CN106700049A - Graphene-modified water-based fluorine alkyd resin and preparation method thereof - Google Patents
Graphene-modified water-based fluorine alkyd resin and preparation method thereof Download PDFInfo
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- CN106700049A CN106700049A CN201611175463.7A CN201611175463A CN106700049A CN 106700049 A CN106700049 A CN 106700049A CN 201611175463 A CN201611175463 A CN 201611175463A CN 106700049 A CN106700049 A CN 106700049A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention relates to graphene-modified water-based fluorine alkyd resin and a preparation method thereof. The graphene-modified water-based fluoroalate resin consists of vegetable oil fatty acid, organic acid anhydride, polyatomic alcohol, polybasic acid, dimethylolpropionic acid, a fluoroelene monomer, a neutralizing agent, polyisocyanate, grapheme, an acrylic monomer and deionized water. The graphene-modified water-based fluorine alkyd resin prepared by the preparation method provided by the invention has good adhesion, stain resistance, water resistance, alkali resistance and wear resistance, good electrical conductivity, excellent antistatic performance and the like, and is widely used for water-based wood coatings, water-based industrial coatings, water-based anti-fouling coatings, water-based anti-corrosion coatings and water-based special function coatings.
Description
Technical field
The present invention relates to a kind of preparation method of modified water-based alkyd resin, more particularly to a kind of hardness is high, low cost,
Surface tension is extremely low, conduct electricity very well, antifouling, electrostatic-proof function Graphene modified water-soluble fluorine alkyd resin, belongs to aqueous conjunction
Resin technical field.
Background technology
Alkyd resin is developed in the thirties in 20th century, its have paint film adhesion it is good, bright, it is plentiful the features such as, and have
Good application property, but its film is softer, it is slow to dry, and hardening time is long, and weather-proof, water-fast, alkali resistance is not good enough.Alkyd resin is mesh
Before be widely used in the resin of coating.
With the continuous enhancing of continuous progressive and people's environmental consciousness of scientific and technological level, to the environmental requirement of coating increasingly
Height, without or less system containing volatile organic matter oneself turn into new developing direction, solvent type resin is just progressively by water-base resin institute
Substitute, exploitation and the research of water-base resin are increasingly valued by people, and alkyd resin molecule has polarity main chain and non-pole
Property side chain, on molecule contain hydroxyl, carboxyl and double bond isoreactivity group, this provides condition for alkyd resin chemical modification.
In order to improve the deficiency of alkyd resin presence, modified alkyd resin turns into the inexorable trend of development.
C-C, C-O key are comprised only in common Structure Detemination of Alkyd Resins, so common alkyd resin is made surface tension after paint
Higher, antistatic property is bad, although alkyd resin is cheap, but can not meet the requirement of some special coatings；And it is resistance to
Aging, self-cleaning function are also poor, develop a kind of multi-functional, cost performance water-base resin high and especially seem important.
Being applied to the alkyd resin on the surfaces such as plastics, timber, metal its anti-soil, waterproof, antistatic at present needs to add it
His auxiliary agent, the shortcomings of auxiliary agent easily has uneven dispersion, functional limitation in coating, therefore develops a kind of anti-soil, antistatic work(
The modified alkyd resin gesture of energy is in necessity.
The content of the invention
There is shielding protection to act on carbochain because fluorine atom radius is small, it is excellent thermally-stabilised that this causes that fluoropolymer has
Property, weatherability and chemical inertness, and the low surface tension of uniqueness, low surface free energy, low-friction coefficient and low dielectric are normal
Number, this gives fluoropolymer and possesses excellent water and oil repellence, is the important polymerization of a class of low-surface-energy material research field
Thing.
And graphite it is dilute be one kind by individual layer sp2The two-dimensional sheet material of hydbridized carbon atoms composition, its special structures shape
It has peculiar electric property, good mechanical property, excellent physical and mechanical properties and a gas barrier property, graphite
Graphite oxide can be prepared into after being aoxidized via strong oxidizer, oxidized graphite flake layer contains substantial amounts of oxygen-containing polar group, such as hydroxyl
Base, carboxyl, epoxy radicals etc., with specific surface area higher.The nano composite material for being prepared with graphene oxide in recent years is showed
Go out very superior performance, be increasingly valued by people.
Fluoropolymer it is relatively costly, it is difficult to adapt to the development of existing market, therefore the present invention in lower-cost alkyd
The fluorine element that low-surface-energy is introduced in resin not only can preferably retain the physical and chemical performance of alkyd resin but also can effectively drop
The surface of low material can be to meet the hydrophobic of material and hate oily requirement, and this is both adapted to economic development, and application demand is met again.
The present invention introduces Graphene simultaneously in alkyd resin, compensate for alkyd resin antistatic performance deficiency, electric conductivity
Bad the shortcomings of, and introduce dihydromethyl propionic acid DMPA, this enables it to and in organic amino and rear forms water-base resin stably.
In order to solve the problems, such as techniques as described above, the present invention introduces organic fluorine element on molecular structure in alkyd resin
And Graphene is modified to it, the weatherability that modified alkyd resin has had, anti-soil, antistatic and good electric conductivity
Can, improve the deficiency of alkyd paint performance；The problems such as wearability and hardness of alkyd resin can also be improved simultaneously.And this hair
Bright introducing in alkyd resin has Graphene and fluorine element, can effectively improve the deficiency of alkyd paint performance, improves resin
Wearability, anti-soil, anti-static function etc..
The purpose of the present invention aims to provide a kind of Graphene modified water-soluble fluorine alkyd resin.
Another object of the present invention provides a kind of preparation method of Graphene modified water-soluble fluorine alkyd resin.
The present invention takes following technical scheme：The present invention relates to a kind of Graphene modified water-soluble fluorine alkyd resin, by weight
Percentages, consisting of：4.0~10.0 parts of vegetable fatty acids, 2.0~5.0 parts of organic acid anhydride, polyacid 3.0~6.0
Part, 2.0~8.0 parts of polyalcohol, 1.5~5.0 parts of dimethylbenzene, 1.0~4.0 parts of benzoic acid, 1.0~2.5 parts of dihydromethyl propionic acid,
2.0~5.0 parts of acetone, 2.0~5.0 parts of fluorine vinyl monomer, 1.5~5.0 parts of Graphene, 4.0~10.0 parts of polyisocyanates, third
2.0~6.0 parts of alkene acrylic monomer, 1.5~4.0 parts of nertralizer, 0.02~0.08 part of dibutyl tin laurate, the isobutyl of azo two
0.04~0.1 part of nitrile, 40.0~60.0 parts of deionized water.
The third described vinyl monomer is methyl acrylate, 2- methyl methacrylates, butyl acrylate, methacrylic acid
Butyl ester, hydroxypropyl acrylate, 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy methacrylates, tert-butyl acrylate, methyl-prop
Olefin(e) acid N-butyl, Isobutyl methacrylate, EHMA, cyclohexyl methacrylate, isobornyl acrylate,
Isobornyl methacrylate, acrylic acid, methacrylic acid, 2- propylheptyls acrylate, lauryl alcohol ester, third
Olefin(e) acid lauryl, octadecyl methacrylate, octadecyl acrylate, GMA, ring trimethylolpropane
The combination of one or more in dimethoxym ethane acrylate, acrylic acid tetrahydrofurfuryl alcohol ester, methacrylic acid tetrahydrofurfuryl alcohol ester；According to
The functional requirement of water-base resin can carry out collocation and use using the monomer of soft or hard different proportion.
Described fluorine vinyl monomer be hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid hexafluoro isopropyl ester,
Methacrylic acid hexafluoro isopropyl ester, acrylic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, perfluoro hexyl ethyl propylene acid esters,
Perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group acrylate, perfluorooctylethyl group methacrylate, perfluor alkane
The combination of one or more in base ethyl propylene acid esters, perfluor alkyl ethide methacrylate.
Described organic acid anhydride is the one or more combination in phthalic anhydride, acetic anhydride, maleic anhydride.
Described polyalcohol is ethylene glycol, propane diols, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, a contracting
One or more in DPG, trimethylolpropane, glycerine, trimethylolethane, pentaerythrite, xylitol, sorbierite
Combination.
Described polyacid is the group of one or more in phthalic acid, M-phthalic acid, hexanedioic acid, decanedioic acid
Close.
During described vegetable fatty acids are refined linseed oil, soybean oil, castor oil, tall oil, coconut oil, rapeseed oil
The combination of one or more.
Described Graphene for hydroxyl graphene oxide, by Hummers methods, Staudemaier methods, electrochemical process or
It is prepared by Brodie methods；Further, it is the graphene oxide of Hummers methods preparation.
Described nertralizer is the combination of one or more in triethylamine, ammoniacal liquor, dimethylethanolamine.
Described polyisocyanates is toluene di-isocyanate(TDI) TDI, IPDI IPDI, hexa-methylene two
Isocyanates HDI, XDI XDI, cyclohexanedimethyleterephthalate diisocyanate H6XDI, durol two
The combination of one or more in methylene diisocyanate TMXDI.
The preparation method of described Graphene modified water-soluble fluorine alkyd resin, comprises the following steps：
A, four mouthfuls of reactors that graphene oxide and dihydromethyl propionic acid addition are carried thermometer, condenser pipe, agitator
In, under agitation, polyisocyanates being at the uniform velocity added dropwise in 60~70 DEG C, time for adding is 1h, then proceedes to be warming up to 80 DEG C, insulation
Reaction 2h, that is, obtain reactive intermediate A, stand-by；
B, with stirring, in the reactor of dropper, add acrylic monomer, fluorine vinyl monomer by recipe requirements
With catalyst azodiisobutyronitrile, stir to obtain a monomer mixture B, stand-by；
C, in equipped with thermometer, condenser pipe, water knockout drum, four mouthfuls of reactors of agitator, by formulation weight percentage, according to
Secondary addition vegetable fatty acids, organic acid anhydride, polyalcohol, polyacid, dimethylbenzene and benzoic acid, are heated to 140 DEG C, change down
Speed stirring, is warming up to 180 DEG C after 1h, be incubated about 2h, when water outlet is little, is continuously heating to 210~220 DEG C, and it is determined after 1h
Acid number, when acid number reaches Theoretical Design value, solvent is evaporated off under vacuum；80 DEG C are cooled to, the fourth of catalyst dibutyltin cinnamic acid two is added
Ji Xi, under agitation, is at the uniform velocity added dropwise reactive intermediate A, and completion of dropping continues to react 2h, plus proper amount of acetone regulation viscosity, determines
NCO content, when NCO content is close to Theoretical Design value, is cooled to less than 50 DEG C, adds nertralizer, stirs 0.5h, adds formula
The deionized water of amount, filtering takes off acetone, obtains Graphene modified alkyd resin C, stand-by；
D, the alkyd resin C that Graphene is modified add reactor, are warming up to 82 DEG C, under agitation, monomer are at the uniform velocity added dropwise
Mixture B, time for adding is 3~5h；Completion of dropping is continuously heating to 85 DEG C, and insulation reaction 1h, cooling, filtering obtains one kind
Graphene modified water-soluble fluorine alkyd resin.
The present invention provides a kind of function admirable, free of contamination Graphene modified water-soluble fluorine alkyd resin and preparation method thereof.
Graphene modified water-soluble fluorine alkyd resin of the invention obtained has good adhesive force, pollution resistance, water resistance, alkali resistance, resistance to
Mill property, conduct electricity very well, the performance such as antistatic effect is excellent, be widely used in marine field, woodwork coating, electrically-conducting paint, antifouling
Water-repellent paint, its application potential is all very huge.
Specific embodiment
Graphene modified water-soluble fluorine alkyd resin of the invention is further described with reference to embodiment.Can manage
Solution, specific embodiment described herein is used only for explaining related invention, rather than the restriction to the invention.
Embodiment 1
A kind of Graphene modified water-soluble fluorine alkyd resin, its preparation technology is as follows：
A, 2.0 parts of 2.0 parts of graphene oxide and dihydromethyl propionic acid are added with thermometer, condenser pipe, agitator
In four mouthfuls of reactors, 8.0 parts of polyisocyanates is at the uniform velocity added dropwise in 60~70 DEG C under stirring condition, time for adding is 1h, Ran Houji
Continuous to be warming up to 80 DEG C, insulation reaction 2h obtains reactive intermediate A, stand-by；
B, with stirring, in the reactor of dropper, add 4.0 parts of acrylic monomer, fluorine alkene by recipe requirements
0.07 part of 3.0 parts of class monomer and catalyst azodiisobutyronitrile, stir to obtain a monomer mixture B, stand-by；
C, in equipped with thermometer, condenser pipe, water knockout drum, four mouthfuls of reactors of agitator, by formulation weight percentage, according to
It is secondary addition 8.0 parts of vegetable fatty acids, 2.5 parts of phthalic anhydride, 4.0 parts of neopentyl glycol, 3.5 parts of M-phthalic acid, 3.0 parts of dimethylbenzene and
2.5 parts of benzoic acid, is heated to 140 DEG C, opens low rate mixing, and 180 DEG C are warming up to after 1h, is incubated about 2h, when water outlet is little,
210~220 DEG C are continuously heating to, its acid number is determined after 1h, when acid number reaches Theoretical Design value, solvent is evaporated off under vacuum；Drop
Temperature adds 0.03 part of catalyst dibutyltin dilaurylate to 80 DEG C, under agitation, reactive intermediate A is at the uniform velocity added dropwise, and drips
Bi Jixu reacts 2h, plus 3.0 parts of regulation viscosity of acetone, determines NCO content, when NCO content is close to Theoretical Design value, is cooled to
Less than 50 DEG C, 2.0 parts of nertralizer is added, stir 0.5h, add 52.4 parts of deionized water, filtering takes off acetone, obtains Graphene and change
The alkyd resin C of property, it is stand-by；
D, the alkyd resin C that Graphene is modified add reactor, are warming up to 82 DEG C, under agitation, monomer are at the uniform velocity added dropwise
Mixture B, time for adding is 3~5h；Completion of dropping is continuously heating to 85 DEG C, and insulation reaction 1h, cooling, filtering obtains one kind
Graphene modified water-soluble fluorine alkyd resin.
Embodiment 2
A kind of Graphene modified water-soluble fluorine alkyd resin, its preparation technology is as follows：
A, 2.0 parts of 2.5 parts of graphene oxide and dihydromethyl propionic acid are added with thermometer, condenser pipe, agitator
In four mouthfuls of reactors, 8.5 parts of polyisocyanates is at the uniform velocity added dropwise in 60~70 DEG C under stirring condition, time for adding is 1h, Ran Houji
Continuous to be warming up to 80 DEG C, insulation reaction 2h obtains reactive intermediate D, stand-by；
B, with stirring, in the reactor of dropper, add 4.5 parts of acrylic monomer, fluorine alkene by recipe requirements
0.08 part of 3.5 parts of class monomer and catalyst azodiisobutyronitrile, stir to obtain a monomer mixture E, stand-by；
C, in equipped with thermometer, condenser pipe, water knockout drum, four mouthfuls of reactors of agitator, by formulation weight percentage, according to
It is secondary addition 8.5 parts of vegetable fatty acids, 2.0 parts of phthalic anhydride, 4.5 parts of neopentyl glycol, 3.0 parts of M-phthalic acid, 2.5 parts of dimethylbenzene and
3.5 parts of benzoic acid, is heated to 140 DEG C, opens low rate mixing, and 180 DEG C are warming up to after 1h, is incubated about 2h, when water outlet is little,
210~220 DEG C are continuously heating to, its acid number is determined after 1h, when acid number reaches Theoretical Design value, solvent is evaporated off under vacuum；Drop
Temperature adds 0.02 part of catalyst dibutyltin dilaurylate to 80 DEG C, under agitation, reactive intermediate D is at the uniform velocity added dropwise, and drips
Bi Jixu reacts 2h, plus 4.0 parts of regulation viscosity of acetone, determines NCO content, when NCO content is close to Theoretical Design value, is cooled to
Less than 50 DEG C, 2.0 parts of nertralizer is added, stir 0.5h, add 48.9 parts of deionized water, filtering takes off acetone, obtains Graphene and change
The alkyd resin F of property, it is stand-by；
D, the alkyd resin F that Graphene is modified add reactor, are warming up to 82 DEG C, under agitation, monomer are at the uniform velocity added dropwise
Mixture E, time for adding is 3~5h；Completion of dropping is continuously heating to 85 DEG C, and insulation reaction 1h, cooling, filtering obtains one kind
Graphene modified water-soluble fluorine alkyd resin.
Embodiment 3
A kind of Graphene modified water-soluble fluorine alkyd resin, its preparation technology is as follows：
A, 1.5 parts of 3.5 parts of graphene oxide and dihydromethyl propionic acid are added with thermometer, condenser pipe, agitator
In four mouthfuls of reactors, 9.5 parts of polyisocyanates is at the uniform velocity added dropwise in 60~70 DEG C under stirring condition, time for adding is 1h, Ran Houji
Continuous to be warming up to 80 DEG C, insulation reaction 2h obtains reactive intermediate G, stand-by；
B, with stirring, in the reactor of dropper, add 3.5 parts of acrylic monomer, fluorine alkene by recipe requirements
0.06 part of 2.5 parts of class monomer and catalyst azodiisobutyronitrile, stir to obtain a monomer mixture H, stand-by；
C, in equipped with thermometer, condenser pipe, water knockout drum, four mouthfuls of reactors of agitator, by formulation weight percentage, according to
It is secondary addition 9.5 parts of vegetable fatty acids, 2.5 parts of phthalic anhydride, 5.5 parts of neopentyl glycol, 4.0 parts of M-phthalic acid, 3.5 parts of dimethylbenzene and
2.5 parts of benzoic acid, is heated to 140 DEG C, opens low rate mixing, and 180 DEG C are warming up to after 1h, is incubated about 2h, when water outlet is little,
210~220 DEG C are continuously heating to, its acid number is determined after 1h, when acid number reaches Theoretical Design value, solvent is evaporated off under vacuum；Drop
Temperature adds 0.04 part of catalyst dibutyltin dilaurylate to 80 DEG C, under agitation, reactive intermediate G is at the uniform velocity added dropwise, and drips
Bi Jixu reacts 2h, plus 4.5 parts of regulation viscosity of acetone, determines NCO content, when NCO content is close to Theoretical Design value, is cooled to
Less than 50 DEG C, 1.5 parts of nertralizer is added, stir 0.5h, add 45.9 parts of deionized water, filtering takes off acetone, obtains Graphene and change
The alkyd resin J of property, it is stand-by；
D, the alkyd resin J that Graphene is modified add reactor, are warming up to 82 DEG C, under agitation, monomer are at the uniform velocity added dropwise
Mixture H, time for adding is 3~5h；Completion of dropping is continuously heating to 85 DEG C, and insulation reaction 1h, cooling, filtering obtains one kind
Graphene modified water-soluble fluorine alkyd resin.
According to relevant criterion, embodiments of the invention are contrasted with fluorine richness alkyd resin, aqueous alkide resin, examined
The performance indications of survey are as shown in table 1.
Adhesive force：According to the regulation of GB/T1720-1988, tested using cross-hatching；
Hardness：Hardness of paint film is determined according to GB/T6739-2006 colored paints and clear pencil method；
Surface tension：Using suspension ring tensammetric determination；
Water resistance：Regulation according to GB/T1733-93 is detected；
Salt fog resistance：Regulation according to GB/T1771-1991 is detected；
Surface resistivity：Regulation according to SJ/T 11294-2003 is detected.
Table 1：Embodiment and fluorine richness alkyd resin, aqueous alkide resin performance comparison
Although the present invention has been explained in detail and has been cited embodiment, for one of ordinary skill in the art, show
So can as specified above and make various schemes, modification and change, should be construed as being included within the scope of claim.
Claims (9)
1. a kind of Graphene modified water-soluble fluorine alkyd resin, it is characterised in that：Described Graphene modified water-soluble fluorine alkyd resin,
By weight percentage, consisting of：4.0~10.0 parts of vegetable fatty acids, 2.0~5.0 parts of organic acid anhydride, polyacid 3.0
~6.0 parts, 2.0~8.0 parts of polyalcohol, 1.5~5.0 parts of dimethylbenzene, 1.0~4.0 parts of benzoic acid, dihydromethyl propionic acid 1.0~
2.5 parts, 2.0~5.0 parts of acetone, 2.0~5.0 parts of fluorine vinyl monomer, 1.5~5.0 parts of Graphene, polyisocyanates 4.0~
10.0 parts, 2.0~6.0 parts of acrylic monomer, 1.5~4.0 parts of nertralizer, 0.02~0.08 part of dibutyl tin laurate,
0.04~0.1 part of azodiisobutyronitrile, 40.0~60.0 parts of deionized water；
Wherein, described Graphene is the graphene oxide of hydroxyl, by Hummers methods, Staudemaier methods, electrochemical process
Or prepared by Brodie methods；Further, it is the graphene oxide of Hummers methods preparation.
2. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described propylene class
Monomer is methyl acrylate, 2- methyl methacrylates, butyl acrylate, butyl methacrylate, hydroxypropyl acrylate, propylene
Acid -2- hydroxy methacrylates, methacrylic acid -2- hydroxy methacrylates, tert-butyl acrylate, n-BMA, methacrylic acid
Isobutyl ester, EHMA, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, third
Olefin(e) acid, methacrylic acid, 2- propylheptyls acrylate, lauryl alcohol ester, lauryl acrylate, methacrylic acid
Octadecyl ester, octadecyl acrylate, GMA, ring trimethylolpropane dimethoxym ethane acrylate, acrylic acid
The combination of one or more in tetrahydrofurfuryl alcohol ester, methacrylic acid tetrahydrofurfuryl alcohol ester.
3. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described fluorine alkenes list
Body be hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid hexafluoro isopropyl ester, methacrylic acid hexafluoro isopropyl ester,
Acrylic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, perfluoro hexyl ethyl propylene acid esters, perfluoro hexyl ethyl methacrylate
Ester, perfluorooctylethyl group acrylate, perfluorooctylethyl group methacrylate, perfluor alkyl ethyl acrylate, perfluor alkane
The combination of one or more in base ethylmethyl acrylate.
4. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described vegetable fat
Fat acid is the combination of one or more in refined linseed oil, soybean oil, castor oil, tall oil, coconut oil, rapeseed oil.
5. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described organic acid anhydride
It is the one or more combination in phthalic anhydride, acetic anhydride, maleic anhydride；Described polyacid be phthalic acid, M-phthalic acid,
One or more combination in hexanedioic acid, decanedioic acid.
6. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described polyisocyanic acid
Ester is toluene di-isocyanate(TDI) TDI, IPDI IPDI, hexamethylene diisocyanate HDI, phenylenedimethylidyne
Diisocyanate XDI, cyclohexanedimethyleterephthalate diisocyanate H6In XDI, tetramethylxylylene diisocyanate TMXDI
The combination of one or more.
7. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described polyalcohol is
Ethylene glycol, propane diols, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, trimethylolpropane,
One or more combination in glycerine, trimethylolethane, pentaerythrite, xylitol, sorbierite.
8. a kind of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：Described nertralizer is
The combination of one or more in triethylamine, ammoniacal liquor, dimethylethanolamine.
9. a kind of preparation method of Graphene modified water-soluble fluorine alkyd resin as claimed in claim 1, it is characterised in that：It is described
Preparation method, its preparation technology is as follows：
A, graphene oxide and dihydromethyl propionic acid are added with thermometer, condenser pipe, four mouthfuls of reactors of agitator, stirred
Polyisocyanates is at the uniform velocity added dropwise under the conditions of mixing in 60~70 DEG C, time for adding is 1h, then proceedes to be warming up to 80 DEG C, insulation reaction
2h, that is, obtain reactive intermediate A, stand-by；
B, with stirring, in the reactor of dropper, add acrylic monomer, fluorine vinyl monomer by recipe requirements and urge
Agent azodiisobutyronitrile, stir to obtain a monomer mixture B, stand-by；
C, in equipped with thermometer, condenser pipe, water knockout drum, four mouthfuls of reactors of agitator, by formulation weight percentage, successively plus
Enter vegetable fatty acids, organic acid anhydride, polyalcohol, polyacid, dimethylbenzene and benzoic acid, be heated to 140 DEG C, change down speed and stir
Mix, 180 DEG C be warming up to after 1h, be incubated about 2h, when water outlet is little, be continuously heating to 210~220 DEG C, its acid number is determined after 1h,
When acid number reaches Theoretical Design value, solvent is evaporated off under vacuum；80 DEG C are cooled to, catalyst dibutyltin dilaurylate is added,
Under agitation, reactive intermediate A is at the uniform velocity added dropwise, completion of dropping continues to react 2h, plus proper amount of acetone regulation viscosity, determines NCO and contain
Amount, when NCO content is close to Theoretical Design value, is cooled to less than 50 DEG C, adds nertralizer, stirs 0.5h, adds formula ratio
Deionized water, filtering takes off acetone, obtains Graphene modified alkyd resin C, stand-by；
D, the alkyd resin C that Graphene is modified add reactor, are warming up to 82 DEG C, under agitation, monomer mixing are at the uniform velocity added dropwise
Thing B, time for adding is 3~5h；Completion of dropping is continuously heating to 85 DEG C, and insulation reaction 1h, cooling, filtering obtains a kind of graphite
Alkene modified water-soluble fluorine alkyd resin.
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| CN107903755B (en) * | 2017-12-26 | 2019-07-05 | 海安常州大学高新技术研发中心 | A kind of preparation method of graphene oxide modified aqueous acrylic acid anticorrosive paint |
| CN108250957A (en) * | 2018-01-15 | 2018-07-06 | 江苏冠军科技集团股份有限公司 | A kind of graphene modified water coating type anti-corrosion resin and preparation method |
| CN108795107A (en) * | 2018-03-24 | 2018-11-13 | 成都迪泰化工有限公司 | The method of modifying and its product and UV photocureable coating of a kind of graphene |
| CN108531028A (en) * | 2018-03-27 | 2018-09-14 | 上海利物盛纳米科技有限公司 | A kind of low viscosity environment-friendly electronic three-proofing coating and its preparation method and application |
| CN112279999A (en) * | 2020-11-09 | 2021-01-29 | 广东石油化工学院 | Biodegradable radiation-curable urethane (meth) acrylate and preparation method thereof |
| CN112279999B (en) * | 2020-11-09 | 2022-03-11 | 广东石油化工学院 | Biodegradable radiation-curable urethane (meth) acrylate and preparation method thereof |
| CN113698563A (en) * | 2021-08-05 | 2021-11-26 | 明光科迪新材料有限公司 | Thioxanthone polyurethane modified epoxy acrylate LED (light-emitting diode) photocuring resin |
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