CN110183587A - Photocuring selfreparing polyurethane acrylic resin and preparation method thereof - Google Patents
Photocuring selfreparing polyurethane acrylic resin and preparation method thereof Download PDFInfo
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- CN110183587A CN110183587A CN201910369168.2A CN201910369168A CN110183587A CN 110183587 A CN110183587 A CN 110183587A CN 201910369168 A CN201910369168 A CN 201910369168A CN 110183587 A CN110183587 A CN 110183587A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses a kind of photocuring selfreparing polyurethane acrylic resins and preparation method thereof, the resin prepolymer includes that following raw material in parts by mass is made: macromolecule dihydric alcohol 100, diisocyanate 10 ~ 25, hydroxy acrylate 5 ~ 12, to phenylmethylene bismaleimide 3.0 ~ 6.0, furfuryl alcohol 1.0 ~ 2.0, polymerization inhibitor 0.1 ~ 2.0, catalyst 0.1 ~ 2.0.Its by select macromolecule dihydric alcohol be soft segment, diisocyanate is hard section, and on its macromolecular main chain of base polyurethane prepolymer for use as introduce can occur thermal reversion Diels-Alder reaction to phenyl-bismaleimide and furfuryl alcohol, assign polyurethane material self-healing properties, finally blocked with hydroxy acrylate, it is prepared for photocuring selfreparing polyurethane resin, not only have self-repair function, but also meet photocuring increasing material manufacturing needs.
Description
Technical field
The present invention relates to Photocurable oligomers field, specially a kind of photocuring selfreparing polyurethane acrylic resin and its
Preparation method.
Background technique
Polyurethane acrylate resin is the main light-sensitive material of current stereolithograghy (SLA) increasing material manufacturing, because
The neck such as has the characteristics that fast solidification rate, environmental-friendly, save the cost and the energy and is widely used in material, ink, adhesive
Domain.Main body of the oligomer as photocurable resin material, determine light-cured resin ink rheological property and solidification after material
Physicochemical property.Curable urethane acrylate resin function is more single at present, self-repair function missing, limit its
Further genralrlization application in terms of increasing material manufacturing.Self-repair function material can effectively solve conventional polymer based composites vulnerable to ring
Border influences the problem of cracking, leading to material apparent mass, safeguard function, mechanical properties decrease, significantly improves material
Service life, apparent mass and product durability are compeled in dual-use domain requirements such as automobile, aerospace, furniture building materials
It cuts.
Intrinsical self-repair material mainly passes through D-A key, cystine linkage, hydrogen bond, hydrophobic effect, pi-pi accumulation, ionization
With the realizations fast and efficiently selfreparing such as host-guest interaction, without harsh reaction condition and cumbersome coating technology is used.This
During sign type self-repair material realizes self-regeneration, to guarantee its self-repair efficiency with higher, most of working set
In in the preferable soft polymer material of Chain Flexibility, but its glass transition temperature is lower, and material hardness is caused to decline, Wu Fabao
Demonstrate,prove its demand in use.
Summary of the invention
The present invention provides a kind of photocuring selfreparing polyurethane acrylic resin and preparation method thereof, has both had selfreparing function
Can, and meet photocuring increasing material manufacturing needs, and the two effect collaboration, it has complementary functions, can greatly push urethane acrylate
Resin is applied in the increasing material manufacturing of high solids content composite material.
Concrete scheme of the invention is to provide a kind of photocuring selfreparing polyurethane acrylic resin prepolymer, molecule knot
Structure formula are as follows:
Wherein: R1Residual groups after losing two hydroxyls for macromolecule dihydric alcohol,
R2Residual groups after losing two isocyanate group for diisocyanate,
R3Residual groups after losing hydroxyl for hydroxy acrylate.
The invention further relates to the method for preparing the photocuring selfreparing polyurethane acrylic resin, the resin prepolymer packets
The following raw material included in parts by mass is made:
Specific preparation step:
1) phenylmethylene bismaleimide will be dissolved with organic solvent, furfuryl alcohol is added dropwise, and be warming up to 50~70 DEG C instead
Stop after answering 12~36h, product is added in organic solvent and stirs purification, drying for 24 hours, it is mono- to obtain DA in vacuum drying oven
Body；
2) DA monomer obtained by step 1) and macromolecule dihydric alcohol are dissolved with organic solvent, diisocyanate and catalysis is added dropwise
Agent is warming up to 40~60 DEG C and is stirred to react, and judges its extent of reaction by NCO content in di-n-butylamine method detection architecture,
When its content drops to original 1/3, polymerization inhibitor and hydroxy acrylate is added, continues through in di-n-butylamine method detection architecture
NCO content judges its extent of reaction, and when its content < 0.05%, reaction is reached home, obtain the poly- ammonia of photocuring selfreparing
Ester acrylic ester prepolymer.
Further, the macromolecule dihydric alcohol is end hydroxy butadiene, hydroxyl telechelic polyester dihydric alcohol, terminal hydroxy group gather
Ether dihydric alcohol, terminal hydroxy group long chain alkane dihydric alcohol glycidyl azide polymer, terminal hydroxy group ethylene oxide tetrahydrofuran copolyether, end
Hydroxyl polylactic acid it is one or more.
Further, the diisocyanate is isophorone diisocyanate, hexamethylene diisocyanate, dimerization
Fatty acid diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate,
One of 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate is a variety of.
Further, the hydroxy acrylate be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl,
Hydroxyethyl methacrylate, hydroxy propyl methacrylate, trimethylolpropane diacrylate, pentaerythritol diacrylate,
One of pentaerythritol triacrylate, 1,6 hexanediol diacrylate are a variety of.
Further, the polymerization inhibitor is hydroquinone, p-hydroxyanisole, p methoxy phenol, adjacent methyl to benzene
One of diphenol, 2,6 di tert butyl 4 methyl phenol are a variety of.
Further, the catalyst is triphenyl bismuth, three (ethoxyl phenenyl) bismuths, ferric acetyl acetonade, tin dilaurate two
One of butyl tin, triphenyltin chloride are a variety of.
Further, it also needs to use organic solvent, active monomer diluent, photoinitiator in the resin preparation process,
Levelling agent and coupling agent, the organic solvent are n,N-Dimethylformamide, n,N-dimethylacetamide, chloroform, acetic acid
Ethyl ester, dimethyl sulfoxide, methylene chloride, methanol, ethyl alcohol, ether, tetrahydrofuran, dioxane, acetone, n-butanol one kind or
It is a variety of.
The invention further relates to the photocuring selfreparing polyurethane acrylic resins using prepolymer preparation comprising light
Solidify selfreparing polyurethane acrylate prepolymer, active monomer diluent, photoinitiator, levelling agent and coupling agent, by weight
Percentages, are followed successively by 75~90%:5~20%:1~3%:1~3%:0.1~2%, weight percent shared by each raw material it
Be 100%, when specific preparations, all raw materials are added, are mixed at 30~70 DEG C, under the ultraviolet light of 360~380nm of wavelength
10~15min crosslinking curing is irradiated, photocuring selfreparing polyurethane-acrylate resin is obtained.
Further, the active monomer diluent is with one or more acrylate functional compounds or these chemical combination
The combination of object；The photoinitiator is alpha-hydroxyalkyl benzophenone class, azodiisobutyronitrile, benzil class, α-amine alkylbenzene ketone, acyl
One or more of base phosphorous oxides, acylphosphine oxide, fragrant peroxy esters, 3- ketocoumarin；The levelling agent is poly-
One or more of ether azo polyether polyeste, polyester modified organic siloxane, acrylate copolymer；The coupling agent is
Titanate coupling agent, boric acid ester coupler, ethanolamines coupling agent, polyamines polyene class coupling agent, the coupling of phosphorous oxide aziridines
One or more of agent.
It requires to select different macromolecule dihydric alcohols, diisocyanate for the different parameters of light-cured resin, such as molten
Point, tensile strength, degradable speed, glass transition temperature, the demand of energy water equality and carry out different selections, hydroxy acrylic acid
Ester is mainly to be determined according to the demand of laser curing velocity, the solidification intensity of resin etc..
The invention has the following advantages:
1, the present invention by selection macromolecule dihydric alcohol is soft segment, diisocyanate is hard section, and in base polyurethane prepolymer for use as
Introduced on its macromolecular main chain can occur thermal reversion Diels-Alder reaction to phenyl-bismaleimide and furfuryl alcohol, assign
Polyurethane material self-healing properties, are finally blocked with hydroxy acrylate, due to the presence of photosensitive double bond in its structure, Gu
The crosslink density of material, mechanical property and good flexibility can be increased after chemical conversion film well, to improve its hardness etc.
Performance.And photocuring selfreparing polyurethane has suitable fusing point and glass transition temperature, higher degree of functionality, have light it is solid,
Thermoplastic dual cure systems not only have self-repair function, but also meet photocuring increasing material manufacturing needs, and the two effect collaboration, function
Complementation can greatly push polyurethane acrylate resin to apply in the increasing material manufacturing of high solids content composite material.
2, the present invention uses substep preparation method, first obtains polyurethane prepolymer, then carry out acyl with to phenylmethylene span
Imines is polymerize to obtain selfreparing polyurethane with furfuryl alcohol dimerization zoarium, carries out DA again compared to the selfreparing polyurethane first obtained
The selfreparing polyurethane that heat cross-linking obtains, the self-repair efficiency of the selfreparing polyurethane that the present invention obtains is high, and mechanical property compared with
It is excellent.
3, photocuring light-sensitive material of the invention belongs to liquid resin composition nontoxic, nonflammable, that volatility is small, not
In the case where contacting ultraviolet light, it will not occur to polymerize and generate flocculation.Adjusted by different raw material ratios viscosity of material,
Curing time, material property, with the different type of printer and product adapted to；And radical UV curing system is used, have
The advantages that curing rate is fast, abundant raw materials, controllable performance, is produced on a large scale.
Specific embodiment
Below with reference to embodiment, the present invention is furture elucidated.
Embodiment 1:
Photocuring selfreparing polyurethane acrylic resin preparation method
1) synthesis of DA monomer: vacuum 30.2g dissolves phenylmethylene bismaleimide with chloroform, is added
In single-necked flask equipped with stirrer, the furfuryl alcohol of 12.3g is added dropwise, stops after being warming up to 50~70 DEG C of 12~36h of reaction, will generate
Object, which is added in organic solvent, stirs purification, and drying for 24 hours, obtains DA monomer in an oven；
2) it the synthesis of photocuring selfreparing polyurethane acrylate prepolymer: is stirred equipped with thermometer, condenser pipe and machinery
In the three-necked flask mixed, the 42.3gDA monomer and 980g hydroxyl telechelic polyester dihydric alcohol of addition are molten with n,N-dimethylacetamide
Solution.The 103.4g isophorone diisocyanate and 1.5g ferric acetyl acetonade being added dropwise with constant pressure funnel, are warming up to 40~60
DEG C and be stirred to react.In reaction process, its extent of reaction is judged by NCO content in di-n-butylamine method detection architecture, to it
When content drops to original 1/3, the 100g hydroxy acrylate containing 2.5g p-hydroxyanisole is added, continues through two positive fourths
NCO content judges its extent of reaction in amine method detection architecture, and when its content < 0.05%, reaction is reached home, and light is obtained
Solidify selfreparing polyurethane acrylate prepolymer.
3) synthesis of photocuring selfreparing polyurethane-acrylate resin: the light that step 2 synthesis is added in Xiang Qingjie container is solid
Change 87.5% selfreparing polyurethane acrylate prepolymer, 8% ethyl acrylate, 3% alpha-hydroxyalkyl benzophenone, 1% poly-
Ether azo polyether polyeste, 0.5% titanate coupling agent；Said mixture mixes at 40 DEG C, 360~380nm's of wavelength
1~5min crosslinking curing is irradiated under ultraviolet light, obtains photocuring selfreparing polyurethane-acrylate resin.
The photocuring selfreparing polyurethane-acrylate resin has the following performance:
Embodiment 2:
Photocuring selfreparing polyurethane acrylic resin preparation method
1) synthesis of DA monomer: 120.2g dissolves phenylmethylene bismaleimide with methylene chloride, and dress is added
Have in the single-necked flask of stirrer, the furfuryl alcohol of 48.3g is added dropwise, stops after being warming up to 50 DEG C of reaction 36h, product is added organic
Purification is stirred in solvent, drying for 24 hours, obtains DA monomer in vacuum drying oven；
2) it the synthesis of photocuring selfreparing polyurethane acrylate prepolymer: is stirred equipped with thermometer, condenser pipe and machinery
In the three-necked flask mixed, the 167.3gDA monomer and 3780g end hydroxy butadiene of addition are dissolved with organic solvent.Use constant pressure
The 401.4g hexamethylene diisocyanate and 7.4g tri- (ethoxyl phenenyl) bismuth that dropping funel is added dropwise, are warming up to 40~60 DEG C simultaneously
It is stirred to react.In reaction process, its extent of reaction is judged by NCO content in di-n-butylamine method detection architecture, to its content
When dropping to original 1/3, the 420g trimethylolpropane diacrylate containing 8.5g hydroquinone is added, is continuing through two just
NCO content judges its extent of reaction in butylamine method detection architecture, and when its content < 0.05%, reaction is reached home, and is obtained
Photocuring selfreparing polyurethane acrylate prepolymer.
3) synthesis of photocuring selfreparing polyurethane-acrylate resin: the light that step 2 synthesis is added in Xiang Qingjie container is solid
Change 77.5% selfreparing polyurethane acrylate prepolymer, 18.4% propyl acrylate, 2% azodiisobutyronitrile, 2%
Polyester modified organic siloxane, 0.1% boric acid ester coupler；Said mixture mixes at 70 DEG C, in 360~380nm of wavelength
Ultraviolet light under irradiate crosslinking curing, obtain photocuring selfreparing polyurethane-acrylate resin.
The photocuring selfreparing polyurethane-acrylate resin has the following performance:
Embodiment 3:
Photocuring selfreparing polyurethane acrylic resin preparation method
1) synthesis of DA monomer: 300.2g dissolves phenylmethylene bismaleimide with dioxane, and dress is added
Have in the single-necked flask of stirrer, the furfuryl alcohol of 124.2g is added dropwise, be warming up to 50 DEG C of reactions and stop afterwards for 24 hours, product addition is had
Purification is stirred in solvent, drying for 24 hours, obtains DA monomer in vacuum drying oven；
2) it the synthesis of photocuring selfreparing polyurethane acrylate prepolymer: is stirred equipped with thermometer, condenser pipe and machinery
In the three-necked flask mixed, the 421.4gDA monomer and 8500g polyether glycol of addition are dissolved with tetrahydrofuran.With perseverance
The 953.4g3 for pressing dropping funel to be added dropwise, 3 '-dimethyl -4,4 '-biphenyl diisocyanates and 1.5g catalyst, it is warming up to 40~
It 60 DEG C and is stirred to react.In reaction process, its extent of reaction is judged by NCO content in di-n-butylamine method detection architecture, to
When its content drops to original 1/3, the 945g pentaerythritol diacrylate containing 25g neighbour's methyl hydroquinone is added, continues
Its extent of reaction is judged by NCO content in di-n-butylamine method detection architecture, and when its content < 0.05%, reaction is reached eventually
Point obtains photocuring selfreparing polyurethane acrylate prepolymer.
3) synthesis of photocuring selfreparing polyurethane-acrylate resin: the light that step 2 synthesis is added in Xiang Qingjie container is solid
Change 87.5% selfreparing polyurethane acrylate prepolymer, 8% hydroxy propyl methacrylate, 3% α-amine alkyl phenones,
1% organic silicon modified by polyether oxygen alkane, 0.5% polyamines polyene class coupling agent；Said mixture mixes at 45 DEG C, in wavelength 360
Crosslinking curing is irradiated under the ultraviolet light of~380nm, obtains photocuring selfreparing polyurethane-acrylate resin.
The photocuring selfreparing polyurethane-acrylate resin has the following performance:
Embodiment 4:
Photocuring selfreparing polyurethane acrylic resin preparation method
1) synthesis of DA monomer: 900.8g dissolves phenylmethylene bismaleimide with chloroform, and dress is added
Have in the single-necked flask of stirrer, the furfuryl alcohol of 376.3g is added dropwise, stop after being warming up to 70 DEG C of reaction 12h, product addition is had
Purification is stirred in solvent, drying for 24 hours, obtains DA monomer in vacuum drying oven；
2) it the synthesis of photocuring selfreparing polyurethane acrylate prepolymer: is stirred equipped with thermometer, condenser pipe and machinery
In the three-necked flask mixed, the 1267.3gDA monomer and 26780g terminal hydroxy group ethylene oxide tetrahydrofuran copolyether of addition, with N, N-
Dimethyl acetamide dissolution.Two fourth of 3467.4g toluene di-isocyanate(TDI) and 3.5g tin dilaurate being added dropwise with constant pressure funnel
Ji Xi is warming up to 40~60 DEG C and is stirred to react.In reaction process, sentenced by NCO content in di-n-butylamine method detection architecture
The 2400g1 containing 56.5g hydroquinone, 6- hexylene glycol two is added when its content drops to original 1/3 in its extent of reaction of breaking
Acrylate continues through in di-n-butylamine method detection architecture NCO content to judge its extent of reaction, to its content < 0.05%
When, reaction is reached home, and photocuring selfreparing polyurethane acrylate prepolymer is obtained.
3) synthesis of photocuring selfreparing polyurethane-acrylate resin: the light that step 2 synthesis is added in Xiang Qingjie container is solid
Change 88.2% selfreparing polyurethane acrylate prepolymer, 7% ethyl acrylate, 3% alpha-hydroxyalkyl benzophenone, 1% poly-
Ether azo polyether polyeste, 0.8% titanate coupling agent；Said mixture mixes at 70 DEG C, 360~380nm's of wavelength
Crosslinking curing is irradiated under ultraviolet light, obtains photocuring selfreparing polyurethane-acrylate resin.
The preferred n,N-Dimethylformamide of organic solvent described above, n,N-dimethylacetamide, chloroform, acetic acid second
One kind or more of ester, dimethyl sulfoxide, methylene chloride, methanol, ethyl alcohol, ether, tetrahydrofuran, dioxane, acetone, n-butanol
Kind.
The photocuring selfreparing polyurethane-acrylate resin has the following performance:
Claims (10)
1. photocuring selfreparing polyurethane acrylic resin prepolymer, which is characterized in that molecular structural formula are as follows:
Wherein: R1Residual groups after losing two hydroxyls for macromolecule dihydric alcohol,
R2Residual groups after losing two isocyanate group for diisocyanate,
R3Residual groups after losing hydroxyl for hydroxy acrylate.
2. the method for preparing photocuring selfreparing polyurethane acrylic resin prepolymer described in claim 1, which is characterized in that should
Resin prepolymer includes that following raw material in parts by mass is made:
Specific preparation step:
1) phenylmethylene bismaleimide will be dissolved with organic solvent, furfuryl alcohol is added dropwise, and be warming up to 50~70 DEG C of reactions 12
Stop after~36h, product is added in organic solvent and stirs purification, drying for 24 hours, obtains DA monomer in vacuum drying oven；
2) DA monomer obtained by step 1) and macromolecule dihydric alcohol are dissolved with organic solvent, diisocyanate and catalyst are added dropwise,
It is warming up to 40~60 DEG C and is stirred to react, its extent of reaction is judged by NCO content in di-n-butylamine method detection architecture, to it
When content drops to original 1/3, polymerization inhibitor and hydroxy acrylate is added, continues through NCO in di-n-butylamine method detection architecture
Content judges its extent of reaction, and when its content < 0.05%, reaction is reached home, obtain photocuring selfreparing polyurethane third
Olefin(e) acid ester prepolymer.
3. according to the method described in claim 2, it is characterized by: the macromolecule dihydric alcohol be end hydroxy butadiene,
Hydroxyl telechelic polyester dihydric alcohol, polyether glycol, terminal hydroxy group long chain alkane dihydric alcohol glycidyl azide polymer, terminal hydroxy group
Ethylene oxide tetrahydrofuran copolyether, hydroxyl-terminated polylactic acid it is one or more.
4. according to the method described in claim 2, it is characterized by: the diisocyanate is isophorone diisocyanate
Ester, hexamethylene diisocyanate, dimer (fatty acid) yl diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanate
One of ester, dicyclohexyl methyl hydride diisocyanate, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate are a variety of.
5. according to the method described in claim 2, it is characterized by: the hydroxy acrylate is hydroxy-ethyl acrylate, third
Olefin(e) acid hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, two propylene of trimethylolpropane
One of acid esters, pentaerythritol diacrylate, pentaerythritol triacrylate, 1,6 hexanediol diacrylate are more
Kind.
6. according to the method described in claim 2, it is characterized by: the polymerization inhibitor be hydroquinone, p-hydroxyanisole,
One of p methoxy phenol, adjacent methyl hydroquinone, 2,6 di tert butyl 4 methyl phenol are a variety of.
7. photocuring selfreparing polyurethane acrylic resin prepolymer according to claim 1, it is characterised in that: described to urge
Agent is triphenyl bismuth, in three (ethoxyl phenenyl) bismuths, ferric acetyl acetonade, dibutyl tin dilaurate, triphenyltin chloride
It is one or more.
8. the photocuring selfreparing using the preparation of photocuring selfreparing polyurethane acrylic resin prepolymer described in claim 1 is poly-
Urethane acrylate resin comprising photocuring selfreparing polyurethane acrylate prepolymer, active monomer diluent, light-initiated
Agent, levelling agent and coupling agent, by weight percentage, be followed successively by 75~90%:5~20%:1~3%:1~3%:0.1~
2%, the sum of weight percent shared by each raw material is 100%, when specific preparation, all raw materials is added, mix at 30~70 DEG C,
10~15min crosslinking curing is irradiated under the ultraviolet light of 360~380nm of wavelength, obtains photocuring selfreparing polyurethane-acrylate
Resin.
9. photocuring selfreparing polyurethane acrylic resin according to claim 8, it is characterised in that: the activated monomer
Diluent is the combination with one or more acrylate functional compounds or these compounds；The photoinitiator is α-hydroxyl alkane
Base benzophenone class, azodiisobutyronitrile, benzil class, α-amine alkylbenzene ketone, acyl group phosphorous oxides, acylphosphine oxide, fragrance
One or more of peroxy esters, 3- ketocoumarin.
10. photocuring selfreparing polyurethane acrylic resin according to claim 8, it is characterised in that: the levelling agent
For one or more of organic silicon modified by polyether oxygen alkane, polyester modified organic siloxane, acrylate copolymer；The coupling
Agent is titanate coupling agent, boric acid ester coupler, ethanolamines coupling agent, polyamines polyene class coupling agent, phosphorous oxide aziridines
One or more of coupling agent.
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