WO2020024763A1 - 可光固化的亲水聚合物、基于其的涂料组合物及亲水润滑涂层和制品 - Google Patents

可光固化的亲水聚合物、基于其的涂料组合物及亲水润滑涂层和制品 Download PDF

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WO2020024763A1
WO2020024763A1 PCT/CN2019/094679 CN2019094679W WO2020024763A1 WO 2020024763 A1 WO2020024763 A1 WO 2020024763A1 CN 2019094679 W CN2019094679 W CN 2019094679W WO 2020024763 A1 WO2020024763 A1 WO 2020024763A1
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Prior art keywords
hydrophilic
coating
hydrophilic polymer
photocurable
monomer
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PCT/CN2019/094679
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English (en)
French (fr)
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唐增超
雷杰华
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江苏百赛飞生物科技有限公司
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Priority to US17/265,009 priority Critical patent/US20210309781A1/en
Priority to EP19843268.4A priority patent/EP3819288A4/en
Publication of WO2020024763A1 publication Critical patent/WO2020024763A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/10—Materials for lubricating medical devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate

Definitions

  • the present invention belongs to the field of photo-curing technology, and particularly relates to photo-curable hydrophilic polymers and coating compositions based thereon, and also relates to the field of hydrophilic lubricating coatings, which are used in medical devices such as catheters / Guide wire.
  • interventional medical devices such as cardiovascular system guidewires / catheters, urinary system catheters, and digestive system catheters
  • cardiovascular system guidewires / catheters urinary system catheters
  • digestive system catheters need to be inserted into the patient's body when in use, and in direct contact with the patient's tissues.
  • untreated guidewires / catheters the surface smoothness is usually low, and there will be greater resistance when inserting or removing the body, which will easily cause discomfort and tissue damage to the patient, and at the same time make it inconvenient for medical staff to operate.
  • Proper lubrication technology needs to be developed to improve the surface lubrication of medical guidewires / catheters.
  • the commonly used lubrication method is to apply a lubricant (such as paraffin oil, silicone oil, vaseline, etc.) before the guidewire / catheter is used.
  • a lubricant such as paraffin oil, silicone oil, vaseline, etc.
  • the catheter because the lubricant cannot be stabilized on the surface of the catheter, it is still easy to cause damage to the tissue.
  • Some researchers have covered the catheter with materials such as perfluoroethylene propylene to improve the lubricity of the catheter to a certain extent, but the lubricity of the catheter with such coatings is still insufficient to avoid damage to the body. Therefore, some researchers have devoted themselves to researching the method of forming a more lubricious hydrophilic coating on the surface of a guide wire / catheter.
  • Patent Document 1 discloses a method for preparing a composition containing a hydrophilic polymer, a polyelectrolyte, a photoinitiator, and a carrier liquid.
  • the composition can form a lubricating coating under ultraviolet light treatment conditions.
  • no effective cross-linking component is added to the composition, which is likely to cause insufficient cross-linking and a weak coating.
  • the system uses a small molecular photoinitiator with problems such as odor and easy migration of debris. Reduce the biological safety of the coating and affect the overall performance.
  • Patent Document 2 discloses a hydrophilic coating containing a polyelectrolyte.
  • a clear cross-linking component polyethylene glycol diacrylate is added to the composition, and the degree of cross-linking and firmness of the coating is guaranteed, but the system Small-molecule photoinitiators are still used, and there is still the problem that small molecules and fragments are easy to migrate out of the coating.
  • Patent Document 3 discloses a method for preparing and using a photoactive hydrophilic resin and a photoactive hydrophilic crosslinker coating, which polymerizes a small-molecule photoinitiator and a hydrophilic monomer, effectively It can prevent the residual and migration of small molecule initiator, and at the same time enhance the coating's firmness, which can meet the requirements of fifteen cycles of friction test.
  • this system needs to copolymerize a certain amount of cross-linking agent with hydrophilic monomers and small-molecule photoinitiators. Theoretically, there is a problem that a gel is easily generated during the polymerization process.
  • Patent Document 4 discloses a hydrophilic coating containing a copolymer of N-vinylpyrrolidone and a benzophenone vinyl monomer, and the hydrophilic coating has a friction coefficient of not more than 0.2.
  • the copolymer covalently binds a small molecule benzophenone initiator to a polymer chain, effectively avoiding the migration of small molecules.
  • the benzophenone vinyl monomer used in this copolymer is a (meth) acrylate group directly connected to the benzophenone group, the molecular chain length is short, and free radicals are not easy to collide; at the same time, the molecular chain is not It has obvious initiator structure and relatively low initiation efficiency.
  • Patent Document 1 CN102947376B
  • Patent Document 2 CN101365501B
  • Patent Document 3 CN105732848A
  • Patent Document 4 CN103209717A
  • the present invention provides a photocurable hydrophilic polymer and a coating composition based thereon.
  • the photo-curable hydrophilic polymer has high photo-curing efficiency, simple preparation method, high production efficiency, less environmental pollution, and basically no problem of gel generation.
  • a hydrophilic coating having high fastness, high lubricity, and excellent biological safety and compatibility can be obtained.
  • the present invention also provides a hydrophilic lubricating coating obtained from the aforementioned coating composition and an article thereof such as a medical device.
  • the present invention provides a photocurable hydrophilic polymer, which is formed by copolymerizing a polymerizable photosensitive monomer and a hydrophilic monomer;
  • the polymerizable photosensitive monomer contains: 1) a photosensitive structure 2) a unit containing a co-initiator tertiary amine structure; 3) a unit containing an unsaturated bond structure;
  • the units containing the photosensitive structure are connected.
  • the polymerizable photosensitive monomer has a structure of the general formula (I):
  • n is an integer of 1-20, preferably 1 or 2;
  • R 1 0 or NR, and R is H, a linear alkyl group having 1 to 20 C atoms or a branched chain alkyl group having 3 to 20 C atoms
  • R 2 H, a linear alkyl group having 1 to 20 C atoms or a branched alkyl group having 3 to 20 C atoms.
  • the hydrophilic monomer includes unsaturated carboxylic acid or carboxylate, unsaturated carboxylic acid ester, unsaturated acid hydroxyalkyl ester, unsaturated acid polyether ester, unsaturated acid anhydride, unsaturated amide, unsaturated One or more of a saturated lactam and an alkylene oxide; preferably, the hydrophilic monomer is selected from (meth) acrylic acid, (meth) acrylamide, vinylpyrrolidone, hydroxyethyl (meth) acrylate ( One or more of: c) ester, polyethylene glycol methyl ether (meth) acrylate, dimethylacrylamide; more preferably, the hydrophilic monomer is selected from polyethylene glycol methyl ether acrylate.
  • the molar fraction of the polymerizable photosensitive monomer in the hydrophilic polymer is 0.05-10%, preferably 0.5-5%, and still more preferably 0.8-1.5%.
  • the number-average molecular weight of the photocurable hydrophilic polymer ranges from 0.2 to 1.5 million, preferably from 5 to 600,000, and even more preferably from 15 to 300,000.
  • a coating composition including:
  • the photocurable hydrophilic polymer according to the present invention has a mass fraction of 0.1-20%, preferably 1-10%, and more preferably 3-5% based on the total amount of the coating composition;
  • the solvent has a mass fraction of 60-99.9%, preferably 90-99%, and more preferably 95-98%.
  • the solvent includes one or more of water, a low molecular weight alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetone, and phenol, preferably Preferably, the solvent is a mixture of water and ethanol, and more preferably, the volume ratio of water to ethanol is 2: 3-3: 2.
  • the present invention provides a hydrophilic lubricating coating, which is obtained by curing the above coating composition.
  • the present invention provides an article such as a medical device comprising at least one layer of a hydrophilic lubricating coating as described above.
  • the present invention has the following beneficial effects:
  • the present invention uses a new polymerizable photosensitive monomer having a longer linking chain and a co-initiated tertiary amine structure to prepare a photocurable hydrophilic polymer that is cured by ultraviolet light. High, strong glue.
  • the photocurable hydrophilic polymer in the present invention is simple to synthesize, the reaction conditions are easy to control, and there is basically no gelation.
  • the present invention is based on the curable polymer to obtain a coating composition for the preparation of a photocurable hydrophilic lubricating coating.
  • the photocurable polymer used in the present invention contains a photosensitive structural unit, so there is no need to add a small molecular photoinitiator in the coating composition, which can overcome the problems of residual and migration of the small molecular photoinitiator in the coating, and has excellent biological safety and compatibility. , Suitable for the medical field.
  • the coating composition can form a uniform and stable hydrophilic lubricating coating through a simple continuous dip coating-light curing process. After coating it on the surface of medical equipment, the touch feels very lubricated after wetting, in a simulated human tissue environment Repeated rubbing 30 times, the coating did not fall off, the lubricity did not decrease, and the coating was firm.
  • the present invention regulates the types of hydrophilic monomers, the molar ratio of polymerizable photosensitive monomers to hydrophilic monomers, and the molecular weight of photocurable hydrophilic polymers, and finds that the effect for the preparation of hydrophilic coatings is optimal. polymer.
  • a hydrophilic coating with high firmness and high lubricity is prepared by selecting the type and content of each component of the coating composition.
  • the meaning of the term "monomer” in the present invention is any chemical that can be characterized by a chemical formula with a polymerizable group (including (meth) acrylate groups) capable of polymerizing into an oligomer or polymer to increase molecular weight. substance.
  • the molecular weight of a monomer can usually be calculated simply from the given chemical formula.
  • a portion of a molecule when a portion of a molecule is described as “optionally substituted” or “substituted”, this means that the portion may be substituted with one or more substituents selected from the group consisting of: C 1 -C 6 linear, Branched or cyclic alkyl, aryl, -OH, -CN, halogen, amine, amide, alcohol, ether, thioether, sulfone and its derivative, sulfoxide and its derivative, carbonate, isocyanate, nitrate And acrylate.
  • substituents selected from the group consisting of: C 1 -C 6 linear, Branched or cyclic alkyl, aryl, -OH, -CN, halogen, amine, amide, alcohol, ether, thioether, sulfone and its derivative, sulfoxide and its derivative, carbonate, isocyanate, nitrate And acrylate.
  • unit in the present invention includes not only functional groups (such as photoactive groups, quaternary ammonium salt groups, unsaturated groups), but also additional chemical groups that have less influence on the functional groups.
  • functional groups such as photoactive groups, quaternary ammonium salt groups, unsaturated groups
  • additional chemical groups that have less influence on the functional groups.
  • Groups such as alkyl, alkylene, and the like.
  • the term "polymer” refers to a molecule containing two or more repeating units. Specifically, the polymer may be formed of two or more same or different monomers. When used in the present invention, the The term also includes oligomers or prepolymers.
  • the term "molecular weight” means number average molecular weight (M n), M n is defined by light scattering (SEC optionally in combination with size exclusion chromatography) measurement M n.
  • curing is understood in the present invention to mean physical or chemical hardening or solidification by any method such as heating, cooling, drying, crystallization, or solidification by a chemical reaction, such as radiation curing, thermal curing or addition of curing molecules Initiator curing.
  • the term "photocuring" can be achieved in an exemplary manner in which a photo-initiated process occurs through irradiation with light having a wavelength ranging from 100 nm to 600 nm or UV irradiation.
  • Possible sources of illumination are sunlight or artificial lights or lasers.
  • high-, medium- or low-pressure mercury lamps and xenon and tungsten lamps are advantageous.
  • excimer, solid-state, and diode-based lasers are advantageous. Diode-based light sources are often good for initiating chemical reactions.
  • a first embodiment of the present invention provides a photocurable hydrophilic polymer, which is formed by copolymerizing a polymerizable photosensitive monomer and a hydrophilic monomer, and the photosensitive structural unit can be used as a macromolecular photoinitiator. Therefore, when it is formulated into a coating composition, it is not necessary to add a small molecule photoinitiator, which can overcome the problems such as the residual and migration of the small molecule photoinitiator in the coating, and has excellent biological safety and compatibility, and is suitable for medical treatment. field.
  • the polymerizable photosensitive monomer contains: the polymerizable photosensitive monomer contains: 1) a unit containing a photosensitive structure; 2) a unit containing a co-initiator tertiary amine structure; 3) a unit containing an unsaturated bond structure; and the photosensitive unit
  • the units are connected.
  • the photosensitive structure-containing unit of the present invention is derived from an aryl ketone type photoinitiator structure, which includes a carbonyl functional group and one or more aromatic rings.
  • the aryl ketone type structure may further include a sulfur atom and contain a photosensitive
  • the structural units may be derived from, but not exclusively limited to, substituted or substituted benzophenones, acetophenones, thioxanthone, xanthone, fluorenone and derivatives thereof.
  • the unit typically containing a photosensitive structure may be a benzophenone having the general formula (II):
  • Ar 1 and Ar 2 are independently selected from the same or different optionally substituted aryl groups, wherein the wavy line indicates that they are connected to a structural unit containing a co-initiator tertiary amine through a linking group.
  • both Ar 1 and Ar 2 may be optionally substituted phenyl, further preferably both phenyl.
  • the structural unit containing the co-initiator tertiary amine is preferably present in the para position of Ar 2 because this provides the greatest opportunity for electronic interaction with the carbonyl group and therefore the maximum stabilization of the formation of free radicals.
  • the inventors of the present invention have found that when a benzophenone unit is used as the photosensitive structural unit of the present invention, a better photo-initiating efficiency can be achieved than a small molecule photosensitizer or a combination thereof.
  • the unsaturated bond-containing unit contained in the polymerizable photosensitive monomer may be a polymerizable group containing a double bond.
  • a reactive group can cause the photosensitive structural unit to be incorporated into the polymer's main chain in the form of a repeating unit by means of radical polymerization.
  • the unit containing an unsaturated bond may be selected from units having a (meth) acryloyl group.
  • the unit may be a (meth) acrylic acid ester or a (meth) acrylamide.
  • the presence of polymerizable groups can overcome the problems of toxicity and high mobility of conventional small-molecule photoinitiators, promote photoinitiators to be anchored in the polymer network, and also improve material properties by copolymerizing with other monomers, while inhibiting Unwanted volatility caused by small molecule photoinitiator residues.
  • the unit containing a co-initiator tertiary amine structure includes a tertiary amine group, and may further include several alkylene groups.
  • tertiary amines Under UV irradiation, tertiary amines have the ability to take protons from carbon atoms adjacent to the amino nitrogen, which can effectively act as H donors for reactive functional groups, which can produce reactive groups that can initiate polymerization or cross-linking.
  • the units of the photosensitive structure are connected.
  • the nitrogen atom in the tertiary amine structure is connected to the above (meth) acryloyloxy or (meth) acrylamide, and an ester bond existing on the aromatic ring of the photosensitive structural unit via an alkylene group, respectively.
  • the polymerizable photosensitive monomer containing a co-initiator tertiary amine has a structural formula as follows:
  • n is an integer of 1-20, preferably 1 or 2;
  • R 1 0 or NR, and R is H, a linear alkyl group having 1 to 20 C atoms or a branched chain alkyl group having 3 to 20 C atoms
  • R 2 H, a linear alkyl group having 1 to 20 C atoms or a branched alkyl group having 3 to 20 C atoms.
  • a unit of a photosensitive structure is connected to a nitrogen atom in a structural unit containing a co-initiator tertiary amine.
  • Action provides the greatest opportunity, is conducive to the energy transfer between the two, can produce more free radical active species, faster, and improve the initiation efficiency.
  • suitable polymerizable photosensitive monomers according to the present invention include one or more compounds of the following structure:
  • the polymerizable photosensitive monomer of the present invention is obtained by combining an alkylamino group-containing (meth) acrylate or an alkylamino group-containing (meth) acrylamide compound with a substance having a halogenated ester group and containing a photosensitive structure. The reaction was obtained.
  • reaction scheme of the polymerizable photosensitive monomer of the present invention is as follows:
  • R 2 H or a linear alkyl group having 1 to 20 C atoms or a branched alkyl group having 3 to 20 C atoms.
  • R 2 H or a linear alkyl group having 1 to 20 C atoms or a branched alkyl group having 3 to 20 C atoms, and n is an integer of 1-20.
  • the molar fraction of the polymerizable photosensitive monomer in the polymer affects the lubricity of the hydrophilic coating prepared therefrom. If the molar fraction is too high, the content of hydrophilic monomers will be relatively reduced. The initial lubricity of the obtained hydrophilic coating is not good, and the friction is high. If the molar fraction is too low, the curing efficiency will be affected, and with the increase of the number of cycles, The friction of the coating increases rapidly.
  • the molar fraction of the polymerizable photosensitive monomer in the copolymer is 0.05-10%, preferably 0.5-5%, and further preferably 0.8-1.5%.
  • the molar fraction of the polymerizable photosensitive monomer in the copolymer is 1%, and using this specific molar fraction can obtain the lowest frictional force (0.12N) and the frictional force hardly increases with the increase of the number of cycles. The friction force did not increase after more than 30 cycles.
  • the hydrophilic monomer means a monomer capable of dissolving more than 1 g in 100 g of water at 25 ° C.
  • the hydrophilic monomer is mainly used to provide hydrophilicity to the polymer.
  • Hydrophilic monomers include, but are not limited to, unsaturated carboxylic acids or carboxylates, unsaturated carboxylic acid esters, unsaturated acid hydroxyalkyl esters, unsaturated acid polyether esters, unsaturated acid anhydrides, unsaturated amides, unsaturated One or more of an amide and an alkylene oxide; preferably, the hydrophilic monomer is selected from the group consisting of (meth) acrylic acid, (meth) acrylamide, vinylpyrrolidone, and hydroxyethyl (propylene) (meth) acrylate One or more of an ester, polyethylene glycol methyl ether (meth) acrylate, dimethylacrylamide; more preferably, the hydrophilic monomer is selected from polyethylene glycol methyl ether acrylate.
  • the inventors found that when using polyethylene glycol methyl ether acrylate as the hydrophilic monomer, the obtained hydrophilic coating has better lubricating effect, which is prominently reflected in the low friction and increasing with the number of cycles, The friction is almost unchanged, even lower than the first cycle friction.
  • the photocurable hydrophilic polymer in the present invention is prepared by a radical polymerization method, including but not limited to ordinary radical polymerization and living controllable radical polymerization.
  • the photocurable hydrophilic polymer is composed of Prepared by ordinary free radical polymerization.
  • the photocurable hydrophilic polymer is prepared in a certain medium, including but not limited to solution polymerization, emulsion polymerization, inverse emulsion polymerization, suspension polymerization, and bulk polymerization. From the perspective of easy operation, preferably, the photocurable The hydrophilic polymer is completed by solution polymerization. From an environmental perspective, more preferably, the photocurable hydrophilic polymer is copolymerized in an aqueous solution.
  • a polymerizable photosensitive monomer and a hydrophilic monomer are dissolved in water, a radical initiator is added to the system, oxygen is removed, and the reaction is performed at a specific temperature. When the reaction is completed, the reaction is The solution was precipitated with 95% ethanol, and the obtained precipitate was dried in an oven to obtain a photocurable hydrophilic polymer.
  • a radical initiator in a polymerization reaction refers to a substance that can generate radicals when activation energy is applied, and includes thermally activated initiators, such as organic peroxides, organic hydrogen peroxide, and azo compounds.
  • thermally activated initiators such as organic peroxides, organic hydrogen peroxide, and azo compounds.
  • these initiators include, but are not limited to, benzoyl peroxide, t-butyl perbenzoate, diisopropyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, and the like.
  • the free radical initiator is azobisisobutyronitrile.
  • the thermal initiator is usually used in an amount of 0.01 to 5% by mass, preferably 0.05 to 0.15% by mass.
  • the photocurable hydrophilic polymer preferably has a number average molecular weight of at least 2000, and a relatively high molecular weight photocurable hydrophilic polymer is preferred, but for ease of application of the coating, it is preferably 1.5 million or less.
  • the invention also finds that the molecular weight of the photocurable hydrophilic polymer will affect the lubricity of the hydrophilic coating.
  • the photocurable The number average molecular weight of the hydrophilic polymer is preferably 5 to 600,000, more preferably 150,000 to 300,000.
  • a second embodiment of the present invention provides a coating composition, including: 1) the photocurable hydrophilic polymer according to the present invention, with a mass fraction of 0.1-20%, preferably 1-10%, and more preferably Is 3-5%;
  • the mass fraction of the solvent ranges from 60% to 99.9%, preferably, the mass fraction ranges from 90 to 99%, and preferably, the mass fraction ranges from 95 to 98%.
  • the photocurable hydrophilic polymer uses the polymer according to the first embodiment of the present invention, which has photo-initiated activity. Since the photocurable hydrophilic polymer is hydrophilic in nature, it can be directly formulated into a coating composition and applied to the surface of the product, and the photocurable coating can be used to obtain a hydrophilic coating. Add another hydrophilic polymer.
  • the amount of photocurable hydrophilic polymer has an important effect on the curing speed of the coating composition, the firmness and lubricity of the coating.
  • the mass fraction of the photocurable hydrophilic polymer in the coating composition is 0.1-20%. From the viewpoint of improving lubricity, it is further preferably 1-10%, and more preferably 3-5%.
  • the solvent is one or a mixed solvent that can dissolve the photocurable hydrophilic polymer and form the hydrophilic polymer into a homogeneous solution.
  • Solvents include water, low molecular weight alcohols (methanol, ethanol, isopropanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerol, etc.), N, N-dimethylformamide, N, N-dimethylformamide One or more of acetylacetamide, dimethyl sulfoxide, acetone, and phenol.
  • the solvent is one or a mixed solvent that can dissolve the photo-curable hydrophilic polymer to form a homogeneous solution.
  • the solvent The solvent is a mixture of water and ethanol, and preferably, the volume ratio of water to ethanol is 2: 3-3: 2.
  • the mass fraction of the solvent in the coating composition ranges from 60% to 99.9%, preferably, the mass fraction ranges from 90 to 99%, and preferably, the mass fraction ranges from 95 to 98%.
  • Lubricating additives such as surfactants, waxes, lubricants, soaps and detergents can also be added to the coating composition as needed. These lubricant additives do not add too much osmotic concentration to the coating, but they can increase the lubricity when wet and reduce adhesion. Their low solubility in water helps to keep them in the coating. Other additives may include supporting polymers, polyelectrolytes, wetting agents, leveling agents, defoamers, film-forming aids, thickeners, pigments, antibacterial agents, colorants, surfactants, and the like. In the specific embodiment of the present invention, in addition to the photocurable hydrophilic polymer and solvent, the coating composition can obtain good lubricity and firmness without adding additional optional components.
  • the coating composition of the present invention can be prepared by adding a light-curable hydrophilic polymer and optionally a hydrophilic polymer to a mixed solvent prepared in advance under a condition protected from light, and stirring and dissolving overnight to prepare the coating composition. Got. The resulting solution was a colorless, clear solution.
  • a third embodiment of the present invention provides a hydrophilic lubricating coating, which is obtained by curing the coating composition described in the second embodiment of the present invention.
  • Hydrophilic lubricant coatings can be formed by:
  • the composition is cured.
  • the coating composition can be applied to an article by, for example, dip coating.
  • Other methods of coating include spray coating, wash coating, vapor deposition, brush coating, roll coating, and other methods known in the art.
  • Curing can be performed at any suitable temperature, depending on the article, provided that the mechanical or other properties of the article are not adversely affected to an unacceptable degree.
  • the ultraviolet light intensity during curing is 5-25 mW / cm 2
  • the time for curing the coating composition is 2-7 minutes, preferably 3-5 minutes.
  • the thickness of the hydrophilic coating can be controlled by changing the soaking time, changing the traction rate, or changing the viscosity of the coating composition and the number of coating steps.
  • the thickness of the hydrophilic coating on the product is in the range of 0.1-200 ⁇ m, preferably in the range of 0.5-100 ⁇ m, and more preferably in the range of 1-20 ⁇ m.
  • the catheter is immersed in a cylinder containing the coating liquid composition of the present invention, left for 0.5-2 min, and pulled up at a speed of 0.5-1 cm / s.
  • the catheter with the coating liquid is irradiated with an ultraviolet lamp.
  • the curing process is performed within 3-5 minutes, and the cured sample is dried in the air to obtain a catheter with a hydrophilic lubricating coating.
  • a fourth embodiment of the present invention provides an article including at least one layer of the hydrophilic lubricating coating according to the third embodiment of the present invention.
  • various products having the hydrophilic lubricating coating according to the present invention can be obtained by coating and curing.
  • the shape of the product is not limited, including films, sheets, rods, tubes, molded parts, fibers, Fabrics and particles.
  • the hydrophilic lubricating coating can be applied directly to the surface of the product, or it can be applied to a pre-treated or coated surface.
  • the pre-treatment method includes wiping the surface of the product with ethanol and then drying it.
  • the hydrophilic lubricating coating according to the invention is applied to a biomedical substrate such as a medical device to reduce friction under wet conditions.
  • a biomedical substrate such as a medical device to reduce friction under wet conditions.
  • Coated medical devices can be inserted into various living tissues and into physiological solutions containing media. These tissues include, for example, mucous membranes such as the urethra, blood vessels, heart, kidneys, lungs, throat, eyes.
  • the invention provides a medical device with a very smooth touch, so that it can be easily inserted into body tissues or cavities, and can maintain hydrophilicity and lubricity after being in contact with tissues, such as mucous membranes for a long time, and can easily make the product Take out, rub repeatedly 30 times in the simulated human tissue environment, the coating does not fall off, the lubricity does not decrease, and the firmness is excellent.
  • the coating does not significantly increase its frictional force after 30 cycles, which is an embodiment of excellent fastness. It is known in the art that if the frictional force of the coating increases, it means that the coating is peeled off and the fastness is not good; The friction has not increased, which means that the coating has not come off and the coating is firm.
  • the “medical device” in the present invention should be interpreted in a broad sense.
  • the medical device may be an implantable device or an extracorporeal device.
  • the device can be used temporarily for short periods or permanently implanted for long periods.
  • suitable medical devices are catheters, guidewires, endoscopes, laryngoscopes, feeding tubes, drainage tubes, medical leads, condoms, barrier coatings such as for gloves, stents, stent grafts, anastomotic connectors, extracorporeal Blood catheters, membranes such as those used in dialysis, blood filters, circulation aids, wound dressings, urine collection bags, ear tubes, intraocular lenses, and any tubes used in minimally invasive surgery.
  • the medical device is selected from a catheter, a guide wire, an endoscope, a laryngoscope, a feeding tube, a drainage tube, and a medical lead.
  • Articles particularly suitable for use in the present invention include catheters (e.g., intermittent catheters, balloon catheters, PTCP catheters, stent delivery catheters), guidewires, leads, syringes, contact lenses, medical tubes and stents, and other other metals or polymers Implant of the substrate.
  • the present invention is applicable to catheters / guide wires of various materials, including polyurethane, silicone rubber, latex, nylon, polyvinyl chloride, Pebax, nitinol and the like.
  • the lubricating performance of the present invention is tested by a clip-type friction tester. Specifically, the pipe is clamped with double clamps, the clamps are placed in deionized water, and a certain pressure is applied through the clamps to test the force required to lift the pipe. The ratio of the force to the clamping force is the coefficient of friction for evaluation. Coating lubrication performance.
  • the clamping force used was 300 g, the pulling speed was 10 mm / s, and the test cycle was 30 times.
  • the catheter was immersed in a cylinder containing the coating solution composition prepared in step 3, left for 1 minute, and the catheter was pulled at a speed of 0.5 cm / s.
  • the catheter with the coating solution was irradiated with an ultraviolet lamp for 5 minutes for curing treatment.
  • the intensity of ultraviolet light It was 10 mW / cm 2 and the rotation speed of the catheter was 4 rpm.
  • the cured sample is air-dried.
  • Step 5 Test the lubrication performance
  • the amount of the photocurable hydrophilic polymer in step 3 was changed, and the amount of the ethanol / water mixed solvent was adaptively adjusted according to the amount of the photocurable hydrophilic polymer.
  • the formulation of the coating composition is shown in Table 1.
  • Other steps The lubricating performance was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • the molecular weight of the photocurable hydrophilic polymer is preferably relatively high, which can reduce the initial frictional force. Considering the lubrication performance after the 30th cycle, the molecular weight is most preferably 150k-300k.
  • Example 1 The mole fraction of the polymerizable photosensitive monomer in the copolymer in step 2 in Example 1 was changed.
  • the formulation of the coating composition is shown in Table 5.
  • the other steps were the same as in Example 1.
  • the lubrication performance was evaluated. The results are shown in Table 6.
  • the molar fraction of the polymerizable photosensitive monomer in the copolymer has a large effect on the lubricating performance.
  • the mole fraction is the best in the range of 0.8-1.5%.
  • the molar fraction is too low, and the number of cycles that can keep the friction low is too small.
  • step 1 the hydrophilic monomer polyethylene glycol methyl ether acrylate was replaced with acrylic acid, acrylamide, vinylpyrrolidone, hydroxyethyl acrylate, and methacrylamide to prepare a series of similar molecular weights.
  • Photocurable polymer The formulation of the coating composition is shown in Table 7. Other steps are the same as in Example 1. The lubrication performance is evaluated. The results are shown in Table 8.
  • Example 1 0.1 g of the hydrophilic polymer prepared in Example 1 and Comparative Example 1 were weighed, dissolved in 1 mL of water, and irradiated with 10 mW / cm 2 of ultraviolet light for 2 minutes to observe the curing state of the two solutions.
  • Example 1 The results showed that the coating solution containing the hydrophilic polymer prepared in Example 1 was cured to form a glue after irradiation, and the solution could not flow.
  • the coating solution containing the hydrophilic polymer prepared in Comparative Example 1 became slightly viscous after irradiation, but Flowing, uncured into glue.
  • the photocurable hydrophilic polymerization prepared by using the polymerizable photosensitive monomer according to the present invention because of its longer linking chain and the co-initiated tertiary amine structure The object is cured by ultraviolet light with high curing efficiency and strong gelation.

Abstract

一种可光固化的亲水聚合物、基于其的涂料组合物及亲水润滑涂层和制品。可光固化的亲水聚合物由特定结构的可聚合光敏单体与亲水性单体共聚而成。所述可光固化的亲水聚合物具有高的光固化效率，制备方法简易、生产效率高、环境污染少，基本不存在凝胶化的问题。通过固化所述涂料组合物可以获得高牢固度、高润滑性、具有优异的生物安全性和相容性的亲水涂层。

Description

可光固化的亲水聚合物、基于其的涂料组合物及亲水润滑涂层和制品 技术领域
本发明属于光固化技术领域，具体涉及可光固化的亲水聚合物和基于其的涂料组合物，另外还涉及亲水润滑涂层领域，该亲水润滑涂层用于体内医疗器械诸如导管/导丝。
背景技术
随着医学技术的发展，以介入治疗等微创方式进行疾病治疗的方式越来越受到医疗工作者及患者的青睐。许多介入医疗器械，如心血管系统导丝/导管、泌尿系统导管、消化系统导管等，在使用时需插入患者体内，与患者组织直接接触。对于未经处理的导丝/导管，其表面光滑度通常较低，插入或拔出体内时会有较大阻力，易给患者带来不适感及组织损伤，同时让医护工作人员操作不便，因此需开发恰当的润滑技术，提高医用导丝/导管的表面润滑程度。
当前普遍使用的润滑方法是在导丝/导管使用前涂覆润滑剂(如石蜡油、硅油及凡士林等)，但因润滑剂不能稳定在导管表面，仍易对组织造成损伤。有研究人员采用全氟乙丙烯等材料包覆导管，在一定程度上提高了导管的润滑性，但带有此类涂层的导管润滑度仍不足以避免对机体的损伤。因此有研究人员致力于研究在导丝/导管表面形成润滑度更高的亲水涂层的方法。
专利文献1公开了一种包含亲水性聚合物、聚电解质、光引发剂、载体液的组合物制备方法，该组合物可在紫外光处理条件下形成润滑涂层。同时但该组合物中未加入有效的交联组分，易产生交联度不够、涂层不牢固的情况，同时，该体系使用小分子光引发剂，伴有异味、碎片易迁移的问题，降低涂层的生物学安全性，影响综合性能。
专利文献2公开了一种包含聚电解质的亲水性涂料，该组合物中加入了明确的交联组分聚乙二醇二丙烯酸酯，涂层交联度、牢固度得以保障，但该体系仍使用小分子光引发剂，仍存在小分子及碎片易迁移出涂层的问题。
专利文献3公开了一种含带光活性的亲水性树脂、带光活性的亲水性交联剂涂料的制备方法及使用方法，将小分子光引发剂与亲水性单体进行聚合，有效地防止小分子引发剂的残留与迁出，同时增强了涂层牢固度，可满足十 五个循环摩擦力测试的要求。但该体系需将一定量交联剂与亲水性单体、小分子光引发剂共聚，从理论上存在聚合过程易产生凝胶的问题。
专利文献4公开了一种包含N-乙烯基吡咯烷酮与二苯甲酮乙烯基单体共聚物的亲水涂层，该亲水涂层具有不超过0.2的摩擦系数。该共聚物将小分子二苯甲酮引发剂共价结合到聚合物链，有效避免了小分子的迁出。但该共聚物中采用的二苯甲酮乙烯单体为(甲基)丙烯酸酯基团与二苯甲酮基团直接连接，分子链长度较短，自由基不易碰撞；同时，分子链未带有明显助引发剂结构，引发效率相对偏低。
专利文献1：CN102947376B
专利文献2：CN101365501B
专利文献3：CN105732848A
专利文献4：CN103209717A
发明内容
发明要解决的问题
为解决以上现有技术的缺点和不足之处，本发明提供一种可光固化的亲水聚合物以及基于其的涂料组合物。所述可光固化的亲水聚合物具有高的光固化效率，并且制备方法简易、生产效率高、环境污染少，基本不存在产生凝胶的问题。通过固化所述涂料组合物可以获得高牢固度、高润滑性、具有优异的生物安全性和相容性的亲水涂层。
此外，本发明还提供一种由上述涂料组合物所得到的亲水润滑涂层及其制品如医疗器械。
用于解决问题的方案
本发明提供一种可光固化的亲水聚合物，所述亲水聚合物由可聚合光敏单体与亲水性单体共聚而成；所述可聚合光敏单体含有：1)含光敏结构的单元；2)含共引发剂叔胺结构的单元；3)含有不饱和键结构的单元；
所述含光敏结构的单元至少通过-OC(＝O)-与含共引发剂叔胺的单元相连接，所述含有不饱和键结构的单元通过所述含共引发剂叔胺的单元与所述含光敏结构的单元相连接。
优选地，所述可聚合光敏单体具有通式(I)的结构：
Figure PCTCN2019094679-appb-000001
其中：n为1-20的整数，优选为1或2；R 1＝O或NR，R为H、1至20个C原子的直链烷基或具有3至20个C原子的支链烷基；R 2＝H、具有1至20个C原子的直链烷基或具有3至20个C原子的支链烷基。
优选地，所述亲水性单体包括不饱和羧酸或羧酸盐、不饱和羧酸酯、不饱和酸羟烷基酯、不饱和酸聚醚酯、不饱和酸酐、不饱和酰胺、不饱和内酰胺、环氧烷烃中的一种或多种；优选地，亲水性单体选自(甲基)丙烯酸、(甲基)丙烯酰胺、乙烯基吡咯烷酮、(甲基)丙烯酸羟乙(丙)酯、聚乙二醇甲醚(甲基)丙烯酸酯、二甲基丙烯酰胺中的一种或多种；更优选地，亲水性单体选自聚乙二醇甲醚丙烯酸酯。
优选地，所述可聚合光敏单体在所述亲水聚合物中摩尔分数为0.05-10％，优选为0.5-5％，进一步优选为0.8-1.5％。
优选地，所述可光固化的亲水聚合物数均分子量的范围为0.2-150万，优选为5-60万，进一步优选为15-30万。
进一步，本发明提供一种涂料组合物，其包括：
1)本发明所述的可光固化的亲水聚合物，基于涂料组合物总量而言，其质量分数为0.1-20％，优选为1-10％，进一步优选为3-5％；
2)溶剂，质量分数为60-99.9％，优选为90-99％，更优选为95-98％。
优选地，所述溶剂包括水、低分子量醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、丙酮、苯酚中的一种或多种，优选地，所述溶剂为水与乙醇的混合物，更优选地，水与乙醇的体积比为2:3-3:2。
更进一步，本发明提供一种亲水润滑涂层，所述涂层通过将上述涂料组合物固化得到。
此外，本发明还提供一种包含至少一层如上所述亲水润滑涂层的制品如医疗器械。
发明的效果
与现有技术相比，本发明具有如下有益效果：
1.本发明通过使用一种新的可聚合光敏单体，其具有较长的连接链以及 可参与共引发的叔胺结构，制备得到的可光固化的亲水聚合物经紫外光照射固化效率高，成胶牢固。
2.本发明中可光固化的亲水聚合物的合成简单，反应条件易于控制，基本不存在凝胶化的情况。
3.本发明基于该可固化的聚合物配制得到用于光固化亲水润滑涂层的制备所用的涂料组合物，与其他现有的光固化涂料相比，本发明采用的可光固化的聚合物本身就含有光敏结构单元，因此涂料组合物中无需添加小分子光引发剂，进而可以克服小分子光引发剂在涂层中的残留、迁移等问题，具有优异的生物安全性和相容性，适用于医疗领域。
4.该涂料组合物可通过简单连续的浸涂-光固化工艺形成均匀稳定的亲水润滑涂层，将其涂覆在医疗器械表面后，润湿后触感十分润滑，在模拟人体组织环境中反复摩擦30次，涂层无脱落，润滑度没有下降，涂层牢固度佳。
5.本发明对亲水性单体种类、可聚合光敏单体与亲水性单体摩尔比例、可光固化的亲水聚合物分子量进行调控，发现用于亲水涂层制备的效果最优聚合物。
6.本发明通过对涂料组合物各组分的种类和含量选择，制备得到高牢固度、高润滑性的亲水涂层。
具体实施方式
下面将结合实施例对本发明的技术方案进行详细的描述。
在本发明中术语“单体”的含义是可以用化学式表征的带有能聚合成低聚物或聚合物以增加分子量的可聚合基团(包括(甲基)丙烯酸酯基团)的任何化学物质。单体的分子量通常可以简单地根据给出的化学式计算出。
在下文中，当将分子的部分描述为“任选地取代的”或“取代”时，这表示所述部分可以被选自以下的一个或多个取代基取代：C 1-C 6直链、支链或环状烷基、芳基、-OH、-CN、卤素、胺、酰胺、醇、醚、硫醚、砜及其衍生物、亚砜及其衍生物、碳酸酯、异氰酸酯、硝酸盐和丙烯酸酯。
在本发明中术语“单元”的含义不仅仅包括功能性基团(如光敏基团、季铵盐基团、不饱和基团)，还可以包括对功能性基团影响较小的额外化学基团如烷基、亚烷基等。
在本发明中术语“聚合物”是指含有两个或多个重复单元的分子，具体地， 聚合物可以由两个或多个相同或不同的单体形成，当用于本发明时，该术语还包括低聚物或预聚物。在本发明中术语“分子量”是指数均分子量(M n)，M n被定义为通过光散射(可选与尺寸排斥色谱SEC组合)测定的M n。
在本发明中术语“固化”被理解为：通过例如加热、冷却、干燥、结晶的任何方法造成物理或化学硬化或凝固，或由化学反应造成的固化，例如辐射固化、热固化或加入固化分子、引发剂固化。
在本发明中术语“光固化”可用过如下示例性的方式来实现：经由用波长范围从100nm至600nm的光照射或UV照射而发生光引发过程。可以使用的照射源是阳光或人工灯或激光。例如，高压、中压或低压汞灯以及氙和钨灯是有利的。同样，基于准分子、固态和二极管的激光是有利的。基于二极管的光源通常有利于引发化学反应。
<第一实施方式>
本发明的第一实施方式中提供了一种可光固化的亲水聚合物，其由可聚合光敏单体与亲水性单体共聚而成，其具有光敏结构单元可以作为大分子光引发剂，因此将其配制成涂料组合物时无需添加小分子光引发剂，可以克服小分子光引发剂在涂层中的残留、迁移等问题，具有优异的生物安全性和相容性，适用于医疗领域。
可聚合光敏单体
可聚合光敏单体含有：所述可聚合光敏单体含有：1)含光敏结构的单元；2)含共引发剂叔胺结构的单元；3)含有不饱和键结构的单元；所述含光敏结构的单元至少通过-OC(＝O)-与含共引发剂叔胺的单元相连接，所述含有不饱和键结构的单元通过所述含共引发剂叔胺的单元与所述含光敏结构的单元相连接。
本发明的含光敏结构的单元源自于芳基酮类光引发剂结构，其包含羰基官能团以及一个或多个芳环，同时该芳基酮类结构中也可以进一步的包含硫原子,含光敏结构的单元可以源自但不排他地限于取代或为取代的二苯甲酮、苯乙酮、噻吨酮、占吨酮、芴酮及其衍生物。在本发明的一个实施方式中，典型地含光敏结构的单元可以是具有通式(II)的二苯甲酮：
Figure PCTCN2019094679-appb-000002
其中Ar 1和Ar 2独立地选自相同或不同的任选地取代的芳基，其中波浪线表示其通过连接基团与含共引发剂叔胺的结构单元相连。优选地，Ar 1和Ar 2两者可以是任选地取代的苯基，进一步优选地均为苯基。含共引发剂叔胺的结构单元优选在Ar 2的对位存在，因为这提供了与羰基发生电子相互作用的最大机会，因此形成自由基的最大稳定化。
本发明的发明人发现，当使用二苯甲酮单元作为本发明的光敏结构单元时，相对于小分子光敏化剂或它们的组合能够取得更优的光引发效率。
聚合性光敏单体中含有的含有不饱和键的单元可以为含双键的可聚合基团。这样的反应性基团可以使得光敏结构单元以重复单元的形式，借助自由基聚合而结合到聚合物的主链中。
本发明中，含有不饱和键的单元可以选自具有(甲基)丙烯酰基团的单元，例如典型地，可以为(甲基)丙烯酸酯、(甲基)丙烯酰胺。可聚合基团的存在可以克服常规小分子光引发剂存在的毒性和高迁移率的问题，促使光引发剂得以锚固在聚合物网络中，还可以通过与其他单体共聚改进材料性能，同时抑制小分子光引发剂残留所导致的不期望的挥发。
含共引发剂叔胺结构的单元包含叔胺基团，除此之外还可以包含若干个亚烷基基团。在UV照射时，叔胺具有从毗邻氨基氮的碳原子夺取质子的能力，其能有效地作为活性官能团的H供体，这就可以产生能够引发聚合或交联的活性基团。
光敏结构单元通过存在于芳环上的酯键(-O-C(＝O)-)与共引发剂叔胺结构相连接，而所述含有不饱和键的单元通过含共引发剂叔胺的结构单元与所述光敏结构的单元相连接。本发明优选的方案中，叔胺结构中的氮原子分别借助亚烷基与以上(甲基)丙烯酰氧或(甲基)丙烯酰胺、以及存在于光敏结构单元芳环上的酯键相连接。
在本发明的一个优选实施方式中，含共引发剂叔胺的聚合性光敏单体，其结构式如下：
Figure PCTCN2019094679-appb-000003
其中：n为1-20的整数，优选为1或2；R 1＝O或NR，R为H、1至20个C原 子的直链烷基或具有3至20个C原子的支链烷基；R 2＝H、具有1至20个C原子的直链烷基或具有3至20个C原子的支链烷基。
本发明通过选择特定的连接基团即酯基和亚甲基将光敏结构的单元与含共引发剂叔胺的结构单元中的氮原子连接，该连接方式给上述两个结构单元之间的相互作用提供了最大的机会，有利于两者间的能量转移，能更多、更快的产生自由基活性种，提高引发效率。
进一步优选地，根据本发明的适合的聚合性光敏单体包括以下结构的一种或多种化合物：
Figure PCTCN2019094679-appb-000004
本发明的可聚合光敏单体是通过将含烷基氨基的(甲基)丙烯酸酯类或 含烷基氨基的(甲基)丙烯酰胺类化合物与具有卤代酯基且含光敏结构的物质进行反应得到。
示例性地本发明的聚合性光敏单体的反应流程如下：
Figure PCTCN2019094679-appb-000005
其中，R 2＝H或具有1至20个C原子的直链烷基或具有3至20个C原子的支链烷基。
或者，
Figure PCTCN2019094679-appb-000006
其中，R 2＝H或具有1至20个C原子的直链烷基或具有3至20个C原子的支链烷基，n为1-20的整数。
本发明发现可聚合光敏单体在聚合物即共聚物中的摩尔分数会影响其制备得到的亲水性涂层的润滑性。摩尔分数过高，亲水性单体的含量相对减少，所得到的亲水性涂层的初期润滑性不佳，摩擦力高；摩尔分数过低会影响固化效率，且随循环次数的增加，涂层的摩擦力会迅速增加。在本发明中，可聚合光敏单体在共聚物中摩尔分数0.05-10％，优选0.5-5％，进一步优选为0.8-1.5％。在本发明的一个优选实施方式中，可聚合光敏单体在共聚物中摩尔分数为1％，采用该特定摩尔分数可以获得摩擦力最低(0.12N)且摩擦力几乎不随循环次数的增加而增加，循环30次以上摩擦力基本没有升高。
亲水性单体
亲水性单体是指在100g25℃的水中能溶解1g以上的单体。亲水性单体主要是为了给聚合物提供亲水性。
亲水单体包括但不限定于不饱和羧酸或羧酸盐、不饱和羧酸酯、不饱和酸羟烷基酯、不饱和酸聚醚酯、不饱和酸酐、不饱和酰胺、不饱和内酰胺、环氧烷烃中的一种或多种；优选地，亲水性单体选自(甲基)丙烯酸、(甲基)丙烯酰胺、乙烯基吡咯烷酮、(甲基)丙烯酸羟乙(丙)酯、聚乙二醇甲醚(甲基)丙烯酸酯、二甲基丙烯酰胺中的一种或多种；更优选地，亲水性单体选自聚乙二醇甲醚丙烯酸酯。
本发明人发现，当采用聚乙二醇甲醚丙烯酸酯作为亲水性单体时，所得的亲水性涂层具有更佳的润滑效果，突出体现在摩擦力低且随着循环次数增加，摩擦力几乎没有变化，甚至还低于第1个循环摩擦力。对于聚乙二醇甲醚丙烯酸酯可以使用市售产品例如，Sigma-Aldrich(M n＝480)。
聚合
本发明中可光固化的亲水聚合物是由自由基聚合方法制备完成，包括但不限定于普通自由基聚合、活性可控自由基聚合，优选地，该可光固化的亲水聚合物由普通自由基聚合方法制备。可光固化的亲水聚合物是在一定介质中制备得到，包括但不限定于溶液聚合、乳液聚合、反相乳液聚合、悬浮聚合、本体聚合，从操作简易角度，优选地，该可光固化的亲水聚合物由溶液聚合完成，从环保角度，更优选地，该可光固化的亲水聚合物在水溶液中共聚完成。在本发明的一个实施方式中，将可聚合光敏单体、亲水性单体溶于水，向体系内加入自由基引发剂，除氧，在特定温度下进行反应，反应完成时，将反应液用95％乙醇沉淀，所得沉淀于烘箱干燥后即可得到可光固化的亲水性聚合物。
在聚合反应中自由基引发剂是指施加激活能时可产生自由基的物质，包括热活化引发剂，例如有机过氧化物、有机过氧化氢和偶氮化合物。这些引发剂的代表性实例包括但不限于过氧化苯甲酰、过苯甲酸叔丁酯、过氧化二碳酸二异丙酯、氢过氧化枯烯、偶氮二异丁腈等，在本发明的一个优选实施方式中自由基引发剂为偶氮二异丁腈。热引发剂通常以单体的0.01-5质量％的量使用，优选0.05-0.15质量％。
为了减少迁移性，可光固化的亲水聚合物优选数均分子量至少为2000，优选相对高分子量的可光固化的亲水聚合物，但为了易于施加涂层，优选150万以下。本发明还发现可光固化的亲水聚合物分子量的大小会对亲水涂层的润滑性会带来影响，为了获得多次循环仍具有良好的润滑性能的亲水涂层，可光固化的亲水聚合物数均分子量优选为5-60万，进一步优选为15-30万。
<第二实施方式>
本发明的第二实施方式提供一种涂料组合物，其包括：1)本发明所述的可光固化的亲水聚合物，质量分数为0.1-20％，优选为1-10％，更优选为3-5％；
2)溶剂，溶剂的质量分数范围为60％-99.9％，优选地，质量分数范围为90-99％，优选地，质量分数范围为95-98％。
可光固化的亲水聚合物
可光固化的亲水聚合物采用本发明第一实施方式所述的聚合物，其具有光引发活性。由于可光固化的亲水聚合物本身具有亲水性，故可以使用其直接配制成涂料组合物，并将其涂覆到制品表面，经光固化得到亲水性涂层，也可以选择性地添加另一种亲水性聚合物。可光固化的亲水聚合物的用量对涂料组合物的固化速度、涂层的牢固度和润滑性有着重要的影响。在本发明中可光固化的亲水聚合物在涂料组合物中的质量分数为0.1-20％，从提高润滑性角度，进一步优选为1-10％，更优选为3-5％。
溶剂
允许在表面上涂敷具有亲水性的涂料组合物的任何溶剂都是满足需要的。优选地，该溶剂为可溶解可光固化亲水性聚合物、亲水性聚合物形成均相溶液的一种或混合溶剂。
溶剂包含水、低分子量醇(甲醇、乙醇、异丙醇、丁醇、戊醇、乙二醇、丙二醇、丙三醇等)、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、丙酮、苯酚中的一种或多种，优选地，该溶剂为可溶解可光固化亲水聚合物形成均相溶液的一种或混合溶剂，优选地，该溶剂为水与乙醇的混合物，优选地，水与乙醇的体积比为2:3-3:2。
在涂料组合物中溶剂的质量分数范围为60％-99.9％，优选地，质量分数范围为90-99％，优选地，质量分数范围为95-98％。
任选组分
涂料组合物中还可以根据需要加入润滑添加剂，如表面活性剂、蜡、润滑剂、肥皂和去污剂。这些润滑添加剂不会使涂层增加太多的渗透压浓度，但可以增加润湿时的润滑性，并且降低粘接，它们在水中的低溶解度有助于使它们保留在涂层中。其它的添加剂可以包括支撑聚合物、聚电解质、润湿剂、流平剂、消泡剂、成膜助剂、增稠剂、颜料、抗菌剂、着色剂、表面活性剂等。本发明的具体实施方式中涂料组合物除了可光固化的亲水聚合物、溶剂外，不添加额外的任选组分，即可获得良好的润滑性和牢固性。
配制
本发明涂料组合物的配制可通过在避光条件下，将可光固化的亲水聚合物、任选的亲水性聚合物加入到提前配制好的混合溶剂中，搅拌溶解过夜，即可制得。所得溶液为无色澄清溶液。
<第三实施方式>
本发明的第三实施方式提供一种亲水润滑涂层，其通过将本发明第二实施方式中所述的涂料组合物固化得到。
可以通过如下方法形成亲水润滑涂层：
将本发明的涂料组合物涂覆到制品的至少一个表面上；并且通过将所述涂料组合物暴露于电磁辐射优选通过紫外辐射从而激发可光固化聚合物中的光敏结构单元来使所述涂料组合物固化。
一般而言，涂料组合物可以通过例如浸涂涂覆到制品上。涂覆的其它方法包括喷涂、洗涂、气相沉淀、刷涂、辊涂和其它本领域已知的方法。固化可以在任何合适的温度下来实施，依赖于制品，前提条件是：制品的机械性质或其它性质不会受到不可接受程度上的不利影响。优选地，固化时紫外光强度为5-25mW/cm 2，固化涂料组合物的时间在2-7分钟，优选3-5分钟。亲水性涂层的厚度可以通过如下方法控制：改变浸泡时间、改变牵引速率或改变涂料组合物的粘度和涂覆步骤的次数。通常，亲水性涂层在制品上的厚度在0.1-200μm的范围内、优选在0.5-100μm的范围内、更优选在1-20μm的范围内。
在本发明的一个实施方式中将导管浸入盛有本发明涂液组合物的料筒，静置0.5-2min，以0.5-1cm/s的速度提拉导管，带涂液的导管用紫外灯照射3-5min进行固化处理，固化完成的样品置于空气中晾干即得到具有亲水润滑涂层的导管。
<第四实施方式>
本发明的第四实施方式提供一种包含至少一层本发明第三实施方式所述的亲水润滑涂层的制品。
根据以上所述，通过涂覆、固化可以得到具有本发明所述的亲水润滑涂层的各种制品，制品的形状不限，包括薄膜、片材、棒、管、模制部件、纤维、织物和颗粒。亲水润滑涂层可以直接施加到所述制品表面上，或者可以施加到经预处理或被涂布的表面上，预处理的方式包括将制品表面用乙醇擦拭洁净后晾干。
在本发明的一个实施方式中，根据本发明的亲水润滑涂层涂覆到生物医 学基材上如医疗器械上，以降低湿润条件下的摩擦。可以将经涂覆的医疗器械插入各种活体组织中和含有介质的生理溶液中。举例来说这些组织包括粘膜，如尿道、血管、心脏、肾、肺、咽喉、眼睛。本发明提供了触感十分润滑的医疗器械，从而容易将其插入身体组织或空腔中，并且在与组织，如粘膜接触一段长时间以后能保持亲水性和润滑性，并且很容易地将制品取出，在模拟人体组织环境中反复摩擦30次，涂层无脱落，润滑度没有下降，牢固度优。本发明的一个具体实施例中，涂层经过30个循环摩擦力没明显上升即是优异的牢固度的体现，本领域公知若涂层摩擦力增大，代表涂层脱落，牢固度不好；摩擦力未增大，代表涂层未脱落，涂层牢固。
本发明中“医疗器械”应该解释为广义。医疗器械可以为可植入器械或体外器械。该器械可以短期暂时使用或者长期永久性植入。适合的医疗器械的例子为导管、导丝、内窥镜、喉镜、饲管、引流管、医用导线、避孕套、屏障涂层如用于手套、支架、支架移植物、吻合连接器、体外血导管、薄膜如用于透析、血液过滤器、循环辅助器材、伤口敷料、集尿袋、耳管、眼内晶状体和在微创手术中使用的任何管等。典型的，该医疗器材选自导管、导丝、内窥镜、喉镜、饲管、引流管、医用导线。特别适于用在本发明中的制品包括导管(例如间歇性导管、球囊导管、PTCP导管、支架输送导管)、导丝、导线、注射器、接触镜、医用管和支架及其他其它金属或聚合物基体的植入体。特别地，本发明适用于多种材质导管/导丝，包括聚氨酯、硅橡胶、乳胶、尼龙、聚氯乙烯、Pebax、镍钛合金等。
实施例
以下列举实施例来说明本发明，本领域技术人员能够理解，该例子仅是示例性的说明，并非穷尽性的说明。
测试方法
本发明的润滑性能采用夹片式摩擦力测试仪进行测试。具体而言即使用双夹片夹持管材，夹片置于去离子水中，通过夹片施加一定压力，测试提拉管材所需的力，其与夹持力的比值为摩擦系数，用以评价涂层润滑性能。所用夹持力为300g，提拉速度为10mm/s，测试循环30次。
实施例1：
步骤一：可聚合光敏单体的合成
称取3.35g(26mmol)2-(甲基氨基)乙基丙烯酸酯，3.95g(28mmol)碳 酸钾和0.02g对苯二酚溶于30mL乙腈并置于100mL烧瓶中，加热回流2h。将20mL 4-苯甲酰基苯基溴乙酸酯(8.3g，26mmol)的乙腈溶液缓慢滴加至烧瓶中，1h内滴加完毕。在80℃条件下反应10h。反应结束，冷却至室温并将粗产物溶于二氯甲烷，依次用饱和食盐水、盐酸(1M)和饱和碳酸氢钠洗涤2次，无水硫酸镁干燥过夜，过滤并旋干溶剂，以乙酸乙酯和正己烷为淋洗剂，通过柱层析纯化后得到5.12g浅黄色固体，如结构式1所示。核磁氢谱结果:2.24ppm(s,3H,CH 3),2.58ppm(m,2H,CH 2),3.52ppm(s,2H,CH 2),4.46ppm(m,2H,CH 2),5.83-6.42ppm(m,H,CH 2),6.12ppm(m,H,CH),7.43-7.82ppm(m,9H,苯环)。
Figure PCTCN2019094679-appb-000007
步骤二：可光固化的亲水聚合物的合成
称取47.52g(0.099mol)聚乙二醇甲醚丙烯酸酯、0.367g(0.001mol)步骤一所得到的可聚合光敏单体、0.048g偶氮二异丁腈加入到500mL圆底烧瓶，加入150mL去离子水、80mL甲醇，机械搅拌溶解。溶液通N 2 30min除氧，将反应瓶放入65℃油浴加热开始反应。反应6h后，将反应溶液取下冷却至室温，用95％乙醇中沉淀，沉淀于真空烘箱35℃避光干燥36h。所得可光固化的亲水聚合物经GPC测得数均分子量Mn为254k，PDI为2.21。
步骤三：涂料组合物的制备
称取3g步骤二所制备得到的可光固化的亲水聚合物(Mn＝254k，可聚合光敏单体摩尔分数＝1％)加入到棕色瓶中，而后加入97g乙醇/水的混合溶剂(体积比1:1)，避光搅拌溶解24h。所得溶液为无色澄清溶液。
步骤四：亲水性涂层及其制品的制备
将聚氨酯导管(导管直径Fr＝5.5mm)表面用蘸有75％乙醇的无尘纸擦拭洁净，晾干。将导管浸入盛有步骤三所制得的涂液组合物的料筒，静置1min，以0.5cm/s的速度提拉导管，带涂液的导管用紫外灯照射5min固化处理，紫外光强度为10mW/cm 2，导管旋转速度为4rpm。固化完成的样品置于空气中晾干。
步骤五：测试润滑性能
步骤四所得涂层导管肉眼观察无明显不均匀处，置于夹片式摩擦力测试仪测试润滑性能，具体结果参见表2。
实施例2：
改变步骤三中可光固化的亲水聚合物的用量，乙醇/水混合溶剂的用量随可光固化的亲水聚合物的用量变化进行适应性调整，涂料组合物的配方见表1，其他步骤同实施例1，对润滑性能进行评价，结果见表2。
表1含不同质量分数的可光固化的亲水聚合物的涂料组合物的配方
Figure PCTCN2019094679-appb-000008
表2可光固化的亲水聚合物浓度对涂层性能的影响
Figure PCTCN2019094679-appb-000009
由表2可知，可光固化的亲水聚合物添加3％-5％时均能获得润滑性能优 异的制品。相对而言，添加量0.1％时初始摩擦力偏高，添加量增大到20％时，第30个循环之后摩擦力有明显增加。
实施例3：
改变实施例1中的步骤二反应时间和引发剂的用量以获得不同分子量的可光固化的亲水聚合物(表4中的分子量采用四舍五入方式计整)，涂料组合物的配方见表3，其他步骤同实施例1，对润滑性能进行评价，结果见表4。
表3不同分子量可光固化的亲水聚合物的涂料组合物的配方
Figure PCTCN2019094679-appb-000010
表4可光固化的亲水聚合物分子量对涂层性能的影响
Figure PCTCN2019094679-appb-000011
由表4可知，可光固化的亲水聚合物的分子量优选相对高分子量，可以降低初始摩擦力，综合考虑第30个循环后的润滑性能，最优选的是分子量为150k-300k。
实施例4：
改变实施例1中的步骤二中可聚合光敏单体在共聚物中的摩尔分数，涂料组合物的配方见表5，其他步骤同实施例1，对润滑性能进行评价，结果见表6。
由表6可知，可聚合光敏单体在共聚物中的摩尔分数对于润滑性能的影响较大。摩尔分数在0.8-1.5％范围内润滑性能最为优异。摩尔分数过低，能够保持较低摩擦力的循环次数偏少。
表5不同摩尔分数的可聚合光敏单体合成的可光固化聚合物的涂料组合物的配方
Figure PCTCN2019094679-appb-000012
表6可聚合光敏单体摩尔分数对涂层性能的影响
Figure PCTCN2019094679-appb-000013
实施例5：
将实施例1中的步骤二中亲水性单体聚乙二醇甲醚丙烯酸酯替换为丙烯 酸、丙烯酰胺、乙烯基吡咯烷酮、丙烯酸羟乙酯、二甲基丙烯酰胺，制备得到一系列分子量相近的可光固化聚合物。涂料组合物的配方见表7，其他步骤同实施例1，对润滑性能进行评价，结果见表8。
由表8可知，使用聚乙二醇甲醚丙烯酸酯的摩擦力最低，使用丙烯酸羟乙酯也可以获得优异的润滑性能。
表7不同亲水性单体合成的可光固化的亲水聚合物的涂料组合物的配方
Figure PCTCN2019094679-appb-000014
表8亲水单体对涂层性能的影响
Figure PCTCN2019094679-appb-000015
比较例1：
丙烯酸4-苯甲酰基苯酯的制备
称取19.8g(0.1mol)4-羟基二苯甲酮、量取16.6mL三乙胺加入500mL圆底烧瓶，加入200mL二氯甲烷，搅拌溶解。反应溶液冰水浴15min，而后半小时内向溶液中滴加9.78mL丙烯酰氯，冰水浴反应1h，而后室温反应3h。反应混合液过滤，滤液用饱和碳酸氢钠溶液洗涤三次、饱和氯化钠溶液洗涤三次，有机相用无水硫酸镁干燥，旋转蒸发浓缩，柱层析得到产物。
含丙烯酸4-苯甲酰基苯酯的亲水聚合物的制备
称取47.52g(0.099mol)聚乙二醇甲醚丙烯酸酯、0.252g(0.001mol)上述丙烯酸4-苯甲酰基苯酯、0.048g偶氮二异丁腈加入到500mL圆底烧瓶，加入150mL去离子水、80mL甲醇，机械搅拌溶解。溶液通N 2 30min除氧，将反应瓶放入65℃油浴加热，开始反应。反应6h后，将反应溶液取下冷却至室温，用95％乙醇中沉淀，沉淀于真空烘箱35℃避光干燥36h。所得可光固化聚合物经GPC测得数均分子量M n为217k，PDI为2.08。
固化实验
分别称取0.1g实施例1、比较例1制得的亲水聚合物，溶于1mL水中，于10mW/cm 2的紫外光下照射2min，观察两个溶液固化状态。
结果表明，含实施例1制得的亲水聚合物的涂液在照射后固化成胶，溶液无法流动，含比较例1制得的亲水聚合物的涂液照射后稍变粘稠，可流动，未固化成胶。通过实施例1和比较例1的对比可知，采用本发明所述的可聚合光敏单体由于具有较长的连接链以及可参与共引发的叔胺结构，制备得到的可光固化的亲水聚合物经紫外光照射固化效率高，成胶牢固。
惟以上所述者，仅为本发明的较佳实施例而已，举凡熟悉此项技艺的专业人士在了解本发明的技术手段之后，自然能依据实际的需要，在本发明的教导下加以变化。因此凡依本发明申请专利范围所作的同等变化与修饰，曾应仍属本发明专利涵盖的范围内。

Claims (9)

  1. 一种可光固化的亲水聚合物，其特征在于：
    所述亲水聚合物由可聚合光敏单体与亲水性单体共聚而成；
    所述可聚合光敏单体含有：1)含光敏结构的单元；2)含共引发剂叔胺结构的单元；3)含有不饱和键结构的单元；
    所述含光敏结构的单元至少通过-OC(＝O)-与含共引发剂叔胺的单元相连接，所述含有不饱和键结构的单元通过所述含共引发剂叔胺的单元与所述含光敏结构的单元相连接。
  2. 根据权利要求1所述的可光固化的亲水聚合物，其特征在于：
    所述可聚合光敏单体具有通式(I)的结构：
    Figure PCTCN2019094679-appb-100001
    其中：n为1-20的整数，优选为1或2；R 1＝O或NR，R为H、1至20个C原子的直链烷基或具有3至20个C原子的支链烷基；R 2＝H、具有1至20个C原子的直链烷基或具有3至20个C原子的支链烷基。
  3. 根据权利要求1或2所述的可光固化的亲水聚合物，其特征在于：
    所述亲水性单体包括不饱和羧酸或羧酸盐、不饱和羧酸酯、不饱和酸羟烷基酯、不饱和酸聚醚酯、不饱和酸酐、不饱和酰胺、不饱和内酰胺、环氧烷烃中的一种或多种；优选地，亲水性单体选自(甲基)丙烯酸、(甲基)丙烯酰胺、乙烯基吡咯烷酮、(甲基)丙烯酸羟乙(丙)酯、聚乙二醇甲醚(甲基)丙烯酸酯、二甲基丙烯酰胺中的一种或多种；更优选地，亲水性单体选自聚乙二醇甲醚丙烯酸酯。
  4. 根据权利要求1或2所述的可光固化的亲水聚合物，其特征在于：
    所述可聚合光敏单体在所述亲水聚合物中摩尔分数为0.05-10％，优选为 0.5-5％，进一步优选为0.8-1.5％。
  5. 根据权利要求1或2所述的可光固化的亲水聚合物，其特征在于：
    所述可光固化的亲水聚合物数均分子量的范围为0.2-150万，优选为5-60万，进一步优选为15-30万。
  6. 一种涂料组合物，其特征在于：
    所述组合物包括：
    1)如权利要求1-5任一项所述的可光固化的亲水聚合物，基于涂料组合物总量而言，其质量分数为0.1-20％，优选为1-10％，进一步优选为3-5％；
    2)溶剂，质量分数为60-99.9％，优选为90-99％，更优选为95-98％。
  7. 根据权利要求6所述的涂料组合物，其特征在于：
    所述溶剂包括水、低分子量醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、丙酮、苯酚中的一种或多种，优选地，所述溶剂为水与乙醇的混合物，更优选地，水与乙醇的体积比为2:3-3:2。
  8. 一种亲水润滑涂层，所述涂层通过将权利要求6或7中任一项所述的涂料组合物固化得到。
  9. 一种包含至少一层权利要求8所述的亲水润滑涂层的制品如医疗器械。
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