CN108219101A - Excellent dual cure urethane acrylate of a kind of chemical resistance and preparation method thereof - Google Patents
Excellent dual cure urethane acrylate of a kind of chemical resistance and preparation method thereof Download PDFInfo
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- CN108219101A CN108219101A CN201711452787.5A CN201711452787A CN108219101A CN 108219101 A CN108219101 A CN 108219101A CN 201711452787 A CN201711452787 A CN 201711452787A CN 108219101 A CN108219101 A CN 108219101A
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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
- C08G18/28—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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/28—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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
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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
- C08G18/28—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
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- 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
- 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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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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Abstract
The present invention relates to excellent dual cure urethane acrylates of a kind of chemical resistance and preparation method thereof, belong to chemical coating field.Mainly the component including following mass parts is made the resin of the present invention:43 ~ 60 parts of dihydric alcohol, 35.5 ~ 45.5 parts of isocyanates, 1.4 ~ 2.6 parts of chain extender, 25.5 ~ 34.5 parts of pentaerythritol triacrylate, 31.5 ~ 40.5 parts of epoxy acrylate, 15.5 ~ 25.5 parts of hydroxy-ethyl acrylate, 0.04 ~ 0.09 part of polymerization inhibitor, 0.04 ~ 0.09 part of catalyst, 0 ~ 50 part of acetone.Contain the double bond that can carry out radically curing in resin provided by the invention, also the epoxy group of cation photocuring or heat cure can be carried out by having, available for the configuration of plastic basis material priming, finishing coat and finishing varnish, can be very good to improve levelability, adhesive force and the various excellent chemical resistances of paint film.
Description
Technical field
The invention belongs to chemical coating fields, and in particular to a kind of dual cure urethane acrylate of chemical resistance;
In addition, the preparation method of the dual cure urethane acrylate the invention further relates to the chemical resistance.
Background technology
Ultraviolet light(UV)Curing technology is since it is with curing rate is fast, curing membrane performance is excellent, solvent-free using process
Release, low in the pollution of the environment, solidification process energy expenditure is low, can automated production, the advantages that being suitable for use on heat-sensitive substrate material, and
It obtains widely studying and applying.
UV coating material solidified is a kind of environmental type coating, has many advantages, such as that low energy consumption, volatile matter is few, hardening time is short.
UV is coating material solidified to be mainly made of prepolymer, activated monomer, photoinitiator and auxiliary agent, and wherein prepolymer constitutes cured film friendship
Join the skeleton of reticular structure, it is the main determining factor of product physical and chemical performance.Using aliphatic made from IPDI, HDI
UV cures prepolymer has the advantages that color inhibition compared with aromatic series UV cures prepolymer, and assigns the better toughness of film.Water
UV is coating material solidified can very easily adjust coating thickness for property, and taste is small, is more suitable for meeting the needs of modern society.
Coating is a kind of containing pigment or without pigment, the chemical products made of resin and oil etc..Coating is coated in
It dry and hard can forming a film on body surface, the surface and surrounding medium for making coated article body are isolated, so as to be played to coated article body
Protection and the effect of decoration.According to function difference, coating includes:Decorative paint, anticorrosive paint, insulating moulding coating and fireproof coating
Deng.In recent years, with continuous enhancing of the people to environmental protection consciousness, own health is constantly paid close attention to, there is an urgent need to one kind both
Environmentally friendly low-carbon, but to construction personnel itself without the coating of too big murder by poisoning, thus UV coating is also just born, and quickly sent out
Exhibition.
Existing UV coating is typically all simple photocuring reaction, that is, passes through the irradiation of ultraviolet light so that photoinitiator
Free radical is decomposited, these free radicals generate cross-linking reaction by UV resins, obtain cured paint film.According to the mode used not
Together, it is divided into as roller coating UV coating, showering UV coating, brushing UV coating, spraying UV coating etc..Roller coating UV coating exists in itself
Have preferable adhesive force above timber, bamboo wood and part high molecular polymer, but for metal material, the power that just seems not from
The heart, face easily comes off the paint film after curing on the metal material, leads to not face on the metal material and uses UV coating and UV
For coating in itself without what chemicals-resistant corrosive nature, mechanical flexibility is very poor.
Therefore, it is necessary to a kind of environmental protection, solvent-free volatilization, rapid curing, and can have preferable attachment in face on the metal material
Power has preferable flexibility, acidproof, alkaline-resisting, water resistance coating.
Invention content
The purpose of the present invention is on the basis of existing technology, provide a kind of dual cure polyurethane third of chemical resistance
Olefin(e) acid ester can solve the problems, such as that resin endurance, cementability are poor.
Another mesh of the present invention is to provide a kind of preparation side of the dual cure urethane acrylate of above-mentioned chemical resistance
Method.
Containing the double bond that can carry out radically curing in the resin of the present invention, cation photocuring or heat can be carried out by also having
Cured epoxy group.Resin can carry out free radical-cationic curing(Photoinitiator collocation salt cure agent), both work
Property group between there is intramolecular interaction, the progress of free radical and cationic photopolymerization can be effectively facilitated, made anti-
Rate and final conversion ratio is answered to be significantly improved, and greatly reduces the effect of oxygen inhibition.Due to introducing ring in resin
Oxygen groups enhance the indices such as endurance, the cementability of resin.
The resin of the present invention can be used for the configuration of plastic basis material priming, finishing coat and finishing varnish, can be very good to improve
Levelling, attachment and the various chemical resistances of paint film.
Technical scheme is as follows:
A kind of excellent dual cure urethane acrylate of chemical resistance, mainly the component including following mass parts is made for it:
43 ~ 60 parts of dihydric alcohol, 35.5 ~ 45.5 parts of isocyanates, 1.4 ~ 2.6 parts of chain extender, pentaerythritol triacrylate 25.5 ~
34.5 parts, 31.5 ~ 40.5 parts of epoxy acrylate, 15.5 ~ 25.5 parts of hydroxy-ethyl acrylate, 0.04 ~ 0.09 part of polymerization inhibitor urges
0.04 ~ 0.09 part of agent, 0 ~ 50 part of acetone.
In a kind of preferred embodiment, mainly the component including following mass parts is made resin of the invention:Dihydric alcohol 45 ~ 57
Part, 37 ~ 44 parts of isocyanates, 1.6 ~ 2.4 parts of chain extender, 27 ~ 33 parts of pentaerythritol triacrylate, epoxy acrylate
32 ~ 38 parts, 17.5 ~ 23.0 parts of hydroxy-ethyl acrylate, 0.05 ~ 0.08 part of polymerization inhibitor, 0.05 ~ 0.08 part of catalyst, acetone 0 ~
50 parts.
In a kind of more preferable scheme, mainly the component including following mass parts is made resin of the invention:Dihydric alcohol 48 ~
55 parts, 38.5 ~ 42.5 parts of isocyanates, 1.8 ~ 2.2 parts of chain extender, 28.5 ~ 31.5 parts of pentaerythritol triacrylate, epoxy
33.5 ~ 36.5 parts of acrylate, 19.0 ~ 21.5 parts of hydroxy-ethyl acrylate, 0.06 ~ 0.07 part of polymerization inhibitor, catalyst 0.06 ~
0.07 part, 0 ~ 50 part of acetone.
In a kind of scheme, the molecular weight of the dihydric alcohol is 1000.
In a kind of preferred embodiment, the dihydric alcohol can be selected from polycarbonate glycol, polycaprolactone diols, gather oneself two
One or more of sour glycol ester or poly adipate succinic acid ester.
In a kind of more preferable scheme, the dihydric alcohol can be selected from polycarbonate glycol, polycaprolactone diols or poly-
One or more of tetramethylene adipate.
In a kind of scheme, the isocyanates for can be selected from toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate or
One or more of hexamethylene diisocyanate.
In a kind of preferred embodiment, the isocyanates is can be selected from toluene di-isocyanate(TDI) or diphenylmethane diisocyanates
Ester.
In a kind of more preferable scheme, the isocyanates is can be selected from toluene di-isocyanate(TDI).
In a kind of scheme, the preparation method of the epoxy acrylate includes the following steps:
(1)Epoxy resin 2021P is added in into reactor, adds in catalyst tetrabutylammonium bromide and polymerization inhibitor p-hydroxyanisole,
Stir 10 ~ 20min;
(2)Acrylic acid is added in, heating temperature is to 105 ~ 115 DEG C, after reacting 2.5 ~ 3h, acid value is measured per 20min, when measure
When acid value is less than 0.2 mgKOH/g, stop reaction.
In a kind of preferred embodiment, the molar ratio of epoxy resin 2021P epoxide epoxy group groups and acrylic acid is 1:0.45.
In a kind of scheme, the chain extender can be selected from trimethyolol propane monoallyl ether, ethylene glycol, propylene glycol, one
One or more of diglycol ethylene or butanediol.
In a kind of preferred embodiment, the chain extender can be selected from trimethyolol propane monoallyl ether, diglycol
Or one or more of butanediol.
In a kind of more preferable scheme, the chain extender can be selected from trimethyolol propane monoallyl ether or butanediol.
In a kind of scheme, the polymerization inhibitor can be selected from p-hydroxyanisole, p methoxy phenol, hydroquinone or to benzene
One or more of quinone.
In a kind of preferred embodiment, the polymerization inhibitor can be selected from p-hydroxyanisole, p methoxy phenol or hydroquinone
One or more of.
In a kind of more preferable scheme, the polymerization inhibitor can be selected from p-hydroxyanisole or hydroquinone.
In a kind of scheme, the catalyst can be selected from dibutyl tin laurate, tetrabutylammonium bromide, triethylamine or three
One or more of phenyl phosphorus.
In a kind of preferred embodiment, the catalyst can be selected from dibutyl tin laurate, tetrabutylammonium bromide or triphen
One or more of base phosphorus.
In a kind of more preferable scheme, the catalyst can be selected from dibutyl tin laurate or tetrabutylammonium bromide.
A kind of preparation method of the excellent dual cure urethane acrylate of chemical resistance, it includes the following steps:
(1)Dihydric alcohol pre-processes:Dihydric alcohol is added in the four-hole boiling flask equipped with mechanical agitation, thermometer and vacuum plant,
0.5 ~ 1.5 h is dehydrated in the case where 105 ~ 115 DEG C, vacuum degree is 0.80 ~ 0.95 MPa;
(2)Dewatered material is cooled to 75 ~ 85 DEG C, isocyanates is added in four-hole boiling flask by several times, controlled at 75 ~ 85
DEG C, it reacts for after 1.5 ~ 2 h, nco value is measured per 20min, after nco value reaches theoretical value, adds in chain extender, reaction 20 ~ 40
Min, acetone can be added in reaction process reduces viscosity;
(3)Be cooled to 65 ~ 75 DEG C, by pentaerythritol triacrylate, epoxy acrylate, hydroxy-ethyl acrylate, polymerization inhibitor and
Catalyst is added sequentially in four-hole boiling flask, adds acetone, and control temperature waits nco values to be down to less than 0.1% and stop at 55 ~ 65 DEG C
Reaction;
(4)45 ~ 55 DEG C are cooled to, which is poured into addition deionized water in dispersion machine makes solid content be 88 ~ 92%, in rotating speed
10 ~ 20 min are stirred during for 1800 ~ 2200r/min, obtain the lotion of clear;
(5)Through vacuum distillation removing acetone to get.
Technical solution using the present invention, advantage are as follows:
Containing the double bond that can carry out radically curing in resin provided by the invention, cation photocuring or heat can be carried out by also having
Cured epoxy group.Resin can carry out free radical-cationic curing, and there is the phases of intramolecular between both active groups
Interaction can effectively facilitate the progress of free radical and cationic photopolymerization, and reaction rate and final conversion ratio is made to have significantly
It improves, and greatly reduces the effect of oxygen inhibition.
Resin provided by the invention can be used for the configuration of plastic basis material priming, finishing coat and finishing varnish, can be very good
Improve levelability, adhesive force and the various excellent chemical resistances of paint film.
Specific embodiment
Pass through dual cure urethane acrylate of the following embodiment to a kind of chemical resistance of the present invention and its preparation
Method is further described, but these embodiments do not form any restrictions to the present invention.
The preparation method of the excellent dual cure urethane acrylate of chemical resistance provided by the invention, it includes following
Step:
(1)Dihydric alcohol pre-processes:Dihydric alcohol is added in the four-hole boiling flask equipped with mechanical agitation, thermometer and vacuum plant,
0.5 ~ 1.5 h is dehydrated in the case where 105 ~ 115 DEG C, vacuum degree is 0.80 ~ 0.95 MPa;
(2)Dewatered material is cooled to 75 ~ 85 DEG C, isocyanates is added in four-hole boiling flask by several times, controlled at 75 ~ 85
DEG C, it reacts for after 1.5 ~ 2 h, nco value is measured per 20min, after nco value reaches theoretical value, adds in chain extender, reaction 20 ~ 40
Min, acetone can be added in reaction process reduces viscosity;
(3)Be cooled to 65 ~ 75 DEG C, by pentaerythritol triacrylate, epoxy acrylate, hydroxy-ethyl acrylate, polymerization inhibitor and
Catalyst is added sequentially in four-hole boiling flask, adds acetone, and control temperature waits nco values to be down to less than 0.1% and stop at 55 ~ 65 DEG C
Reaction;
(4)45 ~ 55 DEG C are cooled to, which is poured into addition deionized water in dispersion machine makes solid content be 88 ~ 92%, in rotating speed
10 ~ 20 min are stirred during for 1800 ~ 2200r/min, obtain the lotion of clear;
(5)Through vacuum distillation removing acetone to get.
Wherein, the preparation method of epoxy acrylate includes the following steps:
(1)Epoxy resin 2021P is added in into reactor, adds in catalyst tetrabutylammonium bromide and polymerization inhibitor p-hydroxyanisole,
Stir 10 ~ 20min;
(2)Acrylic acid is added in, heating temperature is to 105 ~ 115 DEG C, after reacting 2.5 ~ 3h, acid value is measured per 20min, when measure
When acid value is less than 0.2 mgKOH/g, stop reaction.
Embodiment 1
A kind of excellent dual cure urethane acrylate of chemical resistance, it includes following component and mass fraction:
Dihydric alcohol(Polycaprolactone diols, molecular weight 1000)18 parts;
Dihydric alcohol(Polyethylene glycol adipate, molecular weight 1000)26 parts;
Isocyanates('-diphenylmethane diisocyanate)12 parts;
Isocyanates('-diphenylmethane diisocyanate)24 parts;
Chain extender(Butanediol)1.4 part;
25.8 parts of pentaerythritol triacrylate;
33.0 parts of epoxy acrylate;
16 parts of hydroxy-ethyl acrylate;
0.07 part of polymerization inhibitor (p methoxy phenol);
Catalyst(Tetrabutylammonium bromide)0.04 part;
20 parts of acetone.
The preparation method of this resin includes the following steps:
(1)Dihydric alcohol pre-processes:Dihydric alcohol is added in the four-hole boiling flask equipped with mechanical agitation, thermometer and vacuum plant,
0.5 ~ 1.5 h is dehydrated in the case where 108 DEG C, vacuum degree is 0.85 MPa;
(2)Dewatered material is cooled to 77 DEG C, isocyanates is added in four-hole boiling flask by several times, controlled at 77 DEG C, instead
After should be 1.5 ~ 2 h, nco value is measured per 20min, after nco value reaches theoretical value, chain extender is added in, reacts 27 min, reacted
Cheng Zhongke addition acetone reduces viscosity;
(3)72 DEG C are cooled to, by pentaerythritol triacrylate, epoxy acrylate, hydroxy-ethyl acrylate, polymerization inhibitor and catalysis
Agent is added sequentially in four-hole boiling flask, adds acetone, and control temperature waits nco values to be down to less than 0.1% stopping reaction at 58 DEG C;
(4)48 DEG C are cooled to, which is poured into addition deionized water in dispersion machine makes solid content be 88 ~ 92%, is in rotating speed
12 min are stirred during 1900r/min, obtain the lotion of clear;
(5)Through vacuum distillation removing acetone to get.
Embodiment 2
A kind of excellent dual cure urethane acrylate of chemical resistance, it includes following component and mass fraction:
Dihydric alcohol(Polycarbonate glycol, molecular weight 1000)17.5 parts;
Dihydric alcohol(Polyethylene glycol adipate, molecular weight 1000)30 parts;
Isocyanates(Toluene di-isocyanate(TDI))12.5 parts;
Isocyanates('-diphenylmethane diisocyanate)26 parts;
Chain extender(Butanediol)1.8 part;
27 parts of pentaerythritol triacrylate;
32.1 parts of epoxy acrylate;
23.2 parts of hydroxy-ethyl acrylate;
0.05 part of polymerization inhibitor (p-hydroxyanisole);
Catalyst(Dibutyl tin laurate)0.08 part;
30 parts of acetone.
The preparation method of this resin includes the following steps:
(1)Dihydric alcohol pre-processes:Dihydric alcohol is added in the four-hole boiling flask equipped with mechanical agitation, thermometer and vacuum plant,
0.5 ~ 1.5 h is dehydrated in the case where 110 DEG C, vacuum degree is 0.85 MPa;
(2)Dewatered material is cooled to 82 DEG C, isocyanates is added in four-hole boiling flask by several times, controlled at 82 DEG C, instead
After should be 1.5 ~ 2 h, nco value is measured per 20min, after nco value reaches theoretical value, chain extender is added in, reacts 32 min, reacted
Cheng Zhongke addition acetone reduces viscosity;
(3)70 DEG C are cooled to, by pentaerythritol triacrylate, epoxy acrylate, hydroxy-ethyl acrylate, polymerization inhibitor and catalysis
Agent is added sequentially in four-hole boiling flask, adds acetone, and control temperature waits nco values to be down to less than 0.1% stopping reaction at 60 DEG C;
(4)50 DEG C are cooled to, which is poured into addition deionized water in dispersion machine makes solid content be 88 ~ 92%, is in rotating speed
12 min are stirred during 1900r/min, obtain the lotion of clear;
(5)Through vacuum distillation removing acetone to get.
Embodiment 3
A kind of excellent dual cure urethane acrylate of chemical resistance, it includes following component and mass fraction:
Dihydric alcohol(Polycarbonate glycol, molecular weight 1000)50 parts;
Isocyanates(Toluene di-isocyanate(TDI))50 parts;
Chain extender(Trimethyolol propane monoallyl ether)2.0 part;
30 parts of pentaerythritol triacrylate;
35 parts of epoxy acrylate;
20 parts of hydroxy-ethyl acrylate;
0.065 part of polymerization inhibitor (p-hydroxyanisole);
Catalyst(Dibutyl tin laurate)0.065 part;
40 parts of acetone.
The preparation method of this resin includes the following steps:
(1)Dihydric alcohol pre-processes:Dihydric alcohol is added in the four-hole boiling flask equipped with mechanical agitation, thermometer and vacuum plant,
0.5 ~ 1.5 h is dehydrated in the case where 110 DEG C, vacuum degree is 0.9 MPa;
(2)Dewatered material is cooled to 80 DEG C, isocyanates is added in four-hole boiling flask by several times, controlled at 80 DEG C, instead
After should be 1.5 ~ 2 h, nco value is measured per 20min, after nco value reaches theoretical value, chain extender is added in, reacts 30 min, reacted
Cheng Zhongke addition acetone reduces viscosity;
(3)70 DEG C are cooled to, by pentaerythritol triacrylate, epoxy acrylate, hydroxy-ethyl acrylate, polymerization inhibitor and catalysis
Agent is added sequentially in four-hole boiling flask, adds acetone, and control temperature waits nco values to be down to less than 0.1% stopping reaction at 60 DEG C;
(4)50 DEG C are cooled to, which is poured into addition deionized water in dispersion machine makes solid content be 88 ~ 92%, is in rotating speed
12 min are stirred during 2000r/min, obtain the lotion of clear;
(5)Through vacuum distillation removing acetone to get.
Comparative example 1
A kind of excellent dual cure urethane acrylate of chemical resistance, it includes following component and mass fraction:
Dihydric alcohol(Polycaprolactone diols, molecular weight 1000)18 parts;
Dihydric alcohol(Polyethylene glycol adipate, molecular weight 1000)26 parts;
Isocyanates('-diphenylmethane diisocyanate)12 parts;
Isocyanates('-diphenylmethane diisocyanate)24 parts;
Chain extender(Butanediol)1.4 part;
25.8 parts of pentaerythritol triacrylate;
33.0 parts of epoxy acrylate;
16 parts of hydroxy-ethyl acrylate;
Catalyst(Tetrabutylammonium bromide)0.04 part;
20 parts of acetone.
The preparation method of this resin is with reference to embodiment 1.
Comparative example 2
A kind of excellent dual cure urethane acrylate of chemical resistance, it includes following component and mass fraction:
Dihydric alcohol(Polycarbonate glycol, molecular weight 1000)18.5 parts;
Dihydric alcohol(Polyethylene glycol adipate, molecular weight 1000)30 parts;
Isocyanates(Toluene di-isocyanate(TDI))12.5 parts;
Isocyanates('-diphenylmethane diisocyanate)26 parts;
Chain extender(Butanediol)2.8 part;
27 parts of pentaerythritol triacrylate;
32.1 parts of epoxy acrylate;
23.2 parts of hydroxy-ethyl acrylate;
0.05 part of polymerization inhibitor (p-hydroxyanisole);
Catalyst(Dibutyl tin laurate)0.08 part;
30 parts of acetone.
The preparation method of this resin is with reference to embodiment 2.
Comparative example 3
A kind of excellent dual cure urethane acrylate of chemical resistance, it includes following component and mass fraction:
Dihydric alcohol(Polycarbonate glycol, molecular weight 1000)49 parts;
Isocyanates(Toluene di-isocyanate(TDI))50 parts;
Chain extender(Trimethyolol propane monoallyl ether)3.0 part;
30 parts of pentaerythritol triacrylate;
35 parts of epoxy acrylate;
20 parts of hydroxy-ethyl acrylate;
0.065 part of polymerization inhibitor (p-hydroxyanisole);
Catalyst(Dibutyl tin laurate)0.065 part;
40 parts of acetone.
The preparation method of this resin is with reference to embodiment 3.
Embodiment 4
Performance test after the resinous coat of the present invention is as follows:
Performance after 1 resinous coat of table
Sample | Hardness | Adhesive force | Film RCA | Toughness | Alkali resistance | Acid resistance | Resistance to alcohol test |
Embodiment 1 | 5H | 5B | 620 | 1mm | Normally | Normally | It is unchanged |
Embodiment 2 | 5H | 5B | 650 | 1mm | Normally | Normally | It is unchanged |
Embodiment 3 | 5H | 5B | 660 | 1mm | Normally | Normally | It is unchanged |
Comparative example 1 | 3H | 2B | 410 | 1mm | There is peeling | There is peeling | Have and come off |
Comparative example 2 | 2H | 3B | 440 | 1mm | There is peeling | There is peeling | Have and come off |
Comparative example 3 | 2H | 3B | 455 | 1mm | There is peeling | There is peeling | Have and come off |
The test method of the present invention is as follows:
Pencil hardness:GB/T 6739-2006.
Adhesive force:3M adhesive tapes, the test of hundred lattice, GB/T 5210-2006.
Film RCA:Wearability, load 175g.
Toughness:GB/T1731-1993 is measured.
Alkali resistance:It immerses in 25 DEG C of 5%NaOH seven days, visual evaluation appearance.
Alkali resistance:Immerse 25 DEG C of 5%H2SO4In seven days, visual evaluation appearance.
Resistance to alcohol test(98% ethyl alcohol):Room temperature 48 hours, visual evaluation appearance.
Although above having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. the excellent dual cure urethane acrylate of a kind of chemical resistance, which is characterized in that it mainly includes following quality
The component of part is made:43 ~ 60 parts of dihydric alcohol, 35.5 ~ 45.5 parts of isocyanates, 1.4 ~ 2.6 parts of chain extender, pentaerythrite 3 third
25.5 ~ 34.5 parts of olefin(e) acid ester, 31.5 ~ 40.5 parts of epoxy acrylate, 15.5 ~ 25.5 parts of hydroxy-ethyl acrylate, polymerization inhibitor
0.04 ~ 0.09 part, 0.04 ~ 0.09 part of catalyst, 0 ~ 50 part of acetone.
2. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that it leads
The component that include following mass parts is made:45 ~ 57 parts of dihydric alcohol, 37 ~ 44 parts of isocyanates, 1.6 ~ 2.4 parts of chain extender, season
Penta 27 ~ 33 parts of tetrol triacrylate, 32 ~ 38 parts of epoxy acrylate, 17.5 ~ 23.0 parts of hydroxy-ethyl acrylate, polymerization inhibitor
0.05 ~ 0.08 part, 0.05 ~ 0.08 part of catalyst, 0 ~ 50 part of acetone.
3. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that it leads
The component that include following mass parts is made:48 ~ 55 parts of dihydric alcohol, 38.5 ~ 42.5 parts of isocyanates, chain extender 1.8 ~ 2.2
Part, 28.5 ~ 31.5 parts of pentaerythritol triacrylate, 33.5 ~ 36.5 parts of epoxy acrylate, hydroxy-ethyl acrylate 19.0 ~
21.5 parts, 0.06 ~ 0.07 part of polymerization inhibitor, 0.06 ~ 0.07 part of catalyst, 0 ~ 50 part of acetone.
4. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that described
The molecular weight of dihydric alcohol be 1000, can be selected from polycarbonate glycol, polycaprolactone diols, polyethylene glycol adipate or
One or more of poly adipate succinic acid ester.
5. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that described
Isocyanates is can be selected from one in toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate or hexamethylene diisocyanate
Kind is several.
6. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that described
The preparation method of epoxy acrylate includes the following steps:
(1)Epoxy resin 2021P is added in into reactor, adds in catalyst tetrabutylammonium bromide and polymerization inhibitor p-hydroxyanisole,
Stir 10 ~ 20min;
(2)Acrylic acid is added in, heating temperature is to 105 ~ 115 DEG C, after reacting 2.5 ~ 3h, acid value is measured per 20min, when measure
When acid value is less than 0.2 mgKOH/g, stop reaction.
7. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that epoxy
Resin 2021P epoxide epoxy group groups and the molar ratio of acrylic acid are 1:0.45.
8. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that described
Chain extender can be selected from one in trimethyolol propane monoallyl ether, ethylene glycol, propylene glycol, diglycol or butanediol
Kind is several.
9. the excellent dual cure urethane acrylate of chemical resistance according to claim 1, which is characterized in that described
One or more of polymerization inhibitor p-hydroxyanisole, p methoxy phenol, hydroquinone or 1,4-benzoquinone;The catalyst is selected from
One or more of dibutyl tin laurate, tetrabutylammonium bromide, triethylamine or triphenyl phosphorus.
10. a kind of preparation method of the excellent dual cure urethane acrylate of chemical resistance as described in claim 1,
It is characterized in that, it includes the following steps:
(1)Dihydric alcohol pre-processes:Dihydric alcohol is added in the four-hole boiling flask equipped with mechanical agitation, thermometer and vacuum plant,
0.5 ~ 1.5 h is dehydrated in the case where 105 ~ 115 DEG C, vacuum degree is 0.80 ~ 0.95 MPa;
(2)Dewatered material is cooled to 75 ~ 85 DEG C, isocyanates is added in four-hole boiling flask by several times, controlled at 75 ~ 85
DEG C, it reacts for after 1.5 ~ 2 h, nco value is measured per 20min, after nco value reaches theoretical value, adds in chain extender, reaction 20 ~ 40
Min, acetone can be added in reaction process reduces viscosity;
(3)Be cooled to 65 ~ 75 DEG C, by pentaerythritol triacrylate, epoxy acrylate, hydroxy-ethyl acrylate, polymerization inhibitor and
Catalyst is added sequentially in four-hole boiling flask, adds acetone, and control temperature waits nco values to be down to less than 0.1% and stop at 55 ~ 65 DEG C
Reaction;
(4)45 ~ 55 DEG C are cooled to, which is poured into addition deionized water in dispersion machine makes solid content be 88 ~ 92%, in rotating speed
10 ~ 20 min are stirred during for 1800 ~ 2200r/min, obtain the lotion of clear;
(5)Through vacuum distillation removing acetone to get.
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CN109608611A (en) * | 2018-10-23 | 2019-04-12 | 合肥科天水性科技有限责任公司 | A kind of epoxy acrylic resin modified aqueous polyurethane and preparation method thereof |
CN111100261A (en) * | 2018-10-26 | 2020-05-05 | 乐凯华光印刷科技有限公司 | Hyperbranched polyurethane acrylate monomer, and preparation method and application thereof |
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