CN108219076A - The preparation method of water-based hydroxyl polyurethane-acrylate and its application in anti-graffiti coating - Google Patents
The preparation method of water-based hydroxyl polyurethane-acrylate and its application in anti-graffiti coating Download PDFInfo
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- CN108219076A CN108219076A CN201711433868.0A CN201711433868A CN108219076A CN 108219076 A CN108219076 A CN 108219076A CN 201711433868 A CN201711433868 A CN 201711433868A CN 108219076 A CN108219076 A CN 108219076A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The preparation method and its application in anti-graffiti coating that the present invention provides a kind of water-based hydroxyl polyurethane acrylate, the preparation method of water-based hydroxyl polyurethane acrylate provided by the invention, include the following steps, by the monomer solution containing monomer and hydroxy-end capped prepolymer mixed dissolution, shearing is carried out after neutralized reaction and disperses to obtain mixed emulsion, initiator is added in into mixed emulsion and carries out initiation polymerization；Wherein, the monomer includes at least one of acrylate monomer and hydroxy-acrylate monomer；The hydroxy-end capped prepolymer is made for the raw material hybrid reaction comprising following each component：Diisocyanate, dihydroxy based polyalcohol, chain extender；The dihydroxy based polyalcohol includes at least one of polyether Glycols, polyester diol.Not only preparation process is simply controllable for water-based hydroxyl polyurethane acrylate obtained by preparation method provided by the invention, can obtain the product compared with large arch dam, and with good anti-antigraffiti effect.
Description
Technical field
The invention belongs to anti-graffiti coating field, more particularly to a kind of water-based hydroxyl that can be used for preparing anti-graffiti coating gathers
Urethane-acrylate.
Background technology
With the fast development of social information, in countries such as America and Europes, scribble phenomenon is more universal compared with small advertisement is pasted.There is money
Material display, in Britain, the annual expense for removing scribble has been more than 200,000,000 pounds, and the U.S. is more than 20,000,000,000 pounds.At home, closely
Over year the phenomenon that writing without basis getting worse is disorderly sprayed in Urban Underground Passage, culvert, building exterior wall face etc..In order to fast and effeciently clear
Except scribble pollutes, barrier together can be established between protected surface and contaminated materials, i.e., anti-graffiti coatings make to scribble and are difficult to
It carries out, scribble pollution is easy to remove.Additionally, due to the raising of mankind's environmental consciousness, how to develop a kind of anti-scribble, easy cleaning,
The anti-scribble resin of the high-performance environment protection type with preferable recoatability has become the emphasis of current coating research again.
A kind of preparation method of the coating resin of height resistant to damage is disclosed in Chinese patent application CN102533093BA.
After such coating is by photocuring, the dyeing to ink and colorant in pen or marking pen, particularly permanent marker,
With good anti-antigraffiti effect.It mainly uses polyurethane, acrylate, epoxy resin, polyamide, chloridized polyolefin, gathers
At least one of ester is realized by being blended or being copolymerized functionalized resins.In application process, need through UV photocurings ability
It realizes higher-strength, certain trouble is brought to construction.
A kind of fluorinated with good anti-scribble and anti-pollution effect is described in U.S. Patent application US7501472B2
Aqueous polyurethane coating, preparation process are simple.Due to needing relatively low surface energy, so introducing halogen in the side chain of polyurethane
Element, this type coating in combustion, easily generate Toxic, unfavorable to environmental protection and human health.
Acrylate is widely used in anti-graffiti coating is built due to its price advantage, but simple third
There are feel deviation, when temperature is relatively low, brittleness increases olefin(e) acid resin, it is impossible to meet requirement well.
And the anti-scribble resin of traditional aqueous polyurethane exists due to containing relatively low (being generally lower than 30%) admittedly in application
Slow drying speed, particularly temperature are than in the case of relatively low, rate of drying seriously affects speed of application, is brought to worker very big
Trouble.In addition, present inventor's research also found, hydroxyl aqueous polyurethane emulsion under the conditions of high hydroxyl value, realize not by lotion
Large arch dam, and there are emulsion viscosity it is big the phenomenon that, be unfavorable for constructing.In addition, the preparation of hydroxyl dispersion is needed in high temperature
It is carried out under environment, process is difficult to control.Although resin is had excellent performance in application process, dispersion grain size itself is smaller,
Matt effect difficult to realize, and containing a large amount of solvents in system, it is all harmful to environmental protection and health.
Therefore, it is simple how to develop a kind of preparation process, and high hydroxyl value and large arch dam can be taken into account, and can bring good anti-
The resin of the performances such as antigraffiti effect and faster rate of drying, it has also become one of technological difficulties that this field urgently makes a breakthrough.
Invention content
The present invention provides a kind of water-based hydroxyl polyurethane-acrylate to make up the shortcomings of the prior art
Application of the resin in anti-graffiti coating made from preparation method and the preparation method, obtained by preparation method provided by the invention
Water-based hydroxyl polyurethane-acrylate not only preparation process is simply controllable, the product compared with large arch dam can be obtained, and have
Good anti-antigraffiti effect.
For the present invention to reach its purpose, the technical solution of use is as follows：
First aspect present invention provides a kind of preparation method of water-based hydroxyl polyurethane-acrylate, including as follows
Step,
By monomer solution and hydroxy-end capped prepolymer mixed dissolution, shearing is carried out after neutralized reaction and disperses to obtain mixing breast
Liquid, into mixed emulsion, addition initiator carries out initiation polymerization；
Wherein, the monomer contained in the monomer solution includes acrylate monomer, styrene-based monomers and hydroxy
At least one of acid ester monomer；
The hydroxy-end capped prepolymer is made for the raw material hybrid reaction comprising following each component：Diisocyanate, dihydroxy
Based polyalcohol, chain extender；The dihydroxy based polyalcohol includes at least one of polyether Glycols, polyester diol.
The preparation method of the present invention, it is preferred that based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate
Gross mass prepares each component that the raw material used in the hydroxy-end capped prepolymer includes following dosage：Diisocyanate 10-
40wt%, preferably 15-30wt%；Chain extender 1.5-25wt%, preferably 6-18wt%；Molar ratio with diisocyanate is 1:
1.8-1:4.8 dihydroxy based polyalcohol, molar ratio are more preferably 1:2.5-1:4.
The preparation method of the present invention, it is preferred that the number-average molecular weight of the polyether Glycols or polyester diol is 500-
3000, further preferred 800-2000, more preferably 1000-2000 are conducive to improve the resin anti-graffiti coating institute shape are made
Into the hardness of film, in favor of obtaining more preferably anti-antigraffiti effect.
The preparation method of the present invention, it is preferred that the chain extender includes polyol chain extender and carboxylic acid type hydrophilic chain extender.
Preferably, the gross mass based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate, the polyol chain extender and
The dosage of carboxylic acid type hydrophilic chain extender is respectively 1-20wt% (preferably 5-15wt%), 0.5-5wt% (preferably 1-3wt%).It is excellent
Choosing, the polyol chain extender is the polyol chain extender containing active hydrogen, and molecule amount is preferably 30-200g/mol.
Preferably, the carboxylic acid type hydrophilic chain extender is the carboxylic acid type hydrophilic chain extender containing active hydrogen.
The preparation method of the present invention in a kind of preferred embodiment, is prepared in the raw material of hydroxy-end capped prepolymer preferably
Further include the vegetable oil alcoholysate with double bond, more preferable soybean oil alcoholysate is made coating to improve resin and forms painting
The hardness and strength of film, its more preferable hydroxyl average functionality are 2, and further preferred vegetable oil alcoholysate molecular weight is 300-
400g/mol.Preferably, the average hydroxyl value of the vegetable oil alcoholysate is 100-500mgKOH/g, more preferably 200-
400mgKOH/g.By vegetable oil alcoholysate of the addition with double bond in the formula system of the present invention, particular with double bond
Soybean oil alcoholysate, can self-crosslinking in air, in application process, under conditions of curing agent is not consumed, by with
Other components synergy in formula can cooperate with curing agent crosslinked emulsions resin, to improve coating formation obtained by resin
The hardness and strength of film；Vegetable oil alcoholysate is renewable resource simultaneously, is protected conducive to the mankind.Vegetable oil alcoholysate (or
For plant oil modified polyalcohol) can be obtained by vegetable oil (such as soybean oil) and glycerine ester exchange reaction, vegetable oil with it is sweet
Grease exchange reaction is common organic reaction in organic chemistry, this is no longer repeated one by one.
In a kind of currently preferred embodiment, the preferred soybean oil alcoholysate of vegetable oil alcoholysate.This field is public
Know, soybean oil alcoholysate can carry out ester exchange reaction acquisition by soybean oil and glycerine, and the existing work of this field can be used
Prepared by skill, this is repeated no more.The soybean oil alcoholysate preferably comprises three kinds of compounds of following structure formula (I)-(III)
Mixture：
One ester,
Diester,Three esters.There is no particular restriction for the ratio of three, a kind of specific reality
It applies in mode, the mass ratio of structure formula (I), (II) and (III) three is followed successively by 52%, 40% and 8%, but the present invention is simultaneously
It is not only limited to this；Such as can be 48-52%, 38-42%, 7-9%.
In the preparation method of the present invention, it is preferred that based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate
Gross mass, the dosage of the soybean oil alcoholysate is 0.5-20wt%, further preferably 1-10wt%.
The preparation method of the present invention in a kind of preferred embodiment, is prepared and is also wrapped in the raw material of hydroxy-end capped prepolymer
Sulfonic acid type compound is included, the sulfonic acid type compound carries the active hydrogen and polymerizable double bond that can be reacted with isocyanates, to obtain
Obtain relatively stable relatively high hydroxyl value lotion；It is further preferred that the hydroxy functionality of the sulfonic acid type compound is at least 1, more
It is preferred that degree of functionality is 1；Still more preferably, the sulfonic acid type compound is alkene butoxy hydroxypropionate sodium, allyloxy
One or both of hydroxyl sulfoacid sodium, wherein more preferably allyloxy hydroxyl sulfoacid sodium, structural formula are as follows：
The preparation method of the present invention, it is preferred that based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate
Gross mass, the dosage of the sulfonic acid type compound is 0.5-10wt%, preferably 1-5wt%.
The preparation method of the present invention, more preferably, prepares in the raw material of hydroxy-end capped prepolymer simultaneously added with soybean
Oily alcoholysate and sulfonic acid type compound add both components simultaneously in the formula system of the present invention, the two synergy, more
Hardness, the strength and stability of product are further improved, and obtains more preferably anti-antigraffiti effect.
The preparation method of the present invention, it is preferred that the dosage of the monomer is the 0.5-1.1 of hydroxy-end capped pre-polymerization amount of substance
Times, preferably 0.8-1.0 times.Preferably, the solvent used in the monomer solution is less than 100 DEG C of organic solvent for boiling point,
Such as acetone, butanone etc. are, it is preferable to use acetone.The dosage of the solvent is preferably the 0.7-1.2 of hydroxy-end capped pre-polymerization amount of substance
Times,
The preparation method of the present invention, it is preferred that the dosage of the initiator is the 0.05-0.3% of the monomer mass,
Preferably 0.1-0.2%；Preferably, the initiator includes Oxidizing and Reducing Agents；It is further preferred that the oxidant packet
Include it is one or more in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate and tert-butyl hydroperoxide, it is further preferred that described
Reducing agent includes one or more in sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium hydrogensulfite and arabo-ascorbic acid.More preferably initiator
For tert-butyl hydroperoxide and sodium hydrosulfite combination.
The preparation method of the present invention, in a kind of more preferably scheme, based on preparing water-based hydroxyl polyurethane-acrylate tree
The gross mass of the reaction solution of fat, the hydroxy-end capped prepolymer are made for the component hybrid reaction comprising following mass percent：
Diisocyanate 10-40wt%, polyol chain extender 1-20wt%, carboxylic acid type hydrophilic chain extender 0.5-5wt%, soybean oleyl alcohol
Solve object 0.5-20wt%, sulfonic acid type compound 0.5-10wt%；Also containing dihydroxy based polyalcohol, the dihydroxy based polyalcohol and two
The molar ratio of isocyanates is 1:1.8-1:4.8；Based on the total of the reaction solution for preparing water-based hydroxyl polyurethane-acrylate
Quality, the dosage of the monomer are 0.5-1.1 times of dihydroxy blocked prepolymer quality；The dosage of the initiator is
The 0.05-0.3% of the monomer mass.
The preparation method of the present invention, in a kind of preferred scheme, based on preparing water-based hydroxyl polyurethane-acrylate tree
The gross mass of the reaction solution of fat, the hydroxy-end capped prepolymer are made for the component hybrid reaction comprising following mass percent：
Diisocyanate 15-30wt%, polyol chain extender 5-15wt%, carboxylic acid type hydrophilic chain extender 1-3wt%, soybean oil alcoholysis
Object is 1-10wt%, sulfonic acid type compound 1-5wt%；Also contain dihydroxy based polyalcohol, the dihydroxy based polyalcohol and two isocyanides
The molar ratio of acid esters is 1:2.5-1:4；Based on the gross mass for the reaction solution for preparing water-based hydroxyl polyurethane-acrylate,
The dosage of the monomer is 0.8-1 times of dihydroxy blocked prepolymer quality；The dosage of the initiator is the monomer mass
0.1-0.2%.
The preparation method of the present invention, preferably in a kind of specific embodiment, the monomer includes but not limited to acrylic acid
Methyl esters, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, methacrylic acid
Ethyl ester, hydroxyethyl methacrylate, butyl methacrylate, styrene, methyl styrene, isobornyl acrylate and acrylic acid
It is one or more in different monooctyl ester, preferably hydroxyethyl methacrylate and/or methyl methacrylate.
The preparation method of the present invention, preferably in a kind of specific embodiment, the diisocyanate includes but not limited to
Toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and two
Diphenylmethane diisocyanate it is one or more.
The preparation method of the present invention, in a kind of preferred specific embodiment, the dihydroxy based polyalcohol includes but unlimited
In polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diols, makrolon
Dihydric alcohol, polyethylene glycol adipate dihydric alcohol, polyadipate 1,4- butanediol esters dihydric alcohol, polyneopentyl glycol adipate two
One in first alcohol, polyadipate 1,6-HD ester dihydric alcohol and polyneopentyl glycol adipate 1,6-HD ester dihydric alcohol
Kind or a variety of, more preferably polyneopentyl glycol adipate dihydric alcohol, further preferred number-average molecular weight 800-2000's gathers oneself two
Sour neopentyl glycol ester dihydric alcohol, the polyneopentyl glycol adipate dihydric alcohol of more preferable number-average molecular weight 1000-2000.
The preparation method of the present invention, preferably in a kind of specific embodiment, the chain extender includes polyol chain extender
With carboxylic acid type hydrophilic chain extender；Polyol chain extender further preferably active hydrogen can simultaneously be reacted containing two or more with isocyanates
Active group, preferably include, but is not limited to one or both of trimethylolpropane and diethanol amine, it is preferable to use three hydroxyls
Methylpropane；Carboxylic acid type hydrophilic chain extender preferably includes, but is not limited to the dihydroxy compounds with carboxylate group, preferably wraps
Include dihydromethyl propionic acid, dimethylolpropionic acid, tartaric acid, N, it is one or more in N- dihydroxymethyl maleamic acids, it is more excellent
Select dihydromethyl propionic acid.
The preparation method of the present invention, in preferred embodiment, prepares during the hydroxy-end capped prepolymer it is used instead
It is 75-85 DEG C to answer temperature；Reaction end specifically can reach theoretical value to determine with reaction to NCO.
The preparation method of the present invention, in preferred embodiment, the mixed dissolution carries out at 50-60 DEG C, time tool
Body can be 5-10min.
The preparation method of the present invention, in preferred embodiment, the initiation temperature for causing polymerization is 30-35 DEG C.
In a kind of specific embodiment, the time of polymerisation is preferably 1-2h.
The preparation method of the present invention, as a kind of specific embodiment, the neutralization reaction is to monomer solution and hydroxyl
Neutralizer is added in the mixed liquor of blocked prepolymer mixed dissolution and carries out neutralization reaction, this is the routine operation of this field, is not made
It repeats.The neutralizer of neutralization reaction addition is, for example, N, N- dimethylethanolamines (DMEA) etc., and preferably 100% neutralizes.
The preparation method of the present invention in preferred embodiment, further includes following steps after polymerization is initiated：Removing is drawn
Solvent in hair polymerization products therefrom, the concrete mode for removing solvent are not construed as limiting, such as can be the modes such as vacuum distillation.
Second aspect of the present invention provides water-based hydroxyl polyurethane-acrylate tree made from preparation method described above
The application of fat it is especially suitable for preparing anti-graffiti coating, is preferred for preparing suitable for construction wall, bridge or furniture surface
Anti-graffiti coating.
The meaning of " a variety of " described herein is for two kinds and more than two kinds.
Third aspect present invention also provides a kind of anti-graffiti coating, which includes preparation side described above
Water-based hydroxyl polyurethane-acrylate made from method.
Technical solution provided by the invention has the advantages that：
Resin produced by the present invention combines traditional waterborne polyurethane and the advantage of water-and acrylate, compared with high hydroxyl value
Under the conditions of, it can accomplish compared with large arch dam, and emulsion viscosity is smaller, rate of drying is fast in work progress, improves construction efficiency；It is produced
The hydroxy radical content of object reaches 3wt%-5wt%, and solid content more can reach 30-50wt%, such as 35-45wt% in more than 30wt%.
Resin can be realized easily in application process by adding in curing agent solidification made from the preparation method of the present invention
High intensity and hardness can realize excellent anti-antigraffiti effect as building coating.
Compared to traditional aqueous polyurethane/acrylic resin, resin of the invention in application process can be with curing
The radical amount of agent reaction enriches, and more preferably, coating strength, hardness and the anti-scribble performance formed can meet and make comprehensive performance
With requiring.
Compared to existing waterborne polyurethane resin, resin of the invention have faster rate of drying, workability compared with
It is good.
Its average particle size of resin prepared by the present invention is in the range of 30-300nm, in 100-200nm in preferred version
In the range of.
Hydroxy-end capped aqueous polyurethane-acrylate resin provided by the invention, building-up process is safely controllable, operation letter
It is single, large-scale industrial production is easier to realize.
Specific embodiment
For a better understanding of the technical solution of the present invention, with reference to the embodiment content that the present invention is further explained,
But present disclosure is not limited only to following embodiment.
" % " in embodiment or comparative example is referred both to " wt% " if not specified.
Used test method in embodiment or comparative example is introduced below：
Solid content test method：Appropriate lotion is taken in container made of masking foil, weighs the weight before and after 150 DEG C of 20min
Amount variation, calculates its solid content.
Grain size test method：Using Malvern particle instrument.
PH test methods：Using pH meter.
Viscosity determining procedure：Using BROOKFIELD viscosity apparatus, No. 3 rotor/30rpm are tested.
Appearance test method：Eye, which is seen, to be judged.
The lotion formula used when preparing coating see the table below 1 made from following embodiment or comparative example：
Table 1
The method of the application performance of comparative example is described below after detection embodiment：
Workability test method：With reference to GB/T9756-2009, sample is brushed on test plate (panel) even surface with brush, is coated with
It measures as about 100 μm of wet coating thickness.Making the long side of test plate (panel), short side is placed vertically with horizontal plane into about 85 ° in horizontal direction.It is used again after placing 6h
Same method brushing second sample, in second brushing, brush operation can then be assessed as " brushing two without barrier without difficulty
Hinder ".
Dry speed test method：With reference to GB/T1728-79 (1989), coating surface is touched, but stick in finger without paint with finger
On, that is, think dry tack free.
Appearance of film test method：With reference to GB/T9756-2009, the test plate (panel) for applying swiped through sample is placed for 24 hours, is visually seen
Film is examined, if without notable shrinkage cavity, film is uniform, then is assessed as " normal ".
Pencil hardness test method：Using Mitsubishi (UNI) a set of hardness be respectively 6B, 5B, 4B, 3B, 2B, B, HB, F, H,
The pencil of 2H, 3H, 4H, 5H on film, apply 1000 gram forces, 10 millimeters of strokes, different location draws 3, sees by 45 ° of directions
Examine whether sample appearance has apparent cut, pencil hardness of the most hard pencil number of paint film for paint film cannot be scratched.
Anti- scribble performance test methods：With reference to JGT 304-2011.Existed respectively with prepared Chinese ink, permanent pen and black spray painting
The marking that area is 20mm × 20mm is coated at test plate (panel) coat side center, each scribble material four groups of test plate (panel) of painting, every group three pieces.It places
It is to be measured after for 24 hours.By cleaning ability by weak to strong sequence, full 1% aqueous weak cleaning is dipped in dry lint-free cotton, lint-free cotton respectively
Full citrus base detergent is dipped in agent, lint-free cotton and lint-free cotton dips in full alcohol and back and forth wipes 25 on the scribble marking of one group of test plate (panel)
Secondary, wiping pressure is about 1.5kg.Coating is visually inspected, if there are two pieces not stay apparent scribble trace, and coating is not in three pieces of test plate (panel)s
See apparent loss of gloss and discoloration, cleaning process terminates.Otherwise one group of test plate (panel) is replaced, is cleaned with the cleaning material of stronger level-one.
Rank evaluation capable of washing see the table below shown in 2：
Table 2
Stability：50 DEG C of constant temperature ovens are placed one month, and observation emulsion appearance whether there is layering.
The raw material used in embodiment or comparative example is introduced below：
(dicyclohexyl methyl hydride diisocyanate, NCO content are about 32.0% to HMDI, ten thousand magnificent chemical groups
Limited company)；
IPDI (isophorone diisocyanate, NCO content are about 37.8%, Bayer Bitterfeld GmbH)；
PNA-1000 (polyneopentyl glycol adipate glycol, hydroxyl value 112mgKOH/g, number-average molecular weight=1000, function
It is 2 to spend, Yantai Hua Da chemistry)；
PNA-2000 (polyneopentyl glycol adipate glycol, hydroxyl value 56mgKOH/g, number-average molecular weight=2000, degree of functionality
It is 2, Yantai Hua Da chemistry)；
Soybean oil alcoholysate (hydroxyl value 300mgKOH/g, degree of functionality 2, the chemistry self-control of ten thousand China, using soybean oil and glycerine into
Row ester exchange reaction is made, wherein the mixture containing structure formula (I)-(III) three kinds of compounds above, the mass ratio of three
It is followed successively by 52%, 40% and 8%)；
TMP (trimethylolpropane, BASF Corp. of Germany)；
DMPA (dihydromethyl propionic acid, Bai Situo)；
COPS-1 (allyloxy hydroxyl sulfoacid sodium, Rhodia)；
DMEA (N, N- dimethylethanolamine, BASF Corp. of Germany)；
Acetone (Wanhua Chemical Group Co., Ltd. refines)
MMA (methyl methacrylate, Qilu Petrochemical)；
HEMA (hydroxyethyl methacrylate, Wanhua Chemical Group Co., Ltd.)；
BA (butyl acrylate, Wanhua Chemical Group Co., Ltd.)
AA (acrylic acid, Wanhua Chemical Group Co., Ltd.)
St (styrene, sinopec)
APS (ammonium persulfate, Xilong Chemical Co., Ltd)
NaHCO3(sodium bicarbonate, Xilong Chemical Co., Ltd)
DS-4AP (neopelex, Rhodia)
Sodium hydrosulfite (sodium dithionite, Xilong Chemical Co., Ltd)
TBHP (tert-butyl hydroperoxide, Xilong Chemical Co., Ltd)
278 (isocyanate curing agent, Wanhua Chemical Group Co., Ltd.)
BD-109 (wetting agent, DOW Chemical)
Tego 825 (antifoaming agent, Bick)
U604 (thickener, Wanhua Chemical Group Co., Ltd.)
The preparation of soybean oil alcoholysate used in following embodiment or comparative example, using the existing method system in this field
It is standby, it is as follows：
Charge door is opened, 182g vegetable oil (soybean oil), 43g glycerine, 1g lithium hydroxides catalyst (are worn masks, avoided
Sucking) it pours into successively and cleans up and dry in anhydrous reaction vessel, charge door is closed, nitrogen is purged 5 minutes, emptied as early as possible
Air closes all valves；Stirring is opened, between being warming up to 230-235 DEG C and insulation reaction, is opened when temperature reaches 220 DEG C
Beginning timing is reacted after timing 2h and is finished, is cooled to 80 DEG C, and reaction solution is transferred to separatory funnel, leakage is bled off after standing 12 hours
Struggle against lower floor's 7g reaction solutions, retains upper strata alcoholysate.
Comparative example 1：Hydroxy-end capped aqueous polyurethane emulsion
72g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 10g soybean oils alcoholysate, 50gPNA1000 (polyneopentyl glycol adipate glycol),
7.8g dihydromethyl propionic acids are warming up to 80 DEG C of reaction 2h, are then cooled to 60 DEG C or so and add in 44g trimethylolpropanes, 67g
Acetone is warming up to 75 DEG C of reactions, is sampled every 1h and surveys NCO, until NCO reaches 0.1% hereinafter, stopping reaction.
60 DEG C are cooled to hereinafter, addition 134g acetone, is cooled to less than 40 DEG C addition 5.2gN, N- dimethylethanolamines, meter
Shi Fanying 5min.
Obtained performed polymer is poured into dispersion cup, 275g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane emulsion.
The lotion is removed into acetone therein by being evaporated under reduced pressure mode, 40% is obtained and contains admittedly, grain size 36nm, appearance is penetrating
Hydroxy-end capped aqueous polyurethane emulsion.
Comparative example 2：Hydroxyl water-and acrylate lotion
240g distilled water, 16g DS-4AP (22.5%) (neopelex), 192g first are added in wide-mouth bottle
Base hydroxy-ethyl acrylate, 100g styrene, 312g butyl acrylates, 9g acrylic acid are made under (1000r/min) stirring at a high speed
Standby pre-emulsion.
4.2g DS-4AP (22.5%) (neopelex), 3.6g sodium bicarbonates, 600g distilled water is taken to add in
Equipped in reflux condensing tube, thermometer, dropping funel and churned mechanically four-hole boiling flask, being warming up to 85 DEG C, add in 36g and prepare
Pre-emulsion, 2.5g ammonium persulfates, initiation reaction.
Pre-emulsion is slowly dropped into dropping funel in flask after ten minutes, is dripped off within 4 hours, and keeps the temperature 1 hour.Then
70 DEG C are cooled to, adds in 2.4g tert-butyl hydroperoxide and 1.2g sodium dithionites, room temperature discharging is down to after 1 hour, is obtained
Solid content is about 40%, and grain size is the hydroxyl acrylic emulsion of 156nm.
Embodiment 1：
68g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 10g soybean oils alcoholysate, 50gPNA1000 (polyneopentyl glycol adipate glycol),
7.2g dihydromethyl propionic acids are warming up to 80 DEG C of reaction 2h, are then cooled to 60 DEG C or so and add in 30g trimethylolpropanes, 50g
Acetone is warming up to 75 DEG C of reactions, is sampled every 1h and surveys NCO, until NCO reaches 0.1% hereinafter, stopping reaction.
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 99g acetone, 50g hydroxyethyl methacrylates, 100.88g first
Base methyl acrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 4.78gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 399g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane-hydroxy acrylate mixed emulsion.
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.225g tert-butyl hydroperoxide and 0.225g sodium dithionites cause free radical polymerization,
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 136nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
Embodiment 2：
68g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 100gPNA1000 (polyneopentyl glycol adipate glycol), 7.2g dihydroxymethyls third
Acid is warming up to 80 DEG C of reaction 2h, is then cooled to 60 DEG C or so and adds in 30g trimethylolpropanes, 62g acetone, be warming up to 75 DEG C
Reaction samples every 1h and surveys NCO, until NCO reaches 0.1% hereinafter, stopping reaction.
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 123g acetone, 50g hydroxyethyl methacrylates, 100.88g
Methyl methacrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 4.78gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 534g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane-hydroxy acrylate mixed emulsion.
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.225g tert-butyl hydroperoxide and 0.225g sodium dithionites cause free radical polymerization.
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 124nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
Embodiment 3
68g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 10g soybean oils alcoholysate, 50gPNA1000 (polyneopentyl glycol adipate glycol),
7.2g dihydromethyl propionic acids, 9.48g allyloxy hydroxyl sulfoacid sodium are warming up to 80 DEG C of reaction 2h, are then cooled to 60 DEG C or so
28.06g trimethylolpropanes, 50g acetone are added in, is warming up to 75 DEG C of reactions, is sampled every 1h and surveys NCO, until NCO reaches
0.1% hereinafter, stop reaction,
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 99g acetone, 50g hydroxyethyl methacrylates, 100.88g first
Base methyl acrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 4.78gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 399g water is added under the conditions of the high speed shear of 1500r/min, obtains hydroxyl
Base blocks aqueous polyurethane-hydroxy acrylate mixed emulsion,
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.225g tert-butyl hydroperoxide and 0.225g sodium dithionites cause free radical polymerization,
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 136nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
Embodiment 4
66g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 10g soybean oil alcoholysates, 50gPNA2000 (polyneopentyl glycol adipate glycol),
7.5g dihydromethyl propionic acids, 10.05g allyloxy hydroxyl sulfoacid sodium are warming up to 80 DEG C of reaction 2h, are then cooled to 60 DEG C of left sides
Right addition 37.32g trimethylolpropanes, 64g acetone, are warming up to 75 DEG C of reactions, are sampled every 1h and survey NCO, until NCO reaches
0.1% hereinafter, stop reaction.
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 128g acetone, 54g hydroxyethyl methacrylates, 108g methyl
Methyl acrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 4.98gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 562g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane-hydroxy acrylate mixed emulsion.
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.243g tert-butyl hydroperoxide and 0.243g sodium dithionites cause free radical polymerization.
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 131nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
Embodiment 5
68g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 10g soybean oils alcoholysate, 50gPNA1000 (polyneopentyl glycol adipate glycol),
7.2g dihydromethyl propionic acids, 9.48g allyloxy hydroxyl sulfoacid sodium are warming up to 80 DEG C of reaction 2h, are then cooled to 60 DEG C or so
Add in 30g trimethylolpropanes, 50g acetone, be warming up to 75 DEG C of reactions, sampled every 1h and survey NCO, up to NCO reach 0.1% with
Under, stop reaction.
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 99g acetone, 40g hydroxyethyl methacrylates, 110.88g first
Base methyl acrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 4.78gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 399g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane-hydroxy acrylate mixed emulsion.
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.225g tert-butyl hydroperoxide and 0.225g sodium dithionites cause free radical polymerization.
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 140nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
Embodiment 6
80g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI
(dicyclohexyl methyl hydride diisocyanate), 10g soybean oils alcoholysate, 50gPNA1000 (polyneopentyl glycol adipate glycol),
8g dihydromethyl propionic acids, 9.48g allyloxy hydroxyl sulfoacid sodium are warming up to 80 DEG C of reaction 2h, are then cooled to 60 DEG C or so and add
Enter 39.32g trimethylolpropanes, 56g acetone, be warming up to 75 DEG C of reactions, sampled every 1h and survey NCO, until NCO reaches
0.1% hereinafter, stop reaction.
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 112g acetone, 80g hydroxyethyl methacrylates, 100g methyl
Methyl acrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 5.31gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 550g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane-hydroxy acrylate mixed emulsion.
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.27g tert-butyl hydroperoxide and 0.27g sodium dithionites cause free radical polymerization.
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 225nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
Embodiment 7
To equipped with two isocyanide of addition 57.6g isophorones in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask
Acid esters, 10g soybean oils alcoholysate, 50gPNA1000 (polyneopentyl glycol adipate glycol), 7.2g dihydromethyl propionic acids,
9.48g allyloxy hydroxyl sulfoacid sodium is warming up to 80 DEG C of reaction 2h, is then cooled to 60 DEG C or so and adds in 30g trihydroxy methyls third
Alkane, 50g acetone are warming up to 75 DEG C of reactions, are sampled every 1h and survey NCO, until NCO reaches 0.1% hereinafter, stopping reaction.
It is cooled to less than 60 DEG C (between 50-60 DEG C), adds in 99g acetone, 50g hydroxyethyl methacrylates, 100.88g first
Base methyl acrylate, mixed dissolution.
It is cooled to less than 40 DEG C addition 4.78gN, N- dimethylethanolamines, clock reaction 5min.
Obtained performed polymer is poured into dispersion cup, 458g water is added under the conditions of the high speed shear of 1500r/min, is obtained
Hydroxy-end capped aqueous polyurethane-hydroxy acrylate mixed emulsion.
This lotion is transferred to equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask, is warming up to 32 DEG C
Left and right, sequentially adds 0.225g tert-butyl hydroperoxide and 0.225g sodium dithionites cause free radical polymerization.
The lotion is removed into acetone therein by being evaporated under reduced pressure mode after polymerization, 40% is obtained and contains admittedly, grain size 137nm
The hydroxy-end capped water-based polyurethane-acrylate emulsion of white blueing light.
According to the formulation for coating material of confession mentioned above prepared by lotion made from each embodiment and comparative example anti-scribble resin to apply
Material, and be tested for the property.The performance test results of obtained anti-scribble cold coating see the table below 3：
Table 3
As can be seen from the above results, the embodiment of the present invention is compared with comparative example 1, and gained resin grain size is larger, can be simultaneous
High hydroxyl value and large arch dam are cared for, and emulsion viscosity is low is easy to construct, comprehensive performance is preferable；2 phase of the embodiment of the present invention and comparative example
Than the lotion that appropriate viscosity can be made under comparable grain size, painting film property is excellent, and comprehensive performance is preferable.
From embodiment as it can be seen that resin produced by the present invention can take into account high hydroxyl value and large arch dam, and resin grain size is larger, viscosity
Moderate to be easy to construct, rate of drying is very fast, and the film formed also has good hardness, has good anti-scribble performance.
From the point of view of embodiment 1 and embodiment 2, the hardness of 1 its film of embodiment added with soybean oil alcoholysate will in formula system
Higher than the embodiment 2 for being not added with soybean oil alcoholysate.Embodiment 3 is compared with embodiment 1, is only to be added to soybean oil alcoholysis simultaneously
Object and sulfonic acid type compound have the hardness further improved, and anti-antigraffiti effect is also improved, and comprehensive performance is more
It is good.
From the point of view of production practices, the preparation side of the anti-scribble resin of hydroxy-end capped aqueous polyurethane-acrylate of the invention
Not only preparation process is simply controllable for method, can also obtain preferable application property, pencil hardness, also has preferable anti-scribble performance,
It is worth with larger actual use.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (15)
1. a kind of preparation method of water-based hydroxyl polyurethane-acrylate, which is characterized in that include the following steps,
By monomer solution and hydroxy-end capped prepolymer mixed dissolution, shearing is carried out after neutralized reaction and disperses to obtain mixed emulsion, to
Initiator is added in mixed emulsion and carries out initiation polymerization；
Wherein, monomer contained in the monomer solution includes acrylate monomer, styrene-based monomers and hydroxy acrylate
At least one of monomer；
The hydroxy-end capped prepolymer is made for the raw material hybrid reaction comprising following each component：Diisocyanate, dihydroxy gather
Close object, chain extender；The dihydroxy based polyalcohol includes at least one of polyether Glycols, polyester diol.
2. preparation method according to claim 1, which is characterized in that based on preparing water-based hydroxyl polyurethane-acrylate
The gross mass of the reaction solution of resin prepares each component that the raw material used in the hydroxy-end capped prepolymer includes following dosage：Two
Isocyanates 10-40wt%, chain extender 1.5-25wt%, the molar ratio with diisocyanate are 1:1.8-1:4.8 dihydroxy
Polymer.
3. according to claim 1-2 any one of them preparation methods, which is characterized in that the polyether Glycols or polyester binary
The number-average molecular weight of alcohol is 500-3000, further preferred 1000-2000.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that the chain extender includes polyalcohol chain extension
Agent and carboxylic acid type hydrophilic chain extender；
Preferably, the gross mass based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate, the polyalcohol chain extension
The dosage of agent and carboxylic acid type hydrophilic chain extender is respectively 1-20wt%, 0.5-5wt%；
Preferably, the polyol chain extender is the polyol chain extender containing active hydrogen, and molecule amount is preferably 30-
200g/mol；
Preferably, the carboxylic acid type hydrophilic chain extender is the carboxylic acid type hydrophilic chain extender containing active hydrogen.
5. according to claim 1-4 any one of them preparation methods, which is characterized in that
It prepares and the vegetable oil alcoholysate with double bond is further included in the raw material of hydroxy-end capped prepolymer；
Preferably, the average hydroxyl value of the vegetable oil alcoholysate is 100-500mgKOH/g, more preferably 200-400mgKOH/g；
Preferably, the gross mass based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate, the vegetable oil alcoholysis
The dosage of object is 0.5-20wt%, further preferably 1-10wt%.
6. preparation method according to claim 5, which is characterized in that the vegetable oil alcoholysate is soybean oil alcoholysate,
The soybean oil alcoholysate is preferably the mixture of the compound containing following structure formula (I)-(I I I)：
It is further preferred that structure formula (I), (II) and (II I) mass percent of compound shown in three respectively are
48-52%, 38-42%, 7-9%.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that prepare the raw material of hydroxy-end capped prepolymer
In further include sulfonic acid type compound, the sulfonic acid type compound carries the active hydrogen that can react with isocyanates and polymerizable pair
Key；
Preferably, the hydroxy functionality of the sulfonic acid type compound is at least 1, and more preferable degree of functionality is 1；
Preferably, the sulfonic acid type compound is one kind in alkene butoxy hydroxypropionate sodium, allyloxy hydroxyl sulfoacid sodium
Or two kinds；
Preferably, the gross mass based on the reaction solution for preparing water-based hydroxyl polyurethane-acrylate, the sulfonic acid type chemical combination
The dosage of object is 0.5-10wt%, preferably 1-5wt%.
8. according to claim 1-7 any one of them preparation methods, which is characterized in that the dosage of the monomer is hydroxy-end capped
0.5-1.1 times of pre-polymerization amount of substance, preferably 0.8-1.0 times；
Preferably, the solvent used in the monomer solution is less than 100 DEG C of organic solvent for boiling point, and the dosage of the solvent is excellent
It is selected as 0.7-1.2 times of hydroxy-end capped pre-polymerization amount of substance.
9. according to claim 1-8 any one of them preparation methods, which is characterized in that the dosage of the initiator is the list
The 0.05-0.3% of weight, preferably 0.1-0.2%；
Preferably, the initiator includes Oxidizing and Reducing Agents；
It is further preferred that the oxidant is included in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate and tert-butyl hydroperoxide
It is one or more；
It is further preferred that the reducing agent include sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium hydrogensulfite and arabo-ascorbic acid in one kind or
It is a variety of.
10. according to claim 1-9 any one of them preparation methods, which is characterized in that based on prepare water-based hydroxyl polyurethane-
The gross mass of the reaction solution of acrylate, the hydroxy-end capped prepolymer are the component mixing comprising following mass percent
Reaction is made：Diisocyanate 10-40wt%, polyol chain extender 1-20wt%, carboxylic acid type hydrophilic chain extender 0.5-5wt%,
Soybean oil alcoholysate 0.5-20wt%, sulfonic acid type compound 0.5-10wt%；Also containing dihydroxy based polyalcohol, the dihydroxy gathers
The molar ratio for closing object and diisocyanate is 1:1.8-1:4.8；
Based on the gross mass for the reaction solution for preparing water-based hydroxyl polyurethane-acrylate, the dosage of the monomer is dihydroxy
0.5-1.1 times of base blocked prepolymer quality；The dosage of the initiator is the 0.05-0.3% of the monomer mass.
11. preparation method according to claim 10, which is characterized in that based on preparing water-based hydroxyl polyurethane-acrylic acid
The gross mass of the reaction solution of ester resin, the hydroxy-end capped prepolymer are the component hybrid reaction system comprising following mass percent
：Diisocyanate 15-30wt%, polyol chain extender 5-15wt%, carboxylic acid type hydrophilic chain extender 1-3wt%, soybean oleyl alcohol
Solution object is 1-10wt%, sulfonic acid type compound 1-5wt%；Also containing dihydroxy based polyalcohol, the dihydroxy based polyalcohol and two different
The molar ratio of cyanate is 1:2.5-1:4；
Based on the gross mass for the reaction solution for preparing water-based hydroxyl polyurethane-acrylate, the dosage of the monomer is dihydroxy
0.8-1 times of base blocked prepolymer quality；The dosage of the initiator is the 0.1-0.2% of the monomer mass.
12. according to claim 1-11 any one of them preparation methods, feature is being, the monomer includes acrylic acid first
Ester, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, methacrylic acid second
Ester, hydroxyethyl methacrylate, butyl methacrylate, styrene, methyl styrene, isobornyl acrylate and acrylic acid are different
It is one or more in monooctyl ester, preferably hydroxyethyl methacrylate and/or methyl methacrylate；
Preferably, it is different to include toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone two for the diisocyanate
It is one or more in cyanate, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate；
Preferably, the dihydroxy based polyalcohol includes polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether
Glycol, polycaprolactone diols, polycarbonate glycol, polyethylene glycol adipate dihydric alcohol, polyadipate 1,4- butanediols
Ester dihydric alcohol, polyneopentyl glycol adipate dihydric alcohol, polyadipate 1,6-HD ester dihydric alcohol and polyadipate new penta 2
It is one or more in alcohol ester 1,6-HD ester dihydric alcohol；The polyadipate of further preferred number-average molecular weight 800-2000 is new
Pentadiol ester dihydric alcohol, the polyneopentyl glycol adipate dihydric alcohol of more preferable number-average molecular weight 1000-2000；
Preferably, the chain extender includes polyol chain extender and carboxylic acid type hydrophilic chain extender；Polyol chain extender preferably includes
One or both of trimethylolpropane and diethanol amine；Carboxylic acid type hydrophilic chain extender is preferably included with carboxylate group
Dihydroxy compounds, further preferably including dihydromethyl propionic acid, dimethylolpropionic acid, tartaric acid, N, N- dihydroxymethyls Malaysia
It is one or more in amic acid.
13. according to claim 1-12 any one of them preparation methods, which is characterized in that prepare the hydroxy-end capped prepolymer
When used reaction temperature be 75-85 DEG C；
Preferably, the mixed dissolution carries out at 50-60 DEG C；
Preferably, the initiation temperature for causing polymerization is 30-35 DEG C.
14. according to claim 1-13 any one of them preparation methods, which is characterized in that also wrapped after the initiation polymerization
Include following steps：Removing causes the solvent in polymerization products therefrom.
15. a kind of anti-graffiti coating, which is characterized in that including water made from claim 1-14 any one of them preparation methods
Property hydroxyl polyurethane-acrylate.
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