CN106117559A - A kind of water-soluble organic silicon resin and preparation method thereof - Google Patents
A kind of water-soluble organic silicon resin and preparation method thereof Download PDFInfo
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- CN106117559A CN106117559A CN201610508606.5A CN201610508606A CN106117559A CN 106117559 A CN106117559 A CN 106117559A CN 201610508606 A CN201610508606 A CN 201610508606A CN 106117559 A CN106117559 A CN 106117559A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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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
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
Abstract
The present invention provides a kind of organic siliconresin and preparation method thereof, comprises the steps: that bisphenol-A and epoxychloropropane are reacted by (1) at excess NaOH, and reaction temperature is 60 120 DEG C, and the response time is 3 10 hours；(2) by trihydroxylic alcohol, dihydroxylic alcohols and binary acid add in the reaction of step (1), to first heat, antioxidant is added after material dissolution is incubated 1 hour, temperature is controlled at 180 220 DEG C, react to acid number less than after 8.0mgKOH/g, add silicones intermediate, catalyst reacts, reaction temperature is 160 200 DEG C, response time is 34 hours, when reacting acid number less than 8mgKOH/g, dropping aqueous end-capping reagent carries out aqueous end-blocking, keep reaction temperature, react 12 hours, react when acid number is 25 ± 10mgKOH/g, prepare waterborne organic silicon resin.
Description
Technical field
The invention belongs to water-base resin preparation field, be specifically related to a kind of water-soluble organic silicon resin and preparation method thereof.
Background technology
Silicones is to have highly cross-linked cancellated polysiloxane, has the double of organic resin and inorganic material concurrently
Weight characteristic, has the physics of uniqueness, chemical property, and organic siliconresin is that (organosilicon is broadly divided into silicon to one of 4 big organosilicon materials
Oil, silicone rubber, silicones and the big class of silane coupler four), there is general organic resin unapproachable high temperature resistant, weather-proof and resistance to
Chemicals, the research work progress of organic siliconresin is quite fast in recent years, and following achievement is the most industrially used.
In recent years, due to the deterioration of ecological environment, environmental conservation is more and more paid close attention to by the world.Every country is all formulated
Relevant laws and regulations strictly limit the discharge of organic volatile (VOC) in coating.The Chinese government also promulgates in December, 1989
Law on Environmental Protection and " green " mark regulation etc., to limit the discharge of VOC.Solvent based coating contains a large amount of VOC composition, no
Only pollute environment waste resource and also endanger the health of people.Oligosaprobic water paint, photocureable coating, powdery paints and Gao Gu
Body divides coating to become the developing direction of coating.For water paint is relative to other low contamination coating, skill can be realized owing to having
The advantage such as art approach is many, wide application, safety, construction are relatively easy form headed by selection kind, the most vast coating scientific and technical personnel
Paying close attention to and the favor of coating user, VOC is mainly derived from disperse medium and the film forming matter of coating, sending out of water-base resin production technology
Exhibition so that water paint progressively replaces solvent based coating to be possibly realized.
CN103897197A discloses the preparation method of a kind of organosilicon modified polyester epoxy resin, comprises the following steps:
A () provides the mixture of following component: hydroxy radical content 8～the pet reaction thing of 17.1%；Polysiloxanes；Hydroxyl and epoxy official
The epoxy resin of energy base；Optional polymerisation catalysts；Wherein, described polysiloxanes with the weight ratio of pet reaction thing is
(30～90): (10～70)；The weight of the epoxy resin of described hydroxyl and epoxide functional groups accounts for described polysiloxanes and polyester
The 5～15% of the gross weight of reactant；Described polymerisation catalysts accounts for the gross weight of described polysiloxanes and pet reaction thing
0～0.5%；B () described mixture reacts 3～4 hours under the reaction temperature of 120～170 DEG C, obtain of the present invention
Organosilicon modified polyester epoxy resin.This invention combines the advantage of polyester and epoxy resin, has the heat-resisting yellowing resistance of excellence
Can, but its pliability is poor, and do not possess water solublity, it is unfavorable for green environmental friendly coatings.
CN103450465A discloses the preparation method of a kind of organosilicon modified polyester, comprises the steps: 1) in reaction
In container add the polyhydric alcohol of 28.5～50 weight portions, 10～63 weight portion polysiloxanes and 0.01～0.05 weight portion
Polymerisation catalysts, under the reaction temperature of 130～200 DEG C react 2～4 hours；2) polynary by 17～40 weight portions
Acid joins described step 1) in the reactant that obtains, isothermal reaction after continuing to be warmed up to 200～250 DEG C, when acid number be 30 ±
React during 10mgKOH/g, obtained organosilicon modified polyester of the present invention.Water-soluble resin prepared by this invention has
Preferably heat resistance, but its poor dimensional stability,
The water-soluble resin research silicone-modified about polyester is more, but prepares modified resin and be extremely difficult to many property
Can optimize, be difficult to focus on same resin by the advantage of various kinds of resin, the common preparation method of water-base resin is for using aqueous
Group blocks, but because the complexity of many resin reactions, end-capping reagent may react with the ester group in strand, makes
Molecular chain rupture, changes the distribution of molecular resin chain, resin physical property can be made to be affected.
Summary of the invention
For solving the problems referred to above, the present invention provides the preparation method of a kind of water-soluble organic silicon resin, comprises the steps:
(1) bisphenol-A and epoxychloropropane being added reactor, stirring, to being sufficiently mixed, adds excess NaOH and reacts,
Reaction temperature is 60-120 DEG C, and the response time is 3-10 hour；
(2) trihydroxylic alcohol, dihydroxylic alcohols and binary acid are added in the reaction of step (1), by being first heated to 165-180 DEG C, treat
Material dissolution adds antioxidant after being incubated 1 hour, temperature is controlled at 180-220 DEG C, reacts to acid number less than 8.0mgKOH/g
After, addition silicones intermediate, antimony-based catalyst react, and reaction temperature is 160-200 DEG C, and the response time is 3-4 hour,
When reacting acid number less than 8mgKOH/g, dropping aqueous end-capping reagent carries out aqueous end-blocking, keeps reaction temperature, reacts 1-2 hour,
React when acid number is 25 ± 10mgKOH/g, prepared water-soluble organic silicon resin；
Described bisphenol-A, epoxychloropropane, trihydroxylic alcohol, dihydroxylic alcohols, binary acid, antioxidant, catalyst, trimellitic anhydride and
The weight ratio of silicones intermediate is: 5-10:5-10:20-30:20-30:30-40:0.2-0.6:0.1-0.8:5-10:60-
80；
The described water-soluble organic silicon resin viscosity when 25 DEG C is 6000-10000mps.
Preferably, described aqueous end-capping reagent comprise trimellitic anhydride, trimesic acid, 1,2,3-benzenetricarboxylic acids, 1,3,5-
The combination of one or more in tricarboxylic butylcyclohexane, 1,2,4-tricarboxylic butylcyclohexane and 1,2,3-tricarboxylic butylcyclohexane.
Preferably, one or both during described trihydroxylic alcohol is trimethylolpropane and trimethylolethane；
Preferably, one or both during described dihydroxylic alcohols is neopentyl glycol and diglycol；Described binary acid is
One or both in p-phthalic acid and ethanedioic acid.
Preferably, described silicones intermediate comprise methylmethoxysilane, methylethoxy base silane, methoxy silane,
One or more in Ethoxysilane, phenyl methyl silane and phenylmethoxysilane.
Preferably, described antimony-based catalyst is Sb2O3、Sb(Ac)3(S-21) one or one and in antimony glycol (S-24)
More than Zhong.
Preferably, the one during described antioxidant is triphenyl phosphate and triphenyl phosphite.
The present invention also provides for above-mentioned water-soluble organic silicon resin for preparing the purposes of coating.
The present invention also provides for a kind of dispersion liquid containing above-mentioned water-soluble organic silicon resin, the preparation method of dispersion liquid
For: water-soluble organic siliconresin, after acetone solution, add appropriate triethylamine, stir with homogenizer, then toward system
In drip appropriate amount of deionized water, the solution of otherwise transparent slowly becomes milky, add water a certain amount of after, continue high-speed stirred i.e.
Obtaining silicones dispersion liquid, wherein the solid content of water-soluble organic silicon resin is 50-60%.
Beneficial effects of the present invention:
(1) present invention uses trihydroxylic alcohol, dihydroxylic alcohols to cooperate, in conjunction with the technical program remaining adjustment of formula suitably than
Example, it is achieved the resin of preparation not only hardness is high but also impact resistance is good
(2) present invention selects rational aqueous end-capping reagent and consumption to carry out aqueous end-blocking according to the technical program, it is achieved
To water-soluble organic silicon resin possess preferable water solublity；
(3) present invention select bisphenol-A and epoxychloropropane combine remaining component of technical scheme Reasonable adjustment and
Response parameter, the water-soluble resin making the present invention prepare has epoxy resin, polyester resin and organic siliconresin three's performance
In conjunction with, it is achieved the water-soluble organic silicon resin obtained possesses preferable bin stability and heat stability；
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, to the present invention
Further describe, but the protection domain of application claims is not limited to embodiment.
The assay method of the present invention is according to following standard:
1. acid value measuring
Acid number is defined as neutralizing the milligram number of the potassium hydroxide that 1 gram of resin is consumed, and can embody carboxyl in resin
Content.Assay method: add about 0.5g water-soluble organic silicon resin in taper, adds about 30ml acetone soln and dissolves poly-
Ester resin, adds 2-3 and drips phenolphthalein indicator, with the KOH solution titration demarcated, records the volume of KOH solution used,
Measure and average for three times.
2. water solublity test
After preparing aqueous dispersion, observe after standing 1 day, if dispersion presents pellucidity, then good water solubility；As
Really some is muddy, then water solublity is general；If sunk to the bottom or molten thing, then poorly water-soluble.
3. storage stability test
Stand after 3 months under room temperature, if the state of aqueous dispersion with 3 months before identical, then storage stability is good；If
Aqueous dispersion sinks to the bottom appearance, but easily stirs with Glass rod, then stability is general；If aqueous dispersion is layered completely, then it is steady
Qualitative difference.
4. pencil hardness test
Mitsubishi pencil, the method for inspection and standard is used to use GB GB/T 6739-2006 to measure；
5. red hardness test
Sample is electrified heating, treats that sample temperature rises to required temperature, then control voltage, keep temperature steady
Fixed, the method for testing with reference to pencil hardness is tested；
6. thermostability test
Use thermogravimetric analysis (Thermogravimetry is called for short TG) to test, take the meansigma methods measured five times；
7. weatherability
Employing type artificial accelerated aging machine determines resin weatherability, and resin irradiates one under the ultraviolet light that wavelength is
The fixed time, every measuring resinous luster and the change of color, and further characterize the resistance to ag(e)ing of film with this, in 72 hours
Ripple ultra-vioket radiation；
8. resistance to impact test
Resistance to impact is referred to as impact strength, i.e. refers to that the film being applied on base material is made by the impact of two-forty gravity
With, generation rapid deformation is without ability that is cracking or that come off from base material, according to GB/T 1732-93 " the resistance to punching of paint film
Hit algoscopy " standard-required measure the shock resistance of film, weight weight is 1t, can not cause destruction paint film
Highly characterizing greatly, unit is cm.
Embodiment 1
The preparation of water-soluble organic silicon resin:
(1) 20g bisphenol-A and 30g epoxychloropropane are added reactor, stir to being sufficiently mixed holding 50 DEG C, added
Amount NaOH reacts, and keeps 80 DEG C to react 3 hours；
(2) 100g trimethylolpropane, 100g neopentyl glycol and 140g p-phthalic acid are added the reaction of step (1)
In, will first be heated to 165 DEG C, after material dissolution is incubated 1 hour, adds 1g triphenyl phosphate, temperature is controlled at 180 DEG C, instead
100g methylethoxy base silane, 150g phenyl methyl silane and 1g Sb should be added to acid number less than after 8.0mgKOH/g2O3Carry out
Reaction, control temperature is at 180 DEG C, and the response time is sampling and testing acid number after 3 hours, drips when reacting acid number less than 8mgKOH/g
Add 30g trimellitic anhydride and carry out aqueous end-blocking, keep temperature, sampling and measuring acid number after reacting 1 hour, when acid number be 25 ±
React during 10mgKOH/g, cooling, be subsequently adding n-butyl alcohol, the stirring of dimethylbenzene equal solvent 30 minutes, adjust resin viscosity
6000-10000mps, is cooled to room temperature, prepares water-soluble organic silicon Resin A；
The preparation of water-soluble organic silicon resin dispersion liquid:
Take 200g water-soluble organic silicon Resin A, after acetone solution, add appropriate triethylamine, stir with homogenizer,
Then toward dripping appropriate amount of deionized water in system, the solution of otherwise transparent slowly becomes milky, add water a certain amount of after, continue
High-speed stirred i.e. obtains the silicones dispersion liquid A of solid content 55%；
Embodiment 2
The preparation of water-soluble organic silicon resin:
(1) 25g bisphenol-A and 30g epoxychloropropane being added reactor, stirring, to being sufficiently mixed, adds excess NaOH and enters
Row reaction, keeps 100 DEG C to react 4 hours；
(2) 120g trimethylolethane, 130g diglycol and 180g ethanedioic acid are added the reaction of step (1)
In, will first be heated to 170 DEG C, after material dissolution is incubated 1 hour, adds 2g triphenyl phosphite, temperature is controlled at 180-
220 DEG C, react to acid number less than after 8.0mgKOH/g, add 100 methylethoxy base silanes, 250 methoxy silane and 1gSb2O3
Reacting, control temperature is at 180 DEG C, and reaction 4 as a child sampling and testing acid number, when reacting dropping when acid number is less than 8mgKOH/g
40g trimellitic anhydride carries out aqueous end-blocking, keeps reaction temperature, sampling and measuring acid number after reacting 2 hours, when acid number be 25 ±
React during 10mgKOH/g, cooling, be subsequently adding n-butyl alcohol, the stirring of dimethylbenzene equal solvent 30 minutes, adjust resin viscosity
6000-10000mps, is cooled to room temperature, prepares water-soluble organic silicon resin B；
The preparation of water-soluble organic silicon resin dispersion liquid:
Take 200g water-soluble organic silicon resin B, after acetone solution, add appropriate triethylamine, stir with homogenizer,
Then toward dripping appropriate amount of deionized water in system, the solution of otherwise transparent slowly becomes milky, add water a certain amount of after, continue
High-speed stirred i.e. obtains the silicones dispersion liquid B that solid content is 54%；
Comparative example 1
(1) 20g bisphenol-A and 30g epoxychloropropane are added reactor, stir to being sufficiently mixed holding 50 DEG C, added
Amount NaOH reacts, and keeps 80 DEG C to react 3 hours；
(2) 200g trimethylolpropane and 140g p-phthalic acid are added in the reaction of step (1), will first be heated to
165 DEG C, adding 1g triphenyl phosphate, temperature controlled at 180 DEG C after material dissolution is incubated 1 hour, reaction to acid number is less than
After 8.0mgKOH/g, add 100g methylethoxy base silane, 150g phenyl methyl silane and 1g Sb2O3React, control temperature
Degree is at 180 DEG C, and the response time is sampling and testing acid number after 3 hours, the dropping inclined benzene of 30g three when reacting acid number less than 8mgKOH/g
Anhydride carries out aqueous end-blocking, keeps temperature, sampling and measuring acid number after reacting 1 hour, is cooled to room temperature, prepares organosilicon tree
Fat A1；
The preparation of organic siliconresin dispersion liquid:
Take 200g organic siliconresin A1, after acetone solution, add appropriate triethylamine, stir with homogenizer, then
Dripping appropriate amount of deionized water in system, the solution of otherwise transparent slowly becomes milky, add water a certain amount of after, continue at a high speed
Stirring i.e. obtains the silicones dispersion liquid A1 of solid content 55%；
Comparative example 2
In the reaction vessel be connected with nitrogen, add 268g trimethylolpropane, 166g M-phthalic acid, be heated to
Isothermal reaction after 220 DEG C, dehydration, when acid number drops to below 10mgKOH/g, it is cooled to 140 DEG C, adds appropriate propylene glycol monomethyl ether
Acetate (PMA), prepared solid content is the pet reaction thing of 75%, hydroxy radical content 17.1%；Taking the above-mentioned solid content of 40g is 75%
Pet reaction thing join in reaction vessel, after being heated to 100 DEG C, add 70g purified petroleum benzin based polysiloxane, 8g bisphenol-A
Type epoxy resin (epoxide equivalent is 806-909), it is solvent that the butyl titanate of 0.5g makees the PMA of catalyst and 35g, continues to rise
Temperature to about 120 DEG C, dropping 40g trimellitic anhydride blocks, and is cooled to room temperature, prepares organosilicon tree after reacting 1 hour
Fat A2；
The preparation of organic siliconresin dispersion liquid:
Take 200g organic siliconresin A1, after acetone solution, add appropriate triethylamine, stir with homogenizer, then
Dripping appropriate amount of deionized water in system, the solution of otherwise transparent slowly becomes milky, add water a certain amount of after, continue at a high speed
Stirring i.e. obtains the silicones dispersion liquid A1 of solid content 55%；
Comparative example 3
(1) 20g bisphenol-A and 2g epoxychloropropane are added reactor, stir to being sufficiently mixed holding 50 DEG C, add excess
NaOH reacts, and keeps 80 DEG C to react 3 hours；
(2) 100g trimethylolpropane, 100g neopentyl glycol and 140g p-phthalic acid are added the reaction of step (1)
In, will first be heated to 165 DEG C, after material dissolution is incubated 1 hour, adds 1g triphenyl phosphate, temperature is controlled at 180 DEG C, instead
100g methylethoxy base silane, 150g phenyl methyl silane and 1g Sb should be added to acid number less than after 8.0mgKOH/g2O3Carry out
Reaction, control temperature is at 180 DEG C, and the response time is sampling and testing acid number after 3 hours, drips when reacting acid number less than 8mgKOH/g
Add 2g trimellitic anhydride and carry out aqueous end-blocking, keep temperature, sampling and measuring acid number after reacting 1 hour, cooling, be subsequently adding positive fourth
Alcohol, dimethylbenzene equal solvent stir 30 minutes, adjust resin viscosity 6000-10000mps, are cooled to room temperature, prepare organosilicon
Resin A；
Effect example
The organic siliconresin A (embodiment 1) for preparing above-mentioned, organic siliconresin B (embodiment 2), organic siliconresin
A1 (comparative example 1), organic siliconresin A2 (comparative example 2) and organic siliconresin A3 (comparative example 3) carry out red hardness test, thermostability
Test with weatherability；
The silicones dispersion liquid A (embodiment 1) of above-mentioned preparation, silicones dispersion liquid B (embodiment 2), silicones dispersion liquid
A1 (comparative example 1), silicones dispersion liquid A2 (comparative example 2) and silicones dispersion liquid A3 (comparative example 3) carry out water solublity test, storage
The concrete test data depositing stability test, above-mentioned organic siliconresin and silicones dispersion liquid are shown in Table 1.
Table 1 organic siliconresin and silicones dispersion liquid performance
As it can be seen from table 1 the silicones dispersion liquid of embodiment 1 and embodiment 2 preparation has preferable water solublity and storage
Deposit stability, and heat resistance and weather resistance preferable；Comparative example 1 is after removing trihydroxylic alcohol, although red hardness and thermostability
Can not have considerable influence, but its impact resistance is poor, storage stability and weatherability are the most relatively poor；Comparative example 2 is existing
Carrying out aqueous end-blocking with trimellitic anhydride on the basis of technology organosilicon modified polyester epoxy resin, the resin prepared is water-soluble
Property is poor, and storage stability is the most bad；Comparative example 3 is after changing this programme ratio formula, and the resin water solublity of preparation etc. is each
Item performance is the most poor.
Polyester, epoxy resin and organosilicon are combined, more by the described above present invention by rational ratio and method
Mending the deficiency that 3 kinds of resins are mutual, the resin property of preparation is more comprehensively, more excellent.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula changes and revises.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to invention
A little modifications and changes should also be as falling in the scope of the claims of the present invention.Although additionally, this specification employing
Some specific terms, but these terms are merely for convenience of description, and the present invention does not constitute any restriction.
Claims (7)
1. the preparation method of a water-soluble organic silicon resin, it is characterised in that comprise the steps:
(1) bisphenol-A and epoxychloropropane being added reactor, stirring, to being sufficiently mixed, adds excess NaOH and reacts, reaction
Temperature is 60-120 DEG C, and the response time is 3-10 hour；
(2) trihydroxylic alcohol, dihydroxylic alcohols and binary acid are added in the reaction of step (1), by being first heated to 165-180 DEG C, treat material
Add antioxidant after dissolving insulation 1 hour, temperature is controlled at 180-220 DEG C, react to acid number less than after 8.0mgKOH/g, add
Enter silicones intermediate, antimony-based catalyst reacts, and reaction temperature is 160-200 DEG C, and the response time is 3-4 hour, when instead
Drip aqueous end-capping reagent when answering acid number to be less than 8mgKOH/g and carry out aqueous end-blocking, keep reaction temperature, react 1-2 hour, work as acid
Value is to have reacted during 25 ± 10mgKOH/g, prepares water-soluble organic silicon resin；
Described bisphenol-A, epoxychloropropane, trihydroxylic alcohol, dihydroxylic alcohols, binary acid, antioxidant, catalyst, trimellitic anhydride and silicon tree
The weight ratio of fat intermediate is: 5-10:5-10:20-30:20-30:30-40:0.2-0.6:0.1-0.8:5-10:60-80；
The described water-soluble organic silicon resin viscosity when 25 DEG C is 6000-10000mps.
The preparation method of water-soluble organic silicon resin the most according to claim 1, it is characterised in that described aqueous end-capping reagent
Comprise trimellitic anhydride, trimesic acid, l,2,3 benzene tricarboxylic acid, 1,3,5-tricarboxylic butylcyclohexane, 1,2,4-tri-carboxy cyclohex
The combination of one or more in alkane and 1,2,3-tricarboxylic butylcyclohexane.
The preparation method of a kind of water-soluble organic silicon resin the most according to claim 1, it is characterised in that described trihydroxylic alcohol
For one or both in trimethylolpropane and trimethylolethane；Described dihydroxylic alcohols is neopentyl glycol and diglycol
In one or both；Described binary acid is one or both in p-phthalic acid and ethanedioic acid.
The preparation method of a kind of water-soluble organic silicon resin the most according to claim 1, it is characterised in that described silicones
Intermediate comprise methylmethoxysilane, methylethoxy base silane, methoxy silane, Ethoxysilane, phenyl methyl silane and
One or more in phenylmethoxysilane.
The preparation method of a kind of water-soluble organic silicon resin the most according to claim 1, it is characterised in that described antimony system urges
Agent is Sb2O3、Sb(Ac)3(S-21) one or more and in antimony glycol (S-24).
The preparation method of a kind of water-soluble organic silicon resin the most according to claim 1, it is characterised in that described antioxidant
For the one in triphenyl phosphate and triphenyl phosphite.
7. the water-soluble organic silicon resin described in any one of claim 1-6 is for preparing the purposes of coating.
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| CN201610508606.5A CN106117559B (en) | 2016-06-29 | 2016-06-29 | A kind of water-soluble organic silicon resin and preparation method thereof |
| PCT/CN2017/088332 WO2018001100A1 (en) | 2016-06-28 | 2017-06-14 | Water-soluble organosilicon resin and application thereof |
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| CN201610508606.5A CN106117559B (en) | 2016-06-29 | 2016-06-29 | A kind of water-soluble organic silicon resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018001100A1 (en) * | 2016-06-28 | 2018-01-04 | 佛山市珀力玛高新材料有限公司 | Water-soluble organosilicon resin and application thereof |
| CN115477887A (en) * | 2022-10-14 | 2022-12-16 | 林州市工务铁路器材制造有限公司 | Track fastener insulating paint and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897197A (en) * | 2012-12-28 | 2014-07-02 | 慧智科技（中国）有限公司 | Preparation method of organic silicon-modified polyester epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897197A (en) * | 2012-12-28 | 2014-07-02 | 慧智科技（中国）有限公司 | Preparation method of organic silicon-modified polyester epoxy resin |
Non-Patent Citations (1)
| Title |
|---|
| 欧阳鎏，等: ""自乳化聚酯树脂汽车中涂漆的合成及性能研究"", 《热固性树脂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018001100A1 (en) * | 2016-06-28 | 2018-01-04 | 佛山市珀力玛高新材料有限公司 | Water-soluble organosilicon resin and application thereof |
| CN115477887A (en) * | 2022-10-14 | 2022-12-16 | 林州市工务铁路器材制造有限公司 | Track fastener insulating paint and preparation method and application thereof |
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