CN107446116A - Silicone-modified epoxy resin synthesis and its preparation method of water-based anticorrosive paint - Google Patents

Silicone-modified epoxy resin synthesis and its preparation method of water-based anticorrosive paint Download PDF

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CN107446116A
CN107446116A CN201710705133.2A CN201710705133A CN107446116A CN 107446116 A CN107446116 A CN 107446116A CN 201710705133 A CN201710705133 A CN 201710705133A CN 107446116 A CN107446116 A CN 107446116A
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epoxy resin
water
silicone
epoxy
parts
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CN107446116B (en
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蒋瑞霞
张驰
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Shenzhen Shensaier Co Ltd
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention discloses the synthesis of silicone-modified epoxy resin and its preparation method of water-based anticorrosive paint, its synthesis to include 1) preparing siloxanes hydrolyzate；2) low-viscosity epoxy resin and siloxanes hydrolyzate are taken, the mixed in molar ratio by 1: 1.1 the complete clear of reaction solution, reaction completion, that is, obtains silicone-modified epoxy resin in reactor, reacting 2~3h under 60 DEG C of constant temperature stirrings.Silicone-modified epoxy resin is hydrolyzed, the defects of breaching not water-fast paint film after resin Water-borne modification, Corrosion Protection degradation.Through silicone-modified epoxy resin; it is to prepare High performance protective coating material; the steel structure surface anticorrosive paint made of it; combination property has " synergistic effect "; protect light guarantor's anti-aging weather-proof Corrosion Protection of color and be better than unmodified epoxy coating performance, be particularly suitable for the anti-corrosion protection of the steel constructions such as bridge spanning the sea, sea port dock, offshore oil platform, submarine pipeline, ship and container.

Description

Silicone-modified epoxy resin synthesis and its preparation method of water-based anticorrosive paint
Technical field
The present invention relates to new material technology field, more particularly to a kind of silicone-modified epoxy resin synthesis and its water-based anti- The preparation method of rotten coating.
Background technology
Conventional epoxy resin is a kind of widely used matrix material, and filming performance is good, and coating antiseptic corrosion can It is very outstanding, it is to manufacture a kind of high molecular polymer filmogen that solvent-borne type anticorrosive paint dosage is maximum, purposes is most wide.But It is that coating circle due to the pressure by Environmental Protection Situation, forces enterprise to be made the transition to the direction of green environmental friendly coatingses product, to water-based at present The research of corrosion-resistant epoxy paint has turned into the focus of coating circle.However, the general character problem that those skilled in the art commonly encounter, It is exactly that water-resistant coating is poor after epoxy resin and its coating Water-borne modification, this is greatly lowered the anticorrosive property of epoxy coating Energy, it is unable to reach the estimated performance of solvent epoxy coatings coating.It is hydrophobic and refuse it is well known that in macromolecule resin material Water material is the most outstanding with silicon and fluorine material.But the latter's price is too expensive, and the former is more moderate.How this technology is broken through Bottleneck, just turn into one of research topic of coating circle researcher.
With modifying epoxy resin by organosilicon, many researchs are done in industry, as Zhu Huayu et al. uses trimethoxy Siloxanes and phenyl methyl dimethoxysiloxane synthesis polyphenyl methyl siloxane, modified E-20, improve the heat of polymer Stability；By the epoxy radicals of epoxy resin with the hydroxyl on polysiloxane molecule chain ring-opening reaction, system occur for S.Ahmad et al. For polysiloxane modified epoxy resin, its product passes through the heat endurance analyzed and contrast its system using polyamide as curing agent Significantly improve；They are organic-silicon-modified by being carried out to conventional epoxies, improve heat endurance；Also tight a beautiful gem et al. is adopted Aqueous epoxy resins are obtained with acrylated epoxy, then physical blending mode is carried out with self-control siloxane oligomer, Siloxane oligomer modified aqueous epoxy resin is made；Guo Wenlu etc. uses epoxy resin and siloxane oligomer such as KH-550 Deng acrylic acid hydrophilic radical being re-introduced into, in last alkali and obtained waterborne organic silicon modified epoxy；Liu Wenyan etc. is also to use Similar method, waterborne organic silicon modified epoxy being made, they are that aqueous epoxy resins are modified with siloxanes, The problem of general character is that obtained product solid content is not high, and so compared to conventional epoxies, solid content is low, and crosslinking is inadequate, comprehensive Performance is still not ideal enough.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of silicone-modified epoxy resin synthesis and its water-repellent preservation to apply The preparation method of material, to solve the water resistance problem of water corrosion-resistant epoxy paint, while also improve waterborne epoxy coatings Corrosion-resistant and weather resistance.
In order to solve the above technical problems, the purpose of the present invention is achieved through the following technical solutions.
A kind of silicone-modified epoxy resin synthesis, including：
1) siloxanes hydrolyzate is prepared；
2) low-viscosity epoxy resin and siloxanes hydrolyzate are taken, by 1: 1.1 mixed in molar ratio in reactor, 60 2~3h, the complete clear of reaction solution are reacted under DEG C constant temperature stirring, reaction is completed, that is, obtains silicone-modified asphalt mixtures modified by epoxy resin Fat.
Preferably：The step 1) specifically includes：
1. prepare alcohol-acid-aqueous solution by mass fraction：Weigh 80~85 parts of isopropanol, 5~10 parts of ethanedioic acid, pure water 5 ~10 parts, mixed dissolution is uniformly standby；
2. siloxanes hydrolysis：Weigh 65~70 parts of methyltriethoxy silane oxygen alkane MTES, octyl group triethoxy silica Alkane THES or iso-octyl triethoxy silica alkane IYES, in reactor under stirring, be added dropwise 25~35 parts of alcohol-acid-water Solution, 3~5h of slow reaction, treats that solution is completely as clear as crystal at normal temperatures, and it is standby to place 24h；
3. replace phase inversion：By the amount of solid content of the methods of GB/T 1725 measure siloxanes hydrolyzate, surplus is that moisture and alcohol are molten Liquid, the active epoxy diluent of addition same amount, under 120 DEG C of vacuum states, extract alcohol and water point out, mutually convert, produce To anhydrous non-alcoholic siloxanes hydrolyzate.
Preferably：The siloxanes Hydrolysis mechanism following equation：
Wherein, R is methyl, octyl group or iso-octyl.
Preferably：The reaction mechanism mechanism of reaction of the hydrolysis siloxanes and epoxy resin is as follows：
Wherein, R1It is low molecular weight epoxy reactive diluent or low-viscosity epoxy resin.
Preferably：The active epoxy diluent is polypropylene glycol diglycidyl ether (epoxide number is 0.28~0.36).
Preferably：The structural formula of the silicone-modified epoxy resin is as follows：
R1It is low molecular weight epoxy reactive diluent or low-viscosity epoxy resin.
Preferably：The cross-linked structure formula of the silicone-modified epoxy resin is as follows：
Wherein, wherein, R is methyl, octyl group or iso-octyl, R1Low molecular weight epoxy reactive diluent as or low viscosity Epoxy resin.
Preferably：When film forming is dried, following reaction occurs for some siloxanes hydrolyzate：
,
R is methyl, octyl group or iso-octyl.
A kind of water-based anticorrosive paint preparation method of silicone-modified epoxy resin as described above, including step：
A) preparation (being measured with mass parts) of water-based silicone epoxy anti-corrosion primer
1. the preparation of primary coat paint vehicle (component A)
Take silicone-modified 30~35 parts of epoxy resin, 0.5~1.0 part of water and oil applicable type wetting dispersing agent, water and oil applicable Type defoaming levelling agent is each 0.5~1.0 part, 10~15 parts of sheet-shaped fillers, the water and oil applicable type graphene dispersion slurry 10 for containing 6% admittedly ~15 parts, 0.5~1.5 part of water and oil applicable type anti-settling agent, 0.5~1.5 part of thickener, after mixing, upper high speed dispersor scattered 15 ~20 minutes, move on sand mill after being ground to 15~20 μm of fineness, then add 35~45 parts of 800 mesh active zinc powder, stirring point Dissipate；
2. the preparation of epoxy hardener (B component)
90~95 parts of epoxy hardener, 1~3 part of Epoxy curing accelerators, 1~3 part of pure water are taken, is well mixed, as A The self-emulsifying curing agent of component paint vehicle；
3. use proportioning
In use, press A groups: B group=4: the mixing of 1 quality proportioning, construction requirement viscosity can be arbitrarily diluted to pure water, i.e., Obtain water-based silicone-modified epoxy anticorrosion primer.
The synthesis of aqueous epoxy curing agent as described above, the water-based anticorrosive paint of described silicone-modified epoxy resin Preparation method, it is characterised in that including step：
B) preparation (being measured with mass parts) of aqueous silane Epoxy anti-corrosive finish paint
1. face applies the preparation of paint vehicle (component A)
Take 50~60 parts of silane-modified epoxy resin, 0.5~1.0 part of water and oil applicable type wetting dispersing agent, water and oil applicable type Defoam each 0.5~1.0 part levelling agent, 10~15 parts of sheet-shaped fillers, 15~20 parts of coloring pigment, water and oil applicable type anti-settling agent 0.5~1.5 part, 0.5~1.5 part of thickener, after mixing, upper high speed dispersor is scattered 15~20 minutes, moves on sand mill and grinds After being milled to 15~20 μm of fineness, after process of lapping or grinding, appropriate active epoxy diluent can be added and adjust system viscosity to 60 ~80s, you can filter and package；
2. the preparation of curing agent (B component)
90~95 parts of epoxy hardener, 1~3 part of Epoxy curing accelerators, 1~3 part of pure water are taken, is well mixed, as B The self-emulsifying curing agent of component paint vehicle；
3. use proportioning
In use, press A groups: B group=2: the mixing of 1 quality proportioning, pure water dilution can be added, produce aqueous silane and be modified ring Oxygen antisepsis finishing paint.
In the preparation method of silicone-modified epoxy resin synthesis provided by the invention and its water-based anticorrosive paint, silicon is hydrolyzed Siloxane modified epoxy resin, the defects of breaching not water-fast paint film after resin Water-borne modification, Corrosion Protection degradation.Made with it The water corrosion-resistant epoxy paint of work, due to introducing siloxane group in structure, net macromolecular film can be cross-linked into, is had Splendid water proofing property, weatherability, anti-aging, Corrosion Protection.It is to prepare high-performance protective through silicone-modified epoxy resin Coating material, with the steel structure surface anticorrosive paint that it makes, combination property has " synergistic effect ", and it is anti-aging to protect light guarantor's color Weather-proof Corrosion Protection is better than unmodified epoxy coating performance, is particularly suitable for bridge spanning the sea, sea port dock, marine stone The anti-corrosion protection of the steel constructions such as oily platform, submarine pipeline, ship and container.Calculated through experimental data, it is contemplated that apply Service life >=15 year of layer, effect are extremely notable.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also To obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is MTES modified epoxies characteristic spectrum of the present invention；In Fig. 1,1607.58cm-1, 1581.55cm-1, 1509.49cm-1Substitution back skeleton vibration, 1245.95cm are aligned for phenyl ring-1For fragrance-aliphatic ether antisymmetric stretching vibration, 827.98cm-1For the C-H out-of-plane bending vibrations of two neighboring hydrogen atom on contraposition substituted benzene ring, 915.06cm-1To be epoxy terminated Absorb.1102.12cm-1Vibrated for Si-O, 774.95cm-1For Si-C stretching vibrations.
Fig. 2 is THES modified epoxies characteristic spectrum of the present invention；In Fig. 2,1607.36cm-1, 1581.41cm-1, 1509.30cm-1Substitution back skeleton vibration, 1245.20cm are aligned for phenyl ring-1For fragrance-aliphatic ether antisymmetric stretching vibration, 829.55cm-1For the C-H out-of-plane bending vibrations of two neighboring hydrogen atom on contraposition substituted benzene ring, 913.80cm-1To be epoxy terminated Absorb.1102.02cm-1Vibrated for Si-O, 760.41cm-1For Si-C stretching vibrations.
Fig. 3 is IYES modified epoxies characteristic spectrum of the present invention；In Fig. 3,1607.42cm-1, 1582.28cm-1, 1509.41cm-1Substitution back skeleton vibration, 1245.28cm are aligned for phenyl ring-1For fragrance-aliphatic ether antisymmetric stretching vibration, 829.91cm-1For the C-H out-of-plane bending vibrations of two neighboring hydrogen atom on contraposition substituted benzene ring, 914.20cm-1To be epoxy terminated Absorb.1102.65cm-1Vibrated for Si-O, 759.65cm-1For Si-C stretching vibrations.
Embodiment
Core concept of the present invention：The organosiloxane structural of high hydrophobicity is introduced in epoxy resin structural, is made Solvent-free siloxane modified epoxy, it is as shown below：
Wherein, R1It is low molecular weight epoxy reactive diluent or low-viscosity epoxy resin such as E-51 etc..
The technical scheme is that E-51 (or 128) epoxy resin is used to use methyltriethoxy silane for body material Oxygen alkane (MTES), octyl group triethoxy silica alkane (THES) or iso-octyl triethoxy silica alkane (IYES) hydrolysate are as modification Agent, and the compatibility of diglycidyl ether type epoxy reactive diluent increase epoxy resin is introduced, silica is obtained by graft polymerization Alkane modified epoxy.Then prepare corrosion-resistant epoxy paint using the siloxane-modified resins as matrix, then by with it is homemade Large arch dam self-emulsifying epoxy curing agent coordinates, that is, obtains the silicone-modified epoxy anticorrosive coating material of Water-borne modification.
Specific implementation step is described as follows：
1. the preparation (being measured with mass parts) of siloxanes hydrolyzate
1. prepare alcohol-acid-aqueous solution：Weigh 80~85 parts of isopropanol, ethanedioic acid (COOCCOOH, content >=98.0%) 5 ~10 parts, 5~10 parts of pure water, mixed dissolution is uniformly standby.
2. siloxanes hydrolysis：Weigh 65~70 parts of methyltriethoxy silane oxygen alkane (MTES), octyl group triethoxysilicanes Oxygen alkane (THES) or iso-octyl triethoxy silica alkane (IYES), in reactor under stirring, be added dropwise 25~35 parts of alcohol- Acid-the aqueous solution, 3~5h of slow reaction, treats that solution is completely as clear as crystal at normal temperatures, and it is standby to place 24h.
Hydrolysis mechanism following equation：
Wherein, R is methyl, octyl group, iso-octyl etc.；
3. replace phase inversion：By the amount of solid content of the methods of GB/T 1725 measure siloxanes hydrolyzate, surplus is that moisture and alcohol are molten Liquid, the active epoxy diluent (such as glycidol ethers) of addition same amount, to increase the compatibility with epoxy resin；120 Under DEG C vacuum state, extract alcohol and water point out, mutually convert, that is, obtain anhydrous no alcohol (being critical to anhydrous) hydrolysis siloxanes, knot The cross-linking reaction of beam siloxanes, prevent silicone cross-linked reticulate and gel.
2. silicone-modified epoxy resin-graft polymerization reaction
(the E-51 or 128) epoxy resin and hydrolysis siloxanes of low viscosity are taken, by 1: 1.1 mixed in molar ratio in reactor It is interior, 2~3h, the complete clear of reaction solution are reacted under 60 DEG C of constant temperature stirrings, reaction is completed, that is, obtained silicone-modified Epoxy resin.The reaction mechanism mechanism of reaction of hydrolysis siloxanes and epoxy resin is described as follows with reaction principle：
The preferable cross-linked structure below figure of silicone-modified epoxy resin：
Wherein, wherein, R is methyl, octyl group, iso-octyl etc., R1Low molecular weight epoxy reactive diluent as or low viscosity Epoxy resin such as E-51 etc.；
For without the hydrolysis siloxanes with epoxy resin reaction, when film forming is dried, following reaction, increasing also occurs Add paint film combination property：
Wherein, R is methyl, octyl group, iso-octyl etc.
Silicone-modified epoxy resin after synthesis, with infrared spectrum characterization, obtain three kinds of different silicones (MTES, THES, IYES) modified epoxy characteristic spectrum：As Figure 1-3.
Silicone-modified epoxy resin after synthesis, obtains following result after tested, can be used as silicone-modified asphalt mixtures modified by epoxy resin The technical indicator of fat, is shown in Table 1.
The silicone-modified Epoxy Resin Technology index of table 1
3. the preparation (being measured with mass parts) of water-based silicone epoxy anti-corrosion primer
1. the preparation of primary coat paint vehicle (component A)
Take silicone-modified 30~35 parts of epoxy resin, 0.5~1.0 part of water and oil applicable type wetting dispersing agent, water and oil applicable Type defoaming levelling agent is each 0.5~1.0 part, 10~15 parts of sheet-shaped fillers, the water and oil applicable type graphene dispersion slurry 10 for containing 6% admittedly ~15 parts, 0.5~1.5 part of water and oil applicable type anti-settling agent, 0.5~1.5 part of thickener, after mixing, upper high speed dispersor scattered 15 ~20 minutes, move on sand mill after being ground to 15~20 μm of fineness, then add 35~45 parts of 800 mesh active zinc powder, stirring point Dissipate, as system viscosity is excessively sticky.Appropriate active epoxy diluent adjustment system (applying -4 glasss) viscosity can be added to 80~100s, It can filter and package.
2. the preparation of curing agent (B component)
The synthetic method of curing agent presses our company number of patent application CN 201710213593.3, publication date：In July, 2017 19 days, patent name：A kind of progress of synthesis of large arch dam self-emulsifying type epoxy hardener and preparation method thereof, is obtained homemade Large arch dam self-emulsifying epoxy curing agent.90~95 parts of the curing agent, 1~3 part of Epoxy curing accelerators, 1~3 part of pure water are taken, It is well mixed, as the self-emulsifying curing agent of component A paint vehicle.
3. use proportioning
In use, press A groups: B group=4: the mixing of 1 quality proportioning, construction requirement viscosity can be arbitrarily diluted to pure water, i.e., For water-based silicone-modified epoxy anticorrosion primer.
4. the preparation (being measured with mass parts) of water-based silicone epoxy antisepsis finishing paint
1. face applies the preparation of paint vehicle (component A)：
Take silicone-modified 50~60 parts of epoxy resin, 0.5~1.0 part of water and oil applicable type wetting dispersing agent, water and oil applicable Type disappears；
Bubble levelling agent is each 0.5~1.0 part, 10~15 parts of sheet-shaped fillers, 15~20 parts of coloring pigment, water and oil applicable type are prevented Heavy 0.5~1.5 part of agent, 0.5~1.5 part of thickener, after mixing, upper high speed dispersor is scattered 15~20 minutes, moves to sand mill On be ground to 15~20 μm of fineness after.After process of lapping or grinding, appropriate active epoxy diluent adjustment system can be added and (apply -4 Cup) viscosity is to 60~80s, you can filter and package.
2. the preparation of curing agent (B component)
Preparing for topcoating cures agent can be carried out by the preparation method of solidifying priming paint agent.
3. use proportioning
In use, press A groups: B group=2: the mixing of 1 quality proportioning, pure water dilution can be added, it is as water-based silicone-modified Epoxy anti-corrosive finish paint.
The performance indications of water-based silicone-modified corrosion-resistant epoxy paint, are shown in Table 2.
The physicochemical property testing result of the water-based silicone-modified corrosion-resistant epoxy paint of table 2
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not For limiting the present invention.
The MTES modified epoxies of embodiment one
85 parts of isopropanol, 10 parts of ethanedioic acid (COOCCOOH, content >=98.0%), 5 parts of pure water are weighed, mixed dissolution is equal It is even, acidic hydrolysis aqueous catalyst solution is made；Then 30 parts of alcohol-acid-aqueous solution are taken, are dripped in reactor under stirring It is added in 70 parts of MTES, at normal temperatures 3~5h of slow reaction, treats that solution is completely as clear as crystal, places 24h；By the methods of GB/T 1725 Siloxanes hydrolyzate amount of solid content is determined, surplus is moisture and alcoholic solution, the methyl propenoic acid glycidyl of addition same amount Ether MTES, under 120 DEG C of vacuum states, extract alcohol and water point out, complete displacement phase inversion, that is, obtain anhydrous no alcohol hydrolysis siloxanes； (the E-51 or 128) epoxy resin of low viscosity and hydrolysis siloxanes are taken, by 1: 1.1 mixed in molar ratio in reactor, 60 2~3h is reacted under DEG C constant temperature stirring, the complete clear of reaction solution, obtains the low viscosity silicon that amount of solid content is more than 70% Siloxane modified epoxy resin (content of siloxane >=20%, epoxide number 0.40 ± 0.05).
THES the or IYES modified epoxies of embodiment two
The present embodiment is to change the MTES in embodiment one into THES or IYES, and experimental method is identical, repeats no more.
The water-based silicone-modified epoxy anticorrosion primer of embodiment three
Take any silicone-modified 30 parts of epoxy resin, the BYK-192 water and oil applicables prepared in example one or example two 0.5 part of type wetting dispersing agent, 0.5 part of BYK-018 water and oil applicables type defoaming, 0.5 part of DC-57 water and oil applicable types levelling agent, 800 mesh 10 parts of mica powder, it is hydrated admittedly containing 10 parts of 6% water and oil applicable type graphene dispersion slurry, 1 part of A200 gas phase titanium dioxides anti-settling agent, S9 0.5 part of magnesium silicates thickening agents, after mixing, upper high speed dispersor is scattered 15~20 minutes, moves on sand mill and is ground to fineness 15 After~20 μm, then 45 parts of 800 mesh active zinc powder is added, be dispersed with stirring, as system viscosity is excessively sticky, 5 parts of 501B can added and lived Property epoxide diluent, adjustment system (apply -4 glasss) viscosity to 80~100s, you can filter and package, as paint vehicle (component A).
System is derived from admittedly containing 70% 95 parts of SR-S2016B self-emulsifying epoxy curing agents, 3 parts of DMP-30 curing accelerators, pure 2 parts of water purification, it is well mixed, the self-emulsifying curing agent (B component) as paint vehicle.
In use, press A groups: B group=4: the mixing of 1 mass ratio, construction requirement viscosity can be arbitrarily diluted to pure water, is Water-based silicone-modified epoxy anticorrosion primer.
The water-based silicone-modified Epoxy anti-corrosive finish paint of example IV
Take any silicone-modified 60 parts of epoxy resin, the BYK-192 water and oil applicables prepared in example one or example two 0.5 part of type wetting dispersing agent, 0.5 part of BYK-018 water and oil applicables type defoaming, 0.5 part of DC-57 water and oil applicable types levelling agent, 800 mesh 15 parts of mica powder, 20 parts of rutile titanium white powder, 1 part of A200 gas phase titanium dioxides anti-settling agent, 0.5 part of S9 hydrated magnesium silicates thickener, After mixing, upper high speed dispersor is scattered 15~20 minutes, moves on sand mill after being ground to 15~20 μm of fineness.Process of lapping or After grinding, 5 parts of 501B active epoxy diluents, adjustment system (applying -4 glasss) viscosity to 60~80s, you can bag filter can be added Dress, as paint vehicle (component A).
Preparing for topcoating cures agent can be carried out by the curing agent preparation method of embodiment three, obtain the self-emulsifying solidification of paint vehicle Agent (B component).
In use, press A groups: B group=2: the mixing of 1 mass ratio, pure water dilution, as water-based silicone-modified ring can be added Oxygen antisepsis finishing paint.
The water-based silicone-modified Epoxy anti-corrosive finish paint of embodiment five
Two kinds of siloxanes (the MTES+THES or IYES) modified epoxy prepared in example one or example two is taken respectively to take 30 Part, 0.5 part of BYK-192 water and oil applicable types wetting dispersing agent, BYK-018 water and oil applicables type defoam 0.5 part, DC-57 water and oil applicables 0.5 part of type levelling agent, 15 parts of 800 mesh mica powder, 8 parts of sun-proof phthalocyanine blue, 12 parts of rutile titanium white powder, A200 gas phase dioxy chemopreventions Heavy 1 part of agent, 0.5 part of S9 hydrated magnesium silicates thickener, after mixing, upper high speed dispersor is scattered 15~20 minutes, moves to sand mill On be ground to 15~20 μm of fineness after.After process of lapping or grinding, 5 parts of 501B active epoxy diluents can be added, adjust system (apply -4 glasss) viscosity is to 60~80s, you can filters and packages, as paint vehicle (component A).
Preparing for topcoating cures agent can be carried out by the curing agent preparation method of embodiment three, obtain the self-emulsifying solidification of paint vehicle Agent (B component).
In use, press A groups: B group=2: the mixing of 1 mass ratio, pure water dilution, as water-based silicone-modified ring can be added Oxygen antisepsis finishing paint.
Above to silicone-modified epoxy resin synthesis provided by the present invention and its preparation method of water-based anticorrosive paint It is described in detail, specific case used herein is set forth to the principle and embodiment of the present invention, and the above is real The explanation for applying example is only intended to help the method and its core concept for understanding the present invention；Meanwhile for the general technology of this area Personnel, according to the thought of the present invention, there will be changes in specific embodiments and applications, in summary, this theory Bright book content should not be construed as limiting the invention.

Claims (10)

  1. A kind of 1. silicone-modified epoxy resin synthesis, it is characterised in that including：
    1) siloxanes hydrolyzate is prepared；
    2) low-viscosity epoxy resin and siloxanes hydrolyzate are taken, by 1: 1.1 mixed in molar ratio in reactor, in 60 DEG C of perseverances 2~3h, the complete clear of reaction solution are reacted under warm stirring, reaction is completed, that is, obtains silicone-modified epoxy resin.
  2. 2. silicone-modified epoxy resin synthesis as claimed in claim 1, it is characterised in that：The step 1) specifically includes：
    1. prepare alcohol-acid-aqueous solution by mass fraction：Weigh 80~85 parts of isopropanol, 5~10 parts of ethanedioic acid, pure water 5~10 Part, mixed dissolution is uniformly standby；
    2. siloxanes hydrolysis：Weigh 65~70 parts of methyltriethoxy silane oxygen alkane MTES, octyl group triethoxy silica alkane THES or iso-octyl triethoxy silica alkane IYES, under stirring, 25~35 parts of alcohol-acid-water-soluble are added dropwise in reactor Liquid, 3~5h of slow reaction, treats that solution is completely as clear as crystal at normal temperatures, and it is standby to place 24h；
    3. replace phase inversion：By the amount of solid content of the methods of GB/T 1725 measure siloxanes hydrolyzate, surplus is moisture and alcoholic solution, The active epoxy diluent of addition same amount, under 120 DEG C of vacuum states, extract alcohol and water point out, mutually convert, that is, obtain nothing The non-alcoholic siloxanes hydrolyzate of water.
  3. 3. silicone-modified epoxy resin synthesis as claimed in claim 2, it is characterised in that：The siloxanes hydrolysis is gone through Journey following equation：
    Wherein, R is methyl, octyl group or iso-octyl.
  4. 4. silicone-modified epoxy resin synthesis as claimed in claim 3, it is characterised in that：The hydrolysis siloxanes and epoxy The reaction mechanism mechanism of reaction of resin is as follows：
    Wherein, R1It is low molecular weight epoxy reactive diluent or low-viscosity epoxy resin.
  5. 5. silicone-modified epoxy resin synthesis as claimed in claim 2, it is characterised in that：The active epoxy diluent is Polypropylene glycol diglycidyl ether (epoxide number is 0.28~0.36).
  6. 6. silicone-modified epoxy resin synthesis as claimed in claim 4, it is characterised in that：The silicone-modified asphalt mixtures modified by epoxy resin The structural formula of fat is as follows：
    R1It is low molecular weight epoxy reactive diluent or low-viscosity epoxy resin.
  7. 7. silicone-modified epoxy resin synthesis as claimed in claim 6, it is characterised in that：The silicone-modified asphalt mixtures modified by epoxy resin The cross-linked structure formula of fat is as follows：
    Wherein, wherein, R is methyl, octyl group or iso-octyl, R1Low molecular weight epoxy reactive diluent as or low-viscosity epoxy Resin.
  8. 8. silicone-modified epoxy resin synthesis as claimed in claim 3, it is characterised in that：When film forming is dried, portion Divide siloxanes hydrolyzate that following reaction occurs：
    ,
    R is methyl, octyl group or iso-octyl.
  9. 9. a kind of water-based anticorrosive paint preparation method of silicone-modified epoxy resin as claimed in claim 1, its feature exist In, including step：
    A) preparation (being measured with mass parts) of water-based silicone epoxy anti-corrosion primer
    1. the preparation of primary coat paint vehicle (component A)
    Silicone-modified 30~35 parts of epoxy resin, 0.5~1.0 part of water and oil applicable type wetting dispersing agent, water and oil applicable type is taken to disappear Steep each 0.5~1.0 part levelling agent, 10~15 parts of sheet-shaped fillers, admittedly containing 6% water and oil applicable type graphene dispersion slurry 10~15 Part, 0.5~1.5 part of water and oil applicable type anti-settling agent, 0.5~1.5 part of thickener, after mixing, upper high speed dispersor scattered 15~20 Minute, move on sand mill after being ground to 15~20 μm of fineness, then 35~45 parts of 800 mesh active zinc powder is added, it is dispersed with stirring；
    2. the preparation of epoxy hardener (B component)
    90~95 parts of epoxy hardener, 1~3 part of Epoxy curing accelerators, 1~3 part of pure water are taken, is well mixed, as component A The self-emulsifying curing agent of paint vehicle；
    3. use proportioning
    In use, press A groups: B group=4: the mixing of 1 quality proportioning, construction requirement viscosity can be arbitrarily diluted to pure water, produces water The silicone-modified epoxy anticorrosion primer of property.
  10. 10. the synthesis of aqueous epoxy curing agent as claimed in claim 1, it is characterised in that：Described silicone-modified epoxy The water-based anticorrosive paint preparation method of resin, it is characterised in that including step：
    B) preparation (being measured with mass parts) of aqueous silane Epoxy anti-corrosive finish paint
    1. face applies the preparation of paint vehicle (component A)
    Take 50~60 parts of silane-modified epoxy resin, 0.5~1.0 part of water and oil applicable type wetting dispersing agent, the defoaming of water and oil applicable type Levelling agent is each 0.5~1.0 part, 10~15 parts of sheet-shaped fillers, 15~20 parts of coloring pigment, water and oil applicable type anti-settling agent 0.5~ 1.5 parts, 0.5~1.5 part of thickener, after mixing, upper high speed dispersor is scattered 15~20 minutes, moves on sand mill and is ground to carefully After 15~20 μm of degree, after process of lapping or grinding, appropriate active epoxy diluent can be added and adjust system viscosity to 60~80s, It can filter and package；
    2. the preparation of epoxy hardener (B component)
    90~95 parts of epoxy hardener, 1~3 part of Epoxy curing accelerators, 1~3 part of pure water are taken, is well mixed, as B component The self-emulsifying curing agent of paint vehicle；
    3. use proportioning
    In use, press A groups: B group=2: the mixing of 1 quality proportioning, pure water dilution can be added, aqueous silane modified epoxy is produced and prevent Rotten finish paint.
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CN110760238A (en) * 2019-10-30 2020-02-07 广州擎天材料科技有限公司 Powder coating and preparation method thereof
CN110760238B (en) * 2019-10-30 2021-09-07 擎天材料科技有限公司 Powder coating and preparation method thereof
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CN112812270A (en) * 2020-12-31 2021-05-18 深圳飞扬兴业科技有限公司 Modified polyaspartic acid ester resin and synthetic method thereof
CN115124694A (en) * 2021-03-24 2022-09-30 中国科学院海洋研究所 Hydroxyl organic silicon modified epoxy resin and magnesium-rich primer prepared from same
CN115124694B (en) * 2021-03-24 2023-09-19 中国科学院海洋研究所 Hydroxyl organic silicon modified epoxy resin and magnesium-rich primer prepared from same
CN115820070A (en) * 2021-12-29 2023-03-21 郑州格莱菲高铁新材料科技有限公司 Persistent corrosion-resistant zinc-olefin primer composition and preparation method thereof
CN115820070B (en) * 2021-12-29 2024-03-12 郑州格莱菲高铁新材料科技有限公司 Persistent corrosion-resistant zincate primer composition and preparation method thereof
CN114669457A (en) * 2022-04-27 2022-06-28 广船国际有限公司 Spraying method of porcelain-like finish paint

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