CN110124115A

CN110124115A - Hydrophobic coating, preparation method, using and absorbable implantable device

Info

Publication number: CN110124115A
Application number: CN201910288635.9A
Authority: CN
Inventors: 丁建东; 齐永丽; 李昕; 何垚; 李佩泽
Original assignee: Fudan University
Current assignee: Fudan University
Priority date: 2019-04-11
Filing date: 2019-04-11
Publication date: 2019-08-16
Anticipated expiration: 2039-04-11
Also published as: CN110124115B

Abstract

The present invention relates to a kind of hydrophobic coating, preparation method, using and absorbable implantable device, hydrophobic coating be the coating that is cross-linked to form of hydrophobic monomer, hydrophobic monomer be include hydrophobic block, degradable block and the block copolymer for being crosslinked functional group.Hydrophobic coating provided by the present invention, when covering on the surface of degradation material, hydrophobic block can make the hydrophobic coating play good impermeable role in early days, and degradation material is made to hardly happen degradation；In the later period, degradable block is degraded, and the porosity of hydrophobic coating is improved, and body fluid is contacted by the hole of hydrophobic coating with degradable basis material, the degradation of basis material is promoted.

Description

Hydrophobic coating, preparation method, using and absorbable implantable device

Technical field

The invention belongs to degradation material technical fields, and in particular to a kind of hydrophobic coating, preparation method, using and can Absorb implantable device.

Background technique

In medical domain, degradation material can be degraded and be absorbed by body after End Of Service in vivo, can avoid two Negative effect caused by secondary operation is taken out and material exists, therefore be widely used in orthopaedics fixed, medicine sustained and controlled release and carry The fields such as body, tissue engineering bracket, angiocarpy bracket.

The degradation rate and mechanical property of degradation material are two kinds of important performances being concerned when it is applied to clinical.Reason The implantable device (such as degradable blood vessel bracket, absorbable bone plate, bone nail) thought usually requires to maintain in implantation early stage Good mechanical support effect for a period of time, is then degraded and absorbs again.Therefore, realize degradation material degradation rate, Matched well between the time required to mechanical property and implant site reparation is the key that the novel implantable device of exploitation will solve Problem.

Currently, the degradation material for being applied to absorbable implantable device matrix mainly includes degradable polymer (as gathered Lactic acid, polylactide glycolate copolymer, polycaprolactone etc.) and corrodible metal (such as magnesium and magnesium alloy, iron and ferroalloy, zinc And kirsite etc.).Wherein, the mechanical property of degradable polymer is generally poor, when being used for biodegradable stent, to realize enough Mechanical support effect, need the thickness to improve instrument as cost, this not only limits answering for its instrument to a certain extent With range, while being also possible to endothelium is caused to be climbed to cover the risks such as slow.For example, to realize coronary artery bracket early stage to the mechanical support of blood vessel Effect, up to 156 μm, limit it makes the thickness of the cradling piece of the polylactic acid coronary artery bracket of Abbott in thin vessels field With.Corrodible metal phase for degradable polymer have better mechanical property, but the metal or alloy such as magnesium and zinc due to Corrosion rate is fast to cause implantation early stage to be difficult to meet the requirement of mechanical support.

105327397 A of patent CN discloses a kind of mesoporous degradable implantation of calcium silicates coating of medical magnesium alloy surface The preparation of material separates connecing for magnesium alloy and corrosive medium with this in Mg alloy surface composite mesopore calcium silicates coating material Touching improves the too fast problem of Corrosion Behaviors of Magnesium Alloys, controls its degradation rate in vivo.

107789665 A of patent CN discloses a kind of preparation method of super-hydrophobic hydroxyapatite film layer of Mg alloy surface, The bar-shaped hydroxyapatite crystal layer for using hydro-thermal method to prepare a length of micro-meter scale, diameter in Mg alloy surface as nanoscale, Then stearic acid film is prepared on the hydroxyapatite film layer surface of this nanostructure, form the static liquid contact angle that drips and reach 153 ° Hydrophobic film layer, which can make the corrosion electric current density of magnesium alloy reduce by 2 orders of magnitude, and coating impedance modulus value is from 2029 Ω .cm2 117674 Ω .cm2 are increased to, the corrosion of magnesium alloy has been delayed.

Patent CN105420789A discloses pure magnesium or the hydrophobic composite biological coatings of Mg alloy surface and its preparation side Composite bio-active is made in conjunction with magnesium alloy base material and is applied by method for differential arc oxidation coating, electro-deposition hydroxyapatite coating layer Layer has the advantages that high compactness, good biocompatibility and self-bone grafting ability are good, on this basis, using water repellent agent pair Composite biological coatings have carried out hydrophobic treatment, have prepared hydrophobic composite biological coatings, obtained hydrophobic compound life Object active coating can be greatly improved to the corrosion-resistant of simulated body fluid, and improve self-bone grafting ability.

However existing published patent mostly uses the coating prepared based on inorganic material to reduce degradable basis material Degradation rate, and inorganic material coating is often more crisp, therefore it is only applicable to orthopaedics implant, to coating toughness reguirements compared with It is then difficult in high degradable angiocarpy bracket, cerebrovascular stent etc.；In addition, the inorganic material coating in publication There is special requirement to preparation process and basis material, is confined to the processing to magnesium and magnesium alloy materials.And the friendship in this patent Joining hydrophobic coating has preferable obdurability, can be used in a variety of instruments such as cardiovascular and cerebrovascular bracket, orthopaedics implant；And this patent In hydrophobic cross-linker coating have universality, can by common coating production be coated in various degradable basis material tables Regulated and controled in face of its degradation rate.

Summary of the invention

The purpose of the present invention is to solve the above-mentioned problems and provide a kind of hydrophobic coating, preparation method, using and Absorbable implantable device.

The purpose of the present invention is achieved through the following technical solutions:

A kind of hydrophobic coating is covered in the surface of degradation material, which is characterized in that the hydrophobic coating is hydrophobic monomer friendship Join the coating formed or hydrophobic monomer and the cross-linked coating to be formed is blended with non-degradable component, wherein the hydrophobic monomer To include hydrophobic block, degradable block and the block copolymer for being crosslinked functional group.

Preferably, the hydrophobic block is formed by hydrophobic polymer, and the degradable block is by degradable polymer shape At polymerization reaction occurs for hydrophobic polymer and degradable polymer, forms the hydrophobic block being connected by chemical bond and can drop Block is solved, crosslinking functional group is connected with hydrophobic block and/or degradable block by chemical bond, promotes to send out between hydrophobic monomer Life is cross-linked to form hydrophobic coating.

Preferably, the hydrophobic block is by dimethyl silicone polymer, perfluoropolyether, polyvinyldifluoride, polytetrafluoroethylene (PTFE), poly- The formation of at least one of hexafluoropropene or Kynoar-hexafluoropropylene copolymer.

Preferably, the degradable block is formed by degradable polymer, the degradable polymer be selected from polyglycolide, Polyglycolic acid, Poly L-lactide, poly- D, L- lactide, poly butyric ester, poly-epsilon-caprolactone, poly- ε-alkyl replace in oneself At least one of ester, poly- δ-valerolactone, poly-β-hybroxybutyric acid, polycarbonate or polyether ester；

Alternatively, the degradable polymer is to form polyglycolide, polyglycolic acid, Poly L-lactide, poly- D, L- third is handed over Ester, poly butyric ester, poly-epsilon-caprolactone, poly- ε-alkyl replace caprolactone, poly- δ-valerolactone, poly-β-hybroxybutyric acid, poly- carbon At least two copolymers formed in the monomer of acid esters or polyether ester.

Preferably, the molecular weight of the degradable block is 500~20000, and the degree of polymerization of degradable block is 20~40.

Preferably, the crosslinking functional group is selected from allyl, acryloyl group, methylacryloyl, epoxy group, oxazoline At least one of base, cyanic acid base, silicone hydroxyl or siloxy.

Preferably, the non-degradable group is selected from silicon rubber, polysiloxanes, polysilazane or fluoropolymer extremely Few one kind.Preferably, the hydrophobic coating with a thickness of 0.01~100 μm, further preferably 1~20 μm.

A kind of preparation method of hydrophobic coating, comprising:

Hydrophobic monomer is provided, Xiang Suoshu hydrophobic monomer bestows initiation conditions, the hydrophobic monomer is made to crosslink and be formed The hydrophobic coating；

Alternatively, providing the mixture of hydrophobic monomer and non-degradable component, Xiang Suoshu hydrophobic monomer and non-degradable component Mixture bestow initiation conditions, so that the non-degradable component is crosslinked or make the hydrophobic monomer and non-degradable component Between crosslink to form the hydrophobic coating.

The initiation conditions are ultraviolet light, heat treatment or moisture effect.

Ultraviolet light includes: after mixing the hydrophobic monomer with photoinitiator, with the ultraviolet light of 365nm 30min~2h；The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone, and the quality of the photoinitiator is described The 1 ‰ of the quality of hydrophobic monomer.

Heat treatment includes: by the hydrophobic monomer or hydrophobic monomer and the mixture of non-degradable component in 20~150 DEG C Lower processing 30min~72h；

Moisture effect includes: that the mixture of the hydrophobic monomer or hydrophobic monomer and non-degradable component is placed in moisture ring It is reacted 1~5 day under border.

The hydrophobic coating is applied in the degradation behavior for delaying degradation material.

A kind of absorbable implantable device, including absorbable matrix, the surface for caning absorb matrix cover hydrophobic coating.

Preferably, the material of the absorbable matrix is degradable polymer, corrodible metal or corrodible metal With degradable polymer composite material.

Preferably, the absorbable implantable device further includes adhesive layer, and the adhesive layer is located at the absorbable matrix Between the hydrophobic coating.

Preferably, the material of the adhesive layer is selected from least one of dopamine and silane coupling agent.

The absorbable implantable device is angiocarpy bracket, cerebrovascular stent, peripheral vascular stents, biliary tract rack, food Road bracket, airway stent, urethra rack, plugging device, orthopaedics implant or absorbable suture.

Hydrophobic coating provided by the present invention, between hydrophobic monomer or hydrophobic monomer is formed with non-degradable component cross-link Coating, hydrophobic monomer includes degradable block, hydrophobic block and crosslinking functional group, when hydrophobic coating is covered degradable material When expecting on the surface of (such as degradable basis material), hydrophobic block can make the hydrophobic coating play good water proof work in early days With making degradation material hardly happen degradation.In the later period, degradation occurs for degradable block and its catabolite is slowly permeated and dredged Water coating improves the porosity of hydrophobic coating, and body fluid is enabled to pass through the hole of hydrophobic coating and degradable basis material Contact, degradable basis material starts to degrade at this time.Therefore, which can delay the degradation of degradation material.

Detailed description of the invention

Fig. 1 is the schematic cross-section of the absorbable implantable device of an embodiment；

Fig. 2 is the schematic cross-section of the absorbable implantable device of another embodiment；

Fig. 3 is the molecular formula of the hydrophobic monomer of embodiment 1；

Fig. 4 is the physical state figure of the hydrophobic monomer of embodiment 1；

Fig. 5 A is the surface contact angle test result figure of the PLA coating of embodiment 1；

Fig. 5 B is the surface contact angle test result figure of the hydrophobic coating of embodiment 1；

Fig. 6 be embodiment 1 the hydrophobic coating containing different-thickness iron plate and contain only PLA coating iron plate erosion profile Figure；

Fig. 7 is the molecular formula of the hydrophobic monomer of embodiment 2；

Fig. 8 is the physical state figure of the hydrophobic monomer of embodiment 2；

Fig. 9 is atomic force microscope (AFM) scanning figure of the hydrophobic coating of embodiment 2；

Figure 10 be embodiment 2 the hydrophobic coating containing different-thickness iron plate and contain only PLA coating iron plate corrosion shape Looks figure；

Figure 11 is atomic force microscope (AFM) scanning figure of the hydrophobic coating of embodiment 8；

Figure 12 is the magnesium alloy plate containing hydrophobic coating of embodiment 8, the magnesium alloy plate containing hydrophobic coating of embodiment 8 and naked The comparison diagram of the amounts of hydrogen discharged in the corrosion test of magnesium alloy plate；

Figure 13 A~Figure 13 B is the different curing time surface-element distribution maps of organopolysilazane of embodiment 11.

In figure: 100- can absorb matrix；200- hydrophobic coating；300- adhesive layer；The outer surface 110-；120- inner surface； The side 130-.

Specific embodiment

To keep the above objects, features and advantages of the present invention more obvious and easy to understand, with reference to the accompanying drawing to tool of the invention Body embodiment is described in detail.Following description elaborates many details to fully understand the present invention.But The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to originally Similar improvement is done in the case where invention intension, therefore the present invention is not limited by the specific embodiments disclosed below.

Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that the limitation present invention.

The hydrophobic coating of one embodiment, the hydrophobic coating are the cross-linked coating that hydrophobic monomer is cross-linked to form.Hydrophobic monomer To include hydrophobic block, degradable block and the block copolymer for being crosslinked functional group.Wherein, hydrophobic block, degradable block It is connected with crosslinking functional group by chemical bond.Hydrophobic monomer exists with the formation being crosslinked.Crosslinked between hydrophobic monomer and Form hydrophobic coating.

Hydrophobic block is formed by hydrophobic polymer, and degradable block is formed by degradable polymer, hydrophobic polymer And polymerization reaction occurs for degradable polymer, to form the hydrophobic block and degradable block being connected by chemical bond.Crosslinking Functional group is connected with hydrophobic block and/or degradable block by chemical bond, for promoting the crosslinking of hydrophobic monomer.

Hydrophobic block is indicated with A, indicates degradable block with B, is indicated crosslinking functional group with C, in one embodiment, is dredged Aqueous monomer is C-B-A-B-C or C-A-B-A-C.In another embodiment, crosslinking functional group C is not necessarily located in end, can be with Positioned at any position in addition to end of hydrophobic monomer strand.

In one embodiment, hydrophobic block by dimethyl silicone polymer, perfluoropolyether, polyvinyldifluoride, polytetrafluoroethylene (PTFE), The formation of at least one of polyhexafluoropropylene and Kynoar-hexafluoropropylene copolymer.

In one embodiment, degradable block is formed by degradable polymer.In one embodiment, degradable polymer energy Enough degradations generate acid product.In one embodiment, degradable polymer is selected from polyglycolide, polyglycolic acid, poly- L- third and hands over Ester, poly- D, L- lactide, poly butyric ester, poly-epsilon-caprolactone, poly- ε-alkyl replace caprolactone, poly- δ-valerolactone, poly- β-hydroxyl At least one of base butyrate, polycarbonate and polyether ester.

In a further embodiment, degradable polymer is to form polyglycolide, polyglycolic acid, Poly L-lactide, gather D, L- lactide, poly butyric ester, poly-epsilon-caprolactone, poly- ε-alkyl replace caprolactone, poly- δ-valerolactone, Poly-β-hydroxybutyric acid At least two copolymers formed in ester, polycarbonate and polyether ester in monomer.

In one embodiment, crosslinking functional group is selected from allyl, acryloyl group, methylacryloyl, epoxy group, oxazole At least one of quinoline base, cyanic acid base, silicone hydroxyl and siloxy.

In one embodiment, hydrophobic coating include a kind of hydrophobic monomer, same hydrophobic monomer be cross-linked with each other to be formed it is hydrophobic Coating.In another embodiment, hydrophobic coating includes at least two different hydrophobic monomers, at least two different hydrophobic monomers It is cross-linked with each other to form hydrophobic coating.Also, the mass ratio of at least two different hydrophobic monomers can be arbitrary proportion.

Above-mentioned hydrophobic coating is covered on the surface of degradation material, for example, being set to the hydrophobic coating by that can drop When solving the surface for the matrix that material is formed, hydrophobic block can make the hydrophobic coating that can play preferable impermeable role in early stage, make The matrix formed by degradation material is hardly happened in water environment (for example, blood environment) and is corroded or degraded.It, can in the later period Degradation occurs for degradation block and its catabolite slowly permeates hydrophobic coating, the porosity of hydrophobic coating is improved, so that body fluid It can be contacted by the hole of hydrophobic coating with degradation material, at this point, degradation material starts to degrade.Therefore, hydrophobic coating It can delay the degradation of degradation material.

Also, it is degradable embedding when degradable block is generated the degradable polymer of acid product and formed by that can degrade Section degradation generates acid product, and so as to generate local slightly acidic environment around degradation material, further promoting can The degradation of degradable material accelerates the degradation of later period degradation material.

In one embodiment, the molecular weight of degradable block is 500~20000.In another embodiment, degradable block Molecular weight be 1440~4080.In one embodiment, the degree of polymerization of the degradable block in hydrophobic monomer is 20~40.Such as This, is conducive to the catabolite for controlling the degradable block in hydrophobic monomer, to further regulate and control the degradation of degradation material Behavior.

In another embodiment, hydrophobic coating also includes non-degradable component.Non-degradable component cross-link forms cross-linked network Network, hydrophobic monomer are scattered in cross-linked network.Non-degradable component cross-link formed cross-linked network so that the hydrophobic coating have compared with Good hydrophobic performance can delay degradation material to corrode or degrade, in the later period, with degradable in hydrophobic monomer in early stage The degradation of block improves the porosity of hydrophobic coating, and body fluid is enabled to pass through the hole of hydrophobic coating and degradable matrix Material, degradable basis material starts to degrade at this time.In this embodiment, it is not crosslinked between hydrophobic monomer.Another It in outer embodiment, is cross-linked with each other between hydrophobic monomer, is cross-linked with each other between non-degradable component.

Specifically, non-degradable group is selected from least one in silicon rubber, polysiloxanes, polysilazane and fluoropolymer Kind.In one embodiment, silicon rubber is 184 silicon rubber of DOW CORNING, and polysilazane is organopolysilazane.

In one embodiment, hydrophobic coating is the coating that hydrophobic monomer and non-degradable component cross-link are formed.Hydrophobic monomer It is crosslinked with non-degradable component and refers to that the strand of hydrophobic monomer and the strand of non-degradable component crosslink, and dredged Aqueous monomer does not crosslink itself, and non-degradable component does not also crosslink itself.

In one embodiment, no matter in the form of noncrosslinking exist or in the form of crosslinking presence, i.e., no matter hydrophobic list Body, which is scattered in non-degradable component cross-link formation cross-linked network, forms hydrophobic coating or hydrophobic monomer and non-degradable component The mass ratio of the coating being cross-linked to form, hydrophobic monomer and non-degradable component is 1:100~1:0.01.

In one embodiment, hydrophobic coating with a thickness of 0.01~100 μm.By the way that the thickness of hydrophobic coating is rationally arranged, Further to regulate and control the degradation behavior of degradation material, the degradation behavior of degradation material is enable to meet expection.For example, when dredging When water coating is set on the matrix of absorbable stent, early stage implantation, hydrophobic coating can play impermeable role, from And delay the time point of matrix starting corrosion or starting degradation, matrix premature corrosion is avoided, to guarantee at vascular lesion position The reparation phase in, matrix is able to maintain enough radial support performances.In the later period of implantation, after the completion of diseased region reparation, Degradable block is degraded, and acid catabolite is generated, and acid catabolite can promote corroding or degrading for matrix, So that metal degrades as early as possible and by Matrix absorption, to be conducive to avoid Long-Term Clinical risk.

In one embodiment, hydrophobic coating with a thickness of 1~20 μm.

When degradable block is generated the degradable polymer of acid product and is formed by that can degrade, above-mentioned hydrophobic coating energy The behavior for enough regulating and controlling degradation material, that is, delay the degradation of degradation material early stage, and accelerate the degradation in degradation material later period. Thus, which can be applied to need the field of the degradation behavior of degradation material.For example, the hydrophobic coating can Applied to absorbable implantable device field.

The preparation method of the hydrophobic coating of one embodiment, includes the following steps:

Step 110: providing hydrophobic monomer, hydrophobic monomer is comprising hydrophobic block, degradable block and crosslinking functional group Block copolymer.

Hydrophobic monomer is same as described above, and details are not described herein again.

In one embodiment, hydrophobic monomer is prepared using following methods:

With the polymer of the formation hydrophobic block containing terminal hydroxyl, (i.e. hydroxyl, following form of presentation are all contained in A-OH, both ends Indicate the identical meaning, hereafter repeat no more) as initiator, synthesis end hydroxyl includes hydrophobic block and degradable embedding The polymer (i.e. B-A-B-OH) of section then includes hydrophobic block and degradable block with acryloyl chloride and end hydroxyl The terminal hydroxyl of polymer reacts, and obtains hydrophobic monomer of the end containing acryloyl group.Use this method synthesize hydrophobic monomer for C-B-A-B-C, C are acryloyl group.

For example, the polymer of the formation hydrophobic block containing terminal hydroxyl is PDMS₇₆- OH, by PDMS₇₆- OH is as initiation Agent synthesizes PTMC₂₀-PDMS₇₆-PTMC₂₀Then-OH uses acryloyl chloride and PTMC₂₀-PDMS₇₆-PTMC₂₀- OH reaction, generates PTMC₂₀-PDMS₇₆-PTMC₂₀- DA, i.e. hydrophobic monomer.Wherein, DA indicates that the both ends of the strand of hydrophobic monomer are acryloyl group, PDMS₇₆Indicate PDMS₇₆The existence form (i.e. hydrophobic block) after reacted in hydrophobic monomer is participated in, for convenience of indicating, is still used PDMS indicates that PDMS participates in the PDMS block formed after reaction.It is all the same that following table states mode, repeats no more.

In a specific embodiment, the polymer (HO-B- comprising hydrophobic block and degradable block of end hydroxyl A-B-OH synthesis foundation document G.M.Zentner, R.Rathi, C.Shih, J.C.McRea, M.H.Seo, H.Oh), B.G.Rhee,J.Mestecky,Z.Moldoveanu,M.Morgan,S.Weitman,Biodegradable block copolymers for delivery of proteins and water-insoluble drugs, Synthetic method in J.Control.Release 72 (2001) 203-215 carries out.Acryloyl chloride includes with end hydroxyl Specific method foundation document Z.S.Ge, the Y.M.Zhou of the terminal hydroxyl reaction of the polymer of hydrophobic block and degradable block, J.Xu,H.W.Liu,D.Y.Chen,S.Y.Liu,High-Efficiency Preparation of Macrocyclic Diblock Copolymers via Selective Click Reaction in Micellar Media, The method of J.Am.Chem.Soc.131 (2009) 1628-1629 carries out.

In another embodiment, using the polymer (i.e. B-OH) of the degradable block of formation containing terminal hydroxyl as initiation Agent synthesizes the polymer (i.e. HO-A-B-A-OH) comprising degradable block and hydrophobic block of end hydroxyl, then uses propylene Acyl chlorides is reacted with the terminal hydroxyl of the polymer comprising degradable block and hydrophobic block of end hydroxyl, obtains hydrophobic list Body.The hydrophobic monomer for using this method to synthesize is C-A-B-A-C, wherein C is acryloyl group.

In other embodiments, when C is other crosslinking functional groups, with the packet of corresponding compound and end hydroxyl The terminal hydroxyl reaction (HO-A-B-A-OH) of polymer containing degradable block and hydrophobic block with end hydroxyl includes The terminal hydroxyl of the polymer reaction (HO-B-A-B-OH) of hydrophobic block and degradable block reacts, for example, using epoxychloropropane It is reacted with the terminal hydroxyl of the polymer comprising degradable block and hydrophobic block of end hydroxyl, generates crosslinking functional group For the hydrophobic monomer of epoxy group.Include degradable block and hydrophobic embedding with three ethoxy silicon propylisocyanates and end hydroxyl The terminal hydroxyl reaction of the polymer of section generates the hydrophobic monomer that crosslinking functional group is siloxy group.

In a further embodiment, crosslinking functional group C can be located at any in addition to end of hydrophobic monomer strand When position, the method hydrophobic synthetic of 57 (2015) 21-28 of bibliography T.Wang, M.Yan, X.Sun, D.Quan, Polymer Monomer.

In one embodiment, hydrophobic monomer is dissolved in solvent, is configured to the solution containing hydrophobic monomer.The solution is coated In the surface of the matrix formed by degradation material, uncrosslinked coating is formed on the surface of matrix.Solvent is that can dissolve this The solvent of hydrophobic monomer, such as ethyl acetate, acetone, acetonitrile.The method of coating is any side that those skilled in the art grasp Method, such as ultrasonic spraying, spin coating, dip-coating or drop coating.

It should be noted that in one embodiment, a kind of hydrophobic monomer is dissolved in solvent, it is configured to only dredge containing a kind of The solution of aqueous monomer.In another embodiment, at least two different hydrophobic monomers can be dissolved in solvent, be configured to containing The solution of at least two different hydrophobic monomers, also, at least two different hydrophobic monomers can be any proportion.

Step 120: bestowing initiation conditions to hydrophobic monomer, hydrophobic monomer is made to crosslink and form hydrophobic coating.

Initiation conditions are bestowed to the uncrosslinked coating of matrix surface, i.e., bestows initiation conditions to hydrophobic monomer, makes hydrophobic Monomer crosslinks, and generates flexible, rubbery state hydrophobic coating.

In one embodiment, initiation conditions are ultraviolet light, heat treatment or moisture effect.

In one embodiment, ultraviolet light causes the method for crosslinking and includes: after mixing hydrophobic monomer with photoinitiator, With ultraviolet light 30min~2h of 365nm.Specifically, hydrophobic monomer is dissolved in solvent, is configured to containing the molten of hydrophobic monomer After liquid, before being crosslinked, photoinitiator is added to the solution for containing hydrophobic monomer, and after mixing, be coated on by On the surface for the matrix that degradation material is formed, then with ultraviolet light 30min~2h of 365nm, so that between hydrophobic monomer It is cross-linked with each other, to generate hydrophobic coating.

In one embodiment, photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone.It is appreciated that in other realities It applies in example, under action of ultraviolet light, the photoinitiator that can cause hydrophobic monomer crosslinking can be applied for other.It is 5000 in intensity ~15000 μ W/cm²Ultraviolet light under irradiate 30min~2h, the amount of photoinitiator should be enough to keep hydrophobic monomer full cross-linked, with Elasticity, rubbery state hydrophobic coating is generated, makes the hydrophobic coating that there is enough intensity.In one embodiment, photoinitiator Quality be hydrophobic monomer quality 1 ‰.

In one embodiment, the method that heat treatment causes crosslinking includes: to handle hydrophobic monomer at 20~150 DEG C 30min~72h.That is, the solution containing hydrophobic monomer to be coated on to the surface of matrix, uncrosslinked coating is formed on the surface of matrix Afterwards, 30min~72h is handled at 20~150 DEG C, and the hydrophobic monomer of matrix surface is made to crosslink and generate covering matrix surface Hydrophobic coating.

In one embodiment, the step of moisture effect causes crosslinking includes: that hydrophobic monomer is placed under wet gas environments to react 1 ~5 days.Wherein, wet gas environments are air environment or the atmosphere with certain humidity.

In one embodiment, when containing the timesharing of non-degradable group in hydrophobic coating, make to drop using heat-treating methods Solve component cross-link.The method that heat treatment causes non-degradable component cross-link includes: that hydrophobic monomer is dissolved in solvent, is configured to contain After the solution of hydrophobic monomer, non-degradable component is added to the solution for containing hydrophobic monomer, after mixing, is coated on by can On the surface for the matrix that degradable material is formed, 30min~72h is handled at 20~150 DEG C, so that between non-degradable component It is cross-linked with each other to form cross-linked network, hydrophobic monomer is scattered in cross-linked network, to generate hydrophobic coating.

In one embodiment, when containing the timesharing of non-degradable group in hydrophobic coating, non-degradable group is made using moisture effect Divide crosslinking.The step of moisture effect causes crosslinking includes: that hydrophobic monomer is dissolved in solvent, is configured to the solution containing hydrophobic monomer Afterwards, non-degradable component is added to the solution for containing hydrophobic monomer, after mixing, coated on what is formed by degradation material On the surface of matrix, it is subsequently placed under wet gas environments and reacts 2~5 days, non-degradable component is made to crosslink to form cross-linked network, Hydrophobic monomer is scattered in the cross-linked network.Wherein, wet gas environments are air environment or the atmosphere with certain humidity.

It should be noted that can be closed by selection when containing hydrophobic monomer and non-degradable group timesharing in hydrophobic coating Proportion between suitable crosslinking condition and suitable hydrophobic monomer and non-degradable component makes mutually to hand between non-degradable component It is cross-linked with each other between connection and hydrophobic monomer, or the crosslinking between non-degradable component only occurs, do not handed between hydrophobic monomer Connection.

It is the preparation method simple process of above-mentioned hydrophobic coating, low for equipment requirements, further, it is possible to directly need drop Form hydrophobic coating on the matrix of solution behavior, a step is completed, relative to first preparing hydrophobic coating, then by hydrophobic coating with need to adjust The mode that the degradable matrix of control combines, efficiency are higher.

Further, a kind of absorbable implantable device is provided.Referring to Fig. 1, the absorbable implanted of an embodiment Instrument, including absorbable matrix 100 and the hydrophobic coating 200 on absorbable 100 surface of matrix.

Wherein, matrix 100 is can absorb to be formed by the material (i.e. degradation material) of bioabsorbable.In an embodiment In, the material for caning absorb matrix 100 is degradable polymer, corrodible metal or corrodible metal and degradable polymer Composite material.

In one embodiment, degradable polymer is selected from least one of degradable polyester and degradable poly acid anhydrides.Its In, degradable polyester is selected from polyglycolide, polyglycolic acid, Poly L-lactide, Poly D,L-lactide, poly butyric ester, gathers 6-caprolactone, poly- ε-alkyl replace in caprolactone, poly- δ-valerolactone, poly-β-hybroxybutyric acid, polycarbonate and polyether ester extremely Few one kind.Degradable poly acid anhydrides is selected from bis- (to the carboxyphenoxy) propane-decanedioic acid of poly- 1,3-, poly- erucic acid dimer-decanedioic acid And at least one of poly- fumaric acid-decanedioic acid.

In another embodiment, degradable polymer is to be formed in the monomer of aforementioned degradable polyester and degradable poly acid anhydrides At least two copolymerization made of copolymer.

The corrodible corrodible pure metal of metal finger or corrodible alloy.In one embodiment, corrodible metal For pure iron, ferrous alloy, pure magnesium, magnesium base alloy, pure zinc or zinc-containing alloy.In one embodiment, corrodible metal is to pass through The corrodible metal of processing, for example, corrodible metal is the pure iron of nitriding.

In one embodiment, corrodible metal and degradable polymer composite material refer to corrodible metal with it is degradable The material of compression moulding after polymer is blended.Processing further is carried out to the material of the compression moulding and forms absorbable matrix 100.

In another embodiment, corrodible metal refers to corrodible metal and can drop with degradable polymer composite material The material that the object that depolymerizes is combined with layer structure.For example, forming matrix by corrodible metal, degradable polymer is with coating Form or the form of membranoid substance are attached on the surface of matrix, form absorbable matrix 100.Alternatively, by degradable polymer shape At matrix, corrodible metal is attached on the surface of matrix in the form of coating or in the form of membranoid substance, forms absorbable base Body 100.

In one embodiment, corrodible metal be pure iron or ferroalloy, degradable polymer be selected from degradable polyester and At least one of degradable poly acid anhydrides, degradable polymer are attached to iron matrix in the form of coating or in the form of membranoid substance On surface, absorbable matrix 100 is formed.Hydrophobic coating 200 is covered on degradable polymer coating.It is implantation early stage, hydrophobic Coating 200 protects absorbable matrix 100 not degrade.Hole is formed after the degradable block degradation in hydrophobic coating 200, Degradable polymer in absorbable matrix 100 starts to degrade, the acidity that the degradable block degradation in hydrophobic coating 200 generates The acid degradation products that degradable polymer in catabolite and absorbable matrix 100 generates can accelerate the corruption of iron matrix Erosion is not corroded, later period accelerated corrosion to regulate and control absorbable medical instrument early stage.

Referring to Fig. 1, caning absorb matrix 100 has outer surface 110, inner surface 120 and side 130.Wherein, as general Absorbable implantable device is implanted into diseased region, such as when by absorbable implantable device implantable intravascular, outer surface 110 be with The surface of vascular wall contact, inner surface 120 is the surface directly contacted with blood.Outer surface 110 and inner surface 120 are opposite, side Face 130 connects outer surface 110 and inner surface 120.When absorbable implantable device to be implanted into the diseased region of other non-vascular, Inner surface 120 is the surface directly contacted with the body fluid of implant site.Hydrophobic coating 200 at least covers absorbable matrix 100 Inner surface 120, early stage after the implantation, hydrophobic coating 200 can be preferably by the inner surfaces 120 and body of absorbable matrix 100 Liquid isolation avoids the absorbable starting corrosion too early of matrix 100 or starting degradation too early.

As shown in Figure 1, in one embodiment, hydrophobic coating 200 coats all surface of absorbable matrix 100 completely, i.e., Outer surface 110, inner surface 120 and the side 130 of absorbable matrix 100 are covered by hydrophobic coating 200 completely.In this way, one Aspect, hydrophobic coating 200 are complete, continuous coating, during after the implantation expanding absorbable matrix 100, favorably In avoiding hydrophobic coating 200 from falling off；On the other hand, all surfaces of absorbable matrix 100 are completely covered in hydrophobic coating 200, have Preferably protect absorbable matrix 100 conducive to early stage after the implantation, and the later period promote absorbable 100 homogeneous corrosion of matrix or Uniformly degradation.

In another embodiment, hydrophobic coating 200 only covers the inner surface 120 of absorbable matrix 100, and in absorbable base Distribution on the outer surface 110 and side 130 of body 100 without hydrophobic coating 200.In other embodiments, hydrophobic coating 200 Outer surface 110 and the inner surface 120 of absorbable matrix 100 are covered simultaneously.Alternatively, hydrophobic coating 200 covers absorbable base simultaneously 100 inner surface 120 of body and side 130.Hydrophobic coating 200 is arranged such, also can delay to can absorb preferably early stage implantation The time point of starting corrosion or the starting degradation of matrix 100, and in the later period with the drop of the degradable block in hydrophobic coating 200 Solution generates acid product and promotes the fast erosion or fast degradation that can absorb matrix 100.

The material of hydrophobic coating 200 is same as described above, and details are not described herein again.It should be noted that working as hydrophobic coating When can generate acid product after the degradable block degradation in 200, in the later period of implantation, with the continuous drop of degradable block Solution, is constantly be generated acid product, and acid product can infiltrate into the outer of absorbable implantable device from hydrophobic coating 200 Portion, thus the environment of the implant site formation lower ph in absorbable implantable device, so as to further promote to inhale Receive fast erosion or the degradation of matrix 100.Hydrophobic coating 200 can not only delay the absorbable starting of matrix 100 corrosion or starting The time point of degradation, additionally it is possible to which the later period after the early stage to implantation after implantation constantly regulates and controls the degradation of absorbable matrix 100 Behavior.That is, the early stage of hydrophobic coating 200 after the implantation, delays the time of the absorbable starting of matrix 100 corrosion or starting degradation Point avoids the absorbable starting corrosion too early of matrix 100 or starting degradation, to avoid before the reparation of diseased region is completed Absorbable matrix 100 prematurely loses mechanic properties.After the reparation of diseased region is completed, degradable block not stopping pregnancy Raw acid product can promote the fast erosion or fast degradation of absorbable matrix 100, be conducive to avoid Long-Term Clinical risk Generation.

It, can by the way that the hydrophobic coating 200 that thickness is only 0.01~100 μm is arranged on the surface of absorbable matrix 100 Regulate and control the degradation behavior in later period of the absorbable early stage of matrix 100 after the implantation to after being implanted into, so that absorbable matrix 100 is (i.e. Degradation material) degradation rate and mechanical property and implant site repair the time required between can matched well, to make Obtain requirement that the absorbable implantable device meets early stage support and later period fast erosion or degradation.

It should be noted that hydrophobic coating 200 can prematurely degrade when the thickness of hydrophobic coating 200 is less than 0.01 μm, Effect so as to cause the time point for delaying the absorbable starting of matrix 100 corrosion or starting degradation is not significant；When hydrophobic coating 200 Thickness when being greater than 100 μm, a degree of adverse effect may be generated to the adherence quality of absorbable implantable device, and And, it is also possible to can improve absorbable implantable device enters sheath resistance, and causes difficulty of transportation.Therefore, in one embodiment, dredge Water coating 200 with a thickness of 0.01~100 μm.Thickness is only 0.01~100 μm of hydrophobic coating 200 can be from the morning after implantation Rear period regulation of the phase to after being implanted into can absorb the degradation behavior of matrix 100, also, the thickness of hydrophobic coating 200 is arranged 0.01 The compressed radial dimension of absorbable implantable device will not be dramatically increased in~100 μ ms, because without significantly increase can Absorb implantable device enters sheath resistance, also not will cause difficulty of transportation.

After the impermeable role of comprehensive early stage, the promotion in later period degrade or promote corrosiveness, the fairness of conveying and implantation Adherence quality several respects factor, in one embodiment, hydrophobic coating 200 with a thickness of 1~20 μm.

In one embodiment, referring to Fig. 2, absorbable implantable device further includes adhesive layer 300.Adhesive layer 300 is located at Between absorbable matrix 100 and hydrophobic coating 200.Adhesive layer 300 is set, to improve hydrophobic coating 200 and absorbable matrix 100 Between binding force, be securely attached to hydrophobic coating 200 more on the surface of absorbable matrix 100, be conducive to avoid Hydrophobic coating 200 falls off in the process of expansion of the absorbable implantable device, to improve the absorbable implantable device Reliability.

In one embodiment, the material of adhesive layer 300 is selected from least one of dopamine and silane coupling agent.In addition Embodiment in, the material of adhesive layer 300 is not limited to dopamine and silane coupling agent, any to have adhesive property and bio-compatible The preferable material of property can be applied in adhesive layer 300.

It is appreciated that adhesive layer 300 is in the distribution on absorbable 100 surface of matrix and hydrophobic coating 200 in absorbable matrix The distribution on 100 surfaces is identical.

Above-mentioned absorbable implantable device is any implanted device that need to meet early stage support, later period fast erosion or degradation Tool.For example, absorbable implantable device is angiocarpy bracket, cerebrovascular stent, peripheral vascular stents, biliary tract rack, esophagus branch Frame, airway stent, urethra rack, plugging device, orthopaedics implant or absorbable suture etc..

Above-mentioned absorbable implantable device is can absorb the preparation method comprises the following steps: preparing by the method that those skilled in the art grasp After matrix 100, hydrophobic coating 200 is formed on absorbable matrix 100 using with the above-mentioned identical method of hydrophobic coating for preparing, i.e., Solution containing hydrophobic monomer is coated on to the table of absorbable matrix 100 using the methods of ultrasonic spraying, spin coating, dip-coating or drop coating On face, the hydrophobic of absorbable 100 surface of matrix is then made using the method for the crosslinkings such as ultraviolet light, heat treatment or moisture effect Monomer and/or non-degradable component are cross-linked with each other, to form hydrophobic coating 200 on the surface of absorbable matrix 100.

It is appreciated that first being prepared on absorbable matrix 100 when absorbable implantable device includes also adhesive layer 300 After adhesive layer 300, then prepare the hydrophobic coating 200 of covering adhesive layer 300.Ultrasound spraying, rotation can be used in the preparation of adhesive layer 300 The method that the those skilled in the art such as painting, dip-coating or drop coating grasp.In one embodiment, it before preparing adhesive layer 300, also wraps The step of being surface-treated to absorbable matrix 100 is included, so that adhesive layer 300 is more reliably set to absorbable matrix 100 surface.For example, the surface to absorbable matrix 100 carries out oxygen plasma treatment, make the surface shape of absorbable matrix 100 At hydroxyl, is reacted so that with silane coupling agent chemical bonding occurs for hydroxyl, generate adhesive layer 300.

Above-mentioned hydrophobic coating and absorbable implantable device are further described with specific embodiment below, embodiment 1-19 Hydrophobic coating component is shown in Table 1.

20~embodiment of embodiment 24 and 1~comparative example of comparative example 4 use following test method:

Vivo sample metal weightless measurement method: absorbable implantable device was implanted into animal body after a period of time and is put to death Animal, and absorbable implantable device is taken out.High resolution scanning is carried out using the micro-CT that resolution ratio is 5 μm, and to knot Fruit is handled, and the volume of undegraded metal is calculated, to calculate volume/original metal body of the undegraded metal of weightlessness=1- Product.

1 embodiment 1-19 hydrophobic coating component of table

Embodiment 1

It will be cut into 22mm × 26mm with a thickness of 200 μm of pure iron piece (purity > 99.9%), with 800,1500,2000,3000 Purpose sand paper is successively polished, and the iron plate after polishing is placed in acetone and dehydrated alcohol and is successively cleaned by ultrasonic 10min, then uses nitrogen Iron plate is placed in 60 DEG C of baking oven sufficiently dry by the dry iron plate surface of air-blowing.

The polylactic acid (PLA) that molecular weight is 60,000 is dissolved in ethyl acetate, compound concentration is that the polylactic acid of 0.01g/mL is molten Liquid.The PLA solution is sprayed on to the iron plate surface handled well using ultrasonic spray coating method, preparation surface has with a thickness of 4 μm The iron plate of PLA coating.The flow velocity that feed flow is pumped in spraying process is 0.1mL/min, ultrasonic power 5.0W.Surface there is into PLA painting The iron plate of layer, which is placed in draught cupboard, makes ethyl acetate solvent sufficiently volatilize.

With reference to the first dimethyl silicone polymer (PDMS with end containing double alkane hydroxyls of method in above-mentioned document₇₆- OH) it is to draw It sends out agent and synthesizes PTMC of the end containing double hydroxyls₂₀-PDMS₇₆-PTMC₂₀- OH, referring again to the method in document using acryloyl chloride with Terminal hydroxyl reaction obtains polytrimethylene carbonate-dimethyl silicone polymer-polytrimethylene carbonic acid of acryloyl group sealing end Ester, i.e. PTMC₂₀-PDMS₇₆-PTMC₂₀-DA。PTMC₂₀-PDMS₇₆-PTMC₂₀The structural formula and physical state of-DA respectively such as Fig. 3 and Shown in 4.

By macromonomer PTMC₂₀-PDMS₇₆-PTMC₂₀- DA (i.e. hydrophobic monomer) is dissolved in ethyl acetate, prepares concentration For the solution containing hydrophobic monomer of 0.02g/mL；Photoinitiator 2- hydroxyl-is added in the above-mentioned solution containing hydrophobic monomer 2- methyl-1-phenyl-1- acetone obtains mixed liquor, wherein the quality of photoinitiator is the 1 ‰ of the quality of hydrophobic monomer.Using Above-mentioned mixed liquor is sprayed on the PLA coating surface of the above-mentioned iron plate for having PLA coating by ultrasonic spray coating method, pumps feed flow in spraying process Flow velocity is 0.1mL/min, ultrasonic power 4.75W.Number is sprayed by control, preparation surface is with different thickness uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀The sample of-DA coating.

It is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to above-mentioned uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀- DA is applied Layer irradiation 1h, makes PTMC₂₀-PDMS₇₆-PTMC₂₀The acryloyl group of the end-DA reacts, so that hydrophobic monomer be made to be cross-linked with each other.It is purple PTMC can be obviously observed after outer illumination₂₀-PDMS₇₆-PTMC₂₀- DA coating is become by the weaker coating of intensity certain elasticity Rubbery state coating, i.e., form hydrophobic coating on the surface of the PLA coating of iron plate.To PLA coating and hydrophobic coating surface into The test of row water contact angle, as a result respectively as fig. 5 a and fig. 5b, the contact angle of PLA coating are 100 °, the contact of hydrophobic coating Angle is 114 °.Therefore, which has stronger hydrophobicity.With scanning electron microscope to hydrophobic coating Thickness characterization, the thickness for obtaining each hydrophobic coating is respectively 0.5 μm, 1.0 μm and 1.5 μm.

Iron plate and surface with 704 silica gel to surface only containing PLA coating have the iron of PLA coating and hydrophobic coating simultaneously Piece carry out edge sealing, only make it is cated be exposed on one side outside.After 704 silica gel are fully cured, the sample after edge sealing is placed on In Hank ' s liquid, corrosion experiment is carried out in shaking bath (50rpm, 37 DEG C), is taken pictures to sample weekly, observe corrosion condition. As a result as shown in Figure 6, wherein 0 μm indicates that surface only has the iron plate of PLA coating, and 0.5 μm, 1.0 μm and 1.5 μm expression surface is same The iron plate of Shi Hanyou PLA coating and hydrophobic coating, and the thickness of hydrophobic coating is respectively 0.5 μm, 1.0 μm and 1.5 μm.By Fig. 6 It can visually see, hydrophobic coating can inhibit the corrosion of early stage iron Yu PLA coating composite material, and with hydrophobic coating thickness The raising of degree, iron rot repressed time extend.When hydrophobic coating is with a thickness of 1.5 μm, after impregnating 28 days, iron plate only has Very slight corrosion.

Embodiment 2

The iron plate of same size is handled according to the same manner as in Example 1 and in the PLA of iron plate surface preparation same thickness Coating.

Polylactic acid-dimethyl silicone polymer-polylactic acid of synthesis acryloyl group sealing end according to the same manner as in Example 1 (PLA₁₅-PDMS₇₆-PLA₁₅- DA) macromonomer (i.e. hydrophobic monomer), PLA₁₅-PDMS₇₆-PLA₁₅The structural formula and physics of-DA State difference is as shown in Figure 7 and Figure 8.

By PLA₁₅-PDMS₇₆-PLA₁₅- DA is dissolved in ethyl acetate, and compound concentration is the hydrophobic monomer solution of 0.02g/mL； Photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added in the above-mentioned solution containing hydrophobic monomer and obtains mixed liquor, Wherein, the quality of photoinitiator is the 1 ‰ of the quality of hydrophobic monomer.Above-mentioned mixed liquor has been sprayed to using ultrasonic spray coating method The PLA coating surface of the iron plate of PLA coating, pump is 0.1ml/min, ultrasonic power 4.50W for flow velocity in spraying process.Point It does not spray once and twice, forms two kinds of different-thickness, uncrosslinked PLA on the PLA coating of different iron plates₁₅-PDMS₇₆- PLA₁₅- DA coating.

It is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to above-mentioned uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅- DA coating 1h is irradiated, PLA is made₁₅-PDMS₇₆-PLA₁₅The acryloyl group of the end-DA reacts, so that hydrophobic monomer be made to be cross-linked with each other.Observable To after ultraviolet lighting, coating becomes rubbery state smooth and with certain obdurability by original sticky state, i.e., in iron The surface of the PLA coating of piece forms hydrophobic coating.The coating surface after crosslinking is scanned with atomic force microscope, can be seen It is mutually separated to PLA block (degradable block) with nondegradable PDMS block (hydrophobic block), and PLA phase is dispersed in In PDMS phase, as shown in Figure 9.It is respectively 0.5 μm and 1 μ with the thickness that scanning electron microscope characterizes to obtain two kinds of hydrophobic coatings m。

Iron plate and surface with 704 silica gel to surface only containing PLA coating have the iron of PLA coating and hydrophobic coating simultaneously Piece carries out edge sealing, only makes cated to be exposed on one side.Iron plate is placed in 6 well culture plates after the solidification of 704 silica gel, every hole Add 5mL Hank ' s liquid, then culture plate is placed in shaking bath (50rpm, 37 DEG C) and carries out corrosion experiment, Hank ' s liquid is every Replacement in 24 hours is primary.The iron plate with different coating is clapped respectively after corrosion experiment carries out 1 day, 2 days, 3 days and 5 days According to observation.The results are shown in Figure 10, wherein 0 μm indicates that surface only has the iron plate of PLA coating, 0.5 μm and 1.0 μm expression surface Iron plate containing PLA coating and hydrophobic coating simultaneously, and the thickness of hydrophobic coating is respectively 0.5 μm and 1.0 μm.It can by Figure 10 Know, when degrading 3 days, hydrophobic coating obviously inhibits the corrosion of iron plate under PLA coating, at the 5th day, there is the iron plate of hydrophobic coating Also apparent corrosion has occurred, but extent of corrosion is still below the iron plate of no hydrophobic coating, only PLA coating.

Embodiment 3

With reference to the first dimethyl silicone polymer (PDMS with end containing double alkane hydroxyls of method in above-mentioned document₇₆- OH) it is to draw Agent is sent out, with 2- methyl, 2 methyl acrylate bases-dimethylene carbonate reaction synthesizes HO-Ac- of the end containing functional group PDMS₇₆-Ac-OH；Again with HO-Ac-PTMC₁₀- Ac-OH is initiator, is reacted with trimethylene carbonate, is obtained in strand Polytrimethylene carbonate-Ac- dimethyl silicone polymer-Ac- polytrimethylene carbonate of the side group containing acryloxy (PTMC₂₀-Ac-PDMS₇₆-Ac-PTMC₂₀) macromonomer (i.e. hydrophobic monomer).

By PTMC₂₀-Ac-PDMS₇₆-Ac-PTMC₂₀It is dissolved in ethyl acetate, compound concentration is 0.02g/mL containing hydrophobic The solution of monomer；Photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added in the above-mentioned solution containing hydrophobic monomer Obtain mixed liquor, wherein the quality of photoinitiator is the 1 ‰ of the quality of hydrophobic monomer.It will be upper using the method coating of ultrasound spray The PLA coating surface that mixed liquor sprays to the iron plate of PLA coating is stated, uncrosslinked PTMC is obtained₂₀-Ac-PDMS₇₆-Ac- PTMC₂₀Coating.

It is 10000 μ W/cm with 365nm, intensity²Ultraviolet light to above-mentioned uncrosslinked PTMC₂₀-Ac-PDMS₇₆-Ac- PTMC₂₀Coating irradiates 2h, makes PTMC₂₀-Ac-PDMS₇₆-Ac-PTMC₂₀The double bond of middle Ac side group is reacted, to make hydrophobic monomer phase Mutually crosslinking.It can be observed after ultraviolet lighting, coating becomes smooth and with certain obdurability by original sticky state Rubbery state forms hydrophobic coating on the surface of the PLA coating of iron plate.It is characterized to obtain hydrophobic coating with scanning electron microscope With a thickness of 5 μm.

Iron plate and surface with 704 silica gel to surface only containing PLA coating have the iron of PLA coating and hydrophobic coating simultaneously Piece carries out edge sealing, only makes cated to be exposed on one side.Iron plate is placed in 6 well culture plates after the solidification of 704 silica gel, every hole Add 5mL Hank ' s liquid, culture plate is then placed in shaking bath the corrosion experiment that (50rpm, 37 DEG C) is carried out 28 days, Hank ' Replacement in s liquid every 24 hours is primary.Corrosion condition was photographed to record to sample in every 7 days.The result shows that only containing after impregnating 7 days The iron plate surface of PLA coating has occurred that serious corrosion.And when having hydrophobic coating outside PLA coating, iron after impregnating 28 days Piece surface still almost without corroding, shows metallic luster.

Embodiment 4

The iron plate of related specification is handled according to the same manner as in Example 1 and in the PLA of iron plate surface preparation same thickness Coating.

Polytrimethylene carbonate-polydimethylsiloxanes of synthesis acryloyl group sealing end according to the same manner as in Example 1 Alkane-polytrimethylene carbonate (PTMC₁₅-PDMS₇₆-PTMC₁₅- DA) macromonomer (i.e. hydrophobic monomer).

Compound concentration is the PTMC of 0.02g/mL respectively₁₅-PDMS₇₆-PTMC₁₅The DOW CORNING that-DA and concentration are 0.02g/mL The ethyl acetate of 184 silicon rubber presomas (in 184 silicon rubber of DOW CORNING, basic components are 10:1 with crosslinking agent quality ratio) is molten Liquid, by two kinds of solution, 1:5 is blended to obtain mixed liquor by volume, and the mixed liquor is sprayed to iron using the method for ultrasound spraying The PLA coating surface of piece.12h is placed in draught cupboard makes ethyl acetate continue to volatilize, and being subsequently placed in 12h in 60 DEG C of baking oven makes silicon Rubber presoma crosslinks, and forms hydrophobic coating.It is characterizing under a scanning electron microscope the result shows that, hydrophobic coating thickness It is 2.5 μm.

Iron plate and surface using 704 silica gel to surface only containing PLA coating have PLA coating and hydrophobic coating simultaneously Iron plate carries out edge sealing, only makes cated to be exposed on one side.Iron plate is placed in 6 well culture plates, every hole adds 5mL Hank ' s Then culture plate is placed in shaking bath (50rpm, 37 DEG C) and carries out 28 days corrosion experiments by liquid, and Hank ' s liquid every 24 hours Replacement is primary.Corrosion condition was photographed to record to sample in every 7 days.The result shows that the iron plate after impregnating 7 days, only containing PLA coating Surface has occurred that serious corrosion.And when having hydrophobic coating outside PLA coating, impregnate 21 days after iron plate surface still almost There is no corrosion, show metallic luster, and iron plate surface just starts dimmed at the 28th day, there is the sign for starting to corrode.

Embodiment 5

There is the iron plate of PLA coating to handle under oxygen plasma on surface, gas pressure 50Pa, plasma power is 100W, processing time are 30min.The KH-570 silanization coupling agent that 50 μ L are drawn with the liquid-transfering gun of 100 μ L, inside is contained The pipette tips of KH-570 and the surface after corona treatment have the iron plate of PLA coating to be put into drier, after vacuumizing, place 12h makes KH-570 volatilize and is adsorbed on PLA coating surface, and KH-570 layers are formed on PLA coating.

Polylactic acid-dimethyl silicone polymer-polylactic acid of synthesis acryloyl group sealing end according to the same manner as in Example 1 (PLA₁₅-PDMS₇₆-PLA₁₅- DA) polymeric monomer (i.e. hydrophobic monomer).

By PLA₁₅-PDMS₇₆-PLA₁₅- DA is dissolved in ethyl acetate, and compound concentration contains hydrophobic monomer for 0.02g/mL's Solution, and photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added and obtains mixed liquor, wherein the matter of photoinitiator Amount is the 1 ‰ of the quality of hydrophobic monomer.The mixed liquor is sprayed on respectively with silanization coupling agent using the method for ultrasound spraying The PLA coating surface of the PLA coating surface of the iron plate of processing and the iron plate without silanization coupling agent treatment, ultrasonic nozzle is along x Axis movement speed is 15mm/s, and the step-length moved along the y-axis direction is 2mm, and pump is 0.1mL/min for flow velocity, and ultrasonic power is 4.5W repeats spraying five times according to this parameter, forms uncrosslinked PLA on the PLA coating surface of iron plate₁₅-PDMS₇₆- PLA₁₅- DA coating.

It is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅The irradiation of-DA coating 1 hour, make PLA₁₅-PDMS₇₆-PLA₁₅The terminal acryl groups of-DA crosslink, to form hydrophobic coating.It can be sent out after illumination Existing coating becomes smooth by original viscous hand state and has the rubbery state coating of certain elasticity and toughness, under scanning electron microscope Characterization obtain hydrophobic coating with a thickness of 3 μm.

Iron plate and surface with 704 silica gel to surface only containing PLA coating have the iron of PLA coating and hydrophobic coating simultaneously Piece carries out edge sealing, only makes cated to be exposed on one side.After the solidification of 704 silica gel, each iron plate is placed on a dress respectively It in the glass dish for having 50mL Hank ' s liquid, is placed in shaking bath (50rpm, 37 DEG C) and carries out corrosion experiment, Hank ' s liquid is every Replacement in 24 hours is primary.There is the iron plate of different coating to clap on surface when impregnating the 0th day, 1 day, 3 days, 5 days and 7 days respectively According to observation corrosion condition.The result shows that the iron plate of only PLA coating, on day 3 when just have occurred and that heavy corrosion, entire iron Blackish green is presented in piece surface, and surface has the iron plate with a thickness of 3 μm of hydrophobic coating to only have individual positions in iron plate surface at the 7th day Point corrodes.

Hydrophobic coating is scraped with tweezers, and comparison is by KH-570 treated sample and without KH-570 treated sample The adhesive force of its hydrophobic coating and substrate, through KH-570, treated that sample is more difficult to scrape off for discovery.Illustrate to handle through KH-570 Afterwards, the binding force of hydrophobic coating and PLA coating obtains a degree of raising.

Embodiment 6

The iron plate of same size is handled according to the same manner as in Example 1, and 200 μ L concentration of drop coating is on every iron plate PLA (the M of 0.02g/mL_w: 60kDa) ethyl acetate solution, be placed in draught cupboard after so that ethyl acetate is volatilized completely in iron plate Surface formed with a thickness of 4 μm of PLA coating.

By PLA₁₅-PDMS₇₆-PLA₁₅- DA is dissolved in ethyl acetate, and compound concentration is 0.2g/mL containing hydrophobic monomer Solution, and photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added and obtains mixed liquor, wherein the quality of photoinitiator It is the 1 ‰ of the quality of hydrophobic monomer；At the slow-speed of revolution (1500r/min) rapid (8s) by 4~5 drop the mixed liquor be added drop-wise to it is above-mentioned On the surface of the PLA coating of iron plate, and to complete the preparation of coating after the revolving speed of 3000r/min rotation 25s, i.e., in iron plate The surface of PLA coating forms uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅- DA coating.

It is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅The irradiation of-DA coating 1 hour, make PLA₁₅-PDMS₇₆-PLA₁₅The terminal acryl groups of-DA crosslink, to form hydrophobic coating.It is considerable after illumination Observe PLA₁₅-PDMS₇₆-PLA₁₅- DA coating becomes rubber smooth and with certain obdurability by original sticky state State.Scanning electron microscope following table obtains hydrophobic coating with a thickness of 5 μm.

Iron plate and surface with 704 silica gel to surface only containing PLA coating have the iron of PLA coating and hydrophobic coating simultaneously Piece carries out edge sealing, only makes cated to be exposed on one side.Iron plate is placed in 6 well culture plates, every hole adds 10mL Hank ' s Then culture plate is placed in shaking bath (50rpm, 37 DEG C) and carries out 14 days corrosion experiments by liquid, and Hank ' s liquid every 24 hours Replacement is primary.Corrosion condition is photographed to record to sample after impregnating 1 day, 3 days, 5 days, 7 days, 14 days respectively.The result shows that soaking Bubble is after 1 day, and only the iron plate surface containing PLA coating has occurred that apparent corrosion.And have outside PLA coating with a thickness of 5 μm When hydrophobic coating, iron plate surface shows metallic luster still almost without corroding after impregnating 7 days, iron plate at the 28th day Just there is the site corroded individually in surface.

Embodiment 7

It is poly- by method synthesis polylactic acid-dimethyl silicone polymer-of the end containing epoxy group substantially the same manner as Example 1 Lactic acid (PLA₁₅-PDMS₇₆-PLA₁₅- DE) macromonomer (i.e. hydrophobic monomer), different from embodiment 1, using epoxy chlorine The PLA of propane and end hydroxyl₁₅-PDMS₇₆-PLA₁₅- OH reaction, generates polylactic acid-poly dimethyl of the end containing epoxy group Siloxanes-polylactic acid macromonomer, i.e. hydrophobic monomer.Wherein, DE is indicated, the both ends of hydrophobic monomer strand are epoxy group.

By PLA₁₅-PDMS₇₆-PLA₁₅- DE is dissolved in ethyl acetate, and compound concentration contains hydrophobic monomer for 0.02g/mL's Solution；The hydroxy-end capped dimethyl silicone polymer of double alkane (PDMS-OH) is dissolved in ethyl acetate, compound concentration 0.02g/ The solution of mL；The ratio of above two solution 1:1 by volume is mixed to get mixed liquor, and should in the method for ultrasound spraying Mixed liquor is coated on the surface of the PLA coating of iron plate, and ultrasonic power is 4.5W in spraying process, and pump is 0.1mL/ for flow velocity Min repeats spraying 5 times, and the surface of the PLA coating after the completion of spraying in iron plate forms uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅- The coating of DE.

Surface is had to uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅The iron plate of the coating of-DE is placed in 60 DEG C of baking oven and heats 12h reacts the terminal epoxy groups of macromonomer with the terminal hydroxyl of PDMS-OH, the hydrophobic coating being crosslinked, at heating Coating can be observed after reason becomes more tough.Scanning electron microscope detects to obtain hydrophobic coating with a thickness of 2.5 μm.

Edge sealing is carried out to sample according to the same manner as in Example 6 and carries out corrosion test in shaking bath, sight of taking pictures Examine iron plate erosion profile the result shows that, when impregnating 3 days, only the iron plate whole surface containing PLA coating has been corroded, And only occur some corrosion dots when having 2.5 μm of thickness of hydrophobic coating outside PLA coating, when impregnating 7 days, impregnate 14 days Shi Tie Still do not corrode largely on piece surface.

Embodiment 8

Will be with a thickness of 500 μm, the AZ31 magnesium alloy plate having a size of 22mm × 26mm, successively with the sand of 800 mesh and 2000 mesh After paper polishing, successively it is cleaned by ultrasonic 10min with acetone and dehydrated alcohol, with being dried with nitrogen.

Polylactic acid-dimethyl silicone polymer-polylactic acid of synthesis acryloyl group sealing end according to the same manner as in Example 1 (PLA₁₇-PDMS₇₆-PLA₁₇- DA) macromonomer (i.e. hydrophobic monomer).

By PLA₁₇-PDMS₇₆-PLA₁₇- DA is dissolved in ethyl acetate, and compound concentration is 0.1g/mL containing hydrophobic monomer Solution is added photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone and obtains mixed liquor, wherein the quality of photoinitiator is The 1 ‰ of hydrophobic monomer quality.The above-mentioned mixed liquor of drop coating 0.5mL, is placed in draught cupboard, makes acetic acid on every magnesium alloy plate After ethyl ester volatilization, uncrosslinked PLA is formed on the surface of magnesium alloy plate₁₇-PDMS₇₆-PLA₁₇The coating of-DA.

It is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PLA₁₇-PDMS₇₆-PLA₁₇The irradiation of-DA coating 1 hour, terminal acryl groups is made to react, the hydrophobic coating being crosslinked.It can be seen that magnesium alloy plate table after ultraviolet light Face forms one layer of rubbery state coating for having certain toughness.The result being scanned from atomic force microscope to coating surface can It arrives, degradable PLA block has occurred with nondegradable PDMS block and significantly mutually separates in hydrophobic coating, and PLA phase point It is dispersed in PDMS phase, as shown in figure 11.Scanning electron microscope following table obtain hydrophobic coating with a thickness of 10 μm.

To naked magnesium alloy plate and there is the magnesium alloy plate of hydrophobic coating to carry out edge sealing with 704 silica gel, the magnesium containing hydrophobic coating In alloy sheet sample, hydrophobic coating is exposed.After the solidification of 704 silica gel, every sample is placed on to the beaker of 200mL PBS In, and (50rpm, 37 DEG C) is placed the beaker in shaking bath, the hydrogen that Corrosion Behaviors of Magnesium Alloys generates is collected with back-off funnel method Amount.As a result as shown in figure 12, surface has the magnesium alloy of hydrophobic coating in corrosion in 14 days, and the amounts of hydrogen of generation is significantly less than not There is coating group (naked magnesium alloy plate), it was demonstrated that the hydrophobic coating can be used for slowing down the corrosion of magnesium alloy.

Embodiment 9

The AZ31 magnesium alloy plate of same size is handled according to the same manner as in Example 8.

By method substantially the same manner as Example 1 with double hydroxy-end capped perfluoropolyether (PFPE-OH) be initiator synthesis Polycaprolactone-PFPE- polycaprolactone (the PCL of methacryloyl end-capped₂₀-PFPE-PCL₂₀- DMA) macromonomer (i.e. dredge Aqueous monomer).

By PCL₂₀-PFPE-PCL₂₀- DMA is dissolved in ethyl acetate, and compound concentration is 0.1g/mL containing hydrophobic monomer Solution is added photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone and obtains mixture, wherein the quality of photoinitiator is The 1 ‰ of hydrophobic monomer quality.The above-mentioned mixed liquor of drop coating 0.5mL, places in draught cupboard, makes acetic acid on every magnesium alloy plate After ethyl ester volatilization, uncrosslinked PCL is formed on the surface of magnesium alloy plate₂₀-PFPE-PCL₂₀The coating of-DMA.

It is 15000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PCL₂₀-PFPE-PCL₂₀The irradiation of-DMA coating 1 hour, the terminal methyl group acryloyl group in coating is set to react, the hydrophobic coating being crosslinked.It can be seen after ultraviolet lighting Coating, which becomes one layer by the original state slightly scratched at a touch with tweezers, the lubricious of certain toughness.Scanning electron Microscope following table obtain hydrophobic coating with a thickness of 10 μm.

To naked magnesium alloy plate and there is the magnesium alloy plate of hydrophobic coating to carry out edge sealing with 704 silica gel, the magnesium containing hydrophobic coating In alloy sheet sample, hydrophobic coating is exposed.Every sample is placed on to the beaker of 200mL PBS after 704 silica gel solidify In, and (50rpm, 37 DEG C) is placed the beaker in shaking bath, the hydrogen that Corrosion Behaviors of Magnesium Alloys generates is collected with back-off funnel method Amount.The result shows that the volume without coating group magnesium alloy sustained release hydrogen in 14 days is about 10mL, there is hydrophobic painting on surface The magnesium alloy of layer is in corrosion in 14 days, almost without hydrogen is collected into, it was demonstrated that the hydrophobic coating can be used for slowing down magnesium alloy Corrosion.

Embodiment 10

Polytrimethylene carbonate-polydimethylsiloxanes of synthesis acryloyl group sealing end according to the same manner as in Example 1 Alkane-polytrimethylene carbonate (PTMC₁₉-PDMS₇₆-PTMC₁₉- DA) macromonomer (i.e. hydrophobic monomer).

By PTMC₁₉-PDMS₇₆-PTMC₁₉- DA is dissolved in ethyl acetate, and compound concentration contains hydrophobic monomer for 0.1g/mL's Solution, be added photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone obtain mixture, wherein the quality of photoinitiator It is the 1 ‰ of hydrophobic monomer quality.The above-mentioned mixed liquor of drop coating 0.5mL, places in draught cupboard, makes second on every magnesium alloy plate After acetoacetic ester volatilization, uncrosslinked PTMC is formed on the surface of magnesium alloy plate₁₉-PDMS₇₆-PTMC₁₉The coating of-DA.

It is 5000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PTMC₁₉-PDMS₇₆-PTMC₁₉- DA coating shines It penetrates 1 hour, the terminal acryl groups in coating is made to react, the hydrophobic coating being crosslinked.It can be seen that applying after ultraviolet lighting Layer, which becomes one layer by the original state slightly scratched at a touch with tweezers, the lubricious of certain toughness.Scanning electron is aobvious Micro mirror following table obtain hydrophobic coating with a thickness of 10 μm.

To naked magnesium alloy plate and there is the magnesium alloy plate of hydrophobic coating to carry out edge sealing with 704 silica gel, the magnesium containing hydrophobic coating In alloy sheet sample, hydrophobic coating is exposed.Every sample is placed on to the beaker of 200mL PBS after 704 silica gel solidify In, and (50rpm, 37 DEG C) is placed the beaker in shaking bath, the hydrogen that Corrosion Behaviors of Magnesium Alloys generates is collected with back-off funnel method Amount.As a result as shown in figure 12, surface has the magnesium alloy of hydrophobic coating in corrosion in 14 days, and accumulation hydrogen release volume is about 1mL, and almost no hydrogen release in 6 days before corrosion experiment, without coating group, the volume of sustained release hydrogen is about in 14 days For 10mL, it was demonstrated that the hydrophobic coating can be used for slowing down the corrosion of magnesium alloy.

Embodiment 11

Polylactic acid-dimethyl silicone polymer-polylactic acid of synthesis acryloyl group sealing end according to the same manner as in Example 1 (PLA₁₅-PDMS₇₆-PLA₁₅- DA) macromonomer (i.e. hydrophobic monomer).

By PLA₁₅-PDMS₇₆-PLA₁₅- DA is blended with organopolysilazane 1:10 in mass ratio, is configured to total mass concentration For the ethyl acetate mixture of 0.2g/mL；The magnesium alloy plate handled well is adsorbed on the sample stage of spin coating instrument using negative pressure, 6~8 above-mentioned mixed solutions of drop are added dropwise on the surface in magnesium alloy plate at the slow-speed of revolution (1500r/min, 10s), are then kept Revolving speed is 2000r/min, rotates 25s, forms uncrosslinked PLA on the surface of magnesium alloy plate₁₅-PDMS₇₆-PLA₁₅- DA is applied Layer, then sample, which is placed in air, reacts Si-N key in polysilazane and N-H key 5 days under moisture effect.From surface The result of elemental analysis can be seen that compared with solidification the 1st day, can't detect N element in coating at the 5th day, respectively such as Shown in Figure 13 A and 13B, illustrate that polysilazane is crosslinked completely at this time, forms hydrophobic coating.It is characterized under scanning electron microscope Obtain hydrophobic coating with a thickness of 8 μm.

To naked magnesium alloy plate and there is the magnesium alloy plate of hydrophobic coating to carry out edge sealing with 704 silica gel, the magnesium containing hydrophobic coating In alloy sheet sample, hydrophobic coating is exposed.After the solidification of 704 silica gel, by the naked magnesium alloy plate after edge sealing and containing hydrophobic The magnesium alloy plate of coating is individually placed in six orifice plates equipped with 5mL Hank ' s liquid, is placed in shaking bath (50rpm, 37 DEG C) Corrosion experiment is carried out, replacement in Hank ' s liquid every 24 hours is primary.At the 28th day, corrosive liquid inductance coupled plasma is taken to send out Penetrate the concentration of magnesium ion in spectrometer (ICP-OES) test solution.The result shows that naked magnesium alloy plate corrosion produces after impregnating 28 days Raw magnesium ion concentration is 138.1mg/L, is 30.4mg/ containing the magnesium ion concentration that magnesium alloy plate corrosion generates under hydrophobic coating L shows after impregnating 28 days that hydrophobic coating still has apparent inhibiting effect to magnesium alloy plate corrosion.

Embodiment 12

It will be cut into 22mm × 26mm with a thickness of 200 μm of pure magnesium sheet, successively with the sand paper of 800,1500,2000 and 3000 mesh Polishing, after the pure magnesium sheet after polishing is placed on acetone, is successively cleaned by ultrasonic 10min in dehydrated alcohol, with being dried with nitrogen.

Polylactic acid-dimethyl silicone polymer-polylactic acid of synthesis acryloyl group sealing end according to the same manner as in Example 1 (PLA₁₀-PDMS₇₆-PLA₁₀- DA) macromonomer (i.e. hydrophobic monomer) and acryloyl group sealing end polytrimethylene carbonate- Dimethyl silicone polymer-polytrimethylene carbonate (PTMC₂₀-PDMS₇₆-PTMC₂₀- DA) macromonomer (i.e. hydrophobic monomer).

By PLA₁₀-PDMS₇₆-PLA₁₀- DA and PTMC₂₀-PDMS₇₆-PTMC₂₀- DA the ratio of 1:1 in mass ratio is dissolved in acetic acid In ethyl ester, preparing total mass concentration is 0.2g/mL containing there are two types of the solution of hydrophobic monomer, addition photoinitiator 2- hydroxyl -2- Methyl-1-phenyl-1- acetone obtains mixed liquor, wherein the quality of photoinitiator is the 1 ‰ of hydrophobic monomer quality.Utilize negative pressure The pure magnesium sheet handled well is adsorbed on the sample stage of spin coating instrument, it is at the slow-speed of revolution (1500r/min, 8s) that 6~8 drops are above-mentioned mixed It closes solution to be added dropwise on the surface of pure magnesium sheet, then keeping revolving speed is 2000r/min, rotates 30s, being placed in draught cupboard makes acetic acid After ethyl ester volatilization, uncrosslinked PLA is formed on the surface of pure magnesium sheet₁₀-PDMS₇₆-PLA₁₀- DA and PTMC₂₀-PDMS₇₆- PTMC₂₀The mixed coating of-DA.

By uncrosslinked PLA₁₀-PDMS₇₆-PLA₁₀- DA and PTMC₂₀-PDMS₇₆-PTMC₂₀The mixed coating of-DA is placed in 365nm, intensity are 8000 μ W/cm²Ultraviolet light under irradiate 1 hour, react terminal acryl groups, formed hydrophobic coating.It is purple It can be seen that coating becomes the rubbery state for having certain obdurability by original viscous hand state after outer light irradiation, illustrate macromonomer Through being crosslinked.Scanning electron microscope following table obtain the hydrophobic coating with a thickness of 5 μm.

To naked magnesium alloy plate and there is the magnesium alloy plate of hydrophobic coating to carry out edge sealing with 704 silica gel, the magnesium containing hydrophobic coating In alloy sheet sample, hydrophobic coating is exposed to outside.After the solidification of 704 silica gel, the sample after edge sealing is placed on equipped with 200mL In the beaker of Hank ' s liquid, and the amount of the hydrogen using back-off funnel method measurement magnesium corrosion release, corrosion experiment is in shaking bath It is carried out in (50rpm, 37 DEG C).The result shows that naked pure magnesium sheet is after corrosion 7 days, the volume of cumulative release hydrogen is about 12mL, is had The hydrogen volume of the pure magnesium sheet corrosion cumulative release of hydrophobic coating is about 0.5mL, illustrates that the hydrophobic coating can inhibit well pure The corrosion of magnesium early stage.

Embodiment 13

By the pure magnesium sheet of method identical with embodiment 12 processing same size.

Contain the polytrimethylene carbonate-of trimethoxy silicon group by method synthesis end substantially the same manner as Example 1 Dimethyl silicone polymer-polytrimethylene carbonate (PTMC₂₀-PDMS₇₆-PTMC₂₀- DTS) macromonomer (i.e. hydrophobic list Body), different from embodiment 1, using the PTMC of trimethoxy silicon propylisocyanate and end hydroxyl₂₀-PDMS₇₆- PTMC₂₀- OH reaction generates polytrimethylene carbonate-dimethyl silicone polymer-poly- three that trimethoxy silicon group is contained in end Carbonate macromonomer, i.e. hydrophobic monomer.Wherein, DTS is indicated, the both ends of hydrophobic monomer strand are trimethoxy silicon Group.

By PTMC₂₀-PDMS₇₆-PTMC₂₀- DTS is dissolved in ethyl acetate, prepare mass concentration be respectively 0.1g/mL and The solution containing hydrophobic monomer of 0.5g/mL；The above two various concentration of drop coating 0.2mL contains respectively on the different pure magnesium sheets There is the solution of hydrophobic monomer, be placed in draught cupboard, after so that ethyl acetate is volatilized, is formed on pure and beautiful surface uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀The coating of-DTS.

At room temperature, surface is had to uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀The pure magnesium sheet of the coating of-DTS is placed in 3 days in air, trimethoxy silicon group hydrolysis in end is set to generate silicone hydroxyl using moisture, and real using the dehydration between silicone hydroxyl The crosslinking of existing hydrophobic monomer, generates the hydrophobic coating of crosslinking.Coating after crosslinking is become to have certain strong by original viscous hand state The rubbery state of toughness.It is respectively 20 that scanning electron microscope following table, which is obtained to hydrophobic coating thickness prepared by the solution of two kinds of concentration, μm and 100 μm.

To processed naked pure magnesium sheet and there is the pure magnesium sheet of hydrophobic coating to carry out edge sealing with 704 silica gel, makes have hydrophobic coating Be exposed on one side outside.After the solidification of 704 silica gel, the sample after edge sealing is placed on the beaker equipped with 200mL Hank ' s liquid In, and the amount of the hydrogen using back-off funnel method measurement magnesium corrosion release, corrosion experiment is in shaking bath (50rpm, 37 DEG C) It carries out.The result shows that naked pure magnesium sheet is after corrosion 14 days, the volume of cumulative release hydrogen is about 23mL, and surface has with a thickness of 20 μ The hydrogen volume of the pure magnesium sheet corrosion cumulative release of the hydrophobic coating of m is about 0.8mL, and there are 100 μm of hydrophobic coatings of thickness on surface Pure magnesium sheet group is not collected into hydrogen then.Illustrate that the hydrophobic coating can inhibit the corrosion of pure magnesium early stage well.

Embodiment 14

The poly (glycolide-co-lactide) copolymer (PLGA, LA:GA=50:50) for being 60,000 by molecular weight is warm under the conditions of 120 DEG C 300 μm thick, the PLGA piece having a size of 22mm × 26mm is made in pressure.

Polytrimethylene carbonate-polydimethylsiloxanes of synthesis acryloyl group sealing end according to the same manner as in Example 1 Alkane-polytrimethylene carbonate (PTMC₂₀-PDMS₇₆-PTMC₂₀- DA) macromonomer (i.e. hydrophobic monomer).

By PTMC₂₀-PDMS₇₆-PTMC₂₀- DA is dissolved in ethyl acetate, be configured to 0.5g/mL containing the molten of hydrophobic monomer Liquid is added photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone and obtains mixed liquor, wherein the quality of photoinitiator is thin The 1 ‰ of aqueous monomer quality.The mixed liquor 4~6 drop is added dropwise at the slow-speed of revolution (1500r/min, 10s), then with 2000r/min's Revolving speed continues 25s and carries out spin coating, in the uncrosslinked PTMC of the Surface Creation of PLGA piece₂₀-PDMS₇₆-PTMC₂₀- DA coating.

It is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀- DA coating shines It penetrates 1 hour, reacts the terminal acryl groups in macromonomer, the hydrophobic coating being crosslinked.It can see ultraviolet lighting The hydrophobic coating of formation afterwards has certain toughness and elasticity.Characterization obtains the thickness of hydrophobic coating under a scanning electron microscope It is 10 μm.

By 704 silica gel edge sealing of the bottom surface of PLGA piece and surrounding, it is ensured that only test surfaces or the one side with hydrophobic coating It is exposed to outside.After 704 silica gel are fully cured, PLGA piece is immersed in Hank ' s liquid, and with not hydrophobic coating PLGA piece carries out degradation experiment as control in 37 DEG C of shaking bath.After degradation 28 days, PLGA piece is taken to carry out osmogels Chromatography (GPC) test, GPC's the result shows that, the PLGA molecular weight containing hydrophobic coating be higher than no coating group (naked PLGA piece). This method realizes the purpose for slowing down PLGA degradation by coating hydrophobic coating on the surface of PLGA piece.

Embodiment 15

Will be with a thickness of 200 μm, the pure zinc metal sheet having a size of 22mm × 26mm successively uses the sand paper of 800 mesh and 2000 mesh to polish, And successively it is cleaned by ultrasonic 10min with acetone and dehydrated alcohol, with being dried with nitrogen surface.

Polycaprolactone-dimethyl silicone polymer-by method synthesis acryloyl group sealing end substantially the same manner as Example 1 is poly- Caprolactone (PCL₁₅-PDMS₇₆-PCL₁₅- DA) macromonomer (i.e. hydrophobic monomer).

By PCL₁₅-PDMS₇₆-PCL₁₅- DA is dissolved in ethyl acetate, and compound concentration is 0.02g/mL containing hydrophobic monomer Solution, and photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added and obtains mixed liquor, wherein the quality of photoinitiator It is the 1 ‰ of hydrophobic monomer quality.The mixed liquor is sprayed on to the pure zinc metal sheet surface handled well, spraying process using ultrasonic spray coating method Middle pump is 0.1mL/min, ultrasonic power 5.0W for flow velocity；Sample, which is placed in draught cupboard, makes ethyl acetate sufficiently volatilize Afterwards, uncrosslinked PCL is formed on the surface of pure zinc metal sheet₁₅-PDMS₇₆-PCL₁₅- DA coating.

It is 12000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PCL₁₅-PDMS₇₆-PCL₁₅- DA coating shines 40min is penetrated, the acryloyl group in coating is made to react the hydrophobic coating being crosslinked, it can be seen that coating is by not scratch-resistant originally State becomes the rubbery state for having certain toughness.Scanning electron microscope following table obtain hydrophobic coating with a thickness of 5 μm.

There is the pure zinc metal sheet of hydrophobic coating to carry out edge sealing naked pure zinc metal sheet and surface with 704 silica gel, only exposes test surfaces Every sample is immersed in 10mL Hank ' after the solidification of 704 silica gel by (i.e. the correspondence surface of hydrophobic coating and naked pure zinc metal sheet) In s liquid, and (37 DEG C, 50rpm) the progress corrosion experiments in shaking bath.The result shows that impregnating pure zinc metal sheet surface naked at 1 day Have occurred that comprehensive corrosion, and when by the 28th day, surface has the pure zinc metal sheet of hydrophobic coating not yet to corrode.

Embodiment 16

By the pure zinc metal sheet of method identical with embodiment 15 processing same size.

By PLA₁₅-PDMS₇₆-PLA₁₅- DA is blended with organopolysilazane 1:100 in mass ratio, and it is dense to be configured to gross mass Degree is the ethyl acetate solution of 0.02g/mL；The pure zinc metal sheet handled well is adsorbed on the sample stage of spin coating instrument using negative pressure, 6~8 above-mentioned ethyl acetate solutions of drop are added dropwise in the surface of pure zinc metal sheet under the slow-speed of revolution (2000r/min, 10s), then keep turning Speed is 4000r/min, rotates 25s, forms uncrosslinked PLA on the surface of pure zinc metal sheet₁₅-PDMS₇₆-PLA₁₅- DA and organic poly- silicon The blending coating of azane.

It removes and prepares uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅The sample that coating is blended of-DA and organopolysilazane, Being placed in air under room temperature, which makes Si-N key in organopolysilazane and N-H key react 5 angels under moisture effect, applies Layer crosslinks, and generates hydrophobic coating.Scanning electron microscope following table obtain hydrophobic coating with a thickness of 0.01 μm.

There is the pure zinc metal sheet of hydrophobic coating to carry out edge sealing naked pure zinc metal sheet and surface with 704 silica gel, only exposes test surfaces Every sample is immersed in 10mL Hank ' after the solidification of 704 silica gel by (i.e. the correspondence surface of hydrophobic coating and naked pure zinc metal sheet) In s liquid, and (37 DEG C, 50rpm) the progress corrosion experiments in shaking bath.The result shows that impregnating pure zinc metal sheet surface naked at 1 day Have occurred that comprehensive corrosion, and when by the 3rd day, surface has the pure zinc metal sheet of hydrophobic coating to only have individual sites corruption has occurred Erosion.

Embodiment 17

By PTMC₂₀-PDMS₇₆-PTMC₂₀- DA is dissolved in ethyl acetate, and being configured to concentration is 0.3g/mL containing hydrophobic monomer Solution, be added photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone obtain mixed liquor, wherein the quality of photoinitiator It is the 1 ‰ of hydrophobic monomer quality.It is 100,000 by molecular weight, diameter is that 200 μm of PLA silk impregnates 10s in the above solution, and with The rate of 2000 μm/s lifts, and PLA silk table face is made to form one layer of uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀- DA coating.

It is 15000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀- DA irradiation 30min makes acryloyl group in coating react the hydrophobic coating being crosslinked.Scanning electron microscope following table obtains hydrophobic coating With a thickness of 5 μm.

The silk both ends PLA not covered by hydrophobic coating are sealed using 704 silica gel, after the solidification of 704 silica gel, surface is had The PLA silk of hydrophobic coating is immersed in the glass dish equipped with 50mL Hank ' s liquid, and using surface do not have cated PLA as Control, (50rpm, 37 DEG C) carries out degradation experiment in shaking bath.After degradation 28 days, to the PLA silks of different degradation times into The test of row tensile property, the results showed that, surface has the PLA silk of hydrophobic coating after degradation 28 days, and tensile strength and degradation are real Tensile strength before testing is suitable, and surface does not have PLA cated, and mechanical property has been substantially reduced, and illustrates the hydrophobic painting Layer can delay PLA degradations, so as to maintain PLA early mechanics characteristics declines slower.

Embodiment 18

The pure iron silk (iron content > 99.9%) that diameter is 200 μm is successively polished with the SiC sand paper of 800 mesh and 2000 mesh, By pure iron silk around the spring of growth 3cm on the screw that diameter is 5mm, and successively it is cleaned by ultrasonic with acetone and dehydrated alcohol 10min, then with being dried with nitrogen.

Compound concentration is the PLA (M of 0.1g/mL_w: 60kDa) ethyl acetate solution, by by pure iron filament winding at spring exist After impregnating 10s in PLA solution, lifted with the speed of 2000 μm/s, and spring, which is hung in draught cupboard, makes ethyl acetate volatilize PLA coating is formed on the surface of spring afterwards.

By PCL₁₅-PDMS₇₆-PCL₁₅- DA and 184 silicon rubber presoma of DOW CORNING (in 184 silicon rubber of DOW CORNING, base set Divide and be blended with the mass ratio of crosslinking agent for 10:1) 1:5 in mass ratio, is configured to the ethyl acetate solution that total concentration is 0.2g/mL. There is the spring like pure iron silk of PLA coating to submerge in the above solution on surface, and lifted rapidly with the speed of 4000 μm/s, in bullet The surface of the PLA coating of spring shape pure iron silk forms uncrosslinked PCL₁₅-PDMS₇₆-PCL₁₅- DA and 184 silicon rubber forerunner of DOW CORNING The blending coating of body.

Surface is had to uncrosslinked PCL₁₅-PDMS₇₆-PCL₁₅Coating is blended with 184 silicon rubber presoma of DOW CORNING in-DA Spring like pure iron silk suspension place for 24 hours, make the blendings coating on surface crosslink at normal temperature generate be crosslinked hydrophobic coating, It can be seen that coating becomes smooth by original viscous hand state and has the rubbery state of certain toughness.It is characterized under scanning electron microscope Obtain hydrophobic coating with a thickness of 4 μm.

Surface is only had to the spring like pure iron silk and surface while the spring with PLA coating and hydrophobic coating of PLA coating Shape pure iron silk is immersed in Hank ' s liquid, and corrosion experiment is carried out in shaking bath (37 DEG C, 50rpm).The result shows that soaking Bubble is after 7 days, and the pure iron silk that surface only has PLA coating has occurred that serious corrosion, and is broken in moiety site, and table There is the spring like pure iron silk of hydrophobic coating in face almost without corroding, and spring like pure iron silk still maintains when 28 days With the comparable mechanical property of original state.

Embodiment 19

It is carried out processing by iron wire of the method identical with embodiment 18 to same size and is prepared identical PLA on surface to apply Layer.

Contain polycaprolactone-poly dimethyl of three ethoxy silicon propyl by method synthesis end substantially the same manner as Example 1 Siloxanes-polycaprolactone (PCL₁₀-PDMS₇₆-PCL₁₀- DS) macromonomer (i.e. hydrophobic monomer).Wherein, DS indicates hydrophobic list The both ends of body strand are three ethoxy silicon propyl.

By PCL₁₀-PDMS₇₆-PCL₁₀- DS is dissolved in ethyl acetate, and compound concentration is 0.5g/mL containing hydrophobic monomer Solution.There is the spring like pure iron silk of PLA coating to submerge in the above solution on surface, and is mentioned rapidly with the rate of 4000 μm/s It draws, forms uncrosslinked PCL on the surface of spring like pure iron silk₁₀-PDMS₇₆-PCL₁₀- DS coating.

At room temperature, surface is had to uncrosslinked PCL₁₀-PDMS₇₆-PCL₁₀The pure iron silk of-DS coating hangs 48h, So that the hydrolysis of three ethoxy silicon propyl of end is generated silicone hydroxyl using the moisture in air, and is realized by the dehydration between silicone hydroxyl The crosslinking of coating forms the hydrophobic coating of crosslinking, and the hydrophobic coating after crosslinking becomes having one from the state easily scratched before being crosslinked Determine the lubricious of obdurability, scanning electron microscope following table obtain the hydrophobic coating with a thickness of 5 μm.

Corrosion experiment is carried out in Hank ' s liquid by method identical with embodiment 18, the results showed that, after impregnating 7 days, table The pure iron silk that face only has PLA coating has occurred that heavy corrosion, and fracture occurs in individual sites, and there is hydrophobic painting on surface The pure iron silk of layer not yet corrodes when impregnating 7 days, and pure iron silk still maintains comparable with original state when by 28 days Radial strength.

Embodiment 20

One kind caning absorb iron-based coronary artery bracket, and preparation method is as follows: offer quality is 3.8mg, wall thickness is 50 μm, internal diameter For 1.45mm 30008 specification pure iron matrixes (30008 specifications are as follows: name expand pressure 8atm (name expansion pressure refers to Pressure used when by stent-expansion to nominal diameter) under effect, nominal diameter after expansion is 3.0mm, and nominal length is 8.0mm.30008 specifications in following embodiment indicate identical meaning, hereafter repeat no more), compound concentration 0.02g/mL Polylactic acid-dimethyl silicone polymer-polylactic acid (PLA₁₅-PDMS₇₆-PLA₁₅- DA) polymeric monomer (i.e. hydrophobic monomer) acetic acid second Ester solution, and photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added and obtains mixed liquor, wherein the matter of photoinitiator Amount is the 1 ‰ of hydrophobic monomer quality.The mixed liquor is sprayed on all surface of pure iron matrix using the method for ultrasound spraying, After ventilation makes ethyl acetate volatilize completely, uncrosslinked PLA is formed on all surface of pure iron matrix₁₅-PDMS₇₆-PLA₁₅- DA coating.Pump is 0.1mL/min, ultrasonic power 4.75W for flow velocity in spraying process.Then, it is with 365nm, intensity 8000μW/cm²Ultraviolet light to uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅- DA coating irradiates 30min, makes acryloyl group in coating The hydrophobic coating being crosslinked is reacted, to form the hydrophobic of the crosslinking of the outer surface of covering pure iron matrix, inner surface and side Coating.Scanning electron microscope following table obtain hydrophobic coating with a thickness of 8 μm.

Multiple by the batch can absorb iron-based coronary artery bracket and are implanted into the abdominal aorta of more rabbits respectively, implantation process In kept expand than range be 1.1:1 to 1.2:1.Iron weightlessness is calculated using micro-CT, January, iron did not corroded after implantation, implantation 3 months iron weightlessness 20% afterwards, 6 months iron weightlessness 40% after implantation.

Embodiment 21

One kind caning absorb iron-based coronary artery bracket, and preparation method is as follows: offer quality is 3.8mg, wall thickness is 50 μm, internal diameter It is that 60,000 PLA are dissolved in ethyl acetate by molecular weight, compound concentration is 2mg/mL's for the 30008 specification pure iron matrixes of 1.45mm PLA solution is done the PLA solution spraying on the outer surface of pure iron matrix, inner surface and side using the method for ultrasound spraying The PLA coating with a thickness of 4 μm is formed after dry on the outer surface of pure iron matrix, inner surface and side.Compound concentration is 0.02g/ Polytrimethylene carbonate-dimethyl silicone polymer-polytrimethylene carbonate (PTMC of mL₂₀-PDMS₇₆-PTMC₂₀-DA) The ethyl acetate solution of (i.e. hydrophobic monomer), and photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added and is mixed Liquid, wherein the quality of photoinitiator is the 1 ‰ of hydrophobic monomer quality.The mixed liquor is sprayed on by pure iron using ultrasonic spray coating method On the outer surface of matrix, inner surface and side, after ventilation makes ethyl acetate volatilize completely, formed on the inner surface of pure iron matrix Uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀- DA coating.Pump is 0.1mL/min for flow velocity in spraying process, and ultrasonic power is 4.75W.It then, is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PTMC₂₀-PDMS₇₆-PTMC₂₀- DA is applied Layer irradiation 2h, so that acryloyl group in coating is reacted the hydrophobic coating being crosslinked, thus formed covering pure iron matrix outer surface, The hydrophobic coating of the crosslinking of inner surface and side.Scanning electron microscope following table obtain hydrophobic coating with a thickness of 5 μm.

Multiple by the batch can absorb iron-based coronary artery bracket and are implanted into the abdominal aorta of more rabbits respectively, implantation process In kept expand than range be 1.1:1 to 1.2:1.Iron weightlessness is calculated using micro-CT, 1 month iron does not corrode after implantation, plants 3 months iron does not corrode after entering, 6 months iron weightlessness 50% after implantation.

Embodiment 22

One kind caning absorb iron-based coronary artery bracket, and preparation method is as follows: offer quality is 3.8mg, wall thickness is 50 μm, internal diameter For the 30008 specification nitriding iron matrixes of 1.45mm, the PLA that molecular weight is 60,000 is dissolved in ethyl acetate, compound concentration 2mg/ The PLA solution of mL, using the method for ultrasound spraying by the PLA solution spraying in the outer surface of nitriding iron matrix, inner surface and side On face, the PLA coating with a thickness of 4 μm is formed after dry on the outer surface of nitriding iron matrix, inner surface and side.

There is the nitriding iron matrix of PLA coating to handle under oxygen plasma on surface, gas pressure 50Pa, plasma Power is 100W, and the processing time is 30min.The KH-570 silanization coupling agent that 50 μ L are drawn with the liquid-transfering gun of 100 μ L, will be internal Surface after pipette tips and corona treatment containing KH-570 has the pure magnesium matrix of PLA coating to be put into drier, takes out true After sky, 12h is placed, so that KH-570 is volatilized and is adsorbed on PLA coating surface, form adhesive layer on the surface of PLA coating.

Polycaprolactone-dimethyl silicone polymer-by method synthesis acryloyl group sealing end substantially the same manner as Example 1 is poly- Caprolactone (PCL₁₀-PDMS₇₆-PCL₁₀- DA) macromonomer (i.e. hydrophobic monomer).

Compound concentration is polycaprolactone-dimethyl silicone polymer-polycaprolactone (PCL of 0.02g/mL₁₀-PDMS₇₆- PCL₁₀- DA) polymeric monomer (i.e. hydrophobic monomer) ethyl acetate solution, and photoinitiator 2- hydroxy-2-methyl -1- phenyl-is added 1- acetone obtains mixed liquor, wherein the quality of photoinitiator is the 1 ‰ of hydrophobic monomer quality.It will using the method for ultrasound spraying The mixed liquor is sprayed on all surface of nitriding iron matrix, after ventilation makes ethyl acetate volatilize completely, in the institute of pure iron matrix There is (the PCL that uncrosslinked covering adhesive layer is formed on surface₁₀-PDMS₇₆-PCL₁₀- DA) coating.Pump is for liquid stream in spraying process Speed is 0.1mL/min, ultrasonic power 4.75W.It then, is 8000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked (PCL₁₀-PDMS₇₆-PCL₁₀- DA) coating irradiation 1h, so that acryloyl group in coating is reacted the hydrophobic coating being crosslinked, thus shape At the hydrophobic coating of the crosslinking of the outer surface of covering pure iron matrix, inner surface and side.Scanning electron microscope following table is obtained Hydrophobic coating with a thickness of 20 μm.

Multiple by the batch can absorb iron-based coronary artery bracket and are implanted into the abdominal aorta of more rabbits respectively, implantation process In kept expand than range be 1.1:1 to 1.2:1.Iron weightlessness is calculated using micro-CT, 1 month iron does not corrode after implantation, plants 3 months iron does not corrode after entering, 6 months iron weightlessness 55% after implantation.

Embodiment 23

A kind of absorbable zinc-base coronary artery bracket, preparation method are as follows: offer quality is 6mg, wall thickness is 90 μm, internal diameter is The pure Zinc Matrix of 30008 specifications of 1.45mm, compound concentration are the PLA of 0.02g/mL₁₇-PDMS₇₆-PLA₁₇- DA's (hydrophobic monomer) Ethyl acetate solution is added photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone and obtains mixed liquor, wherein photoinitiator Quality be hydrophobic monomer quality 1 ‰.Above-mentioned mixed liquor is sprayed on to the interior table of above-mentioned pure Zinc Matrix using ultrasonic spray coating method Face forms uncrosslinked PLA after ventilation makes ethyl acetate volatilize completely on the surface of pure Zinc Matrix₁₇-PDMS₇₆-PLA₁₇-DA Coating.Pump is 0.1mL/min, ultrasonic power 4.75W for flow velocity in spraying process.It then, is 8000 μ with 365nm, intensity W/cm²Ultraviolet light to uncrosslinked PLA₁₇-PDMS₇₆-PLA₁₇- DA coating irradiates 1h, and acryloyl group in coating is made to react to obtain The hydrophobic coating of crosslinking, to form the hydrophobic coating for covering the inner surface of pure Zinc Matrix.Scanning electron microscope following table is obtained To hydrophobic coating with a thickness of 15 μm.

Multiple absorbable zinc-base coronary artery brackets of the batch are implanted into respectively in the abdominal aorta of more rabbits, implantation process In kept expand than range be 1.1:1 to 1.2:1.Zinc weightlessness is calculated using micro-CT, 1 month zinc weightlessness 4% after implantation is planted 3 months zinc weightlessness 25% after entering, 6 months zinc weightlessness 70% after implantation.

Embodiment 24

A kind of absorbable magnesium-based coronary artery bracket, preparation method are as follows: offer quality is 2mg, wall thickness is 100 μm, internal diameter For the pure magnesium matrix of 30008 specifications of 1.45mm.

Compound concentration is polylactic acid-dimethyl silicone polymer-polylactic acid (PLA of 0.02g/mL₁₅-PDMS₇₆-PLA₁₅-DA) The ethyl acetate solution of polymeric monomer (i.e. hydrophobic monomer), and photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone is added and obtains To mixed liquor, wherein the quality of photoinitiator is the 1 ‰ of hydrophobic monomer quality.The mixed liquor is sprayed by magnesium using ultrasound spraying The surface of matrix, pump are 0.1mL/min, ultrasonic power 4.5W for flow velocity, spraying five times are repeated according to this parameter, in pure magnesium Uncrosslinked PLA is formed on the surface of the adhesive layer of matrix₁₅-PDMS₇₆-PLA₁₅- DA coating.

It is 10000 μ W/cm with 365nm, intensity²Ultraviolet light to uncrosslinked PLA₁₅-PDMS₇₆-PLA₁₅- DA coating shines 1.5h is penetrated, PLA is made₁₅-PDMS₇₆-PLA₁₅The terminal acryl groups of-DA crosslink, to form the appearance for covering pure magnesium matrix Face, inner surface and side hydrophobic coating.PLA can be found after illumination₁₅-PDMS₇₆-PLA₁₅- DA coating is by original viscous hand state Become smooth and have the rubbery state of certain elasticity and toughness, scanning electron microscope following table obtain hydrophobic coating with a thickness of 20 μm。

Multiple absorbable magnesium-based coronary artery brackets of the batch are implanted into respectively in the abdominal aorta of more rabbits, implantation process In kept expand than range be 1.1:1 to 1.2:1.Magnesium weightlessness is calculated using micro-CT, 2 months magnesium does not corrode after implantation, plants 3 months magnesium weightlessness 40% after entering, 6 months magnesium weightlessness 100% after implantation.

Comparative example 1

One kind can absorb iron-based coronary artery bracket, and material is pure iron, specification 30008, quality 3.8mg, wall thickness be 50 μm, Internal diameter is 1.45mm.

Multiple by the batch can absorb iron-based coronary artery bracket and are implanted into the abdominal aorta of more rabbits respectively, implantation process In kept expand than range be 1.1:1 to 1.2:1.Iron weightlessness is calculated using micro-CT, is implanted into (the contact of iron weightlessness 8% in 1 month Body fluid starts to degrade), 3 months iron weightlessness 15% after implantation, 6 months iron weightlessness 30% after implantation.

Compared with comparative example 1, the time point of the iron-based bracket starting corrosion of the absorbable coronary artery of embodiment 20 is later, but is planting Enter the later period, corrosion rate is obviously accelerated.

Comparative example 2

One kind caning absorb iron-based coronary artery bracket, and preparation method is as follows: offer quality is 3.8mg, wall thickness is 50 μm, internal diameter It is that 60,000 PLA are dissolved in ethyl acetate by molecular weight, compound concentration is 2mg/mL's for the 30008 specification pure iron matrixes of 1.45mm PLA solution, using the method for ultrasound spraying by the PLA solution spraying on the outer surface of nitriding iron matrix, inner surface and side, The PLA coating with a thickness of 4 μm is formed after drying on the outer surface of nitriding iron matrix, inner surface and side.

Multiple by the batch can absorb iron-based coronary artery bracket and are implanted into more rabbit abdominal aortas respectively, in implantation process Keeping expanding than range is 1.1:1 to 1.2:1.Iron weightlessness is calculated using micro-CT, 1 month iron weightlessness 20% (connects after implantation Contact liquid starts to degrade), 3 months iron weightlessness 40% after implantation, 6 months iron weightlessness 50% after implantation.

Compared with comparative example 2, the time point of the iron-based bracket starting corrosion of the absorbable coronary artery of embodiment 21 and embodiment 22 It is later, but phase after the implantation, corrosion rate are obviously accelerated.

Comparative example 3

A kind of absorbable zinc-base coronary artery bracket, material are pure zinc, and specification 30008, quality 6mg, wall thickness be 90 μm, interior Diameter is 1.45mm.

Multiple absorbable zinc-base coronary artery brackets of the batch are implanted into respectively in the abdominal aorta of multiple rabbits, implantation process In kept expand than range be 1.1:1 to 1.2:1.Zinc weightlessness is calculated using micro-CT, 1 month zinc weightlessness 12% of implantation (connects Contact liquid starts to degrade), 3 months zinc weightlessness 30% after implantation, 6 months zinc weightlessness 60% after implantation.

Compared with comparative example 3, the time point of the absorbable zinc-base coronary artery bracket starting corrosion of embodiment 23 is later, but is planting Enter the later period, corrosion rate is obviously accelerated.

Comparative example 4

A kind of absorbable magnesium-based coronary artery bracket, material are pure magnesium, specification 30008, quality 2mg, wall thickness be 100 μm, Internal diameter is 1.45mm.

Multiple absorbable magnesium-based coronary artery brackets of the batch are implanted into respectively in the abdominal aorta of multiple rabbits, implantation process In kept expand than range be 1.1:1 to 1.2:1.Magnesium weightlessness, 1 month magnesium weightlessness 30% after implantation are calculated using micro-CT (contact body fluid starts to degrade), 3 months magnesium weightlessness 80% after implantation, 4 months magnesium weightlessness 100% after implantation.

Compared with comparative example 4, the time point of the absorbable magnesium-based coronary artery bracket starting corrosion of embodiment 24 is later, but is planting Enter the later period, corrosion rate is obviously accelerated.

Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.

The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims

1. a kind of hydrophobic coating is covered in the surface of degradation material, which is characterized in that the hydrophobic coating is hydrophobic monomer crosslinking The cross-linked coating to be formed is blended with non-degradable component in the coating or hydrophobic monomer of formation,

Wherein, the hydrophobic monomer is comprising hydrophobic block, degradable block and the block copolymer for being crosslinked functional group.

2. a kind of hydrophobic coating according to claim 1, which is characterized in that the hydrophobic block is by hydrophobic polymer shape At the degradable block is formed by degradable polymer, and the monomer of hydrophobic block polymerize instead with the monomer that can drop block It answers, forms the hydrophobic block and degradable block being connected by chemical bond, crosslinking functional group and hydrophobic block and/or degradable Block is connected by chemical bond, makes to crosslink to form hydrophobic coating between hydrophobic monomer.

3. a kind of hydrophobic coating according to claim 1, which is characterized in that the hydrophobic block is by polydimethylsiloxanes In alkane, perfluoropolyether, polyvinyldifluoride, polytetrafluoroethylene (PTFE), polyhexafluoropropylene or Kynoar-hexafluoropropylene copolymer extremely A kind of few formation.

4. a kind of hydrophobic coating according to claim 1, which is characterized in that the degradable block is by degradable polymer It is formed,

The degradable polymer is selected from polyglycolide, polyglycolic acid, Poly L-lactide, poly- D, L- lactide, poly- hydroxyl fourth Acid esters, poly-epsilon-caprolactone, poly- ε-alkyl replace caprolactone, poly- δ-valerolactone, poly-β-hybroxybutyric acid, polycarbonate or polyether ester At least one of；

Alternatively, the degradable polymer is to form polyglycolide, polyglycolic acid, Poly L-lactide, Poly D,L-lactide, gather Butyric ester, poly-epsilon-caprolactone, poly- ε-alkyl replace caprolactone, poly- δ-valerolactone, poly-β-hybroxybutyric acid, polycarbonate or At least two copolymers formed in the monomer of polyether ester.

5. a kind of hydrophobic coating according to claim 4, which is characterized in that the molecular weight of the degradable block is 500 ~20000, the degree of polymerization of degradable block is 20~40.

6. a kind of hydrophobic coating according to claim 1, which is characterized in that the crosslinking functional group be selected from allyl, At least one of acryloyl group, methylacryloyl, epoxy group, oxazoline group, cyanic acid base, silicone hydroxyl or siloxy.

7. a kind of hydrophobic coating according to claim 1, which is characterized in that the non-degradable group be selected from silicon rubber, At least one of polysiloxanes, polysilazane or fluoropolymer.

8. a kind of hydrophobic coating according to claim 1, which is characterized in that the hydrophobic coating with a thickness of 0.01~ 100μm。

9. a kind of preparation method of hydrophobic coating as described in claim 1 characterized by comprising

Hydrophobic monomer is provided, Xiang Suoshu hydrophobic monomer bestows initiation conditions, crosslinks the hydrophobic monomer and is formed described Hydrophobic coating；

Alternatively, the mixture of offer hydrophobic monomer and non-degradable component, Xiang Suoshu hydrophobic monomer and non-degradable component is mixed It closes object and bestows initiation conditions, the non-degradable component is made to crosslink or make between the hydrophobic monomer and non-degradable component It crosslinks to form the hydrophobic coating.

10. a kind of preparation method of hydrophobic coating according to claim 9, which is characterized in that the initiation conditions are purple Outer light irradiation, heat treatment or moisture effect.

11. a kind of preparation method of hydrophobic coating according to claim 10, which is characterized in that

Ultraviolet light includes: after mixing the hydrophobic monomer with photoinitiator, with the ultraviolet light 30min of 365nm~ 2h；The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone, and the quality of the photoinitiator is the hydrophobic monomer Quality 1 ‰.

Heat treatment include: by the hydrophobic monomer or hydrophobic monomer and the mixture of non-degradable component at 20~150 DEG C Manage 30min~72h；

Moisture effect includes: that the mixture of the hydrophobic monomer or hydrophobic monomer and non-degradable component is placed under wet gas environments Reaction 1~5 day.

12. application of the hydrophobic coating as described in claim 1 in the degradation behavior for delaying degradation material.

13. a kind of absorbable implantable device, including absorbable matrix, which is characterized in that further include as described in claim 1 Hydrophobic coating, the hydrophobic coating are covered in the surface of the absorbable matrix.

14. a kind of absorbable implantable device according to claim 13, which is characterized in that the material of the absorbable matrix Material is the composite material of degradable polymer, corrodible metal or corrodible metal and degradable polymer.

15. a kind of absorbable implantable device according to claim 13, which is characterized in that the absorbable implanted device Tool further includes adhesive layer, and the adhesive layer is between the absorbable matrix and the hydrophobic coating.

16. a kind of absorbable implantable device according to claim 15, which is characterized in that the material of the adhesive layer selects From at least one of dopamine and silane coupling agent.

17. a kind of absorbable implantable device according to claim 13, which is characterized in that the absorbable implanted device Tool is angiocarpy bracket, cerebrovascular stent, peripheral vascular stents, biliary tract rack, esophageal stents, airway stent, urethra rack, envelope Stifled device, orthopaedics implant or absorbable suture.