CN106977690B - A kind of three phosphonitrile type light-cured polyurethane resin of ring and its coatings of preparation - Google Patents

A kind of three phosphonitrile type light-cured polyurethane resin of ring and its coatings of preparation Download PDF

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CN106977690B
CN106977690B CN201710330211.5A CN201710330211A CN106977690B CN 106977690 B CN106977690 B CN 106977690B CN 201710330211 A CN201710330211 A CN 201710330211A CN 106977690 B CN106977690 B CN 106977690B
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ring
phosphonitrile
type light
polyurethane resin
cured polyurethane
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CN106977690A (en
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刘敬成
曹建诚
周珍
刘仁
刘晓亚
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Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Abstract

The invention discloses a kind of three phosphonitrile type light-cured polyurethane resins of ring and its coatings of preparation, first dihydric alcohol, diisocyanate to be reacted；It is reacted again with photo-curing monomer, introduces double bond；It finally reacts with three phosphonitrile monomer of ring, the three phosphonitrile type light-cured polyurethane resin of ring is made；Light-cured polyurethane resin, photoinitiator, reactive diluent, solvent are mixed and made into coatings.Preparation method of the present invention is simple, reaction condition is mild, contained carbon-carbon double bond can be used for the light-cured performance of coating, hydrogen bond between isocyanates can be used for self-healing properties, the introducing of three phosphonitrile kernel of ring makes it have preferable hardness and mechanical performance, make it have self-healing properties again simultaneously, cooperate the coatings for being made and haveing excellent performance between each raw material.

Description

A kind of three phosphonitrile type light-cured polyurethane resin of ring and its coatings of preparation
Technical field
The present invention relates to photo-curing material technical fields, more particularly, to a kind of three phosphonitrile monomer of ring and polyurethane prepolymer Reaction prepares three phosphonitrile type light-cured polyurethane resin of ring, and its application in selfreparing.
Background technique
Coatings refer to after breakdown of coating there is self-repairing capability, or have under certain external environment There is the functional coating of self-repairing capability.Self-healing polymers material passes through as a kind of novel intelligence structure functional material The self-healing for realizing micro-crack, avoids material from further being destroyed.Selfreparing principle mainly includes that extrinsic type (repair by microcapsules Replica, hollow fiber type) and Intrinsical (reversible covalent bonds class, reversible non-covalent key class) two major classes.Foreign aid's type selfreparing can only It realizes primary reparation, therefore greatly limits it in the extensive use of coatings art, and Intrinsical selfreparing repairs spy due to it Point can be used for repeatedly multiple, however coating before selects single armed or few arm configuration mostly, cause its with lower hardness and compared with The mechanical performance of difference keeps it significantly limited in practical applications.
Three phosphonitrile of ring is that one kind by phosphorus atoms and nitrogen-atoms builds alternately arranged hybrid inorganic-organic materials by Dan Shuan, It can be divided into ring phosphonitrile and polyphosphazene, three phosphonitrile of ring is most representative compound in cyclic phosphazene compound, in structure, phosphorus atoms Connection can substituted two active groups, be easy to be substituted by nucleopilic reagent attack, can assign material excellent hard Degree and thermal stability.Therefore it is modified the polyol structure as synthesis of polyurethane and introduces benzene ring structure, guaranteeing it While self-healing properties, its hardness for preparing coatings and mechanical performance are improved.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of three phosphonitrile type light-solidifying poly ammonia of ring Ester resin and its coatings of preparation.Photo curable double bond group is grafted on three phosphonitrile of ring by the present invention, is prepared for Three phosphonitrile type light-cured polyurethane resin of ring substantially increases coatings while guaranteeing preferable self-healing properties Hardness；The photosensitive group of introducing not only may be implemented efficient ultraviolet light solidification, but also the machine of coating can be improved Tool performance.
Technical scheme is as follows:
A kind of three phosphonitrile type light-cured polyurethane resin of ring, the preparation method of the resin include the following steps:
(1) diisocyanate, the dilution of catalyst dibutyltin dilaurylate are placed in reactor using anhydrous solvent, Then the diluted dihydric alcohol of anhydrous solvent is added dropwise into reactor, 2~4h is reacted at 40~50 DEG C, isocyanate group sealing end is made Prepolymer；
(2) then, photo-curing monomer, 60-70 DEG C of stirring are added dropwise in the prepolymer blocked to isocyanate group obtained by step (1) 5-7h is reacted, photosensitive polyurethane solution is obtained；
(3) it finally, three phosphonitrile monomer of ring and catalyst dibutyltin dilaurylate are dissolved in anhydrous solvent, is slowly added dropwise Into photosensitive polyurethane solution obtained by step (2), 50-70 DEG C is stirred to react 10-12h, and reaction terminates, and product is in deionized water Precipitating filters, vacuum drying, obtains the three phosphonitrile type light-cured polyurethane resin of ring.
Diisocyanate described in step (1) is methyl diphenylene diisocyanate, polymeric diphenylmethane diisocyanate Ester, toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate One of or it is a variety of；The dihydric alcohol be PEG-400, PEG-800, PEG-1000, PEG-2000, PEG-10000, T5650E, T5650J, T5651, T5652, polyethylene oxide (polyethylene glycol) glycol, polypropylene oxide (polypropylene glycol) glycol, One of polytetrahydrofuran diol, polyethylene glycol adipate glycol, polyadipate -1,4- butyl glycol ester diol are a variety of； The molar ratio of the diisocyanate and dihydric alcohol is 2~2.2:1.
The dosage of catalyst dibutyltin dilaurylate described in step (1) is dihydric alcohol and diisocyanate gross mass 0.5~1%.
Photo-curing monomer described in step (2) is (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) One of hy-droxybutyl is a variety of；The photo-curing monomer and isocyanate group sealing end prepolymer molar ratio be 1~ 1.1:1。
Three phosphonitrile monomers of ring described in step (3) is six pairs of three phosphonitriles of hydroxymethyl phenoxy basic ring, ten dihydroxy basic rings, three phosphonitrile One or both of mixing；The molar ratio of the three phosphonitrile monomer of ring and photosensitive polyurethane is 1~1.1:1.
The anhydrous solvent is N,N-dimethylformamide, in acetone, anhydrous butanone, tetrahydrofuran, ethyl acetate It is one or more；The dosage of the anhydrous solvent is the 20~30wt% of concentration for making reactant in reaction system.
A kind of application of three phosphonitrile type light-cured polyurethane resin of the ring, the light-cured polyurethane resin can be used for reviewing one's lessons by oneself Recovering technology field.
A kind of coatings containing the three phosphonitrile type light-cured polyurethane resin of ring, raw material contained by the coating and each The mass percent of raw material are as follows:
Each raw material is mixed according to the above ratio, after being protected from light 30~60min of ultrasound, is spun on aluminium sheet, with a thickness of 0.1~ 1mm, under the conditions of 40~100 DEG C, 60~120min of preliminary drying, then in 500-800mJ/cm2Energy under be exposed solidification, Three phosphonitrile type light-cured polyurethane coatings of ring are made.
The reactive diluent is trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate One of or it is a variety of；The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl phenyl first Ketone, 2- hydroxyl-4 '-(2- hydroxy ethoxy)-2- methyl phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- acetone One of or it is a variety of；The solvent is N,N-dimethylformamide, in butanone, dimethyl acetamide, cyclohexanone, ethyl acetate It is one or more.
The present invention is beneficial to be had the technical effect that
(1) polyurethane resin in the present invention is grafted on three phosphonitrile of ring using three phosphonitrile of ring as stone by gradually addition A plurality of linear type flexible polyurethane chain forms the structure of a kind of " stone flexible arm ", the benzene in six pairs of three phosphonitriles of hydroxymethyl phenoxy basic ring The hardness that ring structure can greatly improve, meanwhile, the multi-arm structure of polyurethane can not only be grafted more selfreparing groups, together When can keep the mobility of chain under heating, guarantee that there are preferable self-healing properties.
(2) the three phosphonitrile monomer of ring used in the present invention, synthesis material is simple and easy to get, and synthesis technology is mature, preparation method Simply.
(3) photosensitive group that light-cured polyurethane resin molecule chain end contains in the present invention, by using solidification temperature It is low, curing rate is fast, curing efficiency is high, easy to operate, energy-saving and environment-friendly UV-curing technology, it is solid to prepare three phosphonitrile type light of ring Change polyurethane selfreparing, not only simplify traditional film-forming process, improves production efficiency, while can also be by forming cross-linked network Network is come the mechanical performance that enhances.
Detailed description of the invention
Fig. 1 is reaction process schematic diagram of the present invention；
Fig. 2 be embodiment 1 described in coating repair before (A) and reparation after (a) super depth-of-field microscope picture；
Fig. 3 is the TGA curve graph of coating described in embodiment 1.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
A kind of three phosphonitrile type light-cured polyurethane resin of ring, is made as follows:
(1) use the anhydrous N,N-dimethylformamide of 12.5g (DMF) by two isocyanide of 2.445g (0.011mol) isophorone Acid esters, the dilution of 0.024g dibutyl tin dilaurate are placed in the three-necked flask with stirring and condensation, are then burnt to three mouthfuls The mixture of 12.5g anhydrous DMF and 2.5g (0.005mol) PCDL500 is slowly added dropwise in bottle, reacts 2h at 45 DEG C, is made different The prepolymer of cyanic acid base sealing end；
(2) 0.651g (0.005mol) hydroxyethyl methacrylate is dissolved in 4.4g anhydrous DMF, is added dropwise to step (1) In the prepolymer of isocyanate group sealing end obtained, 6h is reacted at 60 DEG C, photosensitive polyurethane solution is made；
(3) by six pairs of three phosphonitriles of hydroxymethyl phenoxy basic ring of 0.728g (0.000833mol) and 0.01g di lauric dibutyl Tin is dissolved in 3.0g anhydrous DMF, is added dropwise in photosensitive polyurethane solution made from step (2), and 12h is reacted at 70 DEG C, reaction Terminate, product is precipitated in deionized water, filters, is dried in vacuo, and the three phosphonitrile type light-cured polyurethane resin of ring is made.
The 1- hydroxy-cyclohexyl benzene of three phosphonitrile type polyurethane resin of ring, 3wt% prepared by the 60wt% embodiment of the present invention The DMF of base ketone and 37wt% mixing, after being protected from light ultrasonic 30min, are spun on aluminium sheet, with a thickness of 0.3mm, in 70 DEG C of conditions Under, preliminary drying 120min, then in 600mJ/cm2Energy under be exposed solidification, be made three phosphonitrile type light-cured polyurethane of ring Coatings.
After being scratched the three phosphonitrile type light-cured polyurethane coatings surface of ring of preparation using scratching instrument, utilize Heat gun makes the surface of coating heat 10min at 100 DEG C, and observes coating by three-dimensional super depth of field optical microscopy Self-healing properties, coating repairs the comparison of front and back as shown in Fig. 2, the pendulum-rocker hardness (avg) of coating is 147 ± 3, and pencil hardness is 2H。
As seen from Figure 2, the scratch disappearance after coating is destroyed is more obvious, presents good selfreparing effect Fruit.
Coating is broadly divided into three thermal weight loss processes as seen from Figure 3, respectively at 220-280 DEG C, 300-400 DEG C and Between 420-500 DEG C, the decomposition of hard segment structure, soft segment structure and other keys is respectively corresponded, shows that the polyurethane of preparation is reviewed one's lessons by oneself Overcoating layer has preferable thermal stability.
Embodiment 2
A kind of three phosphonitrile type light-cured polyurethane resin of ring, is made as follows:
(1) use 12g anhydrous ethyl acetate by 3.532g (0.021mol) hexamethylene diisocyanate and 0.037g bis- It is added to after dibutyl tin laurate dilution in the three-necked flask with stirring and condensation, is then slowly added dropwise into three-necked flask The mixture of 15g anhydrous ethyl acetate and 4.0g (0.01mol) PEG400, reaction stir 2h at 45 DEG C, prepare isocyanic acid The prepolymer of base sealing end；
(2) 1.301g (0.01mol) hydroxypropyl acrylate is dissolved in 5.0g anhydrous ethyl acetate, is slowly added dropwise into step (1) in the prepolymer of the sealing end of isocyanate group made from, reaction stirs 6h at 60 DEG C, and photosensitive polyurethane solution is made；
(3) by six pairs of three phosphonitriles of hydroxymethyl phenoxy basic ring of 1.449g (0.00166mol) and 0.017g di lauric dibutyl Tin is dissolved in 5.0g anhydrous ethyl acetate, is added dropwise in photosensitive polyurethane solution made from step (2), and reaction is stirred at 70 DEG C 12h, reaction terminate, and product is added drop-wise in deionized water and is precipitated, and filter, and the three phosphonitrile type light of ring is prepared in vacuum drying Curable polyurethane resin.
By light-cured polyurethane prepared by the 50wt% embodiment of the present invention, the triethoxy trihydroxy methyl third of 20wt% 2- hydroxy-2-methyl -1- phenyl -1- the acetone of alkane triacrylate, the ethyl acetate of 27wt% and 3wt% mixes, and is protected from light super It after sound 45min, is spun on aluminium sheet, with a thickness of 0.2mm, under the conditions of 40 DEG C, preliminary drying 120min, then in 700mJ/cm2's It is exposed solidification under energy, prepares three phosphonitrile type light-cured polyurethane coatings of ring.
Embodiment 3
A kind of three phosphonitrile type light-cured polyurethane resin of ring, is made as follows:
(1) use the anhydrous butanone of 10g by 2.753g (0.011mol) diphenylmethylene diisocyanate and 0.035g bis- It is added to after dibutyl tin laurate dilution in the three-necked flask with stirring and condensation；Then it is slowly added dropwise into three-necked flask The mixture of the anhydrous butanone of 15g and 5.0g (0.005mol) PCDL1000, reaction stir 3h at 40 DEG C, prepare isocyanate group The prepolymer of sealing end；
(2) 0.581g (0.005mol) hydroxy-ethyl acrylate is dissolved in the anhydrous butanone of 3.5g, is slowly added dropwise into step (1) In the prepolymer of isocyanate group sealing end obtained, reaction stirs 4h at 60 DEG C, and photosensitive polyurethane solution is made；
(3) three phosphonitrile of 1.570g (0.000833mol) ten dihydroxy basic ring and 0.01g dibutyl tin dilaurate are dissolved in 5g In anhydrous butanone, it is added dropwise in photosensitive polyurethane solution made from step (2), 12h is stirred in reaction at 70 DEG C, and reaction terminates, Product is added drop-wise in deionized water and is precipitated, is filtered, the three phosphonitrile type light-cured polyurethane tree of ring is prepared in vacuum drying Rouge.
By three phosphonitrile type polyurethane resin of ring prepared in the 50wt% embodiment of the present invention, nine ethoxylation three of 10wt% Hydroxymethyl-propane triacrylate, 37wt% ethyl acetate, the mixing of 3wt%1- hydroxy-cyclohexyl phenyl ketone, are protected from light ultrasound It after 60min, is spun on aluminium sheet, with a thickness of 0.15mm, under the conditions of 50 DEG C, preliminary drying 100min, then in 800mJ/cm2Energy It is exposed solidification under amount, prepares three phosphonitrile type light-cured polyurethane coatings of ring.

Claims (7)

1. a kind of three phosphonitrile type light-cured polyurethane resin of ring, it is characterised in that the preparation method of the resin includes following step It is rapid:
(1) diisocyanate, the dilution of catalyst dibutyltin dilaurylate are placed in reactor using anhydrous solvent, then The diluted dihydric alcohol of anhydrous solvent is added dropwise into reactor, 2~4h is reacted at 40~50 DEG C, the pre- of isocyanate group sealing end is made Polymers；
(2) then, photo-curing monomer is added dropwise in the prepolymer blocked to isocyanate group obtained by step (1), 60-70 DEG C is stirred to react 5-7h obtains photosensitive polyurethane solution；The photo-curing monomer is (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid hydroxypropyl One of ester, (methyl) hy-droxybutyl are a variety of；The prepolymer that the photo-curing monomer is blocked with isocyanate group rubs You are than being 1~1.1:1；
(3) finally, three phosphonitrile monomer of ring and catalyst dibutyltin dilaurylate are dissolved in anhydrous solvent, it is slowly dropped to step Suddenly in photosensitive polyurethane solution obtained by (2), 50-70 DEG C is stirred to react 10-12h, and reaction terminates, and product sinks in deionized water It forms sediment, filter, vacuum drying, obtaining the three phosphonitrile type light-cured polyurethane resin of ring；The three phosphonitrile monomer of ring is six pairs of hydroxyls The mixing of one or both of three phosphonitrile of methylenedioxy phenoxy basic ring, ten dihydroxy basic rings, three phosphonitrile；The three phosphonitrile monomer of ring and light The molar ratio of quick polyurethane is 1~1.1:1.
2. three phosphonitrile type light-cured polyurethane resin of ring according to claim 1, it is characterised in that two described in step (1) Isocyanates is methyl diphenylene diisocyanate, polymeric diphenylmethane diisocyanate, toluene di-isocyanate(TDI), six methylenes One of group diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate are a variety of；The dihydric alcohol For PEG-400, PEG-800, PEG-1000, PEG-2000, PEG-10000, T5650E, T5650J, T5651, T5652, polycyclic Oxidative ethane glycol, polypropylene oxide glycol, polytetrahydrofuran diol, polyethylene glycol adipate glycol, polyadipate -1,4- fourth One of glycol esterdiol is a variety of；The molar ratio of the diisocyanate and dihydric alcohol is 2~2.2:1.
3. three phosphonitrile type light-cured polyurethane resin of ring according to claim 1, it is characterised in that step is urged described in (1) The dosage of agent dibutyl tin dilaurate is the 0.5~1% of dihydric alcohol and diisocyanate gross mass.
4. three phosphonitrile type light-cured polyurethane resin of ring according to claim 1, it is characterised in that the anhydrous solvent For one of N,N-dimethylformamide, acetone, anhydrous butanone, tetrahydrofuran, ethyl acetate or a variety of；The anhydrous solvent Dosage be the 20~30wt% of concentration for making reactant in reaction system.
5. a kind of application of any one of Claims 1 to 4 three phosphonitrile type light-cured polyurethane resin of ring, it is characterised in that should Light-cured polyurethane resin can be used for self-repair technology field.
6. a kind of coatings containing any one of Claims 1 to 4 three phosphonitrile type light-cured polyurethane resin of ring, It is characterized in that the mass percent of raw material contained by the coating and each raw material are as follows:
Each raw material is mixed according to the above ratio, after being protected from light 30~60min of ultrasound, is spun on aluminium sheet, with a thickness of 0.1~1mm, Under the conditions of 40~100 DEG C, 60~120min of preliminary drying, then in 500-800mJ/cm2Energy under be exposed solidification, be made ring Three phosphonitrile type light-cured polyurethane coatings.
7. coatings according to claim 6, it is characterised in that the reactive diluent is trimethylolpropane tris One of acrylate, ethoxylated trimethylolpropane triacrylate are a variety of；The photoinitiator is 2- hydroxyl -2- Methyl-1-phenyl-1- acetone, 1- hydroxy-cyclohexyl phenyl ketone, 2- hydroxyl-4 '-(2- hydroxy ethoxy)-2- methyl phenyl ketone, One of 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- acetone is a variety of；The solvent is N, N- dimethyl formyl One of amine, butanone, dimethyl acetamide, cyclohexanone, ethyl acetate are a variety of.
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