CN108219093A - A kind of cured alcohol-soluble polyurethane of ultraviolet light and preparation method thereof - Google Patents
A kind of cured alcohol-soluble polyurethane of ultraviolet light and preparation method thereof Download PDFInfo
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- CN108219093A CN108219093A CN201611155816.7A CN201611155816A CN108219093A CN 108219093 A CN108219093 A CN 108219093A CN 201611155816 A CN201611155816 A CN 201611155816A CN 108219093 A CN108219093 A CN 108219093A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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Abstract
The present invention relates to cured alcohol-soluble polyurethanes of a kind of ultraviolet light and preparation method thereof, it is made including the following raw material：Oligomer polyol, polyisocyanates, hydrophilic chain extender, small molecule chain extender, sealer, diluent, salt forming agent, solvent and catalyst.Specific preparation method is that first oligomer polyol is added in and is dehydrated into the reactor for be passed through nitrogen, then weighs polyisocyanates successively and partial amount catalyst is added in reactor and reacts；Then it weighs hydrophilic chain extender and diluent is added in reactor and reacted, then weigh sealer and be added in reactor and react, the catalyst for then weighing matter small molecule chain extender and surplus is added in reactor；Then it weighs salt forming agent to add in reactor, is then added with stirring stirring solvent reaction, vacuum distillation sloughs diluent, obtains alcohol-soluble polyurethane.Product of the present invention is being kept except original performance, more environmentally protective.
Description
Technical field
The invention belongs to polyurethane binder synthesis technical fields, and in particular to a kind of poly- ammonia of cured alcohol-soluble of ultraviolet light
Ester and preparation method thereof.
Background technology
Ultraviolet curing type adhesive for polyurethane is that polymerization occurs under action of ultraviolet light and causes urethane crosslinks curing
It obtains, compared with other types adhesive, ultraviolet curing type adhesive for polyurethane has lot of advantages：Hardening time is short, because
And labor productivity can be greatly improved；Solidification temperature is low, and object heated time is short, thus can be used for being not suitable for high-temperature baking
Material, such as timber, plastics；With good adhesive force, flexibility, lower temperature resistance etc..Thus in recent years, ultraviolet light curing
Type polyurethane adhesive develops quickly, has been widely used for multiple fields.
With the enhancing of people's environmental consciousness and the reasons such as rise in price of raw material, in recent years, environment-friendly type is gathered
The research of urethane adhesive gradually increases, such as aqueous polyurethane, alcohol-soluble polyurethane and no-solvent type adhesive for polyurethane
There is more progress.Alcohol-soluble polyurethane is exactly using alcohols（Ethyl alcohol etc.）What replacement adhesive for polyurethane used has
The harmful organic solvent of poison, for example use more ethyl acetate etc..
Ultraviolet curing type polyurethane is all organic solvent type at present, and there are no the ultraviolet curing type polyurethane of alcohol-soluble
Report.
Invention content
The purpose of the present invention is to provide cured alcohol-soluble polyurethanes of a kind of ultraviolet light and preparation method thereof, existing to substitute
There is the poisonous and hazardous organic solvent ultraviolet curing urethane used, product of the present invention is being kept except original performance, more
Add environmentally protective.
To achieve these goals, the technical solution adopted by the present invention is as follows：
The present invention provides a kind of cured alcohol-soluble polyurethanes of ultraviolet light, it is characterised in that it is made including the following raw material：It is low
It polymers polyalcohol, polyisocyanates, hydrophilic chain extender, small molecule chain extender, sealer, diluent, salt forming agent, solvent and urges
Agent.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the raw material that it includes following mass percent is made：
Oligomer polyol 5-50%
Polyisocyanates 5-20%
Hydrophilic chain extender 3-15%
Small molecule chain extender 5-20%
Sealer 1-5%
Diluent 1-3%
Salt forming agent 3-10%
Solvent 25-70%
Catalyst 0.2-1.0%.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the oligomer polyol is polybutadiene diol, gathers
Butadiene acrylonitrile copolymer glycols, castor oil, tetrahydrofuran oxidation propylene copolymer glycols, polypropylene oxide castor oil polyhydric alcohol,
Polyoxypropyleneglycol, polybutylene glyool adipate, gathers alcohol ester polyol in oneself, gathers oneself poly- carbonic acid hexylene glycol esterdiol
Naphthalate glycol or grafting Type of Collective object polyalcohol.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the polyisocyanates is six methine diisocyanates
Ester, toluene di-isocyanate(TDI), isophorone isocyanic acid, benzene dimethylene diisocyanate, isocyanatomethyl or two
Cyclohexyl-methane isocyanates.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the hydrophilic chain extender is diaminobenzoic acid, two
Hydroxyl half ester, dihydromethyl propionic acid, dimethylolpropionic acid, N methyldiethanol amine, amino acid or maleic anhydride.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the chain extender is trimethylolpropane, butanediol, second
Diamines, ethylenediamine, epoxy resin, modified epoxy, acryloyloxyethyl isocyanate or methylacryoyloxyethyl isocyanide
Acid esters.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the sealer is methanol, ethyl alcohol, propyl alcohol, isopropanol,
N-butanol, isobutanol, amylalcohol, hydroxy-ethyl acrylate, hydroxyethyl methacrylate or pentaerythritol triacrylate.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the diluent is acetone, butanone, dioxane, two
Methylformamide or methyl cellosolve.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the salt forming agent is sodium hydroxide, triethylamine, ammonium hydroxide or
Diethylamine.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the solvent is methanol, ethyl alcohol, propyl alcohol, isopropanol, just
Butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol or amylalcohol.
According to the above-mentioned cured alcohol-soluble polyurethane of ultraviolet light, the catalyst is dibutyl tin laurate, octanoic acid
Stannous, iron octoate, zinc naphthenate or tetrabutyl titanate.
The preparation method of the cured alcohol-soluble polyurethane of the ultraviolet light, includes the following steps：
（1）, under stirring, the oligomer polyol for first weighing mass fraction 5-50% is added in being passed through in the reactor of nitrogen, Yu Wen
110-115 DEG C of dehydration 1-2h of degree, then weighs the polyisocyanates of mass fraction 5-20% and partial amount mass fraction 0.2- successively
1.0% catalyst is added in reactor, in 50-80 DEG C of reaction 2-4h of temperature, wherein-NCO is 0.7-30 with-OH molar ratios；
（2）, under stirring, weigh the hydrophilic chain extender of mass fraction 5-15% and the diluent of mass fraction 1-3% add in reaction
In device, 1-3h is reacted, the sealer for then weighing mass fraction 1-5% is added in reactor, is reacted at 60-65 DEG C of temperature
0.5-1h, the catalyst of small molecule chain extender and surplus mass fraction 0.2-1.0% for then weighing mass fraction 5-20% add in
Into reactor, reaction solution b is obtained in 80-110 DEG C of reaction 0.5-1h of temperature；
（3）, under stirring, the salt forming agent for weighing mass fraction 3-10% is added in reaction solution b, in 30-50 DEG C of reaction 10-30 of temperature
Minute, then in the solvent for being added with stirring mass fraction 25-70% that rotating speed is 800-1000rpm, 0.5-1h is stirred to react,
Solution is obtained, vacuum distillation sloughs diluent, obtains alcohol-soluble polyurethane.
Step（1）Described in-NCO and-OH molar ratios be 0.8-0.95.
Compared with prior art, beneficial effects of the present invention：
1. the present invention carries the double bond structure living for dialling hydrogen due to being introduced in the segment of polyurethane, can be in the work of ultraviolet light
Polymerization occurs so that urethane crosslinks cure with lower, this alcohol-soluble polyurethane for allowing for the present invention keeps general UV light
The advantages of changing adhesive for polyurethane, if hardening time is short, low grade of solidification temperature etc..
2. the cured alcohol-soluble polyurethane of ultraviolet light of the present invention introduces hydrophilic chain extender in segment, this just makes
The cured alcohol-soluble polyurethane of ultraviolet light can be relatively easy to and be dissolved in alcohols solvent, form alcohol-soluble polyurethane.Also it is exactly
Since alcohol-soluble polyurethane introduces hydrophilic chain extender in segment so that the poly- ammonia of the cured alcohol-soluble of ultraviolet light of the invention
Ester can easily adjust solid content using alcohols solvent, to adapt to the needs of actual production.
3. since the cured alcohol-soluble polyurethane of ultraviolet light of the present invention makees solvent using alcohols, evaporation rate is fast, more
It is suitable in practical application.So ultraviolet light of the invention cured alcohol-soluble polyurethane set ultraviolet curing urethane
And the advantages of alcohol-soluble polyurethane, it is the environment-friendly product that a kind of curing rate is fast, solidification temperature is low, cohesive force is good.
Description of the drawings
Fig. 1 is the schematic diagram of the preparation method of the cured alcohol-soluble polyurethane of ultraviolet light of the present invention；
Fig. 2 is the dried infrared spectrogram of the cured alcohol-soluble polyurethane of ultraviolet light prepared by embodiment 1.
Specific embodiment
Here is the synthesis example of the present invention, but the invention is not limited in following examples.
First enumerate raw material involved in the embodiment of the present invention：
Polyoxypropyleneglycol（PPG）, dicyclohexyl methyl hydride isocyanates（HMDI）, isophorone diisocyanate（IPDI）, first
Phenylene diisocyanate（TDI）, dihydromethyl propionic acid（DMPA）, dimethylolpropionic acid（DMBA）, methanol, butanol, acrylic acid hydroxyl second
Ester, epoxy resin, triethylamine（TEA）, dibutyl tin laurate, stannous octoate.
The preparation method of the cured alcohol-soluble polyurethane of ultraviolet light includes the following steps：
（1）, under stirring, the oligomer polyol for first weighing mass fraction 5-50% is added in being passed through in the reactor of nitrogen, Yu Wen
110-115 DEG C of dehydration 1-2h of degree, then weighs the polyisocyanates of mass fraction 5-20% and partial amount mass fraction 0.2- successively
1.0% catalyst is added in reactor, in 50-80 DEG C of reaction 2-4h of temperature, wherein-NCO is 0.7-30 with-OH molar ratios；
（2）, under stirring, weigh the hydrophilic chain extender of mass fraction 5-15% and the diluent of mass fraction 1-3% add in reaction
In device, 1-3h is reacted, the sealer for then weighing mass fraction 1-5% is added in reactor, is reacted at 60-65 DEG C of temperature
0.5-1h, the catalyst of small molecule chain extender and surplus mass fraction 0.2-1.0% for then weighing mass fraction 5-20% add in
Into reactor, reaction solution b is obtained in 80-110 DEG C of reaction 0.5-1h of temperature；
（3）, under stirring, the salt forming agent for weighing mass fraction 3-10% is added in reaction solution b, in 30-50 DEG C of reaction 10-30 of temperature
Minute, then in the solvent for being added with stirring mass fraction 25-70% that rotating speed is 800-1000rpm, 0.5-1h is stirred to react,
Solution is obtained, vacuum distillation sloughs diluent, obtains alcohol-soluble polyurethane.
Embodiment 1
Add polyoxypropyleneglycol 240g in 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device,
110 DEG C of dehydration 2h, weigh dicyclohexyl methyl hydride isocyanates（HMDI）98.25g, dibutyl tin laurate 1.2g, which are added in, to be burnt
Bottle, 70 DEG C of reaction 2h, is subsequently added into dihydromethyl propionic acid（DMPA）18g, acetone 6g, 70 DEG C of reaction 2h weigh methanol 6g additions
Flask, 60 DEG C of reaction 0.5h, then weighs epoxy resin 30g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to burning
Bottle, 85 DEG C of reaction 0.5h, is then cooled to rapidly 45 DEG C, triethylamine 18g is added under the rotating speed of 800r/min, react 20 minutes
Afterwards, ethyl alcohol 183g is added in, stirs evenly, obtains alcoholic solution, acetone is sloughed into acquired solution vacuum distillation and is gathered to get to alcohol-soluble
Urethane solution product.
Test method is as follows：
The preparation of glued membrane：The alcohol-soluble polyurethane solution prepared according to different formulations is positioned in surface plate, is positioned over baking oven
Within, 60 DEG C of dryings to constant weight are then placed within spare in drying box.
The measure of NCO content：It is measured using di-n-butylamine method.The specific steps are：3 grams of samples are sampled in conical flask
In, 15mL toluene solutions and 5mL di-n-butylamine solution are added in, stands 15min, 50mL ethyl alcohol is added in pipette, uses 0.5mol/
The HCl-C of L2H5OH solution titrates.Calculation formula is：
W%=[(V0-VS)*C*42/(1000m)]*100%V0：Quota of expenditure HCl solution volume, Unit/mL during blank titration；Vs：
Titrate sample solution quota of expenditure HCl solution volume, Unit/mL；C：HCl solution concentration, unit mol/L；42：Mole matter of NCO
Amount, unit g/mol；m：Sample quality, unit g.
Solubility property is tested：Solution obtained is poured into the beaker of water white transparency, visually observed after stirring evenly.
Infrared spectrum measurement：The PerkinElmer 1000PC type examination of infrared spectrum produced using Perkinelmer Inc.
Instrument is tested.
The measure of peeling force：Polyurethane solutions prepared by the present invention are coated on support, after 70 DEG C of dryings, with pleasure
The flexible photosensitive resin layer that the thickness of triumphant group's production is 1.70mm is compound, uses Jiangsu Tai Yi groups flexibility platemaking machine 365nm
Ultraviolet photoetching 5 minutes, the BLD-200S electron detachment testing machines then produced using Labthink Instruments Co., Ltd.
Measure peeling force.
Fig. 2 is the infrared spectrogram of test gained after polyurethane solutions drying prepared in the present embodiment.
By Fig. 2 it can be seen that, 3323cm-1For the stretching vibration absworption peak of N-H keys, 2927cm-1、2853cm-1For CH2、CH
The stretching vibration absworption peak of key, 1099cm-1For the stretching vibration absworption peak of C-O-C keys, and 2270cm-1Left and right has no NCO absorptions
Peak, 1698cm-1For the stretching vibration absworption peak of ester carbonyl group key, and 830~910cm-1The absorption peak for having no epoxy group occurs, this
All show that isocyanate groups react away completely a bit, synthesized polyurethane, and function is connected on the segment of polyurethane
Property group.
Embodiment 2
Add polyoxypropyleneglycol 300g in 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device,
110 DEG C of dehydration 2h, weigh isophorone diisocyanate（IPDI）30g, dibutyl tin laurate 6g add in flask, 70 DEG C of reactions
2h is subsequently added into dihydromethyl propionic acid（DMPA）20g, acetone 8g, 70 DEG C of reaction 2h, weigh methanol 10g and add in flask, 60 DEG C instead
0.5h is answered, then weighs epoxy resin 30g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to flask, 85 DEG C of reactions
Then 0.5h is cooled to rapidly 45 DEG C, triethylamine 20g is added under the rotating speed of 800r/min, and reaction after twenty minutes, adds in ethyl alcohol
176g is stirred evenly, and obtains alcoholic solution, and acquired solution vacuum distillation is sloughed acetone to get to polyurethane solutions product.
Embodiment 3
In 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device plus polyoxypropyleneglycol 36g, 110
DEG C dehydration 2h, weigh dicyclohexyl methyl hydride isocyanates（HMDI）100g, dibutyl tin laurate 3g add in flask, and 70 DEG C anti-
2h is answered, is subsequently added into dimethylolpropionic acid（DMBA）90g, acetone 10g, 70 DEG C of reaction 2h weigh methanol 30g and add in flask, and 60
DEG C reaction 0.5h, then weighs epoxy resin 120g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to flask, 85 DEG C
0.5h is reacted, is then cooled to 45 DEG C rapidly, triethylamine 30g is added under the rotating speed of 800r/min, reaction after twenty minutes, adds in
Ethyl alcohol 181g, stirs evenly, and obtains alcoholic solution, and acquired solution vacuum distillation is sloughed acetone to get to polyurethane solutions product.
Embodiment 4
In 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device plus polyoxypropyleneglycol 30g, 110
DEG C dehydration 2h, weigh dicyclohexyl methyl hydride isocyanates（HMDI）120g, dibutyl tin laurate 6g add in flask, and 70 DEG C anti-
2h is answered, is subsequently added into dimethylolpropionic acid（DMBA）90g, acetone 18g, 70 DEG C of reaction 2h weigh methanol 30g and add in flask, and 60
DEG C reaction 0.5h, then weighs epoxy resin 96g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to flask, 85 DEG C anti-
0.5h is answered, is then cooled to 45 DEG C rapidly, triethylamine 60g is added under the rotating speed of 800r/min, reaction after twenty minutes, adds in second
Alcohol 150g, stirs evenly, and obtains alcoholic solution, and acquired solution vacuum distillation is sloughed acetone to get to polyurethane solutions product.
Embodiment 5
Add polyoxypropyleneglycol 286g in 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device,
110 DEG C of dehydration 2h, weigh dicyclohexyl methyl hydride isocyanates（HMDI）30g, dibutyl tin laurate 5g addition flask, 70 DEG C
2h is reacted, is subsequently added into dihydromethyl propionic acid（DMPA）20g, acetone 10g, 70 DEG C of reaction 2h weigh methanol 8g and add in flask, and 60
DEG C reaction 0.5h, then weighs epoxy resin 30g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to flask, 85 DEG C anti-
0.5h is answered, is then cooled to 45 DEG C rapidly, triethylamine 18g is added under the rotating speed of 800r/min, reaction after twenty minutes, adds in second
Alcohol 193g, stirs evenly, and obtains alcoholic solution, and acquired solution vacuum distillation is sloughed acetone to get to polyurethane solutions product.
Embodiment 6
Add polyoxypropyleneglycol 300g in 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device,
110 DEG C of dehydration 2h, weigh dicyclohexyl methyl hydride isocyanates（HMDI）37.5g, dibutyl tin laurate 5g addition flask, 70
DEG C reaction 2h, be subsequently added into dihydromethyl propionic acid（DMPA）30g, acetone 10g, 70 DEG C of reaction 2h weigh methanol 5g addition flasks,
60 DEG C of reaction 0.5h, then weigh epoxy resin 30g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to flask, 85 DEG C
0.5h is reacted, is then cooled to 45 DEG C rapidly, triethylamine 18g is added under the rotating speed of 800r/min, reaction after twenty minutes, adds in
Ethyl alcohol 164.5g, stirs evenly, and obtains alcoholic solution, and acquired solution vacuum distillation is sloughed acetone and is produced to get to polyurethane solutions
Product.
Embodiment 7
In 1000 mL are with the flask of temperature control heating, mechanical agitation and nitrogen protection device plus polyoxypropyleneglycol 30g, 110
DEG C dehydration 2h, weigh dicyclohexyl methyl hydride isocyanates（HMDI）70g, dibutyl tin laurate 2g add in flask, and 70 DEG C anti-
2h is answered, is subsequently added into dihydromethyl propionic acid（DMPA）18g, acetone 6g, 70 DEG C of reaction 2h weigh methanol 6g and add in flask, 60 DEG C
0.5h is reacted, then weighs epoxy resin 30g, dibutyl tin laurate 2 drips, stannous octoate 1 is added dropwise to flask, 85 DEG C of reactions
Then 0.5h is cooled to rapidly 45 DEG C, triethylamine 18g is added under the rotating speed of 800r/min, and reaction after twenty minutes, adds in ethyl alcohol
420g is stirred evenly, and obtains alcoholic solution, and acquired solution vacuum distillation is sloughed acetone to get to polyurethane solutions product.
According to the polyurethane alcoholic solution performance obtained by above-mentioned different formula, test result is as follows shown in table 1：
It can see as the test data shown in above table：Embodiment 1,2,3,4,5,6 and 7 can be dissolved in ethyl alcohol
In.By testing isocyanate group（NCO）Content, it is recognised that the isocyanate group quilt of polyurethane prepared by each example
It reacts away, while again by the analysis of infrared spectrum, it is known that reaction has synthesized polyurethane, and ethyl alcohol can be dissolved in and form alcohol
Soluble polyurethane solution.The peeling force that can further be seen that embodiment 6 from the test data of above table can reach 30 (N/
2cm）, can be used for printing flexible resin plates and other industry.
Claims (13)
1. a kind of cured alcohol-soluble polyurethane of ultraviolet light, it is characterised in that it is made including the following raw material：Oligomer polyol,
Polyisocyanates, hydrophilic chain extender, small molecule chain extender, sealer, diluent, salt forming agent, solvent and catalyst.
2. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that it includes following quality hundred
The raw material of ratio is divided to be made：
Oligomer polyol 5-50%
Polyisocyanates 5-20%
Hydrophilic chain extender 3-15%
Small molecule chain extender 5-20%
Sealer 1-5%
Diluent 1-3%
Salt forming agent 3-10%
Solvent 25-70%
Catalyst 0.2-1.0%.
3. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The oligomer polyol
Propylene copolymer glycols, polyoxygenated are aoxidized for polybutadiene diol, Polybutadiene Acrylonitrile copolymer glycols, castor oil, tetrahydrofuran
Propylene castor oil polyhydric alcohol, poly- carbonic acid hexylene glycol esterdiol, polybutylene glyool adipate, gathers oneself at polyoxypropyleneglycol
Interior alcohol ester polyol, polyethylene glycol adipate glycol or grafting Type of Collective object polyalcohol.
4. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The polyisocyanates is
Hexamethylene-diisocyanate, toluene di-isocyanate(TDI), isophorone isocyanic acid, benzene dimethylene diisocyanate, methyl ring
Hexyl isocyanates or dicyclohexyl methyl hydride isocyanates.
5. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The hydrophilic chain extender
For diaminobenzoic acid, dihydroxy half ester, dihydromethyl propionic acid, dimethylolpropionic acid, N methyldiethanol amine, amino acid or horse
Carry out acid anhydrides.
6. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The chain extender is three hydroxyls
Methylpropane, butanediol, ethylenediamine, ethylenediamine, epoxy resin, modified epoxy, acryloyloxyethyl isocyanate or first
Base acryloyloxyethyl isocyanate.
7. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The sealer is first
Alcohol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, hydroxy-ethyl acrylate, hydroxyethyl methacrylate or Ji Wusi
Alcohol triacrylate.
8. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The diluent is third
Ketone, butanone, dioxane, dimethylformamide or methyl cellosolve.
9. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The salt forming agent is hydrogen-oxygen
Change sodium, triethylamine, ammonium hydroxide or diethylamine.
10. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The solvent for methanol,
Ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol or amylalcohol.
11. the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that：The catalyst is two
Dibutyl tin laurate, stannous octoate, iron octoate, zinc naphthenate or tetrabutyl titanate.
12. the preparation method of the cured alcohol-soluble polyurethane of ultraviolet light according to claim 1, it is characterised in that including with
Lower step：
（1）, under stirring, the oligomer polyol for first weighing mass fraction 5-50% is added in being passed through in the reactor of nitrogen, Yu Wen
110-115 DEG C of dehydration 1-2h of degree, then weighs the polyisocyanates of mass fraction 5-20% and partial amount mass fraction 0.2- successively
1.0% catalyst is added in reactor, in 50-80 DEG C of reaction 2-4h of temperature, wherein-NCO is 0.7-30 with-OH molar ratios；
（2）, under stirring, weigh the hydrophilic chain extender of mass fraction 5-15% and the diluent of mass fraction 1-3% add in reaction
In device, 1-3h is reacted, the sealer for then weighing mass fraction 1-5% is added in reactor, is reacted at 60-65 DEG C of temperature
0.5-1h, the catalyst of small molecule chain extender and surplus mass fraction 0.2-1.0% for then weighing mass fraction 5-20% add in
Into reactor, reaction solution b is obtained in 80-110 DEG C of reaction 0.5-1h of temperature；
（3）, under stirring, the salt forming agent for weighing mass fraction 3-10% is added in reaction solution b, in 30-50 DEG C of reaction 10-30 of temperature
Minute, then in the solvent for being added with stirring mass fraction 25-70% that rotating speed is 800-1000rpm, 0.5-1h is stirred to react,
Solution is obtained, vacuum distillation sloughs diluent, obtains alcohol-soluble polyurethane.
13. the preparation method of the cured alcohol-soluble polyurethane of ultraviolet light according to claim 12, it is characterised in that：Step
（1）Described in-NCO and-OH molar ratios be 0.8-0.95.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133505A (en) * | 2021-12-30 | 2022-03-04 | 盐城工学院 | Preparation method of photochromic film |
| CN114539505A (en) * | 2022-01-18 | 2022-05-27 | 威斯坦(厦门)实业有限公司 | Amino acid modified waterborne polyurethane acrylate and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230125A (en) * | 2008-02-29 | 2008-07-30 | 安徽大学 | Water-soluble alcohol-soluble polyurethane and preparation method thereof |
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2016
- 2016-12-14 CN CN201611155816.7A patent/CN108219093A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230125A (en) * | 2008-02-29 | 2008-07-30 | 安徽大学 | Water-soluble alcohol-soluble polyurethane and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133505A (en) * | 2021-12-30 | 2022-03-04 | 盐城工学院 | Preparation method of photochromic film |
| CN114539505A (en) * | 2022-01-18 | 2022-05-27 | 威斯坦(厦门)实业有限公司 | Amino acid modified waterborne polyurethane acrylate and preparation method thereof |
| CN114539505B (en) * | 2022-01-18 | 2023-11-03 | 威斯坦(厦门)实业有限公司 | Amino acid modified waterborne polyurethane acrylate and preparation method thereof |
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