CN106832266B - A kind of aqueous polyurethane and UV-curable waterborne polyurethane coating and preparation method thereof - Google Patents
A kind of aqueous polyurethane and UV-curable waterborne polyurethane coating and preparation method thereof Download PDFInfo
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- CN106832266B CN106832266B CN201710104011.8A CN201710104011A CN106832266B CN 106832266 B CN106832266 B CN 106832266B CN 201710104011 A CN201710104011 A CN 201710104011A CN 106832266 B CN106832266 B CN 106832266B
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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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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- 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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Abstract
The application belongs to technical field of polymer, and in particular to a kind of aqueous polyurethane and UV-curable waterborne polyurethane and preparation method thereof.Aqueous polyurethane provided by the present invention be a kind of non-isocyanate based polyurethanes, the isocyanate group without high toxicity and high wet sensitive, no pollution to the environment, to human health fanout free region, nonflammable, safety is good.The present invention, as Water-borne modification group, can also keep stable under certain acid condition using sulfonate groups, and not need that tertiary amine compounds are added, and have no irritating odor, and have higher cohesive force, water resistance, heat resistance than carboxylic acid type aqueous polyurethane；Meanwhile the cyclic carbonate ester class compound that the present invention uses has many advantages, such as higher boiling, low smell, low evaporation rate and low toxicity, and biological degradability is excellent, the raw material using carbon dioxide as cyclic carbonate ester, it is environmentally protective.
Description
Technical field
The invention belongs to technical field of polymer, and in particular to a kind of aqueous polyurethane and UV-curable waterborne polyurethane
Coating and preparation method thereof.
Background technique
Ultraviolet curing urethane is a kind of energy-saving material, and photochemical reaction occurs after by ultraviolet light in it,
So as to cause polymerization, crosslinking, its moment is made to become solid-state by liquid.UV-curable waterborne polyurethane is with water instead of organic molten
New polyurethane system of the agent as decentralized medium, because of its pollution-free, safe and reliable, good mechanical performance, compatibility is good, is easy to
It the advantages that modified, has a wide range of applications in coating and adhesive area.
For most of aqueous polyurethane using carboxylate as hydrophilic radical, preparation method is mostly to use diisocyanate at present
Ester and polyester or polyether polyol react to obtain the lesser isocyanate terminated base polyurethane prepolymer of molecular weight, are added contain carboxylic later
The polyalcohol of base, which carries out chain extension, to be made to contain carboxyl on polyurethane molecular, and polyalcohol containing carboxyl is usually 2,2- dihydromethyl propionic acid,
Carboxyl is finally neutralized into salt using the amines such as triethylamine small molecule and is quickly dispersed in water to obtain the aqueous poly- ammonia of carboxylic acid type
Ester.However, such polyurethane is isocyanate terminated polyurethane, wherein including a large amount of free isocyanate, in construction and material
In solidification process, part free isocyanate is evaporated, especially the substances such as toluene di-isocyanate(TDI), can be detrimental to health
With pollution environment.Meanwhile carboxylic acid type aqueous polyurethane stability is poor, can make in acid condition carboxylic acid combination hydrogen from
Son causes hydrophily to weaken and emulsifiability decline.
Summary of the invention
In view of this, a kind of the purpose of the present invention is to provide stability good, harmless, environmentally protective aqueous purple
Outer light-cured polyurethane and preparation method thereof and coating.
The specific technical solution of the present invention is as follows:
The present invention provides a kind of aqueous polyurethanes, have the structure as shown in formula I:
Wherein, R1Selected from-H ,-OH ,-OCH3, phenyl, C1~12Alkyl or C1~12Alkenyl；
R2It is selected fromOne or both of；
R3It is selected from
R4It is selected from
R5And R6It is independently selected from-H or C1~12Alkyl；
N=1~20.
The present invention also provides a kind of preparation methods of above-mentioned aqueous polyurethane, comprising:
A) under nitrogen or inert gas, cyclic carbonate ester class compound and aminated compounds is reacted, obtain first
Reaction intermediate；
B) it is carried out under the conditions of the first reaction intermediate and Sulfonates compound that step a) is obtained are existing for the catalyst
Reaction, obtains the second reaction intermediate；
C) it is carried out under the conditions of step b) is obtained the second reaction intermediate and acrylic compounds are existing for the polymerization inhibitor
Reaction, obtains the aqueous polyurethane with structure shown in formula I.
Preferably, inert gas described in step a) includes helium and argon gas；
The cyclic carbonate ester class compound is ethylene carbonate, 1- methoxyl group-ethylene carbonate or propene carbonate.
Preferably, aminated compounds described in step a) is diamine；
The diamine is polyetheramine D-400, polyetheramine D-2000 or isophorone diamine.
Preferably, Sulfonates compound described in step b) is 5-sodium sulfo isophthalate；
The catalyst is 4-dimethylaminopyridine or dicyclohexylcarbodiimide；
The additive amount of the catalyst is the 0.3%~0.7% of the Sulfonates compound gross mass.
Preferably, acrylic compounds described in step c) are methacrylic acid or glycidyl methacrylate；
The polymerization inhibitor is p-hydroxyanisole, hydroquinone or 2,6 di tert butyl 4 methyl phenol；
The additive amount of the polymerization inhibitor is 80~120ppm of the acrylic compounds gross mass.
Preferably, the cyclic carbonate ester class compound, aminated compounds, Sulfonates compound and acrylic compounds
Molar ratio be (2~2.5): 1:(0.5~1): 1.
The present invention also provides a kind of UV-curable waterborne polyurethane coating, comprising above-mentioned aqueous polyurethane and/or on
State aqueous polyurethane, photoinitiator and water that preparation method obtains.
Preferably, the photoinitiator be aryl alkyl ketone, benzophenone, heterocycle arone class, aryl diazonium salts or
Iodine salt compounds；
The additive amount of the photoinitiator is the 0.05%~0.15% of the aqueous polyurethane gross mass.
The additive amount of the water is the 10%~60% of the aqueous polyurethane gross mass.
The present invention also provides a kind of preparation method of above-mentioned UV-curable waterborne polyurethane coating, are as follows: it will be aqueous poly-
Urethane, photoinitiator and water mixing；
Described be mixed into stirs 1h at 350rpm.
Compared with prior art, aqueous polyurethane provided by the present invention is a kind of novel poly- ammonia of non-isocyanate base
Ester, the isocyanate group without high toxicity and high wet sensitive, no pollution to the environment, to human health fanout free region；It prepared at it
Cheng Zhong, the present invention, as Water-borne modification group, can keep stable using sulfonate groups in acid condition, and without using
Tertiary amine compounds have no irritating odor, and have higher cohesive force, water resistance, heat resistance than carboxylic acid type aqueous polyurethane；Together
When, the cyclic carbonate ester class compound of use has many advantages, such as higher boiling, low smell, low evaporation rate and low toxicity, and biological degradability
Excellent, using carbon dioxide as cyclic carbonate ester raw material, it is environmentally protective.UV-curable waterborne provided by the present invention is poly-
Urethane coating is free of any reactive diluent, and nonflammable, safety is good, optimum preparation condition, and reaction conversion ratio is high, selects
Property strong, safe preparation process cleaning.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the nuclear magnetic resonance spectroscopy for the aqueous polyurethane that embodiment 1 obtains；
Fig. 2 is the infrared spectroscopy for the aqueous polyurethane that embodiment 1 obtains.
Specific embodiment
In order to overcome existing aqueous polyurethane stability difference and containing the isocyanate group with high toxicity and high wet sensitive
Problem, a kind of the present invention provides stability good, harmless, environmentally protective aqueous polyurethane and UV-curable waterborne
Polyurethane coating and preparation method thereof.
The present invention provides a kind of aqueous polyurethanes with the molecular structure as shown in formula I:
Wherein, R1Selected from-H ,-OH ,-OCH3, phenyl, C1~12Alkyl or C1~12Alkenyl, preferably-H, C1~8Alkyl or C1~8
Alkenyl is further preferably-H and-CH3, most preferably-CH3；
R2It is selected from
R3 is selected from
R4 is selected from
R5And R6It is independently selected from-H or C1~12Alkyl；
N=1~20.
In the present invention, the alkyl includes 1~12 carbon atom or 1~8 carbon atom or 1~6 carbon atom, or
The univalence hydrocarbyl of 1~4 carbon atom or 1~2 carbon atom, wherein alkyl can be individually optionally by this one or more hair
Replaced bright described substituent group.The further example of alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl
It is base, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, 2- amyl, 3- amyl, 2- methyl -2- butyl, n-heptyl, just pungent
Base etc..Term " alkyl " uses here, indicates from straight chain, branch or cricoid saturated carbon chains.
The present invention also provides a kind of preparation methods of above-mentioned aqueous polyurethane, comprising:
A) under nitrogen or inert gas, cyclic carbonate ester class compound and aminated compounds is reacted, obtain first
Reaction intermediate；
B) it is carried out under the conditions of the first reaction intermediate and Sulfonates compound that step a) is obtained are existing for the catalyst
Reaction, obtains the second reaction intermediate；
C) it is carried out under the conditions of step b) is obtained the second reaction intermediate and acrylic compounds are existing for the polymerization inhibitor
Reaction, obtains the aqueous polyurethane.
Further, inert gas described in step a) includes helium and argon gas；
The cyclic carbonate ester class compound is preferably ethylene carbonate, 1- methoxyl group-ethylene carbonate or propene carbonate,
It is further preferably ethylene carbonate and propene carbonate, more preferably propene carbonate.
Further, aminated compounds described in step a) is diamine；
The diamine is polyetheramine D-400, polyetheramine D-2000 or isophorone diamine.
The mixed proportion that the present invention arranges in pairs or groups when using to diamine without specifically limited, according to the needs of practical condition into
Row mixing.
Further, Sulfonates compound described in step b) is preferably 5-sodium sulfo isophthalate.
Further, the catalyst is 4-dimethylaminopyridine or dicyclohexylcarbodiimide.
Further, the additive amount of the catalyst is the 0.3%~0.7% of the Sulfonates compound gross mass.
Further, acrylic compounds described in step c) are preferably that methacrylic acid or Glycidyl methacrylate are sweet
Grease, more preferably methacrylic acid or glycidyl methacrylate.
Further, the polymerization inhibitor be p-hydroxyanisole, hydroquinone or 2,6- di-tert-butyl-4-methy phenol,
Preferably p-hydroxyanisole (MEHQ).
Further, the additive amount of the polymerization inhibitor is 80~120ppm of the acrylic compounds gross mass.
Further, the cyclic carbonate ester class compound, aminated compounds, Sulfonates compound and acrylic compounds chemical combination
The molar ratio of object is preferably (2~2.5): 1:(0.5~1): 1, more preferably 2:1:1:1.
The present invention does not make special limitation to the preparation process condition of above-mentioned aqueous polyurethane, and those skilled in the art can be used
Technological means known to member is adjusted its process conditions according to practical condition.In the present invention, with ring carbon acid propylene
For ester (PC), the preparation of the aqueous polyurethane preferably step in detail below:
(1) PC of 2mol is added in three-necked flask, heating is stirred with the speed of 300~1000rpm under nitrogen protection
To 100 DEG C~150 DEG C, then dropped evenly in 0.5~1h into 1mol isophorone diamine or polyetheramine D-400 or its mixing
Object, 3~5h of insulation reaction obtain transparent first reaction intermediate；Wherein, which is a kind of pale yellow transparent
Liquid non-isocyanate based polyurethanes (NIPU), have the following structure:
(2) when the first reaction intermediate is cooled to 90 DEG C~120 DEG C, catalyst 4-dimethylaminopyridine and isophthalic is added
Dioctyl phthalate -5- sodium sulfonate is warming up to 120 DEG C with the speed of 300~1000rpm after mixing evenly, vacuumizes 3~5h of reaction, obtain
To the second reaction intermediate；Wherein, the second reaction intermediate is a kind of non-isocyanate base water polyurethane of white " milky ", tool
Just like flowering structure:
(3) it when the second reaction intermediate is cooled to 80 DEG C~100 DEG C, is slowly added dropwise in 30~40 minutes into methyl-prop
The mixture of olefin(e) acid or glycidyl methacrylate and polymerization inhibitor, is stirred to react 2h, obtains the aqueous polyurethane.
Non-isocyanate based polyurethanes (NIPU) are a kind of special polyurethane, and raw material is not needed using being more toxic
Isocyanates, the characteristic with safety and stability, each carbamate groups generated relative to traditional polyurethane, NIPU
A hydroxyl being connected with its β carbon atom is all had, hydrogen atom and the carbonylic oxygen atom in-NHCOO- group of the hydroxyl can
To form intramolecular hydrogen bond, becomes a stable hexatomic ring due to forming tautomeric resonant structure in ring and cause electricity
Son is reallocated, to keep six-membered ring structure highly stable.And since the presence of this hydrogen bond plays closing carbamate groups
The effect of ketonic oxygen in group, improves its hydrolytic stability, and the weak bonding structure of conventional urethane is compensated for from molecular structure, is mentioned
High chemical-resistant and permeability resistance.
Synthesis non-isocyanate route mainly includes open loop route, diamines and bischloroformate reaction route, amino and more
First alcohol exchanges polycondensation route, wherein intramolecular hydrogen bond can be formed after cyclic carbonate ester and diamine reactant, prepare it is green, non-porous,
There is potential application in terms of water insensitive PU, and cyclic carbonate ester can be dissolved in most of organic solvent, can be used as titanium dioxide
Absorbent carbon, water-soluble dye and dispersing agent of pigment etc..Industrially take propylene oxide and carbon dioxide under a certain pressure
Addition, then vacuum distillation be made, while the cyclic carbonate ester of low molecular weight have higher boiling, smell, evaporation rate and toxicity compared with
It is low, the good advantage of biological degradability.Carbon dioxide is carbon source cheap and abundant, utilizes carbon dioxide as the original of cyclic carbonate ester
Material can recycle carbon dioxide, reduce carbon dioxide content in atmosphere, this not only conforms with environmental requirement, and be also real
One of the approach of existing green production.
In the present invention, using sulfonate groups as hydrophilic radical, because it is strong electrolyte, between hydrophilic radical
Electrostatic repulsion it is larger so that Zeta point between latex particle is bigger than normal to can be obtained more stable and more large arch dam aqueous poly- ammonia
Ester；Simultaneously as not needing that aminated compounds is added, sulfonate type aqueous polyurethane does not have irritating amine taste, has opposite yet
High water resistance, heat resistance.
The present invention also provides a kind of UV-curable waterborne polyurethane coating, comprising above-mentioned aqueous polyurethane and/or on
State aqueous polyurethane, photoinitiator and water that preparation method obtains.
Further, the photoinitiator be aryl alkyl ketone, benzophenone, heterocycle arone class, aryl diazonium salts or
Iodine salt compounds.
The present invention does not make special limitation to the source of photoinitiator, using well-known to those skilled in the art light-initiated
Agent, such as commercial source.In the present invention, used photoinitiator is preferably photoinitiator 819 and photoinitiator ITX.
Wherein, entitled bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl of Chinese of photoinitiator 819, in photoinitiator ITX
Literary fame is isopropyl thioxanthone.
Further, the additive amount of the photoinitiator be the aqueous polyurethane gross mass 0.05%~
0.15%；
The additive amount of the water is the 10%~60% of the aqueous polyurethane gross mass.
The present invention also provides the preparation method of above-mentioned UV-curable waterborne polyurethane coating, are as follows: it will be above-mentioned aqueous poly-
Urethane, photoinitiator and water mixing.
The present invention does not make special restriction to the preparation method of the UV-curable waterborne polyurethane coating, using ability
Technological means known to field technique personnel.In the present invention, temperature is controlled at 50~60 DEG C, into aqueous polyurethane
Photoinitiator is added, continues to be stirring evenly and then adding into deionized water with the speed of 350rpm, continues high degree of agitation 1h, obtain yellow
The UV-curable waterborne polyurethane coating final product of transparence.
Technical solution of the present invention is clearly and completely described below in conjunction with the specific embodiment of the invention, it is clear that
Described embodiment is a part of the embodiment of the present invention, instead of all the embodiments.Those skilled in the art should manage
Solution, modifies to specific embodiments of the present invention or is replaced on an equal basis to some technical characteristics, without departing from the present invention
The spirit of technical solution should all cover in the scope of protection of the invention.
Embodiment 1
In the three-necked flask with blender, thermometer, it is added 21.44g PC (0.21mol), is passed through nitrogen for system
In air exclude and be heated to 100 DEG C, 17.03g isophorone diamine is then slowly added dropwise, insulation reaction 4h is obtained transparent
The first thick reaction intermediate.Then, the 4- dimethylamino of 13.41g 5-sodium sulfo isophthalate and 0.04g is added
Pyridine is warming up to 150 DEG C after mixing evenly, vacuumizes water removal, and insulation reaction 3h is obtained among the second reaction of white " milky "
Body.Then, be cooled to 100 DEG C, high degree of agitation, then be slowly added dropwise be mixed with 90ppm polymerization inhibitor MEHQ Glycidyl methacrylate it is sweet
It is dripped off in grease 10mL, 40min, insulation reaction 2h obtains a kind of aqueous polyurethane.
Finally, reaction temperature is down to 55 DEG C and by mixing speed control in 350rpm, 0.1g photoinitiator 819 is added,
It is stirring evenly and then adding into 55 DEG C of 15mL of deionized water, high degree of agitation 1h obtains the aquosity ultraviolet light of light yellow transparent liquid shape
Solidify polyurethane.
Embodiment 2
In the three-necked flask with blender, thermometer, it is added 21.44g PC (0.21mol), is passed through nitrogen for system
In air exclude and be heated to 150 DEG C, 41.24mL polyetheramine D-400 (0.1mol), insulation reaction 4h is then slowly added dropwise,
Obtain the first reaction intermediate of clear viscous shape.Then, the 4- of 13.41g 5-sodium sulfo isophthalate and 0.09g is added
Dimethylamino naphthyridine is warming up to 120 DEG C after mixing evenly, vacuumizes water removal, insulation reaction 3h, and obtain white " milky " second is anti-
Answer intermediate.Then, it is cooled to 100 DEG C, high degree of agitation, then the methacrylic acid for being mixed with 120ppm polymerization inhibitor MEHQ is slowly added dropwise
It is dripped off in 12mL, 30min, vacuum distillation removes unreacted monomer after being cooled to 80 DEG C of insulation reaction 2h, obtains a kind of aqueous
Polyurethane.
Finally, reaction temperature is down to 55 DEG C and by mixing speed control in 350rpm, 0.075g photoinitiator is added
ITX, is stirring evenly and then adding into 55 DEG C of 30mL of deionized water, and high degree of agitation 1h obtains the aqueous purple of light yellow transparent liquid shape
Outer light-cured polyurethane.
Embodiment 3
In the three-necked flask with blender, thermometer, it is added 21.44g PC (0.21mol), is passed through nitrogen for system
In air exclude and be heated to 130 DEG C, be then slowly added dropwise 11.0mL polyetheramine D-400's (0.04mol) and 16.5mL
IPDA (0.06mol), insulation reaction 4h obtain the first reaction intermediate of pale yellow transparent liquid.Then, it is added between 13.41g
The 4-dimethylaminopyridine of phthalic acid -5- sodium sulfonate and 0.04g is warming up to 120 DEG C after mixing evenly, vacuumizes water removal, protects
Temperature reaction 3h, obtains the second reaction intermediate of white " milky ".Then, it is cooled to 100 DEG C, high degree of agitation, then be slowly added dropwise mixed
It drips off in the methacrylic acid 8mL, 30min for having 100ppm polymerization inhibitor MEHQ, is evaporated under reduced pressure after being cooled to 80 DEG C of insulation reaction 2h
Unreacted monomer is removed, a kind of aqueous polyurethane is obtained.
Finally, reaction temperature is down to 55 DEG C and by mixing speed control in 350rpm, 0.061g photoinitiator is added
ITX, is stirring evenly and then adding into 55 DEG C of 50mL of deionized water, and high degree of agitation 1h obtains the aqueous of faint yellow translucent liquid shape
Ultraviolet curing urethane.
4 ultraviolet light solidity test of embodiment
The UV-curable waterborne aqueous polyurethane coating that Example 1~3 obtains respectively imports polytetrafluoroethylene (PTFE) in right amount
It in mold, is subsequently placed in 70 DEG C of baking ovens and dries 1h, then be placed under 300W ultraviolet lamp and solidify 30s, it is smooth surface can be formed
Coating is tested for the property, and light-cured performance test result as shown in Table 1 is obtained.
Table 1
| Embodiment | Curing time/s | Pencil hardness/H | Tensile strength/Mpa | Color |
| 1 | 120 | 3 | 5.2 | It is translucent light yellow |
| 2 | 60 | 2 | 4.3 | It is translucent light yellow |
| 3 | 30 | 4 | 6.5 | It is translucent light yellow |
The present invention also uses nuclear magnetic resonance and infrared progress to the UV-curable waterborne aqueous polyurethane that embodiment 1 obtains
Detection, as a result as depicted in figs. 1 and 2.
Claims (10)
1. a kind of aqueous polyurethane has the structure as shown in formula I:
Wherein, R1Selected from-H ,-OCH3Or C1~12Alkyl；
R2It is selected fromOne or both of；
R3It is selected from
R4It is selected from
N=1~20.
2. a kind of preparation method of aqueous polyurethane described in claim 1, comprising:
A) under nitrogen or inert gas, cyclic carbonate ester class compound and aminated compounds are reacted, obtain the first reaction
Intermediate；
B) it is reacted under the conditions of the first reaction intermediate and Sulfonates compound that step a) is obtained are existing for the catalyst,
Obtain the second reaction intermediate；
C) it is reacted under the conditions of step b) is obtained the second reaction intermediate and acrylic compounds are existing for the polymerization inhibitor,
Obtain the aqueous polyurethane with structure shown in formula I.
3. preparation method according to claim 2, which is characterized in that inert gas described in step a) includes helium and argon
Gas；
The cyclic carbonate ester class compound is ethylene carbonate, 1- methoxyl group-ethylene carbonate or propene carbonate.
4. preparation method according to claim 2, which is characterized in that aminated compounds described in step a) is diamine；
The diamine is polyetheramine D-400, polyetheramine D-2000 or isophorone diamine.
5. preparation method according to claim 2, which is characterized in that Sulfonates compound described in step b) is isophthalic
Dioctyl phthalate -5- sodium sulfonate；
The catalyst is 4-dimethylaminopyridine or dicyclohexylcarbodiimide；
The additive amount of the catalyst is the 0.3%~0.7% of the Sulfonates compound gross mass.
6. preparation method according to claim 2, which is characterized in that acrylic compounds described in step c) are methyl
Acrylic or methacrylic acid ethylene oxidic ester；
The polymerization inhibitor is p-hydroxyanisole, hydroquinone or 2,6 di tert butyl 4 methyl phenol；
The additive amount of the polymerization inhibitor is 80~120ppm of the acrylic compounds gross mass.
7. preparation method according to claim 2, which is characterized in that the cyclic carbonate ester class compound, aminated compounds,
The molar ratio of Sulfonates compound and acrylic compounds is (2~2.5): 1:(0.5~1): 1.
8. a kind of UV-curable waterborne polyurethane coating includes aqueous polyurethane described in claim 1 and/or claim
Aqueous polyurethane, photoinitiator and the water that preparation method described in 2 to 7 any one obtains.
9. UV-curable waterborne polyurethane coating according to claim 8, which is characterized in that the photoinitiator is virtue
Base alkyl ketone, benzophenone, heterocycle arone class, aryl diazonium salts or iodine salt compounds；
The additive amount of the photoinitiator is the 0.05%~0.15% of the aqueous polyurethane gross mass；
The additive amount of the water is the 10%~60% of the aqueous polyurethane gross mass.
10. the preparation method of UV-curable waterborne polyurethane coating described in a kind of claim 8 or 9, are as follows: by aqueous poly- ammonia
Ester, photoinitiator and water mixing；
Described be mixed into stirs 1h at 350rpm.
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| CN107586375B (en) * | 2017-10-30 | 2020-04-28 | 广东工业大学 | Water-soluble support material |
| CN109485848A (en) * | 2018-09-20 | 2019-03-19 | 中北大学 | A kind of aqueous polyureas of non-isocyanate and preparation method thereof |
| CN111848910B (en) * | 2020-08-05 | 2022-03-18 | 山东华诚高科胶粘剂有限公司 | Waterborne polyurethane prepared from sulfonated polycarbonate polyol containing amino ester bonds and preparation method thereof |
| CN111944138B (en) * | 2020-08-05 | 2022-03-18 | 山东华诚高科胶粘剂有限公司 | Sulfonated polycarbonate polyol containing amino ester bonds as well as preparation method and application thereof |
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| CN114773307B (en) * | 2022-05-18 | 2024-01-26 | 中国科学院兰州化学物理研究所 | Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof |
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| CN101775137A (en) * | 2010-03-15 | 2010-07-14 | 华中科技大学 | Water-based non-isocyanate polyurethane and preparation method thereof |
| CN104231191A (en) * | 2014-09-16 | 2014-12-24 | 上海金力泰化工股份有限公司 | Preparation method of waterborne non-isocyanate polyurethane modified polyester |
| CN104995270A (en) * | 2012-12-19 | 2015-10-21 | 阿科玛法国公司 | Organic resin bearing cyclic carbonate groups and aqueous dispersion for crosslinked polyurethanes |
| CN105246992A (en) * | 2013-05-24 | 2016-01-13 | 阿科玛法国公司 | Acrylated or methacrylated urethane oligomer without isocyanate |
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2017
- 2017-02-24 CN CN201710104011.8A patent/CN106832266B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775137A (en) * | 2010-03-15 | 2010-07-14 | 华中科技大学 | Water-based non-isocyanate polyurethane and preparation method thereof |
| CN104995270A (en) * | 2012-12-19 | 2015-10-21 | 阿科玛法国公司 | Organic resin bearing cyclic carbonate groups and aqueous dispersion for crosslinked polyurethanes |
| CN105246992A (en) * | 2013-05-24 | 2016-01-13 | 阿科玛法国公司 | Acrylated or methacrylated urethane oligomer without isocyanate |
| CN104231191A (en) * | 2014-09-16 | 2014-12-24 | 上海金力泰化工股份有限公司 | Preparation method of waterborne non-isocyanate polyurethane modified polyester |
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