CN109369880A - A kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate and its preparation method and application - Google Patents
A kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate and its preparation method and application Download PDFInfo
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention discloses a kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylates and its preparation method and application.Its structural formula is Formulas I.The resin enhances water resistance, surface hydrophobic and the thermal stability of traditional photocurable polyurethane (methyl) acrylate；Curing rate is fast；The film haveing excellent performance can be made；The phase separation degree and crosslinking degree of polyurethane resin can be controlled by adjusting the content that (methyl) is acrylate-based in silicone segments；Preparation method is simple.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of photo curable aminomethyl phenyl organic silicon modified polyurethane
(methyl) acrylate and its preparation method and application.
Background technique
Urethane acrylate (PUA) is to introduce third in its strand by acroleic acid esterification on the basis of polyurethane
Olefin(e) acid double bond, then a kind of oligomer by photocuring means initiation double bond cross-linking reaction.It is good that PUA had both remained with polyurethane (PU)
Good cold resistance, physical mechanical property, hardness vary with temperature the advantages that smaller, chemical-resistant reagent, and have polyacrylic acid
Ester solidification rate is fast, high-efficient, good in optical property, do not turn yellow, storage stability is good, volatile organic matter (VOC) content is low etc.
Advantage has broad application prospects.
Organo-silicon compound refer to the compound that at least one organic group is connected with Si.In organo-silicon compound main chain often
Often contain Si-O-Si key, so that organosilicon material has both the performance of inorganic material and organic material, has surface can low, viscous temperature
The advantages that coefficient is small, stability is good, colourless nontoxic.But the adhesion property of organosilicon material and with the compatibility of other materials it is
Its defect.Organo-silicon compound are introduced into organic silicon modified polyurethane (methyl) the acrylate acrylic acid obtained in PUA
Ester (SPU) will have both the excellent properties of polyurethane and organosilicon material and abandon their defect.(the macromolecule material such as such as Sun Fang
Expect scientific and engineering, 2002,18 (5): 58-61) use isophorone diisocyanate (IPDI), hydroxyl-containing silicone, acrylic acid-
Beta-hydroxy ethyl ester (HEA) is raw material, has synthesized a kind of photo curable SPUA prepolymer, curing rate is very fast, resulting crosslinking
The water resistance of organic silicon modified polyurethane (methyl) acrylate acrylic resin mechanical strength and enhancing with higher
Deng.And Wang Xiaojun etc. (modern coatings and coating, 2008,11 (10): 17-20) introduces unsaturated monomer in main chain, and in side
Hydrolyzable organosilicon alkoxide is introduced on chain.The unsaturated unit of high-content increases the friendship of UV photocuring activity on main chain
Join point, improves curing efficiency, while the hydrolytic condensation self-crosslinking of side chain siloxy can form Si-O-Si key, improve film
Crosslinking degree and mechanical performance, and assign film coated surface hydrophobicity and resistance to soiling.(the Progress in Organic such as Ahn
Coatings, 2008,62:258-264.) HDI, HMDI, PTMG, HEA are used, the solidification of the synthesizing ultraviolets such as PETA, APTES is organic
Si modification PUA water-borne dispersions, film, which is made, has good solvent resistance, yellowing resistance, high mechanical strength and high superficiality
Can, and Experimental comparison has found that the water contact angle of organic-silicon-modified rear film, hardness have the increase of different amplitudes, while heat point
Solution temperature significantly improves 30-40 DEG C.
Our patent early period (ZL201410788628.2) phenyl organosilicon is used for it is polyurethane-modified, it is obtained
SPU has many advantages, such as better hydrophobicity, surface gloss, compatibility, heat resistance, mechanical property than traditional polyurethane.So
And the SPU is with-NCO sealing end, there are toxicity for itself, and-NCO easily reacts with moisture in air and influences its stable storing
Property, while Moisture-curing mechanisms cause curing time longer, and bubble is easy to produce after solidification.Additionally there are volatility is organic
The problems such as object (VOC) content is higher.
Summary of the invention
In order to solve disadvantage mentioned above, (methyl) acrylic double bond is introduced and aminomethyl phenyl is wherein made by we on this basis
Organic silicon modified polyurethane (methyl) acrylate (SPUA).This technique avoids patent (ZL201410788628.2)
In many defects as caused by-NCO.Meanwhile photocuring technology has rapid curing, environmental protection, energy conservation, greenization and required
The advantages that solvent is less (can partially solve the problems, such as VOC).
Technical scheme is as follows:
First aspect present invention provides a kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylic acid
Ester resin, structural formula are shown in formula I:
Wherein:
R1、R2For phenyl or methyl；
R3For β-acryl-oyloxyethoxy, Beta-methyl acryl-oyloxyethoxy or alkoxy；
R4For methyl, alkoxy, β-acryl-oyloxyethoxy or Beta-methyl acryl-oyloxyethoxy；
R5For H, phenyl or alkyl；
R6For isophorone base, hexyl, methyldiphenyl base, methyldicyclohexyl or benzyl；
R7For the primitive of polyethers, polyethylene glycol or polyester construction；
R8For hydrogen or methyl；
A is 1 or 3；M, n, y are natural number.
Second aspect provides and a kind of prepares the photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) third
The method of alkene acid ester resin:
(1) R for being 10-50% by mass fraction2SiCH3Cl2Toluene solution is added drop-wise to by diphenyl silanediol, tetrahydrofuran
In the mixed solution of pyridine composition, 2-5h is reacted at 20~80 DEG C, decompression filters, and cleans to get hydroxy-end capped aminomethyl phenyl
Polysiloxanes；Wherein R2SiCH3Cl2For dimethyldichlorosilane, methyl-propyl dichlorosilane, Ethyl methane sulphonate, first
One or more of base diphenyl dichlorosilane, Methyl Octyl dichlorosilane；Diphenyl silanediol is diphenyl silanediol or methyl
Diphenyl silanediol；The R2SiCH3Cl2Molar ratio with diphenyl silanediol is 0.5~0.95；Phenyl silicon in the mixed solution
The mass fraction of glycol is 10-50%；
(2) by catalyst and (R3)2R4Si(CH2)aNHR5It is poly- to be added to hydroxy-end capped aminomethyl phenyl prepared by step (1)
In siloxanes, methyl phenyl silicone is blocked to get amino or imino group in 70-100 DEG C of reaction 7-10h, structural formula is such as
Shown in Formula II:
R in Formula II1And R2For phenyl or methyl, R3For alkoxy；R4For methyl or alkoxy；R5For H, phenyl or alkyl；a
It is 1 or 3；
Wherein, (R3)2R4Si(CH2)aNHR5For gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy dimethoxysilane, γ-urea propyl-triethoxysilicane, γ-
Cyclohexylamino propyl trimethoxy silicane, γ-cyclohexylamino hydroxypropyl methyl dimethoxysilane, γ-three second of cyclohexylamino propyl
Oxysilane, γ-cyclohexylamino hydroxypropyl methyl diethoxy silane, γ-aniline propyl trimethoxy silicane, γ-aniline propyl
Triethoxysilane, γ-aniline hydroxypropyl methyl dimethoxysilane, γ-aniline hydroxypropyl methyl diethoxy silane, α-aniline first
Base trimethoxy silane, α-anilinomethyl triethoxysilane, α-anilinomethyl methyl dimethoxysilane, α-cyclohexylamine methyl
Trimethoxy silane, α-cyclohexylamine methyl diethoxy silane or α-cyclohexylamine methyltriethoxysilane, (R3)2R4Si(CH2)aNHR5With R2SiCH3Cl2Molar ratio be 0.8-8:3-7.6；
Wherein, catalyst is the metatitanic acid tert-butyl ester, butyl titanate, isopropyl titanate or dibutyl tin dilaurate；It is described
Catalyst and (R3)2R4Si(CH2)aNHR5Molar ratio be 0.004-0.09:0.8-8；
(3) (the first for the methyl phenyl silicone and 2.0-4.0 molar equivalent for blocking amino shown in Formula II or imino group
Base) hydroxy-ethyl acrylate and account for overall reaction material quality after mixing than the butyl titanate for 0.5-2.0wt%, water pump depressurizes
Under to 5-10kpa after 80-90 DEG C of reaction 6-10h, the methanol and excessive (methyl) hydroxy-ethyl acrylate of generation is removed under reduced pressure, i.e.,
Obtain the amino of following formula III or the methyl phenyl silicone containing (methyl) acrylic double bond of imino group sealing end；
Wherein:
R1、R2For phenyl or methyl；
R3For β-acryl-oyloxyethoxy, Beta-methyl acryl-oyloxyethoxy or alkoxy；
R4For methyl, alkoxy, β-acryl-oyloxyethoxy or Beta-methyl acryl-oyloxyethoxy；
R5For H, phenyl or alkyl；
(4) diisocyanate is added in mixed organic solvents to two isocyanides for forming 0.5-2.5mol/L in argon atmosphere
Acid esters solution and account for isocyanate than for 0.5-1.0wt% dibutyl tin dilaurate or stannous octoate as be catalyzed
Polyether polyol or polyester polyol or polyethylene glycol and the step being dissolved in mixed organic solvents is added dropwise in agent at 50-70 DEG C
Suddenly amino or imino group prepared by the methyl phenyl silicone or step (3) of amino prepared by (2) or imino group sealing end
The methyl phenyl silicone containing (methyl) acrylic double bond of sealing end is one of or two kinds, obtains isocyanates after reacting 2-4h
The prepolymer of sealing end adds (methyl) acrylic acid isocyano mole excess 1.0-5.0% more remaining than the theory of calculating
Hydroxyl ethyl ester is reacted to the peak infrared monitoring-NCO and is disappeared, then is warming up to 70-80 DEG C, reacts 2-4h to get photo curable methylbenzene
Base organic silicon modified polyurethane (methyl) acrylate (SPUA).
Preferably, the diisocyanate in the step (4) is toluene di-isocyanate(TDI) (TDI), two isocyanide of isophorone
Acid esters (IPDI), methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), hexa-methylene two
It is one or more of in isocyanates (HDI), lysine diisocyanate (LDI).
Preferably, in the step (4) mixed organic solvents be toluene and tetrahydrofuran, ethyl acetate, butyl acetate and
One or more of acetone, wherein toluene be must solvent dissolve the lesser organosilicon of polarity in reactant, and toluene accounts for
The mass fraction of total mixed solvent is 50%-100%.
Preferably, catalyst is dibutyl tin dilaurate or stannous octoate in the step (4)；The catalyst is added
The mass fraction of amount is 0.5%-1.0%.
Preferably, diisocyanate and amino or imino group block in the step (4) methyl phenyl silicone or
The molar ratio of the methyl phenyl silicone containing (methyl) acrylic double bond of amino or imino group sealing end is 1:0.01-2；Two
The molar ratio of isocyanates and polyalcohol or polyethylene glycol is 1:0-1.99；The polyalcohol is polyester polyol or polyether polyols
Alcohol.
The third aspect provides a kind of utilization above-mentioned photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) third
The method that alkene acid ester resin prepares SPUA film, by the photo curable aminomethyl phenyl organic silicon modified polyurethane of 100 mass parts
(methyl) acrylate and the photoinitiator of 0.5-1 mass parts are laid in polytetrafluoroethylene (PTFE) template or glass after mixing
It on plate, is placed at room temperature for after solvent is evaporated completely substantially, is placed in irradiation solidification 2-20min under ultraviolet lamp.
When the preparation of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) the acrylate film,
Photoinitiator is benzoin ethyl ether (BEE), 2- hydroxy-2-methyl-propiophenone (HMPP), a kind of or several in benzophenone (BP)
Kind.
The present invention uses the methods of infrared spectroscopy, nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, scanning electron microscope, thermogravimetric analysis pair
It is characterized.Photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) propylene in embodiment 1 is provided in attached drawing
Infrared spectroscopy, nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra, the scanning electron microscope map of acid ester resin.The result shows that being successfully prepared
Photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate.
It is solid that light is prepared using above-mentioned photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate
Change aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate acrylic resin films method: by it is a certain amount of can
Aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate of photocuring and a certain amount of photoinitiator are uniformly mixed
After be laid on polytetrafluoroethylene (PTFE) template or glass plate, place 5-10 h at room temperature and wait for that solvent sufficiently volatilizees, it is purple under argon gas protection
Outer light can be solidified into hyaline membrane according to 5-20min.
The advantages and benefits of the present invention are:
(1) scanning electron microscope by comparison with or without the curable urethane acrylate resin of organic Si modification is shone
Piece, thermogravimetic analysis (TGA) is as a result, the discoveries such as measuring mechanical property result and contact angle size introduce the light-solidifying poly of organosilicon
Chlorinated polyethylene film can significantly increase the hydrophobicity on surface, reduce its water imbibition and surface energy；Efficiently control it
The microphase separation degree and smoothness on surface；Improve heat resistance and thermal stability；In organosilicon of the side chain containing acrylic double bond
Tensile strength can be significantly improved under conditions of modification.
(2) content of organosilicon influences photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate tree
The viscosity of grease coating material, viscosity reduce with the increase of silicone content.
(3) since acrylate-based or methacrylate polarity is between organosilicon and polyurethane,
Acrylate-based or methacrylate formation SPUA is introduced in SPU makes the compatibility of silicone segments and polyurethane segment more
It is good, and there is no this advantage in PUA.
(4) since used organic silicon fragment contains the siloxy (R in structure3And R4), it is possible in photocuring
Moisture-curable is realized while crosslinking；On the other hand, the alkoxy (R in structure3And R4) substituted acrylic acid can also be converted to
Ester group or methacrylate are better than PUA to increase its crosslinking points.
(5) photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate (SPUA) prepared
Prepolymer due to no longer contain active free isocyano, therefore be protected from light storage under conditions of stability it is good, can store up for a long time
It deposits.
(6) structure of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate of photocuring can
Modulability is strong, has a wide range of application.
(7) principle is cheap and easy to get, and the simple process of preparation is feasible.
Detailed description of the invention
Fig. 1 is photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate prepared by example 1
FT-IR map.
Fig. 2 is photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate prepared by example 1
's1H-NMR map.
Fig. 3 is photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate prepared by example 1
's13C-NMR map.
Fig. 4 is the photo curable aminomethyl phenyl organic silicon modified polyurethane (first of different silicone contents prepared by example 1
Base) acrylate solidfied material scanning electron microscope comparison diagram.
Fig. 5 is the photo curable aminomethyl phenyl organic silicon modified polyurethane (first of different silicone contents prepared by example 1
Base) acrylate solidfied material thermogravimetric analysis map.
Specific embodiment
By following detailed description combination attached drawing it will be further appreciated that the features and advantages of the invention.Provided implementation
Example is only the explanation to the method for the present invention, remaining content without limiting the invention in any way announcement.
Silane compound and diisocyanate are purified by rectification under vacuum using preceding.Polyether polyol, polyether Glycols,
Polyester diol is using preceding by being dried under reduced pressure processing.Solvent for use toluene, tetrahydrofuran steam after flowing back in metallic sodium
Evaporate use；It distills and uses after acetone phosphorus pentoxide drying；The cohobation in calcium chloride of ethyl acetate, butyl acetate is used again
The dry water removal of 4A type molecular sieve.
The methyl phenyl silicone of amino or imino group sealing end is prepared by ZL201410788628.2 method, structural formula
ForWherein R1And R2For phenyl or methyl, R3For alkoxy；R4For first
Base or alkoxy；R5For H, phenyl or alkyl；A is 1 or 3.
Embodiment 1
1, the preparation of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=R4=R8=methyl, R3=Beta-methyl acryl-oyloxyethoxy, R5=cyclohexyl, R6
=4,4'- methyldicyclohexyl, R7For polyether structure unit, a=3]
(1) the methyl phenyl silicone 23g (0.01mol) for blocking cyclohexylimino, 5.2g (0.04 mol) first
After mixing, water pump is decompressed to the lower 90 DEG C of reactions 6h of 5 Kpa for base hydroxy-ethyl acrylate (HEMA) and 0.05g butyl titanate,
Pump of changing oil again, which is decompressed to, pumps extra hydroxyethyl methacrylate and by-product carbinol under 100pa pressure, such as flowering structure is made
Cyclohexylimino sealing end the methyl phenyl silicone containing acrylic double bond.
[wherein R1=phenyl, R2=R4=methyl, R3=Beta-methyl acryl-oyloxyethoxy, R5=cyclohexyl, a=3]
(2) 13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g butyl acetate after mixing, are warming up to 65 DEG C, are added dropwise dropwise
The sealing end of imino group prepared by 11.03g (0.16mol) polyether-tribasic alcohol N307,10.34g (0.004mol) step (1) contains
The methyl phenyl silicone of acrylic double bond, the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas protect atmosphere
After middle reaction 4h, 5.8g (0.045 mol) hydroxyethyl methacrylate (HEMA) is added, and the reaction was continued to the peak infrared monitoring-NCO
It disappears, then is warming up to 70-80 DEG C, polyurethane methyl-prop reaction 2-4h organic-silicon-modified to get photo curable aminomethyl phenyl
The prepolymer of alkene acid ester resin (SPUA).
This prepolymer by experiment, be placed in it is closed, be protected from light, it is shady and cool under the conditions of place 12 months gels not yet, show that this is pre-
Polymers stability preferably can long storage.
Its infrared spectroscopy, nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum are shown in Fig. 1-Fig. 3.By that can be seen in the FT-IR map of Fig. 1
Stretching vibration peak to N-H appears in 3342cm-1The C=O stretching vibration peak of place, ester bond and urea bond respectively appears in 1718cm-1
And 1637cm-1Place.3030cm-1Place is C-H characteristic peak on phenyl ring, 1529,1402cm-1Place is the flexible vibration of C=C of phenyl ring skeleton
Dynamic characteristic absorption peak also demonstrates the presence of phenyl.2990 cm-1Place is C-H characteristic peak on alkyl, 1166,1095cm-1Place is
The stretching vibration absworption peak of Si-O-Si key, Si-CH3Bending vibration and plane wave peak and respectively appear in 1257,800cm-1
Place.It is Si-CH at 0ppm by can see in Fig. 23Proton peak, be proton peak on phenyl ring at 7-8ppm, 5.6,6.2
It is C=CH at ppm2Upper proton peak, 4.5, the proton peak that 4.8ppm is O=C-NH-.It can be seen that being Si- at 0.5ppm in Fig. 3
CH3Locate absorption peak, the carbon peak that the place 155.2ppm is O=C-NH is O=C absorption peak on acrylate at 167.1ppm,
It 126.0, is C=C absorption peak in acrylate at 136.0ppm.These are the result shows that organosilicon containing phenyl is successfully introduced into containing third
In the polyurethane acrylate resin of olefin(e) acid double bond, it is prepared for phenyl organic silicon modified polyurethane (methyl) acrylate.
2, the preparation of aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate acylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Curable urethane acrylate (PUA) without organosilicon and the phenyl containing different quality containing are organic-silicon-modified
Curable urethane acrylate (SPUA) film Electronic Speculum map it is as shown in Figure 4.By Fig. 4 it can be seen that being free of organosilicon
Curable urethane acrylate (PUA) has apparent microphase-separated (figure A), and introduces microfacies point after 10% organosilicon containing phenyl
Most smooth from minimum and surface, after introduction volume continues increase, microphase-separated is also increasingly severe.Show a small amount of containing phenyl
Organosilicon can significantly improve the phase separation degree on polyurethane acrylate resin surface.
Curable urethane acrylate (PUA) without organosilicon and the phenyl containing different quality containing are organic-silicon-modified
Curable urethane acrylate (SPUA) film thermogravimetric (TGA) map it is as shown in Figure 5.Data analysis table is shown in table 1,
By following table it can be seen that 5% thermal weight loss temperature of the organic-silicon-modified posterior photocuring urethane acrylate (SPUA) containing phenyl,
50% thermal weight loss temperature and the mass fraction of ash content are significantly improved.It is poly- to show that the organosilicon containing phenyl can significantly improve
The heat resistance and thermal stability of chlorinated polyethylene.
The thermogravimetric analysis of table 1.PUA and SPUAs
1: T5Temperature when for thermal weight loss 5%；2: T50Temperature when for thermal weight loss 50%；3: ash content when Char is 600 DEG C
Mass fraction.
Curable urethane acrylate (PUA) without organosilicon and the phenyl containing different quality containing are organic-silicon-modified
Curable urethane acrylate (SPUA) film tensile strength test data table it is as shown in the table.It can be seen by following table
Fracture tensile strength to the organic-silicon-modified curable urethane acrylate (SPUA) containing acrylic double bond compares control
The curable urethane acrylate (PUA) without organosilicon be significantly improved, show the organosilicon energy containing acrylic double bond
Improve the tensile strength of modified curable urethane acrylate (SPUA).
The fracture tensile strength of table 2.PUA and SPUA
Embodiment 2
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=R8=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=cyclohexyl, R6
=4,4'- methyldicyclohexyl, R7For polyether structure unit, a=3]
(1) methyl phenyl silicone for blocking cyclohexylimino
[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, a=3] 23g (0.01mol), 10.4g
After mixing, water pump is decompressed under 5kpa for (0.08mol) hydroxyethyl methacrylate (HEMA) and 0.05g butyl titanate
90 DEG C of reaction 6h, then pump of changing oil are decompressed to and pump extra hydroxyethyl methacrylate and by-product carbinol under 100pa pressure,
The methyl phenyl silicone containing acrylic double bond blocked such as the cyclohexylimino of flowering structure is made.
[wherein R1=phenyl, R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=cyclohexyl, a=3]
(2) 13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, are added dropwise dropwise
The sealing end of imino group prepared by 11.22g (0.16mol) polyether-tribasic alcohol N307,10.43g (0.004mol) step (1) contains
The methyl phenyl silicone of acrylic double bond, the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas protect atmosphere
After middle reaction 4h, 5.8g (0.045 mol) hydroxyethyl methacrylate (HEMA) is added, and the reaction was continued to the peak infrared monitoring-NCO
It disappears, then is warming up to 70-80 DEG C, polyurethane methyl-prop reaction 2-4h organic-silicon-modified to get photo curable aminomethyl phenyl
Alkene acid ester resin (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate acylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 3
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=R8=methyl, R3=R4=methoxyl group, R5=cyclohexyl, R6=4,4'- methyl bicyclic
Hexyl, R7For polyether structure unit, a=3]
13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, are added dropwise dropwise
The poly- silicon of aminomethyl phenyl of 11.22g (0.16mol) polyether-tribasic alcohol N307,10.00g (0.004mol) cyclohexylimino sealing end
Oxygen alkane[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5
=cyclohexyl, a=3], the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas protects addition in atmosphere after reaction 4h
The reaction was continued disappears to the peak infrared monitoring-NCO for 5.8g (0.045mol) hydroxyethyl methacrylate (HEMA), then is warming up to 70-
80 DEG C, 2-4h is reacted to get the organic-silicon-modified urethane methacylate resins of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 4
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, R6=4,4'- methyldicyclohexyl,
R7For polyether structure unit, R8=hydrogen, a=3]
13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, are added dropwise dropwise
The methyl phenyl silicone of 11.22g (0.16mol) polyether-tribasic alcohol N307,10.00g (0.004mol) imino group sealing end[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl,
A=3], the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas is protected in atmosphere after reaction 4h, addition 5.22g
The reaction was continued disappears to the peak infrared monitoring-NCO for (0.045mol) hydroxy-ethyl acrylate (HEA), then is warming up to 70-80 DEG C, reacts
2-4h is to get the organic-silicon-modified polyurethane acrylate resin of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 5
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=cyclohexyl, R6=4,4'- first
Base dicyclohexyl, R7For polyether structure unit, R8=hydrogen, a=3]
(1) methyl phenyl silicone for blocking cyclohexylimino[wherein R1=R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, a=
3] 23g (0.01mol), 10.4g (0.08mol) hydroxyethyl methacrylate (HEMA) and 0.05g butyl titanate are uniformly mixed
Afterwards, water pump is decompressed to the lower 90 DEG C of reactions 6h of 5kpa, then pump of changing oil is decompressed under 100 pa pressure and pumps extra methacrylic acid
Methyl phenyl silicone (the structure containing acrylic double bond of cyclohexylimino sealing end is made in hydroxyl ethyl ester and by-product carbinol
It is as follows).
[wherein R1=R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=cyclohexyl, a=3]
(2) the organic-silicon-modified polyurethane acrylate resin of photocuring phenyl is prepared
13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, are added dropwise dropwise
The sealing end of imino group prepared by 11.22g (0.16mol) polyether-tribasic alcohol N307,10.43g (0.004mol) step (1) contains
The methyl phenyl silicone of acrylic double bond, the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas protect atmosphere
After middle reaction 4h, be added 5.22g (0.045mol) hydroxy-ethyl acrylate (HEA) the reaction was continued to the peak infrared monitoring-NCO disappear,
It is warming up to 70-80 DEG C again, urethane acrylate tree reaction 2-4 h organic-silicon-modified to get photo curable aminomethyl phenyl
Rouge (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 6
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=R8=hydrogen, R6=4,
4'- methyldicyclohexyl, R7For polyether structure unit, a=3]
(1) by amino-terminated methyl phenyl silicone[wherein
R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=hydrogen, a=3] 22g (0.01mol), 10.4g (0.08mol) methyl-prop
After mixing, water pump is decompressed to the lower 90 DEG C of reactions 6h of 5kpa, then changes for olefin(e) acid hydroxyl ethyl ester (HEMA) and 0.05 1g butyl titanate
Oil pump, which is decompressed to, pumps extra hydroxyethyl methacrylate and by-product carbinol under 100pa pressure, be made amino-terminated and contain
The methyl phenyl silicone of acrylic double bond (structure is as follows).
[wherein R1=phenyl, R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=hydrogen, a=3]
(2) the organic-silicon-modified polyurethane acrylate resin of photocuring phenyl is prepared
13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, are added dropwise dropwise
It is amino-terminated prepared by 11.22g (0.16mol) polyether-tribasic alcohol N307,10.43g (0.004mol) step (1) to contain propylene
The methyl phenyl silicone of sour double bond, the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas are protected anti-in atmosphere
It after answering 4h, is added 5.22g (0.045mol) hydroxy-ethyl acrylate (HEA) the reaction was continued and disappear to the peak infrared monitoring-NCO, then rise
Temperature is to 70-80 DEG C, polyurethane acrylate resin reaction 2-4h organic-silicon-modified to get photo curable aminomethyl phenyl
(SPUA)。
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 7
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, R6=isophorone base, R7It is poly-
Ether structure unit, R8=hydrogen, a=1.]
11.11g (0.05mol) isophorone diisocyanate (IPDI), 0.05 g dibutyl are added in 250mL there-necked flask
Tin dilaurate tin, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, 11.22g are added dropwise dropwise
The methyl phenyl silicone of (0.16mol) polyether-tribasic alcohol N307,10.00g (0.004mol) imino group sealing end[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=hexamethylene
Base, a=1], the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas is protected in atmosphere after reaction 4h, addition 5.22g
The reaction was continued disappears to the peak infrared monitoring-NCO for (0.045mol) hydroxy-ethyl acrylate (HEA), then is warming up to 70-80 DEG C, reacts
2-4h is to get the organic-silicon-modified polyurethane acrylate resin of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 8
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, R6=benzyl, R7For polyethylene glycol structures
Unit, R8=hydrogen, a=1.]
8.7g (0.05mol) toluene di-isocyanate(TDI) (TDI), 0.05g dibutyl tin cinnamic acid are added in 250mL there-necked flask
Tin, 10.0g toluene and 10.0g acetone after mixing, are warming up to 65 DEG C, and 9.6g (0.024mol) polyethylene glycol is added dropwise dropwise
The methyl phenyl silicone of 400 (PEG400), 10.00g (0.004mol) cyclohexylimino sealing end[wherein R1=R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, a=
1], the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas are protected in atmosphere after reaction 4h, addition 5.22g
The reaction was continued disappears to the peak infrared monitoring-NCO for (0.045mol) hydroxy-ethyl acrylate (HEA), then is warming up to 70-80 DEG C, reacts
2-4h is to get the organic-silicon-modified polyurethane acrylate resin of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 9
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=R8=hydrogen, R6=oneself
Base, R7For polyester structural units, a=3.]
(1) by amino-terminated methyl phenyl silicone[wherein R1
=phenyl, R2=methyl, R3=R4=methoxyl group, R5=hydrogen, a=3] 22g (0.01mol), 10.4g (0.08 mol) methyl-prop
After mixing, water pump is decompressed to the lower 90 DEG C of reactions 6h of 5 kpa, then changes for olefin(e) acid hydroxyl ethyl ester (HEMA) and 0.05g butyl titanate
Oil pump, which is decompressed to, pumps extra hydroxyethyl methacrylate and by-product carbinol under 100pa pressure, be made amino-terminated and contain
The methyl phenyl silicone of acrylic double bond.
[wherein R1=phenyl, R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=hydrogen, a=3]
(2) the organic-silicon-modified polyurethane acrylate resin of photocuring phenyl is prepared
8.4g (0.05mol) hexamethylene diisocyanate (HDI), 0.05g dibutyl tin are added in 250mL there-necked flask
Cinnamic acid tin, 10.0g toluene and 10.0g ethyl acetate after mixing, are warming up to 65 DEG C, and it is poly- that 24g (0.024mol) is added dropwise dropwise
Ethylene glycol adipate 1000 (PEA-1000), it is amino-terminated prepared by 10.03g (0.004mol) step (1) to contain propylene
The methyl phenyl silicone of sour double bond, the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas are protected anti-in atmosphere
It after answering 4h, is added 5.22g (0.045 mol) hydroxy-ethyl acrylate (HEA) the reaction was continued and disappear to the peak infrared monitoring-NCO, then rise
Temperature is to 70-80 DEG C, polyurethane acrylate resin reaction 2-4h organic-silicon-modified to get photo curable aminomethyl phenyl
(SPUA)。
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 10
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=ethyoxyl, R5=R8=hydrogen, R6=hexyl, R7For polyester construction list
Member, a=3.]
8.4g (0.05mol) hexamethylene diisocyanate (HDI), 0.05g dibutyl tin are added in 250mL there-necked flask
Cinnamic acid tin, 10.0g toluene and 10.0g butyl acetate after mixing, are warming up to 65 DEG C, and 24.0g (0.024mol) is added dropwise dropwise
Polyethylene glycol adipate 1000 (PEA-1000), 10.03g (0.004 mol) amino-terminated methyl phenyl silicone[wherein R1=phenyl, R2=methyl, R3=R4=ethyoxyl, R5=
Hydrogen, a=3], the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas is protected in atmosphere after reaction 4h, addition 5.22g
The reaction was continued disappears to the peak infrared monitoring-NCO for (0.045mol) hydroxy-ethyl acrylate (HEA), then is warming up to 70-80 DEG C, reacts
2-4h is to get the organic-silicon-modified polyurethane acrylate resin of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 11
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, R6=methyldiphenyl base, R7It is poly-
Ethylene glycol structure unit, R8=hydrogen, a=1.]
12.5g (0.05mol) methyl diphenylene diisocyanate (MDI), 0.05 g dibutyl are added in 250mL there-necked flask
Tin dilaurate tin, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, 9.6g are added dropwise dropwise
(0.024mol) polyethylene glycol 400 (PEG400), the poly- silicon of aminomethyl phenyl of 10.00g (0.004mol) cyclohexylimino sealing end
Oxygen alkane[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=ring
Hexyl, a=1], the mixed solution of 10.0g toluene and 5.0g tetrahydrofuran and 5.0 g acetone, argon gas, which is protected in atmosphere, reacts 4h
Afterwards, it is added 5.22g (0.045mol) hydroxy-ethyl acrylate (HEA) the reaction was continued and disappear to the peak infrared monitoring-NCO, then be warming up to
70-80 DEG C, 2-4h is reacted to get the organic-silicon-modified polyurethane acrylate resin of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 12
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=R8=hydrogen, R6=hexyl, R7For polyester construction list
Member, a=3]
8.4g (0.05mol) hexamethylene diisocyanate (HDI), 0.05g dibutyl tin are added in 250mL there-necked flask
Cinnamic acid tin, 10.0g toluene and 10.0g tetrahydrofuran after mixing, are warming up to 65 DEG C, and 14.4g (0.024mol) is added dropwise dropwise
Polycaprolactone glycol 600 (PCL-600), 10.03g (0.004mol) amino-terminated methyl phenyl silicone[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=hydrogen,
A=3], the mixed solution of 10.0g toluene and 5.0g tetrahydrofuran and 5.0g ethyl acetate, argon gas is protected in atmosphere after reaction 4h,
It is added 5.22g (0.045mol) hydroxy-ethyl acrylate (HEA) the reaction was continued and disappear to the peak infrared monitoring-NCO, then be warming up to 70-
80 DEG C, 2-4h is reacted to get the organic-silicon-modified polyurethane acrylate resin of photo curable aminomethyl phenyl (SPUA).
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 13
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=phenyl, R6=methyldiphenyl base, R7For poly- second
Diol structure unit, R8=methyl, a=1.]
12.5g (0.05mol) methyl diphenylene diisocyanate (MDI), 0.05 g dibutyl are added in 250mL there-necked flask
Tin dilaurate tin, 10.0g toluene and 5.0g tetrahydrofuran and 5.0g butyl acetate after mixing, are warming up to 65 DEG C, drip dropwise
Add 9.6g (0.024mol) polyethylene glycol 400 (PEG400), the aminomethyl phenyl of 10.00g (0.004 mol) phenylimino sealing end
Polysiloxanes[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group,
R5=phenyl, a=1], the mixed solution of 10.0g toluene and 10.0 g tetrahydrofurans, argon gas protect atmosphere in react 4h after, add
Enter 5.22g (0.045mol) hydroxyethyl methacrylate (HEMA) the reaction was continued to the peak infrared monitoring-NCO to disappear, then is warming up to
70-80 DEG C, urethane methacylate resins reaction 2-4h organic-silicon-modified to get photo curable aminomethyl phenyl
(SPUA)。
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 14
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=phenyl, R2=R8=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=butyl, R6=
4,4'- methyldicyclohexyls and hexyl, R7For polyether structure unit, a=3]
(1) methyl phenyl silicone for blocking cyclohexylimino[wherein R1=phenyl, R2=methyl, R3=R4=methoxyl group, R5=fourth
Base, a=3] 23g (0.01mol), 10.4g (0.08mol) hydroxyethyl methacrylate (HEMA) and 0.05g butyl titanate are mixed
After closing uniformly, water pump is decompressed to the lower 90 DEG C of reactions 6h of 5kpa, then pump of changing oil is decompressed under 100pa pressure and pumps extra methyl-prop
The aminomethyl phenyl containing acrylic double bond blocked such as the Butylimino of flowering structure is made in olefin(e) acid hydroxyl ethyl ester and by-product carbinol
Polysiloxanes.
[wherein R1=phenyl, R2=methyl, R3=R4=Beta-methyl acryl-oyloxyethoxy, R5=butyl, a=3]
(2) 6.55g (0.025mol) 4,4'- dicyclohexyl methyl hydride diisocyanate is added in 250mL there-necked flask
(HMDI), 4.20g (0.025mol) hexamethylene diisocyanate (HDI), 0.05g dibutyl tin dilaurate, 10.0g toluene
After mixing with 10.0g acetone, 65 DEG C are warming up to, 11.22g (0.16mol) polyether-tribasic alcohol N307,4.6g is added dropwise dropwise
The methyl phenyl silicone that cyclohexylimino blocks in (0.002mol) step (1), 5.21g (0.002mol) step (1)
The methyl phenyl silicone containing acrylic double bond of prepared imino group sealing end, 10.0g toluene and 10.0g tetrahydrofuran
Mixed solution, argon gas are protected in atmosphere after reaction 4h, and addition 5.8g (0.045mol) hydroxyethyl methacrylate (HEMA) continues
Reaction to the peak infrared monitoring-NCO disappears, then is warming up to 70-80 DEG C, and reaction 2-4h is organic to get photo curable aminomethyl phenyl
The urethane methacylate resins (SPUA) of Si modification.
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Organic-silicon-modified polyurethane (methyl) acrylate of photocuring phenyl prepared by the above method of 100 mass parts
Resin and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, place 10h after to
After solvent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Embodiment 15
1, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate
[wherein R1=R2=methyl, R3=R4=β-acryl-oyloxyethoxy, R5=cyclohexyl, R6=4,4'- methyl bicyclic
Hexyl, R7For polyether structure unit, R8=hydrogen, a=3]
(1) methyl phenyl silicone for blocking cyclohexylimino[wherein R1=R2=methyl, R3=R4=methoxyl group, R5=cyclohexyl, a=
3] 23g (0.01mol), 9.28g (0.08mol) hydroxy-ethyl acrylate (HEA) and 0.05g butyl titanate after mixing, water
Pump is decompressed to the lower 90 DEG C of reactions 6h of 5kpa, then pump of changing oil is decompressed under 100pa pressure and pumps extra hydroxyethyl methacrylate
And by-product carbinol, the methyl phenyl silicone containing acrylic double bond of cyclohexylimino sealing end is made (structure is as follows).
[wherein R1=R2=methyl, R3=R4=β-acryl-oyloxyethoxy, R5=cyclohexyl, a=3]
(2) the organic-silicon-modified polyurethane acrylate resin of photocuring phenyl is prepared
13.1g (0.05mol) 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) is added in 250mL there-necked flask,
0.05g dibutyl tin dilaurate, 10.0g toluene and 10.0g ethyl acetate after mixing, are warming up to 65 DEG C, are added dropwise dropwise
The sealing end of imino group prepared by 11.22g (0.16mol) polyether-tribasic alcohol N307,10.43g (0.004mol) step (1) contains
The methyl phenyl silicone of acrylic double bond, the mixed solution of 10.0g toluene and 10.0g tetrahydrofuran, argon gas protect atmosphere
After middle reaction 4h, be added 5.22g (0.045mol) hydroxy-ethyl acrylate (HEA) the reaction was continued to the peak infrared monitoring-NCO disappear,
It is warming up to 70 DEG C again, polyurethane acrylate resin reaction 2-4 h organic-silicon-modified to get photo curable aminomethyl phenyl
(SPUA)。
2, the preparation of photocuring phenyl organic silicon modified polyurethane (methyl) acrylate film
Photocuring phenyl organic silicon modified polyurethane (methyl) acrylate tree prepared by the above method of 100 mass parts
Rouge and the photoinitiator of 0.5 mass parts are laid in after mixing on polytetrafluoroethylene (PTFE) template or glass plate, to molten after placement 10h
After agent is evaporated completely substantially, irradiation solidification 10min under ultraviolet lamp is placed in the atmosphere of argon gas protection to form a film.
Claims (8)
1. a kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate, which is characterized in that its
Structural formula is shown in formula I:
Wherein:
R1、R2For phenyl or methyl；
R3For β-acryl-oyloxyethoxy, Beta-methyl acryl-oyloxyethoxy or alkoxy；
R4For methyl, alkoxy, β-acryl-oyloxyethoxy or Beta-methyl acryl-oyloxyethoxy；
R5For H, phenyl or alkyl；
R6For isophorone base, hexyl, methyldiphenyl base, methyldicyclohexyl or benzyl；
R7For the primitive of polyethers, polyethylene glycol or polyester construction；
R8For hydrogen or methyl；
A is 1 or 3；M, n, y are natural number.
2. a kind of prepare photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate tree described in claim 1
The method of rouge, which comprises the steps of:
(1) R for being 10-50% by mass fraction2SiCH3Cl2Toluene solution is added drop-wise to by diphenyl silanediol, tetrahydrofuran and pyrrole
In the mixed solution of pyridine composition, 2-5h is reacted at 20~80 DEG C, decompression filters, and cleans to get the poly- silicon of hydroxy-end capped aminomethyl phenyl
Oxygen alkane；Wherein R2SiCH3Cl2For dimethyldichlorosilane, methyl-propyl dichlorosilane, Ethyl methane sulphonate, methylbenzene
One or more of base dichlorosilane, Methyl Octyl dichlorosilane；Diphenyl silanediol is diphenyl silanediol or aminomethyl phenyl
Silicon diol；The R2SiCH3Cl2Molar ratio with diphenyl silanediol is 0.5~0.95；Diphenyl silanediol in the mixed solution
Mass fraction be 10-50%；
(2) by catalyst and (R3)2R4Si(CH2)aNHR5It is added to the hydroxy-end capped poly- silicon oxygen of aminomethyl phenyl prepared by step (1)
In alkane, methyl phenyl silicone, structural formula such as Formula II are blocked to get amino or imino group in 70-100 DEG C of reaction 7-10h
It is shown:
R in Formula II1And R2For phenyl or methyl, R3For alkoxy；R4For methyl or alkoxy；R5For H, phenyl or alkyl；A is 1
Or 3；
Wherein, (R3)2R4Si(CH2)aNHR5For gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, γ-ammonia
Hydroxypropyl methyl diethoxy silane, γ-aminopropyltriethoxy dimethoxysilane, γ-urea propyl-triethoxysilicane, γ-hexamethylene
Aminocarbonyl propyl trimethoxy silane, γ-cyclohexylamino hydroxypropyl methyl dimethoxysilane, γ-cyclohexylamino propyl triethoxy
Silane, γ-cyclohexylamino hydroxypropyl methyl diethoxy silane, γ-aniline propyl trimethoxy silicane, γ-three second of aniline propyl
Oxysilane, γ-aniline hydroxypropyl methyl dimethoxysilane, γ-aniline hydroxypropyl methyl diethoxy silane, α-anilinomethyl three
Methoxy silane, α-anilinomethyl triethoxysilane, α-anilinomethyl methyl dimethoxysilane, α-cyclohexylamine methyl trimethoxy
Oxysilane, α-cyclohexylamine methyl diethoxy silane or α-cyclohexylamine methyltriethoxysilane, (R3)2R4Si
(CH2)aNHR5With R2SiCH3Cl2Molar ratio be 0.8-8:3-7.6；
Wherein, catalyst is the metatitanic acid tert-butyl ester, butyl titanate, isopropyl titanate or dibutyl tin dilaurate；The catalysis
Agent and (R3)2R4Si(CH2)aNHR5Molar ratio be 0.004-0.09:0.8-8；
(3) (methyl) for the methyl phenyl silicone and 2.0-4.0 molar equivalent for blocking amino shown in Formula II or imino group
Hydroxy-ethyl acrylate and account for overall reaction material quality after mixing than the butyl titanate for 0.5-2.0wt%, water pump is decompressed to
Under 5-10kpa after 80-90 DEG C of reaction 6-10h, be removed under reduced pressure generation methanol and excessive (methyl) hydroxy-ethyl acrylate to get
The amino of following formula III or the methyl phenyl silicone containing (methyl) acrylic double bond of imino group sealing end；
Wherein:
R1、R2For phenyl or methyl；
R3For β-acryl-oyloxyethoxy, Beta-methyl acryl-oyloxyethoxy or alkoxy；
R4For methyl, alkoxy, β-acryl-oyloxyethoxy or Beta-methyl acryl-oyloxyethoxy；
R5For H, phenyl or alkyl；
(4) diisocyanate is added in mixed organic solvents to the diisocyanate for forming 0.5-2.5mol/L in argon atmosphere
Solution and account for isocyanate than for 0.5-1.0wt% dibutyl tin dilaurate or stannous octoate as catalyst,
Polyether polyol or polyester polyol or polyethylene glycol and the step being dissolved in mixed organic solvents (2) are added dropwise at 50-70 DEG C
What amino prepared by the methyl phenyl silicone or step (3) of prepared amino or imino group sealing end or imino group blocked
Methyl phenyl silicone containing (methyl) acrylic double bond is one of or two kinds, reacts after 2-4h isocyanate-terminated
Prepolymer adds (methyl) hydroxy-ethyl acrylate isocyano mole excess 1.0-5.0% more remaining than the theory of calculating
Reaction to the peak infrared monitoring-NCO disappears, then is warming up to 70-80 DEG C, and reaction 2-4h is organic to get photo curable aminomethyl phenyl
Silicon modified polyurethane (methyl) acrylate (SPUA).
3. photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate according to claim 2
Method, which is characterized in that diisocyanate in the step (4) is toluene di-isocyanate(TDI) (TDI), isophorone two is different
Cyanate (IPDI), methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), hexa-methylene
It is one or two kinds of or more in diisocyanate (HDI), lysine diisocyanate (LDI).
4. photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate according to claim 2
Method, which is characterized in that mixed organic solvents are toluene and tetrahydrofuran, ethyl acetate, butyl acetate in the step (4)
One or both of with acetone, wherein toluene be must solvent dissolve the lesser organosilicon of polarity in reactant, and toluene
The mass fraction for accounting for total mixed solvent is 50%-100%.
5. photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate according to claim 2
Method, which is characterized in that in the step (4) catalyst be dibutyl tin dilaurate or stannous octoate；The catalyst
The mass fraction of additional amount is 0.5%-1.0%.
6. photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate according to claim 2
Method, which is characterized in that the methyl phenyl silicone that diisocyanate and amino or imino group block in the step (4)
Amino or imino group sealing end the methyl phenyl silicone containing (methyl) acrylic double bond molar ratio be 1:0.01-2；Two
The molar ratio of isocyanates and polyalcohol or polyethylene glycol is 1:0-1.99；The polyalcohol is polyester polyol or polyether polyols
Alcohol.
7. a kind of utilize photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate described in claim 1
The method that resin prepares SPUA film, which is characterized in that the photo curable aminomethyl phenyl of 100 mass parts is organic-silicon-modified poly-
Urethane (methyl) acrylate and the photoinitiator of 0.5-1 mass parts be laid in after mixing polytetrafluoroethylene (PTFE) template or
It on glass plate, is placed at room temperature for after solvent is evaporated completely substantially, is placed in irradiation solidification 2-20min under ultraviolet lamp.
8. the method according to the description of claim 7 is characterized in that the photoinitiator is benzoin ethyl ether (BEE), 2- hydroxyl
It is one or two kinds of or more in base -2- methyl-propiophenone (HMPP), benzophenone (BP).
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