CN106117449A - A kind of fluorinated silicone modified aqueous alkide resin and preparation method thereof - Google Patents
A kind of fluorinated silicone modified aqueous alkide resin and preparation method thereof Download PDFInfo
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- CN106117449A CN106117449A CN201610555550.9A CN201610555550A CN106117449A CN 106117449 A CN106117449 A CN 106117449A CN 201610555550 A CN201610555550 A CN 201610555550A CN 106117449 A CN106117449 A CN 106117449A
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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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- 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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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Abstract
The present invention relates to a kind of fluorinated silicone modified aqueous alkide resin and preparation method thereof, its composition is made up of vegetable fatty acids, organic acid anhydride, polyhydric alcohol, fluorine vinyl monomer, isocyanates, hydroxy-end capped organosilicon, acrylic monomer and deionized water；Fluorinated silicone modified aqueous alkide resin that the present invention prepares is adjustable allots mono-component aqueous coating, bi-component waterborne coating, air-curing coatings；The fluorinated silicone modified aqueous alkide resin that the present invention prepares has the performances such as good adhesive force, stain resistance, high rigidity, resistance to water, durability, hydrophobicity, self-cleaning, it is widely used in water-borne wood coating, aqueous industrial coating, waterborne anti-fouling coatings, water-based anticorrosive paint, the special engineered coating of aqueous such as radar cover material, wind power generation, nuclear power, marine paint etc..
Description
Technical field
The present invention relates to the preparation method of a kind of modified water-based alkyd resin, refer more particularly to a kind of even structure, cost
Low, surface tension is extremely low, have good hydrophobic, antifouling, the fluorinated silicone modified aqueous alkide resin of high rigidity function.The present invention ties
Close alkyd resin raw material to be easy to get and low cost, Si-O height bond energy, feature that fluorine atom radius is little, prepared fluorinated silicone modified aqueous
Alkyd resin can be used for the base materials such as timber, metal, plastics, belongs to water-base resin synthesis technical field.
Background technology
Alkyd resin is developed in the thirties in 20th century, and it has the features such as paint film adhesion is good, bright, plentiful, and has
Well application property, but its film is softer, it is slow to be dried, hardening time is long, weather-proof, water-fast, alkali resistance is not good enough.Alkyd resin is extensive
Application for the buildings such as bridge and machinery, vehicle, boats and ships, aircraft, instrument etc..
Alkyd resin both can prepare one pack system self-drying paint, it is also possible to preparation two-component air-dry paint or hot curing varnish.Monomer whose comes
Source is abundant, price is low, wide in variety, formula changes greatly, technique is simple, compatibility good, to pigment, the wettability of filler and dispersibility
Good, fluctuated not quite by oil price, there is unique price advantage, meet the social desirability of sustainable development.
Along with the constantly progressive of scientific and technological level and the continuous enhancing of people's environmental consciousness, to the environmental requirement of coating increasingly
Height, does not contains or containing volatile organic matter system, oneself becomes new developing direction less, and solvent type resin is the most progressively by water-base resin institute
Substituting, the exploitation of water-base resin is increasingly subject to people's attention with research, and alkyd resin molecule has polarity main chain and non-pole
Property side chain, containing hydroxyl, carboxyl and double bond isoreactivity group on molecule, this provides condition for alkyd resin chemical modification.
In order to improve these problems of alkyd resin itself, one that has just become alkyd resin to develop alkyd resin modification is necessarily become
Gesture.
Owing to common Structure Detemination of Alkyd Resins comprising only C-C, C-O key, without Si-O key, and in silicone molecules
Si-O has high bond energy, so common alkyd resin does not have resistance to elevated temperatures after making paint；And resistance to ag(e)ing, self-cleaning function
The most poor, develop a kind of water-base resin multi-functional, that cost performance is high and especially seem important.And the present invention draws in alkyd resin
Enter organosilicon, firmness C-C, C-O to be far above key of its Si-O key, use organosilicon modified to alkyd resin, modified
The weatherability that had of alkyd resin, thermostability and electrical insulating property, improve the deficiency of alkyd paint performance.Simultaneously can also
Improve the weatherability of alkyd resin, resistance to ozone, UV resistant etc..
Summary of the invention
In order to solve technical problem described above, the present invention introduces organosilicon in alkyd resin Middle molecule structure, its
Firmness C-C, C-O to be far above key of Si-O key, uses organosilicon modified to alkyd resin, modified alkyd resin tool
The weatherability having had, thermostability and electrical insulating property, improve the deficiency of alkyd paint performance；Alkyd resin can also be improved simultaneously
Weatherability, resistance to ozone, UV resistant etc..
Owing to fluorine atom radius is little and has the strongest electronegativity, therefore it has shielding protection effect to carbochain, and this makes
Obtain fluoropolymer and there is heat stability, weatherability and the chemical inertness of excellence, and the low surface tension of uniqueness, low surface are freely
Energy, low-friction coefficient and low dielectric constant, this give fluoropolymer and have the water and oil repellence of excellence, be low-surface-energy
The one class important polymer in investigation of materials field.Fluoropolymer relatively costly, it is difficult to adapt to the development of existing market, therefore this
Invention introduces the fluorine element of low-surface-energy in lower-cost alkyd resin both can preferably retain the physico of alkyd resin
Performance can be effectively reduced again the surface of material to meet the hydrophobic of material and can hate oil requirement, and this had both been suitable for economy
Exhibition, meets again application demand.
Therefore the present invention is simultaneously introduced fluorine element and Si-O key in alkyd resin.They compensate for alkyd resin not
Foot, and introduce dihydromethyl propionic acid DMPA, this enable it to organic amino in and the stable water-base resin of rear formation.Modified
Alkyd resin has high rigidity, the performance such as hydrophobic, antifouling, self-cleaning, environmentally friendly.
The purpose of the present invention aims to provide a kind of high comprehensive performance, non-environmental-pollution, hydrophobic, antifouling, antiseptical fluorine silicon
Modified water-based alkyd resin.
Another object of the present invention is to provide the preparation method of a kind of fluorinated silicone modified aqueous alkide resin.Fluorinated silicone modified water
Property alkyd resin simplifies the synthesis technique of fluororesin and organic siliconresin, remains fluororesin water proofing property, oil repellency, anti-contamination
Property and weatherability and the high rigidity of Si-O key and temperature tolerance, on the other hand alkyd resin raw material be easy to get cheap and its have well
Richness and gloss.
The present invention takes techniques below scheme: the present invention relates to a kind of fluorinated silicone modified aqueous alkide resin, percentage by weight
Than meter, consisting of: vegetable fatty acids 4.0～10.0 parts, phthalic anhydride 2.0～6.0 parts, trimethylolpropane 4.0～10.0 parts,
Dimethylbenzene 2.0～6.0 parts, M-phthalic acid 2.0～8.0 parts, dihydromethyl propionic acid 1.5～4.5 parts, fluorine vinyl monomer 4.0～
10.0 parts, organosilicon 3.0～8.0 parts, polyisocyanates 4.0～10.0 parts, acrylic monomer 6.0～12.0 parts, nertralizer
1.5～4.0 parts, dibutyl tin laurate 0.02～0.08 part, azodiisobutyronitrile 0.04～0.1 part, deionized water 40.0
～60.0 parts.
The third described vinyl monomer is acrylic acid methyl ester., 2-methyl methacrylate, butyl acrylate, methacrylic acid
Butyl ester, Hydroxypropyl acrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, tert-butyl acrylate, methyl-prop
Olefin(e) acid N-butyl, isobutyl methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester, cyclohexyl methacrylate, isobornyl acrylate,
Isobornyl methacrylate, acrylic acid, methacrylic acid, 2-propylheptyl acrylate, lauryl alcohol ester, third
Olefin(e) acid lauryl, octadecyl methacrylate, octadecyl acrylate, glycidyl methacrylate, 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 use the monomer of soft or hard different proportion to carry out collocation and use.
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 vegetable fatty acids is in refined oleum lini, soybean oil, Oleum Ricini, tall oil, Oleum Cocois, Oleum Brassicae campestris
The combination of one or more.
Described organosilicon is hydroxy-end capped polydimethylsiloxane, the polydimethylsiloxane of hydroxyl alkyl end-blocking and hydroxyl
The combination of one or more in the polydimethylsiloxane of base polyethers end-blocking.
Described nertralizer is the combination of one or more in triethylamine, ammonia, dimethylethanolamine.
Described polyisocyanates is toluene di-isocyanate(TDI) TDI, isophorone diisocyanate 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 fluorinated silicone modified aqueous alkide resin, comprises the following steps:
A, hydroxy-end capped organosilicon is added with thermometer, condensing tube, agitator four mouthfuls of reactors in, be warming up to
80～90 DEG C, the most at the uniform velocity dripping polyisocyanates, time for adding is 1h, continues reaction 2h, i.e. obtains reactive intermediate A, treat
With；
B, with stirring, the reactor of dropper, by recipe requirements add acrylic monomer, fluorine vinyl monomer and
Catalyst azodiisobutyronitrile, stir to obtain a monomer mixture B, stand-by；
C, equipped with thermometer, condensing tube, water knockout drum, agitator four mouthfuls of reactors in, by formulation weight percentage ratio, depend on
Secondary addition vegetable fatty acids, phthalic anhydride, trimethylolpropane, dimethylbenzene, M-phthalic acid and dihydromethyl propionic acid, heat temperature raising
To 140 DEG C, open low rate mixing, after 1h, be warming up to 180 DEG C, be incubated about 2h, when water outlet slack-off or little time, be continuously heating to 210
～220 DEG C, measure its acid number after 1h, when acid number reaches Design Theory value, under vacuum, solvent is evaporated off；It is cooled to 80 DEG C, adds
Catalyst dibutyltin dilaurylate, under agitation, at the uniform velocity dropping reactive intermediate A, drip complete continuation and react 2h, and measure
NCO content, when NCO content is close to Design Theory value, is cooled to less than 50 DEG C, adds nertralizer, stirs 0.5h, adds formula
The deionized water of amount, filters, obtains the alkyd resin C of Si modification, stand-by；
D, the alkyd resin C of Si modification is added reactor, be warming up to 82 DEG C, under agitation, at the uniform velocity dropping monomer mixing
Thing B, time for adding is 3～5h；Drip complete continuation insulation reaction 1h, cooling, filter, obtain a kind of fluorinated silicone modified water alcohol acid
Resin.
The present invention provide the extremely low fluorinated silicone modified aqueous alkide resin of a kind of function admirable, non-environmental-pollution, VOC content and
Its preparation method.The fluorinated silicone modified aqueous alkide resin that the present invention prepares have good adhesive force, stain resistance, corrosion-resistant,
The performances such as resistance to water, alkali resistance, durability, hydrophobicity, low-k, are widely used in marine field, ferrum component, woodenware painting
Material, antifouling water-repellent paint are it can also be used to radome material, and its application potential is the hugest.
Detailed description of the invention
The present invention combines following instance and is described further the preparation of fluorinated silicone modified aqueous alkide resin.
Embodiment 1
A kind of fluorinated silicone modified aqueous alkide resin, its preparation technology is as follows:
A, hydroxy-end capped organosilicon 4.0 parts is loaded with thermometer, condensing tube, agitator four mouthfuls of reactors in rise
Temperature is to 82～85 DEG C, and the most at the uniform velocity dropping toluene di-isocyanate(TDI) 6.0 parts, drips off in 1h, continues reaction 2h, obtains in activity
Mesosome A, stand-by；
B, with stirring, the reactor of dropper, by recipe requirements add acrylic monomer 8.0 parts, fluorine alkenes
Monomer 6.0 parts and catalyst azodiisobutyronitrile 0.07 part, stir to obtain a monomer mixture B, stand-by；
C, equipped with thermometer, condensing tube, water knockout drum, agitator four mouthfuls of reactors in, by the percentage by weight of formula,
It is sequentially added into vegetable fatty acids 6.0 parts, phthalic anhydride 3.0 parts, trimethylolpropane 6.5 parts, dimethylbenzene 3.0 parts, M-phthalic acid
3.5 parts and dihydromethyl propionic acid 2.5 parts, be heated to 140 DEG C, open low rate mixing, be warming up to 180 DEG C after 1h, be incubated about 2h,
When water outlet slack-off or little time, be continuously heating to 210 DEG C, after 1h, measure its acid number, when acid number reaches Design Theory value, vacuum
Under solvent is evaporated off；It is cooled to 80 DEG C, adds catalyst dibutyltin dilaurylate 0.04 part, under agitation, at the uniform velocity drip activity
Intermediate A, drips complete continuation and reacts 2h, and measure NCO content, when NCO content is close to Design Theory value, be cooled to 50 DEG C
Hereinafter, add nertralizer 2.0 parts, stir 0.5h, add the deionized water 49.4 parts of formula ratio, filter, obtain the alcohol of Si modification
Acid resin C, stand-by；
D, the alkyd resin C of Si modification is added reactor, be warming up to 82 DEG C, under agitation, at the uniform velocity dropping monomer mixing
Thing B, drips off in 4h, continues insulation reaction 1h, cooling, filters, obtain a kind of fluorinated silicone modified alkyd resin.
Embodiment 2
A kind of fluorinated silicone modified aqueous alkide resin, its preparation technology is as follows:
A, hydroxy-end capped organosilicon 4.5 parts is loaded with thermometer, condensing tube, agitator four mouthfuls of reactors in rise
Temperature is to 83～87 DEG C, and the most at the uniform velocity dropping isophorone diisocyanate 7.0 parts, drips off in 1h, continues reaction 2h, i.e. obtains
Reactive intermediate A, stand-by；
B, with stirring, the reactor of dropper, by recipe requirements add acrylic monomer 6.0 parts, fluorine alkenes
Monomer 6.5 parts and catalyst azodiisobutyronitrile 0.07 part, stir to obtain a monomer mixture B, stand-by；
C, equipped with thermometer, condensing tube, water knockout drum, agitator four mouthfuls of reactors in, by the percentage by weight of formula,
It is sequentially added into vegetable fatty acids 6.0 parts, phthalic anhydride 3.5 parts, trimethylolpropane 6.5 parts, dimethylbenzene 3.5 parts, M-phthalic acid
3.0 parts and dihydromethyl propionic acid 2.5 parts, be heated to 140 DEG C, open low rate mixing, be warming up to 180 DEG C after 1h, be incubated about 2h,
When water outlet slack-off or little time, be continuously heating to 210～220 DEG C, after 1h, measure its acid number, when acid number reaches Design Theory value
Time, solvent is evaporated off under vacuum；It is cooled to 80 DEG C, adds catalyst dibutyltin dilaurylate 0.04 part, under agitation, at the uniform velocity drip
Add reactive intermediate A, drip complete continuation and react 2h, and measure NCO content, when NCO content is close to Design Theory value, cooling
To less than 50 DEG C, add nertralizer 2.2 parts, stir 0.5h, add the deionized water 48.68 parts of formula ratio, filter, obtain silicon and change
The alkyd resin C of property, stand-by；
D, the alkyd resin C of Si modification is added reactor, be warming up to 82 DEG C, under agitation, at the uniform velocity dropping monomer mixing
Thing B, drips off in 4h, continues insulation reaction 1h, cooling, filters, i.e. obtain fluorinated silicone modified alkyd resin.
Embodiment 3
A kind of fluorinated silicone modified aqueous alkide resin, its preparation technology is as follows:
A, hydroxy-end capped organosilicon 3.5 parts is loaded with thermometer, condensing tube, agitator four mouthfuls of reactors in rise
Temperature is to 83～87 DEG C, and the most at the uniform velocity dropping isophorone diisocyanate 7.0 parts, drips off in 1h, continues reaction 2h, i.e. obtains
Reactive intermediate A, stand-by；
B, with stirring, the reactor of dropper, by recipe requirements add acrylic monomer 8.5 parts, fluorine alkenes
Monomer 7.0 parts and catalyst azodiisobutyronitrile 0.07 part, stir to obtain a monomer mixture B, stand-by；
C, equipped with thermometer, condensing tube, water knockout drum, agitator four mouthfuls of reactors in, by the percentage by weight of formula,
It is sequentially added into vegetable fatty acids 8.0 parts, phthalic anhydride 3.2 parts, trimethylolpropane 6.4 parts, dimethylbenzene 2.5 parts, M-phthalic acid
3.2 parts and dihydromethyl propionic acid 2.6 parts, be heated to 140 DEG C, open low rate mixing, be warming up to 180 DEG C after 1h, be incubated about 2h,
When water outlet slack-off or little time, be continuously heating to 210 DEG C, after 1h, measure its acid number, when acid number reaches Design Theory value, except molten
Agent, is cooled under 80 DEG C, vacuum solvent is evaporated off；It is cooled to 80 DEG C, adds catalyst dibutyltin dilaurylate 0.04 part, stirring
Mix down, at the uniform velocity dropping reactive intermediate A, drip complete continuation and react 2h, and measure NCO content, when NCO content sets close to theory
During evaluation, it is cooled to less than 50 DEG C, adds nertralizer 2.1 parts, stir 0.5h, add the deionized water 45.88 parts of formula ratio, mistake
Filter, obtains the alkyd resin C of Si modification, stand-by；
D, the alkyd resin C of Si modification is added reactor, be warming up to 82 DEG C, under agitation, at the uniform velocity dropping monomer mixing
Thing B, drips off in 4h, continues insulation reaction 1h, cooling, filters, i.e. obtain a kind of fluorinated silicone modified alkyd resin.
According to relevant criterion, embodiments of the invention are contrasted with Si modification alkyd resin, aqueous alkide resin, inspection
The performance indications surveyed are as shown in table 1.
Wherein, rate of drying: detect according to the regulation of GB1728；
Adhesive force: according to the regulation of GB/T1720-1988, uses cross-hatching to test；
Hardness: measure hardness of paint film according to GB/T6739-2006 colored paint and clear pencil method；
Pliability: detect according to the regulation of GB/T1731-1993；
Resistance to impact: detect according to the regulation of GB/T1732-2007；
Surface tension: use suspension ring tensammetric determination；
Resistance to water: detect according to the regulation of GB/T1733-93；
Salt fog resistance: detect according to the regulation of GB/T1771-1991；
Weatherability: detect according to the regulation of GB/T1865-2009；
Resistance to impact: detect according to the regulation of GB/T1732-93.
Table 1 aqueous fluorinated silicone modified alkyd resin performance indications
Although the present invention has been explained in detail and has quoted as proof embodiment, but for those of ordinary skill in the art, aobvious
So the various schemes made, can revise and change as specified above, should be construed as being included within the scope of claim.
Claims (8)
1. a fluorinated silicone modified aqueous alkide resin, it is characterised in that: by weight percentage, consisting of: vegetable fatty
Acid 4.0～10.0 parts, phthalic anhydride 2.0～6.0 parts, trimethylolpropane 4.0～10.0 parts, dimethylbenzene 2.0～6.0 parts, isophthalic two
Formic acid 2.0～8.0 parts, dihydromethyl propionic acid 1.5～4.5 parts, fluorine vinyl monomer 4.0～10.0 parts, organic silicon monomer 3.0～
8.0 parts, polyisocyanates 4.0～10.0 parts, acrylic monomer 6.0～12.0 parts, nertralizer 1.5～4.0 parts, tin dilaurate
Dibutyl tin 0.02～0.08 part, azodiisobutyronitrile 0.04～0.1 part, deionized water 40.0～60.0 parts.
A kind of fluorinated silicone modified aqueous alkide resin the most as claimed in claim 1, it is characterised in that: the third described vinyl monomer
For acrylic acid methyl ester., 2-methyl methacrylate, butyl acrylate, butyl methacrylate, Hydroxypropyl acrylate, acrylic acid-
2-hydroxy methacrylate, methacrylic acid-2-hydroxy methacrylate, tert-butyl acrylate, n-BMA, isobutyl
Ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, propylene
Acid, methacrylic acid, 2-propylheptyl acrylate, lauryl alcohol ester, lauryl acrylate, methacrylic acid ten
Octaester, octadecyl acrylate, glycidyl methacrylate, ring trimethylolpropane dimethoxym ethane acrylate, acrylic acid four
The combination of one or more in hydrogen furfuryl alcohol ester, methacrylic acid tetrahydrofurfuryl alcohol ester.
A kind of fluorinated silicone modified aqueous alkide resin the most as claimed in claim 1, it is characterised in that: described fluorine vinyl monomer is
Hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid hexafluoro isopropyl ester, methacrylic acid hexafluoro isopropyl ester, propylene
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 alkyl ethyl acrylate, perfluoroalkyl second
The combination of one or more in methyl acrylate.
A kind of fluorinated silicone modified aqueous alkide resin the most as claimed in claim 1, it is characterised in that: described vegetable fatty acids
For the combination of one or more in refined oleum lini, soybean oil, Oleum Ricini, tall oil, Oleum Cocois, Oleum Brassicae campestris.
A kind of fluorinated silicone modified aqueous alkide resin the most as claimed in claim 1, it is characterised in that: described organic silicon monomer is
Hydroxy-end capped polydimethylsiloxane, the polydimethylsiloxane of hydroxyl alkyl end-blocking and the poly dimethyl silicon of hydroxy polyethers end-blocking
The combination of one or more in oxygen alkane.
A kind of fluorinated silicone modified aqueous alkide resin the most as claimed in claim 1, it is characterised in that: described nertralizer is three second
The combination of one or more in amine, ammonia, dimethylethanolamine.
A kind of fluorinated silicone modified aqueous alkide resin the most as claimed in claim 1, it is characterised in that: described polyisocyanates is
Toluene di-isocyanate(TDI) TDI, isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, phenylenedimethylidyne two are different
Cyanate XDI, cyclohexanedimethyleterephthalate diisocyanate H6In XDI, tetramethylxylylene diisocyanate TMXDI one
Kind or several combinations.
8. the preparation method of a fluorinated silicone modified aqueous alkide resin as claimed in claim 1, it is characterised in that: described system
Preparation Method, its preparation technology is as follows:
A, hydroxy-end capped organosilicon is added with thermometer, condensing tube, agitator four mouthfuls of reactors in, be warming up to 80～
90 DEG C, the most at the uniform velocity dripping polyisocyanates, time for adding is 1h, continues reaction 2h, i.e. obtains reactive intermediate A, stand-by；
B, with stirring, the reactor of dropper, add acrylic monomer, fluorine vinyl monomer and catalysis by recipe requirements
Agent azodiisobutyronitrile, stir to obtain a monomer mixture B, stand-by；
C, equipped with thermometer, condensing tube, water knockout drum, agitator four mouthfuls of reactors in, by formulation weight percentage ratio, add successively
Enter vegetable fatty acids, phthalic anhydride, trimethylolpropane, dimethylbenzene, M-phthalic acid and dihydromethyl propionic acid, be heated to
140 DEG C, open low rate mixing, after 1h, be warming up to 180 DEG C, be incubated about 2h, when water outlet slack-off or little time, be continuously heating to 210～
220 DEG C, after 1h, measure its acid number, when acid number reaches Design Theory value, under vacuum, solvent is evaporated off；Being cooled to 80 DEG C, addition is urged
Agent dibutyl tin laurate, under agitation, at the uniform velocity dropping reactive intermediate A, drip complete continuation and react 2h, and measure
NCO content, when NCO content is close to Design Theory value, is cooled to less than 50 DEG C, adds nertralizer, stirs 0.5h, adds formula
The deionized water of amount, filters, obtains the alkyd resin C of Si modification, stand-by；
D, the alkyd resin C of Si modification is added reactor, be warming up to 82 DEG C, under agitation, at the uniform velocity dropping monomer mixture B,
Time for adding is 3～5h；Drip complete continuation insulation reaction 1h, cooling, filter, obtain a kind of fluorinated silicone modified water alcohol acid tree
Fat.
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