CN106832266A - 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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- CN106832266A CN106832266A CN201710104011.8A CN201710104011A CN106832266A CN 106832266 A CN106832266 A CN 106832266A CN 201710104011 A CN201710104011 A CN 201710104011A CN 106832266 A CN106832266 A CN 106832266A
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- 0 C*CC(N*CCCNC(OCC*)=O)=O Chemical compound C*CC(N*CCCNC(OCC*)=O)=O 0.000 description 1
- RWOQAYBMSNFOCH-UHFFFAOYSA-N CC(CO)OC(NC)=O Chemical compound CC(CO)OC(NC)=O RWOQAYBMSNFOCH-UHFFFAOYSA-N 0.000 description 1
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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
- C08G71/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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 is a kind of new non-isocyanate based polyurethanes, and the NCO without high toxicity and high wet sensitive is environmentally safe, good to health fanout free region, nonflammable, security.The present invention, as Water-borne modification group, can also keep stabilization using sulfonate groups under certain acid condition, and need not add tertiary amine compounds, have no irritating odor, and have cohesive force higher, water resistance, heat resistance than carboxylic acid type aqueous polyurethane；Meanwhile, the cyclic carbonate ester class compound that the present invention is used has the advantages that higher boiling, low smell, low evaporation rate and low toxicity, and biological degradability is excellent, using carbon dioxide as cyclic carbonate ester raw material, environmental protection.
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 technology
Ultraviolet curing urethane is a class energy-saving material, and it occurs photochemical reaction after by ultraviolet light,
So as to cause polymerization, crosslinking, its moment is set to become solid-state by liquid.UV-curable waterborne polyurethane is to replace organic molten with water
Agent as decentralized medium new polyurethane system, because of its pollution-free, safe and reliable, good mechanical performance, compatibility is good, be easy to
Modified the advantages of, had a wide range of applications in coating and adhesive area.
Using carboxylate as hydrophilic radical, its preparation method is generally using two isocyanic acids to current most aqueous polyurethane
Ester and polyester or PPG reaction obtain the less isocyanate terminated base polyurethane prepolymer of molecular weight, add contain carboxylic afterwards
The polyalcohol of base carries out chain extension to be made to contain carboxyl on polyurethane molecular, and polyalcohol containing carboxyl is usually 2,2- dihydromethyl propionic acids,
Finally will be dispersed in water in carboxyl and into salt and quickly and obtain the aqueous poly- ammonia of carboxylic acid type using the amine such as triethylamine small molecule
Ester.However, such polyurethane is isocyanate terminated polyurethane, wherein comprising substantial amounts of free isocyanate, in construction and material
In solidification process, part free isocyanate is evaporated, especially the material such as toluene di-isocyanate(TDI), can be detrimental to health
With pollution environment.Meanwhile, carboxylic acid type aqueous polyurethane less stable, its can cause in acid condition carboxylic acid combination hydrogen from
Son, causes hydrophily to weaken and emulsifiability decline.
The content of the invention
In view of this, it is an object of the invention to provide a kind of good stability, harmless, environmental protection aqueous purple
Outer light-cured polyurethane and preparation method thereof and coating.
Concrete technical scheme of the invention is as follows：
The invention provides a kind of aqueous polyurethane, with the structure as shown in formula I：
Wherein, R1Selected from-H ,-OH ,-OCH3, phenyl, C1~12Alkyl or C1~12Alkenyl；
R2Selected from-CHNR5R6、In one or two；
R3It is selected from
R4It is selected from
R5And R6It is independently selected from-H or C1~12Alkyl；
N=1~20.
Present invention also offers a kind of preparation method of above-mentioned aqueous polyurethane, including：
A) under nitrogen or inert gas, cyclic carbonate ester class compound and aminated compounds are reacted, is obtained first
Reaction intermediate；
B) the first reaction intermediate and Sulfonates compound that step a) is obtained are carried out under conditions of catalyst presence
Reaction, obtains the second reaction intermediate；
C) the second reaction intermediate and acrylic compounds that step b) is obtained are carried out under conditions of polymerization inhibitor presence
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 groups-ethylene carbonate or propene carbonate.
Preferably, aminated compounds described in step a) is diamine and/or tertiary amine；
The diamine is polyetheramine D-400, polyetheramine D-2000 or IPD；
The tertiary amine is polyetheramine T-403.
Preferably, Sulfonates compound described in step b) is 5-sodium sulfo isophthalate；
The catalyst is DMAP or dicyclohexylcarbodiimide；
The addition of the catalyst is the 0.3%~0.7% of the Sulfonates compound gross mass.
Preferably, acrylic compounds described in step c) are acrylic acid, methacrylic acid or Glycidyl methacrylate
Glyceride；
The polymerization inhibitor is MEHQ, hydroquinones or 2,6 di tert butyl 4 methyl phenol；
The addition 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
Mol ratio be (2~2.5):1：(0.5~1):1.
Present invention also offers a kind of UV-curable waterborne polyurethane coating, comprising above-mentioned aqueous polyurethane and/or on
State aqueous polyurethane, light trigger and water that preparation method is obtained.
Preferably, the light trigger be aryl alkyl ketone, benzophenone, heterocycle arone class, aryl diazonium salts or
Iodine salt compounds；
The addition of the light trigger is the 0.05%~0.15% of the aqueous polyurethane gross mass.
The addition of the water is the 10%~60% of the aqueous polyurethane gross mass.
Present invention also offers a kind of preparation method of above-mentioned UV-curable waterborne polyurethane coating, it is：Will be aqueous poly-
The mixing of urethane, light trigger and water；
Described being mixed into stirs 1h under 350rpm.
Compared with prior art, aqueous polyurethane provided by the present invention is a kind of new poly- ammonia of non-isocyanate base
Ester, the NCO without high toxicity and high wet sensitive is environmentally safe, to health fanout free region；Prepared at it
Cheng Zhong, the present invention, as Water-borne modification group, can keep stable in acid condition using sulfonate groups, and without using
Tertiary amine compounds, have no irritating odor, and have cohesive force higher, water resistance, heat resistance than carboxylic acid type aqueous polyurethane；Together
When, the cyclic carbonate ester class compound of use has the advantages that higher boiling, low smell, low evaporation rate and low toxicity, and biological degradability
It is excellent, using carbon dioxide as cyclic carbonate ester raw material, environmental protection.UV-curable waterborne provided by the present invention gathers
Urethane coating is free of any reactive diluent, and nonflammable, security is good, its optimum preparation condition, and reaction conversion ratio is high, selection
Property strong, safe preparation process cleaning.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the proton nmr spectra of the aqueous polyurethane that embodiment 1 is obtained；
Fig. 2 is the infrared spectrum of the aqueous polyurethane that embodiment 1 is obtained.
Specific embodiment
In order to overcome existing aqueous polyurethane stability difference and containing the NCO with high toxicity and high wet sensitive
Problem, the invention provides a kind of good stability, harmless, environmental protection aqueous polyurethane and UV-curable waterborne
Polyurethane coating and preparation method thereof.
The invention provides a kind of aqueous polyurethane 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；
R2Selected from-CHNR5R6、
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
1~4 carbon atom, or 1~2 univalence hydrocarbyl of carbon atom, wherein alkyl can be with individually optional by one or more this hairs
Bright described substitution base is replaced.Alkyl further example is included, but is not limited to, methyl, ethyl, propyl group, isopropyl
It is base, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, 2- amyl groups, 3- amyl groups, 2- methyl -2- butyl, n-heptyl, just pungent
Base etc..Term " alkyl " is being used herein as, and represents the saturated carbon chains from straight chain, side chain or ring-type.
Present invention also offers a kind of preparation method of above-mentioned aqueous polyurethane, including：
A) under nitrogen or inert gas, cyclic carbonate ester class compound and aminated compounds are reacted, is obtained first
Reaction intermediate；
B) the first reaction intermediate and Sulfonates compound that step a) is obtained are carried out under conditions of catalyst presence
Reaction, obtains the second reaction intermediate；
C) the second reaction intermediate and acrylic compounds that step b) is obtained are carried out under conditions of polymerization inhibitor presence
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 groups-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 and/or tertiary amine；
The diamine is polyetheramine D-400, polyetheramine D-2000 or IPD；
The tertiary amine is polyetheramine T-403.
The present invention to diamine and tertiary amine collocation use when mixed proportion without specifically limited, according to practical condition
The need for mixed.
Further, Sulfonates compound is preferably 5-sodium sulfo isophthalate described in step b).
Further, the catalyst is DMAP or dicyclohexylcarbodiimide.
Further, the addition of the catalyst is the 0.3%~0.7% of the Sulfonates compound gross mass.
Further, acrylic compounds are preferably acrylic acid, methacrylic acid or metering system described in step c)
Acid glycidyl ester, more preferably methacrylic acid or GMA.
Further, the polymerization inhibitor be MEHQ, hydroquinones or 2,6- di-tert-butyl-4-methy phenol,
Preferably MEHQ (MEHQ).
Further, the addition 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 mol ratio of thing 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, can use people in the art
Technological means known to member is adjusted according to practical condition to its process conditions.In the present invention, with ring carbon acid propylene
As a example by ester (PC), the preparation of the aqueous polyurethane is preferably step in detail below：
(1) PC of 2mol is added in there-necked flask, is stirred with the speed of 300~1000rpm heat up under nitrogen protection
It is then uniform in 0.5~1h to be added dropwise to 1mol IPDs or polyetheramine D-400 or its mixing to 100 DEG C~150 DEG C
Thing, 3~5h of insulation reaction obtains transparent first reaction intermediate；Wherein, first reaction intermediate is a kind of pale yellow transparent
Liquid non-isocyanate based polyurethanes (NIPU), with following structure：
(2) when the first reaction intermediate is cooled to 90 DEG C~120 DEG C, catalyst DMAP and isophthalic are added
Dioctyl phthalate -5- sodium sulfonates, are warming up to 120 DEG C after being stirred with the speed of 300~1000rpm, vacuumize 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
There is following structure：
(3) when the second reaction intermediate is cooled to 80 DEG C~100 DEG C, it was slowly added dropwise into methyl-prop in 30~40 minutes
The mixture of olefin(e) acid or GMA and polymerization inhibitor, stirring reaction 2h obtains the aqueous polyurethane.
Non-isocyanate based polyurethanes (NIPU) are a kind of special polyurethane, and its raw material need not be larger using toxicity
Isocyanates, the characteristic with safety and stability, relative to traditional polyurethane, each carbamate groups of NIPU generations
A hydroxyl being connected with its β carbon atom is all carried, the hydrogen atom of the hydroxyl can with the carbonylic oxygen atom in-NHCOO- groups
To form intramolecular hydrogen bond, as a hexatomic ring for stabilization, due to forming tautomeric resonant structure in ring, cause electricity
Son reallocation, so that six-membered ring structure is highly stable.And because the presence of this hydrogen bond serves closing carbamate groups
The effect of ketonic oxygen in group, improves its hydrolytic stability, and the weak bonding structure of conventional urethane is compensate for from molecular structure, carries
High chemical-resistant and permeability resistance.
Synthesis non-isocyanate route mainly include open loop route, diamines and bischloroformate reaction scheme, amino with it is many
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,
Water insensitive PU aspects have potential application, and cyclic carbonate ester can be dissolved in most of organic solvent, can be used as titanium dioxide
Dispersant of absorbent carbon, water-soluble dye and pigment etc..It is industrial to take expoxy propane with carbon dioxide under a certain pressure
Addition, then vacuum distillation is obtained, while the cyclic carbonate ester of low-molecular-weight has a higher boiling, smell, evaporation rate and toxicity compared with
It is low, the good advantage of biological degradability.Carbon dioxide is cheap and abundant carbon source, utilizes carbon dioxide as the original of cyclic carbonate ester
Material, can recycle carbon dioxide, reduce carbon dioxide content in air, and this not only conforms with environmental requirement, and is also real
One of approach of existing green production.
In the present invention, using sulfonate groups as hydrophilic radical, because it is strong electrolyte, therefore between hydrophilic radical
Electrostatic repulsion it is larger so that Zeta points between latex particle position it is bigger than normal it is available more stablize and more large arch dam aqueous poly- ammonia
Ester；Simultaneously as aminated compounds need not be added, sulfonate type aqueous polyurethane does not have irritating amine taste, there is relative yet
Water resistance, heat resistance high.
Present invention also offers a kind of UV-curable waterborne polyurethane coating, comprising above-mentioned aqueous polyurethane and/or on
State aqueous polyurethane, light trigger and water that preparation method is obtained.
Further, the light trigger 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 light trigger, using well-known to those skilled in the art light-initiated
Agent, such as commercial source.In the present invention, the light trigger for being used is preferably light trigger 819 and light trigger ITX.
Wherein, double (2,4,6- trimethylbenzoyl) phosphine oxides of the Chinese entitled phenyl of light trigger 819, in light trigger ITX
Literary fame is isopropyl thioxanthone.
Further, the addition of the light trigger be the aqueous polyurethane gross mass 0.05%~
0.15%；
The addition of the water is the 10%~60% of the aqueous polyurethane gross mass.
Present invention also offers the preparation method of above-mentioned UV-curable waterborne polyurethane coating, it is：Will be above-mentioned aqueous poly-
The mixing of urethane, light trigger and water.
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, by temperature control at 50~60 DEG C, toward aqueous polyurethane
Light trigger is added, continues to be stirring evenly and then adding into deionized water with the speed of 350rpm, continue high degree of agitation 1h, obtain yellow
The UV-curable waterborne polyurethane coating end-product of transparence.
Technical scheme 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 embodiment of the invention, rather than whole embodiments.Those skilled in the art should manage
Solution, modifies to specific embodiment of the invention or some technical characteristics is replaced on an equal basis, without deviating from the present invention
The spirit of technical scheme, all should cover in the scope of protection of the invention.
Embodiment 1
In with agitator, the there-necked flask of thermometer, 21.44g PC (0.21mol) is added, be passed through nitrogen by system
In air exclude and be heated to 100 DEG C, be then slowly added dropwise 17.03g IPDs, insulation reaction 4h obtains transparent
The first thick reaction intermediate.Then, the 4- dimethylaminos of 13.41g 5-sodium sulfo isophthalates and 0.04g are added
Pyridine, is warming up to 150 DEG C after stirring, vacuumize water removal, and insulation reaction 3h is obtained in the middle of 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 inhibitors MEHQ Glycidyl methacrylate it is sweet
Grease 10mL, drips off in 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, adds 0.1g light triggers 819,
The deionized water of 55 DEG C of 15mL is stirring evenly and then adding into, high degree of agitation 1h obtains the aquosity ultraviolet light of light yellow transparent liquid shape
Solidification polyurethane.
Embodiment 2
In with agitator, the there-necked flask of thermometer, 21.44g PC (0.21mol) is added, be passed through nitrogen by system
In air exclude and be heated to 150 DEG C, be then slowly added dropwise 41.24mL polyetheramines D-400 (0.1mol), insulation reaction 4h,
Obtain the first reaction intermediate of clear viscous shape.Then, the 4- of 13.41g 5-sodium sulfo isophthalates and 0.09g is added
Dimethylamino naphthyridine, is warming up to 120 DEG C after stirring, vacuumize water removal, and insulation reaction 3h, obtain white " milky " second is anti-
Answer intermediate.Then, it is cooled to 100 DEG C, high degree of agitation, then it is slowly added dropwise the methacrylic acid for being mixed with 120ppm polymerization inhibitors MEHQ
Dripped off in 12mL, 30min, vacuum distillation removes unreacted monomer after being cooled to 80 DEG C of insulation reaction 2h, obtain a kind of aqueous
Polyurethane.
Finally, reaction temperature is down to 55 DEG C and by mixing speed control in 350rpm, adds 0.075g light triggers
ITX, is stirring evenly and then adding into the deionized water of 55 DEG C of 30mL, and high degree of agitation 1h obtains the aqueous purple of light yellow transparent liquid shape
Outer light-cured polyurethane.
Embodiment 3
In with agitator, the there-necked flask of thermometer, 21.44g PC (0.21mol) is added, be passed through nitrogen by system
In air exclude and be heated to 130 DEG C, be then slowly added dropwise 11.0mL polyetheramines D-400 (0.04mol) and 16.5mL
IPDA (0.06mol), insulation reaction 4h, obtain the first reaction intermediate of pale yellow transparent liquid.Then, between adding 13.41g
The DMAP of phthalic acid -5- sodium sulfonates and 0.04g, is warming up to 120 DEG C after stirring, vacuumize 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
There is the methacrylic acid 8mL of 100ppm polymerization inhibitors MEHQ, dripped off in 30min, be cooled to vacuum distillation after 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, adds 0.061g light triggers
ITX, is stirring evenly and then adding into the deionized water of 55 DEG C of 50mL, and high degree of agitation 1h obtains the aqueous of faint yellow translucent liquid shape
Ultraviolet curing urethane.
The ultraviolet light polymerization of embodiment 4 is tested
The UV-curable waterborne aqueous polyurethane coating that Example 1~3 is obtained respectively imports polytetrafluoroethylene (PTFE) in right amount
In mould, it is subsequently placed in 70 DEG C of baking ovens and dries 1h, then be placed under 300W uviol lamps and solidify 30s, you can forms surface smooth
Coating, is carried out performance test, obtains light-cured performance test result as shown in table 1.
Table 1
| Embodiment | Hardening time/s | Pencil hardness/H | Tensile strength/Mpa | Color and luster |
| 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 UV-curable waterborne aqueous polyurethane that is also obtained to embodiment 1 of the present invention is using nuclear magnetic resonance and infrared carries out
Detection, as a result as depicted in figs. 1 and 2.
Claims (10)
1. a kind of aqueous polyurethane, with the structure as shown in formula I：
Wherein, R1Selected from-H ,-OH ,-OCH3, phenyl, C1~12Alkyl or C1~12Alkenyl；
R2Selected from-CHNR5R6、In one or two；
R3It is selected from
R4It is selected from
R5And R6It is independently selected from-H or C1~12Alkyl；
N=1~20.
2. the preparation method of the aqueous polyurethane described in a kind of claim 1, including：
A) under nitrogen or inert gas, cyclic carbonate ester class compound and aminated compounds are reacted, is obtained the first reaction
Intermediate；
B) the first reaction intermediate and Sulfonates compound that step a) is obtained are reacted under conditions of catalyst presence,
Obtain the second reaction intermediate；
C) the second reaction intermediate and acrylic compounds that step b) is obtained are reacted under conditions of polymerization inhibitor presence,
Obtain the aqueous polyurethane with structure shown in formula I.
3. preparation method according to claim 2, it is characterised in that inert gas described in step a) includes helium and argon
Gas；
The cyclic carbonate ester class compound is ethylene carbonate, 1- methoxyl groups-ethylene carbonate or propene carbonate.
4. preparation method according to claim 2, it is characterised in that aminated compounds described in step a) is diamine
And/or tertiary amine；
The diamine is polyetheramine D-400, polyetheramine D-2000 or IPD；
The tertiary amine is polyetheramine T-403.
5. preparation method according to claim 2, it is characterised in that Sulfonates compound described in step b) is isophthalic
Dioctyl phthalate -5- sodium sulfonates；
The catalyst is DMAP or dicyclohexylcarbodiimide；
The addition of the catalyst is the 0.3%~0.7% of the Sulfonates compound gross mass.
6. preparation method according to claim 2, it is characterised in that acrylic compounds described in step c) are propylene
Acid, methacrylic acid or GMA；
The polymerization inhibitor is MEHQ, hydroquinones or 2,6 di tert butyl 4 methyl phenol；
The addition of the polymerization inhibitor is 80~120ppm of the acrylic compounds gross mass.
7. preparation method according to claim 2, it is characterised in that the cyclic carbonate ester class compound, aminated compounds,
The mol 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, comprising aqueous polyurethane and/or claim described in claim 1
Aqueous polyurethane, light trigger and water that preparation method described in 2 to 7 any one is obtained.
9. UV-curable waterborne polyurethane coating according to claim 8, it is characterised in that the light trigger is virtue
Base alkyl ketone, benzophenone, heterocycle arone class, aryl diazonium salts or iodine salt compounds；
The addition of the light trigger is the 0.05%~0.15% of the aqueous polyurethane gross mass；
The addition of the water is the 10%~60% of the aqueous polyurethane gross mass.
10. the preparation method of the UV-curable waterborne polyurethane coating described in a kind of claim 8 or 9, be：By aqueous poly- ammonia
The mixing of ester, light trigger and water；
Described being mixed into stirs 1h under 350rpm.
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| CN107177035A (en) * | 2017-07-20 | 2017-09-19 | 广东工业大学 | A kind of base polyurethane prepolymer for use as and preparation method thereof and ultraviolet curing urethane performed polymer composition |
| CN107177035B (en) * | 2017-07-20 | 2019-10-15 | 广东工业大学 | A kind of base polyurethane prepolymer for use as and preparation method thereof and ultraviolet curing urethane performed polymer composition |
| CN107586375A (en) * | 2017-10-30 | 2018-01-16 | 广东工业大学 | A kind of water-soluble support materials |
| 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 |
| CN111848910A (en) * | 2020-08-05 | 2020-10-30 | 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 |
| CN111944138A (en) * | 2020-08-05 | 2020-11-17 | 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 |
| CN114763438A (en) * | 2021-01-14 | 2022-07-19 | 万华化学集团股份有限公司 | Organosilicon curing formula, curing method and silicone rubber prepared from organosilicon curing formula |
| CN114763438B (en) * | 2021-01-14 | 2023-08-11 | 万华化学集团股份有限公司 | Organosilicon curing formula, curing method and silicone rubber prepared from organosilicon curing formula |
| 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 |
| CN114874435A (en) * | 2022-06-14 | 2022-08-09 | 广东工业大学 | Washable photocuring 3D printing resin and preparation method thereof |
| CN114874435B (en) * | 2022-06-14 | 2024-02-27 | 广东工业大学 | Washable photo-curing 3D printing resin and preparation method thereof |
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