CN107286319A - A kind of water-borne UV-curing resin of organic fluorine richness and preparation method thereof - Google Patents
A kind of water-borne UV-curing resin of organic fluorine richness and preparation method thereof Download PDFInfo
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- CN107286319A CN107286319A CN201710574776.8A CN201710574776A CN107286319A CN 107286319 A CN107286319 A CN 107286319A CN 201710574776 A CN201710574776 A CN 201710574776A CN 107286319 A CN107286319 A CN 107286319A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a kind of water-borne UV-curing resin of organic fluorine richness, it is characterized in that, the resin is using three-functionality-degree or the polyalcohol of tetra functional as initiation material, with diisocyanate polyaddition reaction, hydrophilic radical is introduced by the dihydric alcohol with carboxyl again, prepared with hydroxy acrylate and perfluorooctanol end-blocking introducing acrylic double bond and organic fluorine richness.Compared with prior art, the water-borne UV-curing resin is also water-soluble with relatively low molecular weight and preferably with higher double bond density and while low surface tension, and the coating of levelling mobility and higher gloss degree can be made, has a wide range of application.
Description
Technical field
The present invention relates to ultraviolet light cured article, more particularly to a kind of water-borne UV-curing tree of organic fluorine richness
Fat and preparation method thereof.
Background technology
Ultraviolet light (UV) cured article makes light trigger resolve into free radical or cation rapidly by UV light, and then triggers
Unsaturated double-bond carries out chain polymerization, makes material solidification complete.Because its processing characteristics is excellent, non-environmental-pollution and high function
The features such as be considered as a kind of clean and environment-friendly " green technology ".Conventional oil-based UV cured articles are single because adding activity dilution in formula
Body or diluent realize the coating decoration of product to adjust product function and resin viscosity.Reactive diluent is although less to be waved
Hair, but penetrating odor, the problems such as worker exposure easily causes allergic are produced when still suffering from construction.In addition, oiliness UV solidifies
Product belongs to harmful influence, all there is certain potential safety hazard in transport and storage.
Water-borne UV-curing system, replaces reactive diluent to have many advantages, such as with water：
(1) levelling and thixotropy are adjustable, are sticked so as to effectively prevent reactive diluent regulation system in conventional oil-based system
The problems such as curing of coatings brought when spending shrinks；
(2) product has the advantages that hypotoxicity, low irritant, low smell, low VOC emission；
(3) product is nonflammable, non-explosive, stores transportation safety；
(4) easily dissipated by moisture or water emulsification prepare the water-based system of HMW, high solids content and low viscosity, it is possible to resolve
(this is also that water-borne UV-curing technology is better than to the problem that conventional oil-based UV solidification coating high rigidity and high-flexibility can not be taken into account simultaneously
One of the characteristics of traditional UV curing technologies).The combination of UV curing technologies and water-base resin, can reach the purpose such as environmentally friendly, efficient, extensively
It is general to be applied to the external coating that environmental protection, decoration and protection require higher various base materials.
Water-borne UV-curing resin makes resin by introducing aqueous group or segment on the basis of traditional UV solidified resins
With certain hydrophily.The synthetic method of common water-borne UV-curing resin has two kinds：A kind of is the molecule in conventional resins
Hydrophilic radical (such as unsaturated polyester (UP) resinoid) is introduced on chain；Another is to generate water-and acrylate with acrylate reactions
Quasi-oligomer (such as urethane acrylate, epoxy acrylate).Water-borne UV-curing resin have it is solvent-free, nontoxic, without dirt
The advantages of dye, easy to use, cull easy to clean, solid content height and storing and transporting security facilitate, is environment-friendly and energy-efficient UV solidified resins
Developing direction.
The water-borne UV-curing coating of urethane acrylate (PUA) has the two-fold advantage of polyurethane and acrylic acid concurrently, has
Wearability is good, pliability is good, impact strength and tensile strength is of a relatively high, chemical resistance and the features such as excellent adhesion,
Because its good combination property is widely used in water-borne UV-curing system.
The fine and close smooth finish surface that high crosslink density and low surface tension are formed is that coating has solvent resistant and anti-pollution characteristic
Essential condition.Current PUA class UV solidified resin Water-borne modifications are blocked on the basis of Waterborne Polyurethane Prepolymer, this
The problem of method has two.One is to reserve more NCO group, then (methyl) acrylic acid for passing through single official when being formulated design
Hydroxyl ethyl ester is blocked, and end-blocking quantity is more, also reduces the content of hydrophilic radical, shadow while the molecular weight for reducing prepolymer
UV Water-borne modification and the outward appearance of coating have been rung, the anti-pollution characteristic of coating is also reduced.Two do molecular weight greatly when being formula design,
Molecular weight is even increased by chain extension after amine, the molecular weight of product is so effectively increased, but relatively low end-blocking brings later stage UV
The relatively low crosslink density of solidification, it is impossible to meet the requirement of the solvent resistant and anti-pollution characteristic of coating.
Research of the prior art to high-performance water-based UV solidified resins has focused largely on the production of PUA (urethane acrylate) class
On product (such as domestic A and B of CN 103232585 of patent of invention CN 103102456).Typically preparation method is：By polyester/
Polyether Glycols, diisocyanate, dihydromethyl propionic acid (DMPA) blending reaction obtain performed polymer, are blocked with hydroxy acrylate
Synthesis, then be dispersed in water by nertralizer of tertiary amine, obtain final urethane acrylate aqueous dispersion after removing organic solvent.
On aqueous UV resin methods are prepared, also there is a certain degree of graft modification by the way of composition, its solvent resistance is equal
There is a certain degree of lifting, but to hardness and flexible balance, and final resin anti-pollution characteristic is not directed to.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of water-borne UV-curing tree of organic fluorine richness
Fat and preparation method thereof, it is intended to while solving the dual property requirement of water-borne UV-curing resin solvent resistant and resistant, have again
Tough and tensile characteristic.
The present invention is achieved by the following technical solutions：
The invention provides a kind of water-borne UV-curing resin of organic fluorine richness, the resin is with three-functionality-degree or tetrafunctional
The polyalcohol of degree is initiation material, and diisocyanate polyaddition reaction, then passes through the dihydric alcohol with carboxyl and introduce hydrophilic group
Group, is prepared with hydroxy acrylate and perfluorooctanol end-blocking introducing acrylic double bond and organic fluorine richness.Specially：By weight
Amount is than counting, and component and its rate of charge in the water-borne UV-curing resin reaction system include：
Wherein：
The HDI provides NCO-NCO for whole reaction and reacted with the raw material containing hydroxyl, reaction generation urethane
While key, straight chain hexa-methylene also provides preferable pliability for material.
The three-functionality-degree or the polyalcohol of tetra functional cause system to have higher acrylic functionalities, so as to effectively carry
Risen the crosslink density of resin, be later stage UV solidify to form densification film layer provide the foundation；Further, the polyalcohol is three
Hydroxymethyl-propane (TMP) or pentaerythrite or propylene oxide triol, wherein, TMP and propylene oxide triol are the three of three-functionality-degree
First alcohol, pentaerythrite is the tetrahydroxylic alcohol of tetra functional.
The catalyst is dibutyl tin laurate or stannous octoate.
The DMBA is a kind of dihydric alcohol with carboxyl, in the present system as hydrophilic chain extender, instead of traditional dihydroxy
Methylpropanoic acid (DMPA), can be added directly into reaction system, it is to avoid need to dissolve by 1-METHYLPYRROLIDONE equal solvent
After the problem of could add, obtained water-borne UV-curing resin can be not added with high boiling solvent, can be led to using a small amount of acetone or butanone
Removed under reduced pressure is crossed, final finished is the no-solvent type product of nearly Diamond Search, safe and healthy, environmental protection, while DMBA has with respect to DMPA
Higher reactivity, product cut size is evenly distributed.
The hydroxy acrylate is reacted by the hydroxyl in molecule and NCO, to be grafted in the form of end-blocking among molecule；
Further, the hydroxy acrylate is the acrylate of two degrees of functionality or three-functionality-degree；Further, two function
Degree acrylate is trimethylolpropane diacrylate (TMPDA), and the three-functionality-degree acrylate is pentaerythrite 3 third
Olefin(e) acid ester (PETA).
The Organic fluoride is similar with hydroxy acrylate grafted forms, is connect by the hydroxyl in molecule with isocyanates reaction
Branch is into molecule, and the grafting of Organic fluoride is introduced, and can effectively be reduced the surface tension on surface after resin coating film, be enable product preferably
Sprawled in low surface tension substrate, while being coating surface is hydrophobic and resistant provides the foundation condition；Further, it is described to have
Machine fluorine is perfluorooctanol.
The TEA finally neutralizes into salt with the carboxyl reaction in DMBA.
Present invention also offers the preparation method of the water-borne UV-curing resin of above-mentioned organic fluorine richness, comprise the following steps：
(1) isocyanic acid of hexa-methylene two is added in equipped with electric mixer, thermometer, the four-hole boiling flask of reflux condensing tube
Ester (HDI), heating is progressively warming up to during 60-80 DEG C, adds polyalcohol and DMBA, and control temperature is anti-at 60-90 DEG C
Theoretical value should be reached to-NCO, and no longer changed；
(2) question response heat release terminates to add catalyst to temperature plateau, is then cooled to 60-70 DEG C, sequentially adds resistance
Poly- agent, hydroxy acrylate and Organic fluoride, reaction to-NCO disappear or only micro presence substantially, and pilot process becomes according to viscosity
Change situation, by supplementing acetone or butanone viscosity reduction, W-response uses less acetone or butanone progressively to add for the liquid phase of solvent
It is prepared by the method into polymerization；
(3) 40-50 DEG C is cooled to, TEA neutralization reaction 3-5min are added, deionized water neutralization, and scattered 20- is added
30min is to translucent；
(4) acetone or butanone are removed through vacuum distillation, obtains PUA photocuring dispersions, as described water-borne UV-curing tree
Fat.
Further, molecular structure can be adjusted by Multistep feeding mode, is first reacted polyalcohol and isocyanates, then draw
Enter hydrophilic chain extender, last blocking modification, synthesis has the product of the class hub-and-spoke configuration of starting point, specifically, the step (1)
In, polyalcohol is first added, control temperature, which is reacted at 60-90 DEG C to-NCO, reaches theoretical value, and when no longer changing, adds
DMBA。
The present invention principle be：It is initial reactant present invention employs three official's trihydroxylic alcohols or the tetrahydroxylic alcohol of tetra functional
Matter, and the acrylate ended of three officials or two degrees of functionality is introduced simultaneously, greatly improve crosslink density and light during UV solidifications
Curing rate, so that light solidifying coating has higher physical strength and stronger solvent resistant anti-pollution characteristic.Formula uses small point
Son design, and introduces Organic fluoride graft modification, effectively reduces the surface tension of coating, improves the surface property of coating and resistance to
Dirty performance, finished product wetting good leveling property, it is easy to highlight coating is made.Using non yellowing but have hexa-atomic carbochain HDI, be
The pliability of coating provides the foundation so that coating has certain pliability, effectively again while preferable physical strength is kept
Balance and unified the hard and flexible contradiction of coating.
The present invention has advantages below compared with prior art：The invention provides a kind of the water-borne UV-curing of organic fluorine richness
Resin and preparation method thereof, the water-borne UV-curing resin also has with higher double bond density and while low surface tension
Relatively low molecular weight and preferable water solubility, can be made the coating of levelling mobility and higher gloss degree, for PVC and furniture top
Layer gloss oil coating to lift the decoration and outer layer protection performance of product, for the aqueous color ink of photocuring or colored paint to be made, with compared with
Good anti-yellowing property, solvent resistance and anti-pollution characteristic, for requiring higher paper to strength of coating, heat-resisting, solvent resistant, resistant
, the preparation of coating such as woodenware, glass, metal etc., have a wide range of application.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
Water-borne UV-curing resin of a kind of organic fluorine richness that the present embodiment is provided and preparation method thereof, wherein：
The reaction system of the water-borne UV-curing resin of organic fluorine richness is (by weight)：
The preparation method of the water-borne UV-curing resin of organic fluorine richness, comprises the following steps：
(1) HDI is added in equipped with electric mixer, thermometer, the four-hole boiling flask of reflux condensing tube, heating progressively heats up
During 60-80 DEG C, TMP and DMBA is added, control temperature, which is reacted at 60-90 DEG C to-NCO, reaches theoretical value, not
Change again, shown in the following structural formula of key reaction product (I)：
In formula, the structure being connected with three-NCO group is R (alkyl).
(2) question response heat release terminates to add dibutyl tin laurate to temperature plateau, is then cooled to 60-70 DEG C,
Polymerization inhibitor, PETA and perfluorooctanol are sequentially added, reaction to-NCO disappears or only micro presence substantially, and pilot process is according to viscous
Situation of change is spent, by supplementing acetone viscosity reduction；According to structure above (I), three NCO groups that R is connected further with containing
There are the PETA and perfluorooctanol reaction end-blocking of active hydroxyl groups, its reaction product is three PETA end-blockings or contains part perfluorooctanol
Graft product, wherein containing perfluorooctanol be grafted and without in amine and when the following structural formula of typical reaction product (II) shown in：
(3) 40-50 DEG C is cooled to, TEA neutralization reaction 3-5min are added, deionized water neutralization, and scattered 20- is added
30min is to translucent.
(4) acetone is removed through vacuum distillation, obtains PUA photocuring dispersions, as described water-borne UV-curing resin.
Embodiment 2
Water-borne UV-curing resin of another organic fluorine richness that the present embodiment is provided and preparation method thereof, wherein：
The reaction system of the water-borne UV-curing resin of organic fluorine richness is (by weight)：
The preparation method comprises the following steps：
(1) HDI is added in equipped with electric mixer, thermometer, the four-hole boiling flask of reflux condensing tube, heating progressively heats up
During 60-80 DEG C, pentaerythrite is first added, control temperature, which is reacted at 60-90 DEG C to-NCO, reaches theoretical value, not
When changing again, DMBA is added.
(2) question response heat release terminates to add dibutyl tin laurate to temperature plateau, is then cooled to 60-70 DEG C,
Polymerization inhibitor, PETA and perfluorooctanol are sequentially added, reaction to-NCO disappears or only micro presence substantially, and pilot process is according to viscous
Situation of change is spent, by supplementing butanone viscosity reduction；
(3) 40-50 DEG C is cooled to, TEA neutralization reaction 3-5min are added, deionized water neutralization, and scattered 20- is added
30min is to translucent.
(4) butanone is removed through vacuum distillation, obtains PUA photocuring dispersions, as described water-borne UV-curing resin.
Embodiment 3
Water-borne UV-curing resin of another organic fluorine richness that the present embodiment is provided and preparation method thereof, wherein：
The reaction system of the water-borne UV-curing resin of organic fluorine richness is (by weight)：
The preparation method be the same as Example 1.
Embodiment 4
Water-borne UV-curing resin of another organic fluorine richness that the present embodiment is provided and preparation method thereof, wherein：
The reaction system of the water-borne UV-curing resin of organic fluorine richness is (by weight)：
The preparation method be the same as Example 2.
The physicochemical characteristicses for the water-borne UV-curing dispersion that detection embodiment 1-4 is prepared, it is specific as follows：Embodiment 1-4
The water-borne UV-curing dispersion translucent appearance prepared, solid content be 40% ± 1, T-4 viscosity (25 DEG C) be 25 ±
5S, the dispersion can be diluted with water with arbitrary proportion, and need not add the dilution dissolving of alcohol equal solvent, through adding appropriate initiator,
Energy after being solidified by UV machines is 200mJ/cm2-300mJ/cm2, the smooth exquisiteness of appearance of coat, hardness is 2H-3H, adhesive force 1
Level, gloss 95 ± 5GU, resistance to butanone wipe 50 times it is unchanged, the greasy dirt such as permanent pen can be wiped easily, and with preferably soft
Toughness.
Be above a kind of detailed embodiment of the invention and specific operating process, be using technical solution of the present invention before
Put and implemented, but protection scope of the present invention is not limited to the above embodiments.
Claims (9)
1. a kind of water-borne UV-curing resin of organic fluorine richness, it is characterised in that the resin is with three-functionality-degree or tetrafunctional
The polyalcohol of degree is initiation material, and diisocyanate polyaddition reaction, then passes through the dihydric alcohol with carboxyl and introduce hydrophilic group
Group, is prepared with hydroxy acrylate and perfluorooctanol end-blocking introducing acrylic double bond and organic fluorine richness.
2. the water-borne UV-curing resin of a kind of organic fluorine richness according to claim 1, it is characterised in that by weight
Component and its rate of charge in meter, the water-borne UV-curing resin reaction system include：
Hexamethylene diisocyanate (HDI) 12.5-30.6
The polyalcohol 5.2-35.8 of three-functionality-degree or tetra functional
Catalyst 0.05-0.1
Dimethylolpropionic acid (DMBA) 3-5
Acetone/butanone 12.5-35.6
Polymerization inhibitor 0.2-0.8
Hydroxy acrylate 16.7-39.4
Triethylamine (TEA) 2.2-7.5
Organic fluoride 1.0-2.8
Surplus is deionized water.
3. a kind of water-borne UV-curing resin of organic fluorine richness according to claim 2, it is characterised in that the polyalcohol
For trimethylolpropane or pentaerythrite or propylene oxide triol.
4. a kind of water-borne UV-curing resin of organic fluorine richness according to claim 2, it is characterised in that the catalyst
For dibutyl tin laurate or stannous octoate.
5. a kind of water-borne UV-curing resin of organic fluorine richness according to claim 2, it is characterised in that the hydroxyl third
Olefin(e) acid ester is the acrylate of two degrees of functionality or three-functionality-degree.
6. a kind of water-borne UV-curing resin of organic fluorine richness according to claim 5, it is characterised in that two function
Degree acrylate is trimethylolpropane diacrylate, and the three-functionality-degree acrylate is pentaerythritol triacrylate.
7. a kind of water-borne UV-curing resin of organic fluorine richness according to claim 2, it is characterised in that the Organic fluoride
For perfluorooctanol.
8. a kind of preparation method of the water-borne UV-curing resin of organic fluorine richness as described in claim 1-7 is any, its feature
It is, comprises the following steps：
(1) hexamethylene diisocyanate is added in equipped with electric mixer, thermometer, the four-hole boiling flask of reflux condensing tube,
Heating is progressively warming up to during 60-80 DEG C, adds polyalcohol and dimethylolpropionic acid, and control temperature is anti-at 60-90 DEG C
Theoretical value should be reached to-NCO, and no longer changed；
(2) question response heat release terminates to add catalyst to temperature plateau, is then cooled to 60-70 DEG C, sequentially add polymerization inhibitor,
Hydroxy acrylate and Organic fluoride, reaction to-NCO disappear or only micro presence substantially, and pilot process is according to viscosity B coefficent feelings
Condition, by supplementing acetone or butanone viscosity reduction；
(3) 40-50 DEG C is cooled to, triethylamine neutralization reaction 3-5min is added, deionized water neutralization, and scattered 20- is added
30min is to translucent；
(4) acetone or butanone are removed through vacuum distillation, obtains PUA photocuring dispersions, as described water-borne UV-curing resin.
9. a kind of preparation method of the water-borne UV-curing resin of organic fluorine richness according to claim 8, it is characterised in that
In the step (1), polyalcohol is first added, control temperature, which is reacted at 60-90 DEG C to-NCO, reaches theoretical value, and no longer changes
When, add dimethylolpropionic acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084401A (en) * | 2017-12-29 | 2018-05-29 | 广州瀚东新材料科技有限公司 | A kind of surfactant of radiation curable aqueous fluorochemical urethane acrylate and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108084401A (en) * | 2017-12-29 | 2018-05-29 | 广州瀚东新材料科技有限公司 | A kind of surfactant of radiation curable aqueous fluorochemical urethane acrylate and its preparation method and application |
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| CN109880055B (en) * | 2019-02-27 | 2022-01-28 | 黑龙江省科学院石油化学研究院 | Preparation method of perfluoroalkyl chain terminated polyurethane acrylate with comb-shaped structure |
| CN112608449A (en) * | 2020-12-03 | 2021-04-06 | 长兴（广州）光电材料有限公司 | Modified polyester type fluorine-containing polyurethane acrylate polymer and synthesis and application thereof |
| CN113354791A (en) * | 2021-06-24 | 2021-09-07 | 哈尔滨工业大学无锡新材料研究院 | UV-curable hyperbranched fluorine-silicon modified polyurethane, preparation method thereof and coating prepared from polyurethane |
| CN116199844A (en) * | 2022-12-31 | 2023-06-02 | 珠海华天印新材料有限公司 | Fluorine-containing acrylic resin, synthesis method thereof and application of fluorine-containing acrylic resin in UV antifouling paint |
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