forming matter, its adhesive force is the most relatively low.

Method disclosed in United States Patent (USP) US 6558798 B2 is to be mixed with aziridine crosslinker CX100 by aqueous polyurethane After be coated on equipment surfaces, to be coated half-dried after, coat acrylic acid-acrylamide copolymer, and then formed with bottom and hand over Connection structure.Acrylic acid-acrylamide copolymer is typically to obtain with acrylic acid for material copolymerization, and acrylic acid is for having corrosion Property and the compound of toxicity, even if a small amount of residual also can produce harm to human body, the monomer simultaneously remained contains irritant gas Taste.Disclosed in United States Patent (USP) US 6468649 B1, technology is similar with US 6558798 B2, and the primary raw material used is also It is aqueous polyurethane, aziridine crosslinker CX100 and acrylic acid-acrylamide copolymer, there is also similar lacking Fall into.Additionally, and in uneven thickness, the surface irregularity of coating poor with the moistening of base material, levelling, adhesion property The problem that always aqueous coating system exists.

The method of United States Patent (USP) US 8455094 B2 and Chinese patent CN 102264403 A report is all to use plasma Body radiation and the method for high-temperature process, be first grafted to mercaptan compound on conduit, be coated with homemade metering system Acid glycidyl ester-DMAA copolymer, makes copolymer also graft on conduit after hot setting.This is coated with The coating processes condition of layer is the harshest, makes the use of a lot of conduit base material be restricted owing to treatment temperature is higher, with Time need expensive equipment.

Methyl vinyl ether-maleic acid copolymer has been widely used in fields such as medicine and food, and it is to human non-toxic, There is hydrophilic carboxyl it can also be used to hydrophilic coating after esterification.

United States Patent (USP) US 5891109 reports and vinyl ether-maleic acid copolymer, polyurethane, butanone is formed Coating, through hot setting after coating conduit, then immerses open loop in ethanol or methylamine water solution, obtains the conduit of hydrophilic lubrication. But the anhydride group on this system medium vinyl ether-copolymer-maleic anhydride can only go out with minimal amount of polyurethane pyrolytic The isocyanate groups come reacts, and crosslinking degree is the highest, and therefore coating fastness is the most poor, and hot setting Condition makes it unsuitable for for most polymeric catheter and apparatus.

United States Patent (USP) US 5229211 discloses a kind of interventional medical device, and claim equipment surfaces has maleic anhydride The coating that analog copolymer obtains after covalent bond is connected with isocyanate prepolymer, the ground of coating is polymer, selected from poly- Vinyl chloride, polyurethane, polyamide or polyester, but it takes a single example in an embodiment, will polrvinyl chloride, little molecularization The 4 of compound, 4'-methyl diphenylene diisocyanate, oxolane composition solution, coat conduit, be coated with methyl after drying Vinyl ether-maleic acid copolymer, immerses sodium salt solution and hot wash, obtains hydrophilic lubrication conduit after solidification.? In this coating system isocyanates can with maleic groups generation chemical reaction, but, only this reaction can not be complete Solve the fastness of coating, it is crucial that, remaining isocyanate groups needs to be combined with ground, just can play fixing The effect of methyl vinyl ether-maleic acid copolymer, and the macromolecules such as the polrvinyl chloride described in this patent can not be with Isocyanates reacts, and therefore cannot be connected by covalent bond with methyl vinyl ether-maleic acid copolymer, and these are high Molecule is the highest to the adhesive force of conduit, and coating is the most firm.

It will be seen that the hydrophilic high mol of response type owing to lacking enough adhesive force and poor film property to conduit, Cannot need by intermediate medium as the main film forming matter of coating with the form of covalent bond, being loaded to another kind can be with The polymeric matrix of conduit firm attachment, so how building this coating architecture will be to solve conduit both hydrophilic lubrications The key of a most wear-resisting difficult problem, it is still necessary to provide new technology to obtain the catheter coatings of higher performance.

Summary of the invention

For the deficiencies in the prior art, the present invention provides a kind of coating for hydrophilic lubrication interposing catheter and preparation thereof and makes Use method.Purpose is to confer to the excellent Hydrophilic lubrication of interposing catheter and wearability.

The present invention is by building two layer coating system, forming many components cross-linked structure with different chemical bond connected modes, both Serve the effect making coating outer surface have hydrophilic lubrication, in turn ensure that bottom and the firm attachment of conduit and bottom with Combining closely between top, makes crocking resistance excellent.

Further summary is exactly, owing to high hydrophilic lubrication sexual needs coating outer surface to possess substantial amounts of hydrophilic group, and lance Shield, if hydrophilic polymer too high levels in system, then the fastness of this film forming matter is inevitable poor, in the present invention The method solved builds duplex coating, and the crosslinking of painting interlayer exactly, i.e. top layer has the hydrophilic polymer of high-load, I.e. polymethyl vinyl ether-maleic anhydride, and a small amount of containing side carboxyl polyurethane, and bottom comprises to be had the most attached with conduit Put forth effort containing side carboxyl polyurethane, and the intermediate medium of upper and lower two layers of coatings can be connected, i.e. isocyanate curing agent. Under normal circumstances, isocyanates is the highest with the reactivity of anhydride group, but being found surprisingly that is the painting in the present invention In coating systems, polymethyl vinyl ether-copolymer-maleic anhydride and isocyanates can be easy to reaction and form cross-linking products, This is likely due in copolymer containing substantial amounts of maleic groups, and the relatively small molecular weight of isocyanate compound, Making to be prone to contact between group, the active group quantity in unit volume is more, and therefore reactivity is greatly increased.So, Isocyanate curing agent in primer coating can be combined with the hydrophilic polymer of top layer securely, additionally, utilize Carbimide. Ester and the reaction of carboxyl, part isocyanates can also react with the side carboxyl polyurethane in upper and lower two-layer, defines The cross-linked structure of many components.It addition, the carboxyl of side carboxyl polyurethane and the NCO of isocyanate curing agent in bottom Group can strengthen the adhesive force of coating and catheter surface.

Above-mentioned purpose can be realized by technical scheme in detailed below:

A kind of coating for hydrophilic lubrication interposing catheter, it is characterised in that coating comprises subbing and top coat paint, Described subbing is formed by containing side carboxyl polyurethane, polyisocyanate curing agent and organic solvent, wherein containing side carboxyl Polyurethane is 1:(0.1～10 with the mass ratio of polyisocyanate curing agent), the quality of organic solvent is subbing gross mass 80wt%～99wt%, described top coat paint is by containing side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride with have Machine solvent forms, and wherein the mass ratio containing side carboxyl polyurethane with polymethyl vinyl ether-maleic anhydride is 1:(0.1～10), The quality of organic solvent is 80wt%～99wt% of top coat paint gross mass.

The described coating for hydrophilic lubrication interposing catheter, it is characterised in that the described molecule containing side carboxyl polyurethane Chain structure is anti-through addition by polyethers or polyester diol, diisocyanate, 2,2-dihydromethyl propionic acid and 1,4-butanediol Should be connected, described polyethers or polyester diol are polyoxypropyleneglycol, polytetrahydrofuran diol, Merlon two One in alcohol, polycaprolactone glycol, number-average molecular weight is 1000～4000, and described diisocyanate is 2,4-toluene Diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone two isocyanide One in acid esters.

The described coating for hydrophilic lubrication interposing catheter, it is characterised in that described polyisocyanate curing agent is 2,4- Toluene di-isocyanate(TDI), hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone two Isocyanates, the prepolymer of 2,4 toluene diisocyanate, the prepolymer of hexa-methylene 1,6-diisocyanate, different Fo Er The prepolymer of ketone diisocyanate, the prepolymer of 4,4'-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate-three Hydroxymethyl-propane addition product, triphenyl methane-4,4', the 4 " one in-triisocyanate, tri o cresyl thiophosphate phenyl isocyanate Or it is several.

The described coating for hydrophilic lubrication interposing catheter, it is characterised in that described organic solvent is N, N-dimethyl Methanamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl sulfoxide, ethyl acetate, butyl acetate, One or more in dichloromethane, chloroform, acetone, butanone, oxolane.

The preparation method of a kind of described coating for hydrophilic lubrication interposing catheter, it is characterised in that comprise the steps:

(1) preparation containing side carboxyl polyurethane: use solvent method synthesis polyurethane Han side carboxyl, by polyethers or polyester two Unit's alcohol and diisocyanate add in reactor, are warming up to 80 DEG C, and stirring reaction obtained performed polymer after 2 hours, added 2,2-dihydromethyl propionic acids and BDO, after reacting 1 hour, add DMF, continue reaction 1 After hour, add dibutyl tin laurate, then react 12 hours, be down to room temperature, pour solution in reactor into dress Have in the container of deionized water, have white depositions to separate out, collect precipitate and be washed with deionized 3 times, being positioned over In vacuum drying oven, it is vacuum dried 48 hours at 90 DEG C, obtains transparent cake product, contained after its pelletize Side carboxyl polyurethane masterbatch, wherein, the molal quantity of described diisocyanate and polyethers or polyester diol, 2,2-dihydroxy first The ratio of the total mole number of base propanoic acid and BDO is (1.05～1.2): 1,2,2-dihydromethyl propionic acid rubs with BDO The quality that ratio is 1:1, polyethers or polyester diol of your number and diisocyanate, 2,2-dihydromethyl propionic acid and Isosorbide-5-Nitrae-fourth two The ratio of the gross mass of alcohol is (1.5～1): 1, and the quality of DMF with the ratio of the gross mass of other all raw materials is 4:1, the quality of dibutyl tin laurate is polyethers or the 1% of polyester diol quality, deionized water used during precipitation The mass ratio of quality and DMF is 2:1, every time the quality of deionized water used and N, N-during washing The mass ratio of dimethylformamide is 2:1.

(2) preparation of subbing: side carboxyl polyurethane, polyisocyanate curing agent, organic solvent addition will be contained extremely In container, it is stirred at room temperature 30 minutes, obtains subbing, wherein solid with polyisocyanates containing side carboxyl polyurethane The mass ratio of agent is 1:(0.1～10), the quality of organic solvent is 80wt%～99wt% of subbing gross mass.

(3) preparation of top coat paint: side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, organic solvent will be contained Add to container, be stirred at room temperature 30 minutes, obtain top coat paint, wherein containing side carboxyl polyurethane and poly-methyl The mass ratio of vinyl ether-maleic acid is 1:(0.1～10), the quality of organic solvent is the 80wt% of top coat paint gross mass ～99wt%.

The preparation method of the described coating for hydrophilic lubrication interposing catheter, it is characterised in that described in step (1) Polyethers or polyester diol be polyoxypropyleneglycol, polytetrahydrofuran diol, PCDL, polycaprolactone two One in alcohol, number-average molecular weight 1000～4000, described diisocyanate be 2,4 toluene diisocyanate, six One in methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone diisocyanate.

The preparation method of the described coating for hydrophilic lubrication interposing catheter, it is characterised in that described in step (2) Polyisocyanate curing agent be 2,4 toluene diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-diphenylmethyl Alkane diisocyanate, isophorone diisocyanate, the prepolymer of 2,4 toluene diisocyanate, hexa-methylene 1,6-bis- The prepolymer of isocyanates, the prepolymer of isophorone diisocyanate, the pre-polymerization of 4,4'-methyl diphenylene diisocyanate Thing, 2,4 toluene diisocyanate-trimethylolpropane addition product, triphenyl methane-4,4', 4 "-triisocyanate, sulfur are for phosphorus One or more in triphenyl phosphate based isocyanate.

The preparation method of the described coating for hydrophilic lubrication interposing catheter, it is characterised in that step (2) and step (3) organic solvent described in be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl sulfoxide, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, oxolane In one or more.

The using method of a kind of described coating for hydrophilic lubrication interposing catheter, it is characterised in that comprise the steps:

(1) coating coating processing: by subbing by dip-coating, spray or brush in the way of coat the table to interposing catheter Face, solidifies 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, in 80 DEG C at 60 DEG C Lower solidification 60 minutes, obtains outer surface and is coated with the interposing catheter of cross-linked structure coating.

(2) coating hydrophilic processes: immersed to strong aqua ammonia by the interposing catheter processed in step (1), in room temperature Lower immersion 60 minutes, is dried 2 hours at 60 DEG C after taking-up, must arrive surface and have Jie of hydrophilic cross-linking structure coating Enter conduit.

The invention has the beneficial effects as follows:

(1) compared with prior art, the present invention efficiently solves the problem that hydrophilic coating fastness is not enough, by building Two layer coating system, form many components cross-linked structure with different chemical bond connected modes, make the most hydrophilic profit of coating outer surface Sliding, in turn ensure that combining closely between bottom and the firm attachment of conduit and bottom and top so that it is there is excellence Wearability.The coating of the present invention, after interposing catheter, can make conduit friction reduce by more than 90%.Repeatedly rubbing After wiping effect, hydrophilic coating retains complete, and conduit friction increasing degree is less than 2%.

(2) present invention is controlled containing the raw material type in side carboxyl polyurethane synthetic reaction, consumption, reaction temperature by strict The conditions such as degree and time, reach molecular structure, NCO and hydroxyl mol ratio, soft or hard section ratio, carboxyl-content The purpose defined, obtains that surface is the most tacky, mechanical strength is high, product yield is high containing side carboxyl polyurethane, thus Obtain the demand meeting bottom matrix material of the present invention, compensate for other macromolecular material performances and the deficiency of function.

(3) different from the using method of polyisocyanate curing agent in other public technologies, the present invention utilizes it with hydrophilic Polyphosphazene polymer methyl vinyl ether-maleic acid, and ground polymer i.e. Han the side carboxyl polyurethane high with adhesive force enters Row reaction, forms firm covalent bond and connects, and the polyisocyanate curing agent in other public technologies is not the most poly-with hydrophilic Compound react, or not with ground polymer reaction, the most hydrophilic component is insecure, and ground also easily comes off from conduit, And the coating system of the present invention can effectively solve the problem that these problems, have more advance and creativeness.

(4) coating provided by the present invention can be that base material provides firm hydrophilic lubrication performance, and the scope of application is relatively wide, especially It is applicable to Endovascular Interventions technical field, the medical apparatus and instruments that can be used for include seal wire, foley's tube, guiding catheter, Thrombus suction catheter, central venous catheter, peripheral venous catheter, angiography catheter, expansion pipe and tear sheath etc..

Detailed description of the invention

Below by specific embodiment, the present invention is described in detail.

Embodiment 1

Preparation containing side carboxyl polyurethane (CPU): use solvent method synthesis polyurethane Han side carboxyl, by polyethers or polyester Dihydroxylic alcohols and diisocyanate add in reactor, are warming up to 80 DEG C, and stirring reaction obtained performed polymer after 2 hours, added 2,2-dihydromethyl propionic acids and BDO, after reacting 1 hour, add DMF, continue reaction 1 After hour, add dibutyl tin laurate, then react 12 hours, be down to room temperature, pour solution in reactor into dress Have in the container of deionized water, have white depositions to separate out, collect precipitate and be washed with deionized 3 times, being positioned over In vacuum drying oven, it is vacuum dried 48 hours at 110 DEG C, obtains transparent cake product, contained after its pelletize Side carboxyl polyurethane masterbatch.

Wherein, described polyethers or polyester diol are selected from polyoxypropyleneglycol (PPG), polytetrahydrofuran diol (PTMG) one, in PCDL (PCDL), polycaprolactone glycol (PCL), number-average molecular weight (Mn) 1000～4000.Described diisocyanate is 2,4 toluene diisocyanate (TDI), hexa-methylene 1,6-bis-isocyanide Acid esters (HDI), 4,4'-methyl diphenylene diisocyanate (MDI), isophorone diisocyanate (IPDI).Described The molal quantity of diisocyanate and polyethers or polyester diol, 2,2-dihydromethyl propionic acid and the total mole number of 1,4-butanediol Ratio be designated as the quality of F-a, polyethers or polyester diol and diisocyanate, 2,2-dihydromethyl propionic acid and BDO The ratio of gross mass be designated as F-b, 2,2-dihydromethyl propionic acids are 1:1 with the ratio of the molal quantity of BDO, N, N-diformazan The quality of base Methanamide is 4:1 with the ratio of the gross mass of other all raw materials, and the quality of dibutyl tin laurate is polyethers The 1% of dihydroxylic alcohols quality, during precipitation, the quality of deionized water used is 2:1 with the mass ratio of DMF, During washing, the quality of deionized water used and the mass ratio of N,N-dimethylformamide are 2:1 every time.

Respectively as shown in table 1 containing side carboxyl polyurethane product code name, raw material and proportioning.

The respectively melt polyurethane Han side carboxyl is processed into sheet material, tests its water contact angle, it appeared that its contact angle is the most relatively low, Carboxyl is contained on illustrative material surface.

Table 1 contains raw material and the consumption of side carboxyl polyurethane

Embodiment 2

To contain side carboxyl polyurethane CPU-1, triphenyl methane-4,4', 4 "-triisocyanate, N,N-dimethylformamide add Enter to container, be stirred at room temperature 30 minutes, obtain subbing, wherein CPU-1 and triphenyl methane-4,4', 4 "- The mass ratio of triisocyanate is 1:1, and DMF quality is the 95wt% of subbing gross mass.To contain Side carboxyl polyurethane CPU-1, polymethyl vinyl ether-maleic anhydride, ethyl acetate add to container, at room temperature Stirring 30 minutes, obtain top coat paint, wherein CPU-1 is 1:8 with the mass ratio of polymethyl vinyl ether-maleic anhydride, Ethyl acetate is the 90wt% of top coat paint gross mass, and polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich is public Department, number-average molecular weight are the product of 80000, triphenyl methane-4,4', and 4 "-triisocyanate is Beyer Co., Ltd Desmodur RE Type product.By the surface of above-mentioned subbing coating to interposing catheter, solidify at 60 DEG C 30 minutes, afterwards will top Coating coats to the conduit having been coated with subbing, solidifies 60 minutes, obtain outer surface and be coated with friendship at 80 DEG C The interposing catheter of connection structure coating, then be dipped in strong aqua ammonia, at room temperature soak 60 minutes, at 60 DEG C after taking-up Under be dried 2 hours, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Interposing catheter lubricity method of testing is as follows: the conduit half length of a length of 20cm coats above-mentioned coating, and Second half length not coating layer, tube at one end is vertically fixed in the lower clamp of stretching-machine, clamps one at catheter surface Self-control slide block, this slide block can be screwed on conduit and give the pressure that conduit is fixing, and the internal interlayer of slide block can carry certain body Long-pending deionized water, can implement to infiltrate continuously to conduit, have the upper clamp of mechanics sensor to press from both sides with connecting in stretching-machine Holding slide block, slide block is pulled to conduit top from conduit bottom according to fixed speed, then the stress change of sensor embodies conduit In the frictional force that two kinds of surfaces are subject to, the difference of friction value reflects the Hydrophilic lubrication of conduit.Record two parts table Friction value corresponding to center, face, then can get the amplitude that water-wetted surface frictional force reduces, be designated as fp-r, fp-r It is worth the biggest, illustrates that lubricity is the best.

Interposing catheter abrasion resistance test method is as follows: load the conduit coating above-mentioned coating to institute in lubricity method of testing On the equipment stated, make slide block up-and-down movement 100 times, record under fixing displacement and speed by programme-control Initial and friction value when terminating, the difference of this friction value reflects degree that coating abrasion comes off and conduit Wearability.The amplitude that frictional force when terminating increases is designated as fp-i, fp-i value the least, illustrates that wearability is the best.

Test result shows, in the present embodiment, conduit friction reduces degree fp-r value is 92.5%, and conduit is rubbed It is 1.7% that rear friction increases degree fp-i value.

Embodiment 3

To add to container containing side carboxyl polyurethane CPU-2, the prepolymer of 2,4 toluene diisocyanate, oxolane, It is stirred at room temperature 30 minutes, obtains subbing, wherein the prepolymer of CPU-2 and 2,4 toluene diisocyanate Mass ratio is 1:3, and oxolane quality is the 80wt% of subbing gross mass.To contain side carboxyl polyurethane CPU-2, Polymethyl vinyl ether-maleic anhydride, dichloromethane add to container, are stirred at room temperature 30 minutes, obtain top layer Coating, wherein CPU-2 is 1:10 with the mass ratio of polymethyl vinyl ether-maleic anhydride, and dichloromethane is top coat paint The 99wt% of gross mass, polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich, number-average molecular weight are The product of 80000, the prepolymer of 2,4 toluene diisocyanate is Beyer Co., Ltd's Desmodur RC type product.By upper State subbing and coat the surface to interposing catheter, solidify at 60 DEG C 30 minutes, afterwards top coat paint is coated to Scribble on the conduit of subbing, solidify 60 minutes at 80 DEG C, obtain outer surface and be coated with Jie of cross-linked structure coating Enter conduit, then be dipped in strong aqua ammonia, at room temperature soak 60 minutes, be dried 2 hours at 60 DEG C after taking-up, Surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 91.2% that wiping power reduces degree fp-r value, and it is 1.5% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 4

Side carboxyl polyurethane CPU-3,2,4 toluene diisocyanate-trimethylolpropane addition product, N-methylpyrrole will be contained Alkanone adds to container, is stirred at room temperature 30 minutes, obtains subbing, wherein CPU-3 and 2,4-toluene two The mass ratio of isocyanates-trimethylolpropane addition product is 1:5, and N-Methyl pyrrolidone quality is subbing gross mass 85wt%.To contain in side carboxyl polyurethane CPU-3, polymethyl vinyl ether-maleic anhydride, acetone addition to container, It is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-3 and the quality of polymethyl vinyl ether-maleic anhydride Ratio is 1:6, and acetone is the 93wt% of top coat paint gross mass, and polymethyl vinyl ether-maleic anhydride is in Sigma's Order Strange company, number-average molecular weight are the product of 80000, and 2,4 toluene diisocyanate-trimethylolpropane addition product is western lattice The product of agate aldrich company.By the surface of above-mentioned subbing coating to interposing catheter, at 60 DEG C, solidify 30 points Clock, afterwards by top coat paint coating to the conduit having been coated with subbing, solidifies 60 minutes, outside obtaining at 80 DEG C Surface is coated with the interposing catheter of cross-linked structure coating, then is dipped in strong aqua ammonia, at room temperature soaks 60 minutes, It is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 91.6% that wiping power reduces degree fp-r value, and it is 1.3% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 5

To add to container containing side carboxyl polyurethane CPU-4, the prepolymer of isophorone diisocyanate, butanone, Stir 30 minutes under room temperature, obtain subbing, wherein the matter of the prepolymer of CPU-4 and isophorone diisocyanate Amount ratio is 1:7, and butanone quality is the 90wt% of subbing gross mass.Side carboxyl polyurethane CPU-4, poly-methyl will be contained Vinyl ether-maleic acid, N, N-dimethyl sulfoxide adds to container, is stirred at room temperature 30 minutes, obtains top layer Coating, wherein CPU-4 is 1:4 with the mass ratio of polymethyl vinyl ether-maleic anhydride, and N, N-dimethyl sulfoxide is top layer The 83wt% of coating gross mass, polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, number-average molecular weight Being the product of 80000, the prepolymer of isophorone diisocyanate is Beyer Co., Ltd's Desmodur Z4470 MPA/X type Number product.By the surface of above-mentioned subbing coating to interposing catheter, solidify 30 minutes at 60 DEG C, afterwards by top layer Coating coats to the conduit having been coated with subbing, solidifies 60 minutes, obtain outer surface and be coated with crosslinking at 80 DEG C The interposing catheter of structure coating, then be dipped in strong aqua ammonia, at room temperature soak 60 minutes, at 60 DEG C after taking-up Under be dried 2 hours, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 90.5% that wiping power reduces degree fp-r value, and it is 1.6% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 6

To add to holding containing side carboxyl polyurethane CPU-5, the prepolymer of hexa-methylene 1,6-diisocyanate, chloroform In device, it is stirred at room temperature 30 minutes, obtains subbing, wherein CPU-5 and hexa-methylene 1,6-diisocyanate The mass ratio of prepolymer be 1:10, chloroform quality is the 98wt% of subbing gross mass.The poly-ammonia of side carboxyl will be contained Ester CPU-5, polymethyl vinyl ether-maleic anhydride, butyl acetate add to container, are stirred at room temperature 30 minutes, Obtaining top coat paint, wherein CPU-5 is 1:2 with the mass ratio of polymethyl vinyl ether-maleic anhydride, and butyl acetate is top The 80wt% of coating gross mass, polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, the equal molecule of number Amount is the product of 80000, hexa-methylene 1, and the prepolymer of 6-diisocyanate is Beyer Co., Ltd's Desmodur N3300 type Number product.By the surface of above-mentioned subbing coating to interposing catheter, solidify 30 minutes at 60 DEG C, afterwards by top layer Coating coats to the conduit having been coated with subbing, solidifies 60 minutes, obtain outer surface and be coated with crosslinking at 80 DEG C The interposing catheter of structure coating, then be dipped in strong aqua ammonia, at room temperature soak 60 minutes, at 60 DEG C after taking-up Under be dried 2 hours, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 91.6% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 7

By the prepolymer containing side carboxyl polyurethane CPU-6,4,4'-methyl diphenylene diisocyanate, N, N-dimethylacetamide Amine adds to container, is stirred at room temperature 30 minutes, obtains subbing, wherein CPU-6 and 4,4'-diphenylmethyl The mass ratio of the prepolymer of alkane diisocyanate is 1:0.1, and N,N-dimethylacetamide quality is subbing gross mass 83wt%.To contain in side carboxyl polyurethane CPU-6, polymethyl vinyl ether-maleic anhydride, oxolane addition to container, It is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-6 and the quality of polymethyl vinyl ether-maleic anhydride Ratio is 1:0.8, and oxolane is the 86wt% of top coat paint gross mass, and polymethyl vinyl ether-maleic anhydride is Sigma Aldrich company, number-average molecular weight are the product of 80000, and the prepolymer of 4,4'-methyl diphenylene diisocyanates is for visiing Ear company Desmodur E21 type product.By the surface of above-mentioned subbing coating to interposing catheter, solid at 60 DEG C Change 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, solidify 60 minutes at 80 DEG C, Obtain outer surface and be coated with the interposing catheter of cross-linked structure coating, then be dipped in strong aqua ammonia, at room temperature soak 60 Minute, it is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 90.1% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 8

To contain side carboxyl polyurethane CPU-7,4,4'-methyl diphenylene diisocyanate, acetone add in container, in room The lower stirring of temperature 30 minutes, obtains subbing, wherein CPU-7 and 4, the mass ratio of 4'-methyl diphenylene diisocyanate For 1:0.3, acetone quality is the 99wt% of subbing gross mass.Side carboxyl polyurethane CPU-7, poly-methyl second will be contained Alkene ether-maleic anhydride, DMF add to container, are stirred at room temperature 30 minutes, obtain top layer Coating, wherein CPU-7 is 1:0.5 with the mass ratio of polymethyl vinyl ether-maleic anhydride, and DMF is The 97wt% of top coat paint gross mass, polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich, counts and divide equally Son amount is the product of 80000, and 4,4'-methyl diphenylene diisocyanates are the product of Sigma-Aldrich.By upper State subbing and coat the surface to interposing catheter, solidify at 60 DEG C 30 minutes, afterwards top coat paint is coated to Scribble on the conduit of subbing, solidify 60 minutes at 80 DEG C, obtain outer surface and be coated with Jie of cross-linked structure coating Enter conduit, then be dipped in strong aqua ammonia, at room temperature soak 60 minutes, be dried 2 hours at 60 DEG C after taking-up, Surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 90.4% that wiping power reduces degree fp-r value, and it is 1.8% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 9

Side carboxyl polyurethane CPU-8, tri o cresyl thiophosphate phenyl isocyanate, the addition of N, N-dimethyl sulfoxide will be contained to container In, it is stirred at room temperature 30 minutes, obtains subbing, wherein CPU-8 and tri o cresyl thiophosphate phenyl isocyanate Mass ratio is 1:0.5, and N, N-dimethyl sulfoxide quality is the 93wt% of subbing gross mass.Side carboxyl polyurethane will be contained CPU-8, polymethyl vinyl ether-maleic anhydride, N, N-dimethyl sulfoxide add to container, are stirred at room temperature 30 Minute, obtain top coat paint, wherein CPU-8 is 1:0.1 with the mass ratio of polymethyl vinyl ether-maleic anhydride, N, N- Dimethyl sulfoxide is the 88wt% of top coat paint gross mass, and polymethyl vinyl ether-maleic anhydride is Sigma-Aldrich Company, number-average molecular weight are the product of 80000, and tri o cresyl thiophosphate phenyl isocyanate is Sigma-Aldrich Product.By the surface of above-mentioned subbing coating to interposing catheter, solidify at 60 DEG C 30 minutes, afterwards top layer is coated with Material coats to the conduit having been coated with subbing, solidifies 60 minutes at 80 DEG C, obtains outer surface and is coated with crosslinking knot The interposing catheter of structure coating, then be dipped in strong aqua ammonia, at room temperature soak 60 minutes, after taking-up at 60 DEG C It is dried 2 hours, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 90.2% that wiping power reduces degree fp-r value, and it is 1.9% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 10

To contain in side carboxyl polyurethane CPU-6,2,4 toluene diisocyanate, chloroform addition to container, in room temperature Lower stirring 30 minutes, obtains subbing, and wherein CPU-6 is 1:0.7 with the mass ratio of 2,4 toluene diisocyanate, Chloroform quality is the 88wt% of subbing gross mass.Side carboxyl polyurethane CPU-6, polymethyl vinyl ether will be contained -maleic anhydride, butyl acetate add to container, are stirred at room temperature 30 minutes, obtain top coat paint, wherein CPU-6 Being 1:0.3 with the mass ratio of polymethyl vinyl ether-maleic anhydride, butyl acetate is the 95wt% of top coat paint gross mass, Polymethyl vinyl ether-maleic anhydride be Sigma-Aldrich, number-average molecular weight be the product of 80000,2,4-first Phenylene diisocyanate is the product of Sigma-Aldrich.By the surface of above-mentioned subbing coating to interposing catheter, Solidify at 60 DEG C 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, solid at 80 DEG C Change 60 minutes, obtain outer surface and be coated with the interposing catheter of cross-linked structure coating, then be dipped in strong aqua ammonia, Soak 60 minutes under room temperature, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived and there is the intervention of Hydrophilic lubrication lead Pipe.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 90.7% that wiping power reduces degree fp-r value, and it is 1.7% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 11

To contain side carboxyl polyurethane CPU-4, hexa-methylene 1,6-diisocyanate, butanone add to container, in room temperature Lower stirring 30 minutes, obtains subbing, wherein CPU-4 and hexa-methylene 1, and the mass ratio of 6-diisocyanate is 1:2, Butanone quality is the 97wt% of subbing gross mass.Side carboxyl polyurethane CPU-4, polymethyl vinyl ether-horse will be contained Carry out anhydride, ethyl acetate adds to container, is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-4 Being 1:9 with the mass ratio of polymethyl vinyl ether-maleic anhydride, ethyl acetate is the 98wt% of top coat paint gross mass, poly- Methyl vinyl ether-maleic acid be Sigma-Aldrich, number-average molecular weight be the product of 80000, six methylenes Base 1,6-diisocyanate is the product of Sigma-Aldrich.Table by above-mentioned subbing coating to interposing catheter Face, solidifies 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, in 80 DEG C at 60 DEG C Lower solidification 60 minutes, obtains outer surface and is coated with the interposing catheter of cross-linked structure coating, then be dipped in strong aqua ammonia, At room temperature soak 60 minutes, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the intervention of Hydrophilic lubrication Conduit.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 93.2% that wiping power reduces degree fp-r value, and it is 1.5% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 12

To contain in side carboxyl polyurethane CPU-2, isophorone diisocyanate, butanone addition to container, at room temperature stir Mixing 30 minutes, obtain subbing, wherein CPU-2 is 1:2 with the mass ratio of isophorone diisocyanate, butanone Quality is the 97wt% of subbing gross mass.Side carboxyl polyurethane CPU-2, polymethyl vinyl ether-maleic acid will be contained Acid anhydride, butanone add to container, are stirred at room temperature 30 minutes, obtain top coat paint, wherein CPU-2 and poly-methyl The mass ratio of vinyl ether-maleic acid is 1:9, and butanone is the 98wt% of top coat paint gross mass, polymethyl vinyl ether -maleic anhydride be Sigma-Aldrich, number-average molecular weight be the product of 80000, isophorone diisocyanate Product for Sigma-Aldrich.By the surface of above-mentioned subbing coating to interposing catheter, solidify at 60 DEG C 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, solidify 60 minutes at 80 DEG C, It is coated with the interposing catheter of cross-linked structure coating to outer surface, then is dipped in strong aqua ammonia, at room temperature soak 60 Minute, it is dried 2 hours at 60 DEG C after taking-up, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 93% that wiping power reduces degree fp-r value, and it is 1.6% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 13

To contain side carboxyl polyurethane CPU-1,4,4'-methyl diphenylene diisocyanate, butanone add in container, in room The lower stirring of temperature 30 minutes, obtains subbing, wherein CPU-1 and 4, the mass ratio of 4'-methyl diphenylene diisocyanate For 1:2, butanone quality is the 95wt% of subbing gross mass.Side carboxyl polyurethane CPU-2, poly-ethylene methacrylic will be contained Base ether-maleic anhydride, butanone add to container, are stirred at room temperature 30 minutes, obtain top coat paint, wherein CPU-1 Being 1:8 with the mass ratio of polymethyl vinyl ether-maleic anhydride, butanone is the 95wt% of top coat paint gross mass, poly-methyl Vinyl ether-maleic acid be Sigma-Aldrich, number-average molecular weight be the product of 80000,4,4'-diphenylmethyls Alkane diisocyanate is the product of Sigma-Aldrich.By the surface of above-mentioned subbing coating to interposing catheter, Solidify at 60 DEG C 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, solid at 80 DEG C Change 60 minutes, obtain outer surface and be coated with the interposing catheter of cross-linked structure coating, then be dipped in strong aqua ammonia, Soak 60 minutes under room temperature, be dried 2 hours at 60 DEG C after taking-up, surface must be arrived and there is the intervention of Hydrophilic lubrication lead Pipe.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 93.1% that wiping power reduces degree fp-r value, and it is 1.3% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 14

Side carboxyl polyurethane CPU-3,4,4'-methyl diphenylene diisocyanate, butanone and ethyl acetate will be contained add to holding In device, it is stirred at room temperature 30 minutes, obtains subbing, wherein CPU-1 and 4,4'-diphenylmethane diisocyanate The mass ratio of ester is 1:2, and butanone quality is the 65wt% of subbing gross mass, and ethyl acetate quality is that subbing is total The 30wt% of quality.Side carboxyl polyurethane CPU-3, polymethyl vinyl ether-maleic anhydride, butanone and acetic acid second will be contained Ester adds to container, is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-3 and poly-methyl ethylene The mass ratio of ether-maleic anhydride is 1:8, and butanone is the 55wt% of top coat paint gross mass, and ethyl acetate quality is that top layer is coated with The 40wt% of material gross mass, polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich, number-average molecular weight are The product of 80000,4,4'-methyl diphenylene diisocyanates are the product of Sigma-Aldrich.By above-mentioned bottom Coating coating, to the surface of interposing catheter, solidifies at 60 DEG C 30 minutes, coats top coat paint to having been coated with the end afterwards On the conduit of coating, solidify 60 minutes at 80 DEG C, obtain outer surface and be coated with the interposing catheter of cross-linked structure coating, It is dipped in again to strong aqua ammonia, at room temperature soaks 60 minutes, be dried 2 hours at 60 DEG C after taking-up, obtain table Mask has the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 93.4% that wiping power reduces degree fp-r value, and it is 1.4% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 15

By containing side carboxyl polyurethane CPU-5,4,4'-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate pre- Polymers, acetone and DMF add to container, are stirred at room temperature 30 minutes, obtain subbing, The wherein mass ratio of the prepolymer three of CPU-5,4,4'-methyl diphenylene diisocyanate and 2,4 toluene diisocyanate For 1:1:1, acetone quality is the 75wt% of subbing gross mass, and DMF quality is that subbing is total The 20wt% of quality.Side carboxyl polyurethane CPU-5, polymethyl vinyl ether-maleic anhydride, acetone and N, N-bis-will be contained Methylformamide adds to container, is stirred at room temperature 30 minutes, obtains top coat paint, wherein CPU-5 and poly-first The mass ratio of base vinyl ether-maleic acid is 1:8, and acetone is the 55wt% of top coat paint gross mass, N, N-dimethyl methyl Amide quality is the 40wt% of top coat paint gross mass, and polymethyl vinyl ether-maleic anhydride is that Sigma-Aldrich is public Department, number-average molecular weight are the product of 80000, and 4,4'-methyl diphenylene diisocyanates are Sigma-Aldrich Product, the prepolymer of 2,4 toluene diisocyanate is Beyer Co., Ltd's Desmodur RC type product.Above-mentioned bottom is coated with Material coating, to the surface of interposing catheter, solidifies at 60 DEG C 30 minutes, coats top coat paint to having been coated with bottom afterwards On the conduit of coating, solidify 60 minutes at 80 DEG C, obtain outer surface and be coated with the interposing catheter of cross-linked structure coating, It is dipped in again to strong aqua ammonia, at room temperature soaks 60 minutes, be dried 2 hours at 60 DEG C after taking-up, obtain table Mask has the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 92.1% that wiping power reduces degree fp-r value, and it is 1.5% that the rubbed rear friction of conduit increases degree fp-i value.

Embodiment 16

By containing side carboxyl polyurethane CPU-7,4,4'-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate pre- Polymers, triphenyl methane-4,4', 4 "-triisocyanate, oxolane and dichloromethane add to container, at room temperature stir Mix 30 minutes, obtain subbing, wherein CPU-7,4,4'-methyl diphenylene diisocyanate, 2,4-toluene diisocyanate The prepolymer of acid esters and triphenyl methane-4,4', 4 " mass ratio of-triisocyanate is 1:1:0.5:0.5, oxolane matter Amount is the 50wt% of subbing gross mass, and dichloromethane quality is the 45wt% of subbing gross mass.Side carboxyl will be contained Polyurethane CPU-7, polymethyl vinyl ether-maleic anhydride, chloroform and butyl acetate add to container, in room The lower stirring of temperature 30 minutes, obtains top coat paint, and wherein CPU-7 with the mass ratio of polymethyl vinyl ether-maleic anhydride is 1:8, chloroform is the 50wt% of top coat paint gross mass, and butyl acetate quality is the 45wt% of top coat paint gross mass, Polymethyl vinyl ether-maleic anhydride be Sigma-Aldrich, number-average molecular weight be the product of 80000,4,4'- Methyl diphenylene diisocyanate is the product of Sigma-Aldrich, and the prepolymer of 2,4 toluene diisocyanate is Beyer Co., Ltd's Desmodur RC type product, triphenyl methane-4,4', 4 "-triisocyanate is Beyer Co., Ltd Desmodur RE type product.By the surface of above-mentioned subbing coating to interposing catheter, solidify at 60 DEG C 30 minutes, afterwards will Top coat paint coats to the conduit having been coated with subbing, solidifies 60 minutes, obtain outer surface and be coated with at 80 DEG C The interposing catheter of cross-linked structure coating, then be dipped in strong aqua ammonia, at room temperature soaks 60 minutes, after taking-up It is dried 2 hours at 60 DEG C, surface must be arrived there is the interposing catheter of Hydrophilic lubrication.

Lubricity and abrasion resistance test method are same as in Example 2, and test result shows, rub in the present embodiment suffered by conduit It is 94% that wiping power reduces degree fp-r value, and it is 1.3% that the rubbed rear friction of conduit increases degree fp-i value.

Claims (9)

1. the coating for hydrophilic lubrication interposing catheter, it is characterised in that coating comprises subbing and top layer is coated with Material, described subbing is formed by containing side carboxyl polyurethane, polyisocyanate curing agent and organic solvent, wherein containing side Carboxyl polyurethane is 1:(0.1～10 with the mass ratio of polyisocyanate curing agent), the quality of organic solvent is that subbing is total 80wt%～99wt% of quality, described top coat paint is by containing side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride Forming with organic solvent, wherein the mass ratio containing side carboxyl polyurethane with polymethyl vinyl ether-maleic anhydride is 1:(0.1～10), the quality of organic solvent is 80wt%～99wt% of top coat paint gross mass.

Coating for hydrophilic lubrication interposing catheter the most according to claim 1, it is characterised in that described contains The molecular chain structure of side carboxyl polyurethane be by polyethers or polyester diol, diisocyanate, 2,2-dihydromethyl propionic acid and BDO is connected through additive reaction, and described polyethers or polyester diol are polyoxypropyleneglycol, poly-tetrahydrochysene furan Mutter the one in glycol, PCDL, polycaprolactone glycol, number-average molecular weight 1000～4000, described two Isocyanates is 2,4 toluene diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-diphenylmethane diisocyanate One in ester, isophorone diisocyanate.

Coating for hydrophilic lubrication interposing catheter the most according to claim 1, it is characterised in that described many Isocyanate curing agent is 2,4 toluene diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-diphenyl methane two Isocyanates, isophorone diisocyanate, the prepolymer of 2,4 toluene diisocyanate, hexa-methylene 1,6-bis-isocyanide The prepolymer of acid esters, the prepolymer of isophorone diisocyanate, the prepolymer of 4,4'-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate-trimethylolpropane addition product, triphenyl methane-4,4', 4 "-triisocyanate, tri o cresyl thiophosphates One or more in phenyl isocyanate.

Coating for hydrophilic lubrication interposing catheter the most according to claim 1, it is characterised in that described has Machine solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl sulfoxide, One or more in ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, oxolane.

5. a preparation method for the coating for hydrophilic lubrication interposing catheter according to claim 1, its feature It is, comprises the steps:

(1) preparation containing side carboxyl polyurethane: use solvent method synthesis polyurethane Han side carboxyl, by polyethers or polyester two Unit's alcohol and diisocyanate add in reactor, are warming up to 80 DEG C, and stirring reaction obtained performed polymer after 2 hours, added 2,2-dihydromethyl propionic acids and BDO, after reacting 1 hour, add DMF, continue reaction 1 After hour, add dibutyl tin laurate, then react 12 hours, be down to room temperature, pour solution in reactor into dress Have in the container of deionized water, have white depositions to separate out, collect precipitate and be washed with deionized 3 times, being positioned over In vacuum drying oven, it is vacuum dried 48 hours at 90 DEG C, obtains transparent cake product, contained after its pelletize Side carboxyl polyurethane masterbatch, wherein, the molal quantity of described diisocyanate and polyethers or polyester diol, 2,2-dihydroxy first The ratio of the total mole number of base propanoic acid and BDO is (1.05～1.2): 1,2,2-dihydromethyl propionic acid rubs with BDO The quality that ratio is 1:1, polyethers or polyester diol of your number and diisocyanate, 2,2-dihydromethyl propionic acid and Isosorbide-5-Nitrae-fourth two The ratio of the gross mass of alcohol is (1.5～1): 1, and the quality of DMF with the ratio of the gross mass of other all raw materials is 4:1, the quality of dibutyl tin laurate is polyethers or the 1% of polyester diol quality, deionized water used during precipitation The mass ratio of quality and DMF is 2:1, every time the quality of deionized water used and N, N-during washing The mass ratio of dimethylformamide is 2:1；

(2) preparation of subbing: side carboxyl polyurethane, polyisocyanate curing agent, organic solvent addition will be contained extremely In container, it is stirred at room temperature 30 minutes, obtains subbing, wherein solid with polyisocyanates containing side carboxyl polyurethane The mass ratio of agent is 1:(0.1～10), the quality of organic solvent is 80wt%～99wt% of subbing gross mass；

(3) preparation of top coat paint: side carboxyl polyurethane, polymethyl vinyl ether-maleic anhydride, organic solvent will be contained Add to container, be stirred at room temperature 30 minutes, obtain top coat paint, wherein containing side carboxyl polyurethane and poly-methyl The mass ratio of vinyl ether-maleic acid is 1:(0.1～10), the quality of organic solvent be top coat paint gross mass 80wt～ 99wt%.

The preparation method of the coating for hydrophilic lubrication interposing catheter the most according to claim 5, it is characterised in that Polyethers described in step (1) or polyester diol are polyoxypropyleneglycol, polytetrahydrofuran diol, Merlon One in glycol, polycaprolactone glycol, number-average molecular weight is 1000～4000, and described diisocyanate is 2,4-first Phenylene diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone two are different One in cyanate.

The preparation method of the coating for hydrophilic lubrication interposing catheter the most according to claim 5, it is characterised in that Polyisocyanate curing agent described in step (2) be 2,4 toluene diisocyanate, hexa-methylene 1,6-diisocyanate, 4,4'-methyl diphenylene diisocyanate, isophorone diisocyanate, the prepolymer of 2,4 toluene diisocyanate, six The prepolymer of methylene 1,6-diisocyanate, the prepolymer of isophorone diisocyanate, 4,4'-diphenyl methane two are different The prepolymer of cyanate, 2,4 toluene diisocyanate-trimethylolpropane addition product, triphenyl methane-4,4', 4 "-three isocyanides One or more in acid esters, tri o cresyl thiophosphate phenyl isocyanate.

The preparation method of the coating for hydrophilic lubrication interposing catheter the most according to claim 5, it is characterised in that Organic solvent described in step (2) and step (3) be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N, N-dimethyl sulfoxide, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, One or more in butanone, oxolane.

9. a using method for the coating for hydrophilic lubrication interposing catheter according to claim 1, its feature It is, comprises the steps:

(1) coating coating processing: by subbing by dip-coating, spray or brush in the way of coat the table to interposing catheter Face, solidifies 30 minutes, afterwards by top coat paint coating to the conduit having been coated with subbing, in 80 DEG C at 60 DEG C Lower solidification 60 minutes, obtains outer surface and is coated with the interposing catheter of cross-linked structure coating；

(2) coating hydrophilic processes: immersed to strong aqua ammonia by the interposing catheter processed in step (1), in room temperature Lower immersion 60 minutes, is dried 2 hours at 60 DEG C after taking-up, must arrive surface and have Jie of hydrophilic cross-linking structure coating Enter conduit.