A kind of standby UV coating of polyurethane based on cyclic carbonate ester synthesis
Technical field
The invention belongs to technical field of coatings, the standby UV of particularly a kind of polyurethane based on cyclic carbonate ester synthesis is applied
Material, this coating especially suitable for family or exterior wall building coating,.
Background technology
UV coating, i.e. uv radiation curing coating, refer to based on oligomer, add specific function monomer, light
Initiator and auxiliary agent, under uv radiation, after photoinitiator absorbs energy, excitation becomes activated centre free radical or ion, so that
React in initiation system containing unsaturated double-bond or epoxy group material, by polymerization, grafting and be cross-linked to form cured film.UV consolidates
It is the new coating kind that the ground such as America and Europe, Japan are popular at twentieth century end to change coating.Earliest be applied to furniture, floor,
The external coating processing of mobile phone, walkman shell, its application field now further expand to cosmetics containers, television set and computer
Etc. the other field such as household appliance technical field and motorcycle and Lacquer finish.UV photocureable coating, which has, is free of volatile organic compounds
(VOC), environmental pollution is small, and curing rate is fast, saves the energy, cured product performance is good, is suitable for high-speed automated production etc.
Advantage.And traditional coating is volatile, curing rate is slow, it is unfavorable for environmental protection.Therefore, UV coating is that the main of traditional coating replaces
Dai Pin.
Nineteen thirty-seven, is synthesized from Germanization scholar Otto Bayer with polyisocyanates and polyol polymerization addition
Since polyurethane, polyurethane is widely used to UV coating with outstanding comprehensive performance.All the time, polyurethane is by more isocyanides
Acid esters reacts to obtain with polyether polyol, but isocyanates has severe toxicity in itself, has strongly to the eyes, skin and respiratory system of people
Stimulation;Polyurethane is produced at the same time and uses phosgenation, and phosgene severe toxicity, is a kind of strong stimulation, asphyxiant gas.Suction phosgene causes
Pulmonary edema, pneumonia etc., have lethal danger, have high risks to direct labor.
Chinese paint industry grows stronger day by day under the promotion of downstream industry, and as the building coating of one of branch,
Also significant progress has been obtained.Under the guiding of Industry Policy and the pulling in market, China's decorative craft of building will enter new hair
Exhibition period, the demand of building coating can continue to increase, and industry market development potentiality is huge.In addition, the new rural village risen is built
If it also greatly have stimulated the popularization and application of all kinds of building coatings.Thus infer, Chinese construction industry at least also had for more than 10 years
The stable development phase, also will be 10 years of domestic construction coating production enterprise high speed development.Building coating is mainly used for as one kind
The coating products of house decoration, its market development develop closely related with real estate industry.But existing family or non-family safe are used
Wall paint contains the harmful components such as isocyanates, and adhesiveness and wearability are bad, is to be directed to exterior coating by it, easily produces
Cracking, wearability is not good enough, scrapes easy damaged.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of polyurethane based on cyclic carbonate ester synthesis is standby
UV coating, solves and existing is applied to the existing pollution environment of UV coating used for building exterior wall, adhesiveness and the skills such as wearability is bad
Art problem.
The technical solution adopted by the present invention to solve the technical problems is:A kind of polyurethane based on cyclic carbonate ester synthesis
Standby UV coating, is formed by the Raw material processing of following parts by weight:
35~45 parts of epoxy acrylate, 10~20 parts of non-isocyanate polyurethane, 20~25 parts of acrylic acid activated monomer,
0.8~1.2 part of pentaerythrite, 6~8 parts of silica nano particle, 2~3 parts of stilbene biphenyl sodium disulfonate, photoinitiator 2
~2.5 parts, 2.5~3.5 parts of defoamer, 1.5~2.5 parts of US surface improvers, 4~8 parts of ABK accelerating agents;
Wherein described non-isocyanate polyurethane is synthesized by the component of following parts by weight:
30~35 parts of cyclic carbonate ester, 60~65 parts of binary primary amine compound, 8~10 parts of acrylic acid activated monomer, E51 epoxies
5~6 parts of resin, 1~2 part of bismuth carboxylate.
Preferably, the binary primary amine compound is benzhydryl methane diamines.
Preferably, the cyclic carbonate ester is preferably terpenyl cyclic carbonate ester.
The standby UV coating of the above-mentioned polyurethane based on cyclic carbonate ester synthesis, the processing step that it is prepared are as follows:
Step 1:A certain amount of epoxy resin, zinc Isoocatanoate and propene carbonate, asphalt mixtures modified by epoxy resin are added in autoclave
Mass ratio between fat, zinc Isoocatanoate and propene carbonate is 5:2:1,120~130 DEG C are heated to, is passed through CO2, protect pressure
Hold between 1.3~1.6MPa, when reaction 5~6 is small, product is poured out while hot, and cyclic carbonate ester is obtained through being evaporated under reduced pressure purifying.
Step 2:The cyclic carbonate ester and E51 epoxy resin for taking respective amount are uniformly mixed in flask, sequentially add acrylic acid
Activated monomer and binary primary amine compound, control temperature are reacted 2~3 hours between 80~90 DEG C, are added dropwise in reaction process
Bismuth carboxylate, after reaction the non-isocyanate polyurethane.
Step 3:It is fitted into after the epoxy acrylate of respective amount and acrylic acid activated monomer are mixed in container and stirs, stirs
Mix 40~60 DEG C of temperature, when stirring 2~3 is small, then add the non-isocyanate polyurethane of respective amount, pentaerythrite, light-initiated
Agent, defoamer, stilbene biphenyl sodium disulfonate, ABK accelerating agents, are uniformly mixed, add uniformly mixed silica nanometer
Particle and US surface improvers, continue after being warming up to 60~80 DEG C stirring 3 it is small when, be cooled to room temperature, ring carbon be based on up to described
The standby UV coating of polyurethane of acid esters synthesis.
The positive effect of the present invention:It is for applied to sapecial coating for building, UV coating of the present invention first
Based on non-isocyanate polyurethane, the harmful substances such as isocyanates are not contained, are avoided during coating use to air
Pollution, inventive formulation are environmentally protective nontoxic.The present invention utilizes and derives from the terebinthine epoxy resin system of renewable resource at the same time
Standby terpenyl cyclic carbonate ester, can be not only the new direction of opening up of China's natural reproducible resource, but also meet
Demands of the people to environment-friendly materials, have highly important economy and a social effect.In addition, the present invention uses epoxy acrylic
Ester, non-isocyanate polyurethane collocation acrylic acid activated monomer, in conjunction with the addition of stilbene biphenyl sodium disulfonate so that UV
Coating has preferable scratch resistance, and the mixing of US surface improvers and silica nano particle adds so that nano particle point
Dissipate the performances such as adhesive force and the wearability that coating is uniformly greatly improved while ensureing and not influencing light absorbs.In a word at this
Under the comprehensive function for inventing formula, it is excellent that product of the present invention has that hardness is good, wearability is good, adhesion is good, solvent resistance is good
Point, at the same it is environmentally protective nontoxic, and the UV coating for solving the problems, such as to use in existing family or non-family safe building well exists,
By it good effect is above achieved in exterior wall application.
Embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Embodiment 1
The preferred embodiment of the present invention 1 provides a kind of polyurethane based on cyclic carbonate ester synthesis standby UV coating, by following
The Raw material processing of parts by weight forms:
35 parts of epoxy acrylate, 10 parts of non-isocyanate polyurethane, 20 parts of acrylic acid activated monomer, pentaerythrite 0.8
Part, 6 parts of silica nano particle, 2 parts of stilbene biphenyl sodium disulfonate, 2 parts of photoinitiator, 2.5 parts of defoamer, US surfaces change
Into 1.5 parts of agent, 4 parts of ABK accelerating agents;
Wherein described non-isocyanate polyurethane is synthesized by the component of following parts by weight:
30 parts of cyclic carbonate ester, 60 parts of binary primary amine compound, 8 parts of acrylic acid activated monomer, 5 parts of E51 epoxy resin, carboxylic acid
1 part of bismuth.
The binary primary amine compound is benzhydryl methane diamines.
The cyclic carbonate ester is terpenyl cyclic carbonate ester.
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone
The standby UV coating of the above-mentioned polyurethane based on cyclic carbonate ester synthesis, the processing step that it is prepared are as follows:
Step 1:A certain amount of epoxy resin, zinc Isoocatanoate and propene carbonate, asphalt mixtures modified by epoxy resin are added in autoclave
Mass ratio between fat, zinc Isoocatanoate and propene carbonate is 5:2:1,120~130 DEG C are heated to, is passed through CO2, protect pressure
Hold between 1.3~1.6MPa, when reaction 5~6 is small, product is poured out while hot, and cyclic carbonate ester is obtained through being evaporated under reduced pressure purifying.
Step 2:The cyclic carbonate ester and E51 epoxy resin for taking respective amount are uniformly mixed in flask, sequentially add acrylic acid
Activated monomer and binary primary amine compound, control temperature are reacted 2~3 hours between 80~90 DEG C, are added dropwise in reaction process
Bismuth carboxylate, after reaction the non-isocyanate polyurethane.
Step 3:It is fitted into after the epoxy acrylate of respective amount and acrylic acid activated monomer are mixed in container and stirs, stirs
Mix 40~60 DEG C of temperature, when stirring 2~3 is small, then add the non-isocyanate polyurethane of respective amount, pentaerythrite, light-initiated
Agent, defoamer, stilbene biphenyl sodium disulfonate, ABK accelerating agents, are uniformly mixed, add uniformly mixed silica nanometer
Particle and US surface improvers, continue after being warming up to 60~80 DEG C stirring 3 it is small when, be cooled to room temperature, ring carbon be based on up to described
The standby UV coating of polyurethane of acid esters synthesis.
Embodiment 2
The preferred embodiment of the present invention 2 provides a kind of polyurethane based on cyclic carbonate ester synthesis standby UV coating, by following
The Raw material processing of parts by weight forms:
45 parts of epoxy acrylate, 20 parts of non-isocyanate polyurethane, 25 parts of acrylic acid activated monomer, pentaerythrite 1.2
8 parts of silica nano particle of part, 3 parts of stilbene biphenyl sodium disulfonate, 2.5 parts of photoinitiator, 3.5 parts of defoamer, US surfaces
2.5 parts of modifier, 8 parts of ABK accelerating agents;
Wherein described non-isocyanate polyurethane is synthesized by the component of following parts by weight:
35 parts of cyclic carbonate ester, 65 parts of binary primary amine compound, 10 parts of acrylic acid activated monomer, 6 parts of E51 epoxy resin, carboxylic
Sour 2 parts of bismuth.
The binary primary amine compound is benzhydryl methane diamines.
The cyclic carbonate ester is terpenyl cyclic carbonate ester.
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Preparation method is the same as embodiment 1.
Embodiment 3
The preferred embodiment of the present invention 3 provides a kind of polyurethane based on cyclic carbonate ester synthesis standby UV coating, by following
The Raw material processing of parts by weight forms:
40 parts of epoxy acrylate, 15 parts of non-isocyanate polyurethane, 22 parts of acrylic acid activated monomer, 1 part of pentaerythrite,
7 parts of silica nano particle, 2.5 parts of stilbene biphenyl sodium disulfonate, 2.5 parts of photoinitiator, 3 parts of defoamer, US surfaces change
Into 2 parts of agent, 5 parts of ABK accelerating agents;
Wherein described non-isocyanate polyurethane is synthesized by the component of following parts by weight:
35 parts of cyclic carbonate ester, 62 parts of binary primary amine compound, 9 parts of acrylic acid activated monomer, 6 parts of E51 epoxy resin, carboxylic acid
1 part of bismuth.
The binary primary amine compound is benzhydryl methane diamines.
The cyclic carbonate ester is terpenyl cyclic carbonate ester.
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Preparation method is the same as embodiment 1.
Embodiment 4
The preferred embodiment of the present invention 4 provides a kind of polyurethane based on cyclic carbonate ester synthesis standby UV coating, and formula is same
Embodiment 3, preparation method comprises the following steps:
Step 1:A certain amount of epoxy resin, zinc Isoocatanoate and propene carbonate, asphalt mixtures modified by epoxy resin are added in autoclave
Mass ratio between fat, zinc Isoocatanoate and propene carbonate is 5:2:1,120~130 DEG C are heated to, is passed through CO2, protect pressure
Hold between 1.3~1.6MPa, when reaction 5~6 is small, product is poured out while hot, and cyclic carbonate ester is obtained through being evaporated under reduced pressure purifying.
Step 2:The cyclic carbonate ester and E51 epoxy resin for taking respective amount are uniformly mixed in flask, sequentially add acrylic acid
Activated monomer and binary primary amine compound, control temperature are reacted 2~3 hours between 80~90 DEG C, are added dropwise in reaction process
Bismuth carboxylate, after reaction the non-isocyanate polyurethane.
Step 3:The magnetic field device for producing magnetic field is set in the periphery of new reaction vessel, under the action of externally-applied magnetic field
It is fitted into after the epoxy acrylate of respective amount and acrylic acid activated monomer are mixed in new reaction vessel and stirs, whipping temp 40
~60 DEG C, when stirring 2~3 is small, the then non-isocyanate polyurethane of addition respective amount, pentaerythrite, photoinitiator, defoaming
Agent, stilbene biphenyl sodium disulfonate, ABK accelerating agents, are uniformly mixed, add uniformly mixed silica nano particle and US
Surface improver, continue after being warming up to 60~80 DEG C stirring 3 it is small when, be cooled to room temperature, synthesized up to described based on cyclic carbonate ester
The standby UV coating of polyurethane.
The magnetic field device is made of iron core and coil, the iron core and coil encircling around the reaction vessel, and
And the iron core is in the outside of the coil, the NS poles in the magnetic field are perpendicular to the reaction vessel, and the magnetic field device
Access is direct current.Wherein, magnetic induction intensity:0.8-1.2 teslas.
The effect in the present embodiment magnetic field generates material impact to high molecular weight reactive, obtained under additional magnetic fields
Coating there is more preferable adhesion and wearability, it is probably in additional magnetic fields in polymerization process to guess its reason
Under, the high molecular weight reactive of magnetohydrodynamics effects caused by Lorentz force, organic ion stream cutting magnetic present in solution
Influenced be subject to Lorentz force during the line of force, so that its orientation accelerates, and played to a certain extent in the process
The effect of agitating solution so that the regularity of final coating, physical property etc. also due to the effect in magnetic field and improved.
Embodiment 5 (comparative example)
A kind of standby UV coating of polyurethane based on cyclic carbonate ester synthesis, is formed by the Raw material processing of following parts by weight:
40 parts of epoxy acrylate, 15 parts of isocyanate polyurethane, 2.5 parts of photoinitiator, 3 parts of defoamer, US surfaces change
Into 2 parts of agent, 5 parts of ABK accelerating agents;
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Preparation method:Epoxy acrylate, isocyanate polyurethane, 2- hydroxy-2-methyl -1- phenyl -1- acetone press than
Example mixing, is fitted into the container of belt stirrer, is warming up to 40 DEG C, 400 revs/min of mixing speed, when stirring 1 is small;Add remaining
Raw material, is warming up to 60 DEG C, 500 revs/min of mixing speed, when stirring 2 is small, is cooled to room temperature, up to UV coating.
Prepared UV coating, its performance test results are shown in Table 1. in embodiment 1 to 5
Table 1
Wherein, wear-resisting property is tested using Taber CS17 methods, loads 1000g, is rotated 2000 weeks, and measure paint film is weightless
(i.e. wearing valve).Test for xanthochromia grade, under the irradiation of natural light, carries out the xanthochromia grade of paint film by ocular estimate
Evaluation.
By table 1 as it can be seen that the UV coating for preparing of the present invention has the advantages that environment-protecting and non-poisonous, and its adhesive force and wearability are all
Have compared to the existing coating applied to external wall and be obviously improved, and it is with stronger yellowing resistance.
It is above-described to be merely a preferred embodiment of the present invention, it should be understood that the explanation of above example is simply used
Understand the method and its core concept of the present invention in help, the protection domain being not intended to limit the present invention is all the present invention's
Any modification for being made within thought and principle, equivalent substitution etc., should all be included in the protection scope of the present invention.