CN108503846A - A kind of method and its application of solid acid catalysis synthesis nonionic emulsifier - Google Patents
A kind of method and its application of solid acid catalysis synthesis nonionic emulsifier Download PDFInfo
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- CN108503846A CN108503846A CN201810411618.5A CN201810411618A CN108503846A CN 108503846 A CN108503846 A CN 108503846A CN 201810411618 A CN201810411618 A CN 201810411618A CN 108503846 A CN108503846 A CN 108503846A
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Abstract
A kind of method and its application of solid acid catalysis synthesis nonionic emulsifier, are related to polymeric material field.It is always solid-state during the reaction with solid acid catalyst, can be being detached from product completely after completion of the reaction, and can reuse after cleaning, effectively reducing production cost；Solid acid has higher catalytic efficiency, so that the reaction time is further shortened, improves production efficiency；Solid acid reduces the reaction temperature of acid anhydrides and polyethylene glycol, and reaction can carry out at low temperature, and reaction is made to have selectivity.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of special nonionic emulsifier of aqueous epoxy resins
Preparation method and applications.
Background technology
Epoxy resin as a kind of common thermosetting resin, have excellent adhesive force, heat resistance, chemical-resistant,
Insulating properties and mechanical strength etc., are widely used in paint field.Epoxy resin is mostly solid or liquid and viscosity is higher,
Solubility in water is extremely low, therefore the organic solvents such as addition aromatic hydrocarbons, ketone or alcohols is needed to reduce its viscosity in use
In order to construct.Limitation with people to volatile organic compounds (VOC) discharge capacity, solvent epoxy varnish are led in coating
The use in domain is limited.Aqueous epoxy resins are using water as decentralized medium, and VOC emission amount is relatively low in use, so aqueous
Epoxy resin becomes new research direction.
It needing to introduce hydrophilic radical during the Water-borne modification of epoxy resin, the method introduced according to hydrophilic radical is different, point
For self-emulsification and additional emulsifier method.Self-emulsification is to be connect hydrophilic radical with epoxy resin by the form of chemical bond,
To make epoxy resin itself that there is hydrophily.Additional emulsifier method is so that epoxy resin is emulsified by the way that emulsifier is added.Due to
Self-emulsification can change the structure and functional group of epoxy resin itself, so will produce crosslink density decline, water resistance reduces,
The problems such as reaction process is complicated, poor repeatability.Additional emulsifier method is reviewed, epoxy resin structural will not be had an impact；It is general
Property is strong, can emulsify various kinds of resin system；Reproducible, performance is stablized.
The synthesis of nonionic emulsifier for emulsion epoxy resin can generally use epoxy resin and other hydrophilic point
Son is condensed.The nonionic emulsifier one or both ends of synthesis carry epoxy group, can during emulsion epoxy resin
Increase the compatibility with epoxy resin, and curing reaction can be participated in the curing process, reduces in cured product and dissociate
The content of emulsifier is to improve the water resistance of cured product.In the synthesis process since reaction speed is slower, can generally select
With boron trifluoride ether, tetrabutylammonium bromide, N, N- dimethylethanolamines, imidazoles etc. accelerate reaction rate as catalyst.This
A little catalyst can effectively accelerate reaction rate, reduce the reaction time, but finally can remain and be not easily separate in the product.It is special
It is not the hydrofluoric acid that boron trifluoride ether can generate strong corrosive in water, this does not meet the theory of Green Chemistry.Solid acid exists
It is used it is possible to prevente effectively from the above problem as catalyst in the building-up process of nonionic emulsifier：Catalyst is in reaction process
In be always solid-state, can detached from product completely after completion of the reaction, and can reuse after cleaning, effectively reduce
Production cost；Solid acid has higher catalytic efficiency, so that the reaction time is further shortened, improves production efficiency；Solid
Acid reduces the reaction temperature of acid anhydrides and polyethylene glycol, and reaction can carry out at low temperature, and reaction is made to have selectivity.
Invention content
The technical problem to be solved by the present invention is to：A kind of non-ionic epoxy resin emulsification is synthesized using solid acid catalysis
Agent, has in reaction process highly selective, can make emulsifier and molecule sieve separation after reaction, raising reaction rate and urges
The utilization rate of agent avoids the residual of impurity in emulsifier, is not necessarily to post-processing.
A kind of synthetic method of the nonionic emulsifier of solid acid catalysis synthesis provided by the present invention, feature exist
In including the following steps：
(1) under inert gas protection, 1~16 mass parts acid anhydrides and 0.5 is added after 100 mass parts polyethylene glycol being melted
~3 mass parts solid acid catalysts, esterification is carried out at 50 DEG C~100 DEG C, and reaction obtains carboxylate solution after 1-3 hours；
(2) by carboxylate solution and 1~95 mass parts epoxy resin obtained by 100 mass parts steps (1) at 60 DEG C~170 DEG C
Under reacted, reaction 1-4 hours after obtain the mixture of nonionic emulsifier and catalyst；
(3) mixture obtained by above-mentioned steps (2) is filtered while hot, liquid cooling to be filtered but obtains nonionic emulsifier afterwards.
Preferably, the molecular weight polyethylene glycol is 1000~10000.
Preferably, the acid anhydrides is one kind in phthalic anhydride, maleic anhydride.
Preferably, the epoxy resin is liquid epoxies, one kind or several in the trade mark E44, E51, F51
Kind.
Preferably, the catalyst is one or more of 3A molecular sieves, 4A molecular sieves, 5A molecular sieves.
Whether general formula below is for the nonionic emulsifier obtained by bisphenol A type epoxy resin and maleic anhydride：
(n=24~250, n are integer)
Wherein
(m=1~70, m are integer)
R1=H or R.
A kind of preparation method of aqueous epoxy resin emulsion provided by the present invention, is emulsified using nonionic described above
Agent prepares aqueous epoxy resin emulsion, includes the following steps：
By 0.1~20 mass parts nonionic emulsifier, 100 mass parts epoxy resin and 0.1~20 mass parts ionic
Emulsifier after mixing, is added dropwise 50~100 mass parts deionized waters, is stirred at 40 DEG C~80 DEG C, obtains the water
Property epoxy resin latex.
Using above-mentioned gained aqueous epoxy resin emulsion prepare water paint, prepared varnish paint component A by with
The group of lower parts by weight is grouped as：0.1-1 parts of antifoaming agent is added in 100 parts of the aqueous epoxy resin emulsion；B component is modified virtue
The aqueous epoxy curing agent of fragrant amine；Component A and B component are 1 according to the ratio of epoxide equivalent and active hydrogen equivalent weight when use：
(0.8~1.2) is mixed.
Or the water paint prepared, prepared color paint coating component A are grouped as by the group of following parts by weight：It is described aqueous
60~70 parts of epoxy resin latex, 8~10 parts of talcum powder, 10~15 parts of iron oxide red, 10~13 parts of trbasic zinc phosphate, wetting dispersing agent 0.3
~1.2 parts, 0.1~1 part of antifoaming agent；B component is the aqueous epoxy curing agent of modified aromatic amine；Component A and B component are according to ring
The ratio of oxygen equivalent and active hydrogen equivalent weight is 1：(0.8~1.2).
Preferably, the ionic emulsifying agent is allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, allyl oxygen
Base fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether ammonium sulfate, AEO carboxylic acid sodium, more aromatic ring phosphoric acid
One or more mixing in salt, dodecyl sodium sulfate, alkylbenzene ethoxylated sulfate, alkyl ethylene oxide ether ammonium sulfate
Object.
Preferably, epoxy resin described in aqueous epoxy resin emulsion is E-01, E-03, E-06, E-12, E-
14, one or more mixtures in E-20, E-31, E-35, E-42, E-44, E-51, E-55.
Preferably, the rotating speed of the stirring is 400~5000rpm.
The solid content of aqueous epoxy resin emulsion is 30%-80%.
Lotion prepared by the present invention can store placement and stablize more than half a year.It is multiple using this lotion as main film forming substance
With varnish and colored paint made from various auxiliary agents and anticorrosive pigment/filler, corrosion resistant metal anticorrosive paint is obtained after solidification, is with steel plate
When base material film thickness is 70 μm, salt-fog resistant time was at 700 hours or more.
Specific implementation method
To the further explanation of the present invention when following instance, rather than limit the range of the present invention.
1 the present embodiment of embodiment is related to the preparation method of solid acid catalysis non-ionic epoxy resin emulsifier special
250g Macrogol 6000s are added into tetra- mouthfuls of reaction flasks of 500ml, load onto reflux and under nitrogen atmosphere,
Heating stirring makes raw material melt, and 4.08g maleic anhydrides, 0.8g 5A molecular sieves are added in Macrogol 6000 solution, 80 DEG C of constant temperature
Reaction 2 hours.16.33g epoxy resin E-51 are added into system again, 130 DEG C of constant temperature is filtered after reacting for 3 hours, obtain it is non-from
Subtype emulsifier.
Embodiment 2
The 16.33g epoxy resin E-51 being added in the synthesis of present embodiment nonionic emulsifier replaces with 18.94g
Epoxy resin E-44, other are same as Example 1.
Comparative example 3
The 16.33g epoxy resin E-51 being added in the synthesis of present embodiment nonionic emulsifier replaces with 41.67g
Epoxy resin E-20.Other are same as Example 1.
Embodiment 4
The 0.8g 5A molecular sieves being added in the synthesis of present embodiment nonionic emulsifier replace with 0.8g 4A molecules
It is same as Example 1 to sieve other.
Embodiment 5
The 0.8g 5A molecular sieves being added in the synthesis of present embodiment nonionic emulsifier replace with 0.8g 3A molecules
Sieve, reaction time are extended for 3 hours and 4 hours respectively, other are same as Example 1.
Embodiment 6
The 0.8g 5A molecular sieves being added in the synthesis of present embodiment nonionic emulsifier replace with 0.8g ion exchanges
Film, other are same as Example 1.
Embodiment 7
The 4.08g maleic anhydrides being added in the synthesis of present embodiment nonionic emulsifier replace with 6.16g neighbour's benzene two
Formic anhydride, other are same as Example 1.
Embodiment 8
It is poly- that the 250g Macrogol 6000s being added in the synthesis of present embodiment nonionic emulsifier replace with 166.67g
Ethylene glycol 4000, other are same as Example 1.
Embodiment 9
It is poly- that the 250g Macrogol 6000s being added in the synthesis of present embodiment nonionic emulsifier replace with 83.33g
Ethylene glycol 2000, other are same as Example 1.
Embodiment 10
The 250g Macrogol 6000s being added in the synthesis of present embodiment nonionic emulsifier replace with the poly- second of 125g
Glycol 6000, other are same as Example 1.
Embodiment 11
250g Macrogol 6000s, the 16.33g epoxy resin being added in the synthesis of present embodiment nonionic emulsifier
E-51 replaces with 83.33g Macrogol 4000s, 18.94g epoxy resin E-44s, other are same as Example 1.
Embodiment 12
It is poly- that the 250g Macrogol 6000s being added in the synthesis of present embodiment nonionic emulsifier replace with 83.33g
Ethylene glycol 4000, other are same as Example 1.
Embodiment 13
It is poly- that the 250g Macrogol 6000s being added in the synthesis of present embodiment nonionic emulsifier replace with 41.67g
Ethylene glycol 2000, other are same as Example 1.
Embodiment 14
80 DEG C of reactions are reacted 3 hours for 2 hours with 130 DEG C in the synthesis of present embodiment nonionic emulsifier is changed to respectively
70 DEG C of reactions are reacted 2 hours for 3 hours with 110 DEG C
Embodiment 15
80 DEG C of reactions are reacted 3 hours for 2 hours with 130 DEG C in the synthesis of present embodiment nonionic emulsifier is changed to respectively
80 DEG C of reactions are reacted 3 hours for 1.5 hours with 120 DEG C
Embodiment 16
80 DEG C of reactions are reacted 3 hours for 2 hours with 130 DEG C in the synthesis of present embodiment nonionic emulsifier is changed to respectively
90 DEG C of reactions are reacted 1.5 hours for 2 hours with 120 DEG C
17 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 1 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
18 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyl phenols that 4g embodiments 2 are prepared
Polyoxyethylene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, under mechanical agitation (3000rpm) be added dropwise 114.15g go from
Sub- water, obtains aqueous epoxy resin emulsion.
19 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 2 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
20 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 14g embodiments 2 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
21 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 18g embodiments 2 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
22 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 3 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
23 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 4 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
24 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 5 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
25 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 6 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
26 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 7 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
27 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 8 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
28 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the alkyl ethylene oxide ethers that 10g embodiments 8 are prepared
Ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain water
Property epoxy resin latex.
29 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the alkylbenzene ethyoxyls that 10g embodiments 8 are prepared
Change sulfate to be put into 1L beakers, be heated to 40 DEG C, 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
Aqueous epoxy resin emulsion.
30 the present embodiment of comparative example is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g BVCONC that 10g embodiments 8 are prepared are put into 1L
In beaker, 40 DEG C are heated to, 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtains aqueous epoxy resins breast
Liquid.
31 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier, 200g epoxy resin E-51,2g the allyloxy nonyls that 10g embodiments 9 are prepared
Phenol polyethenoxy ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g is added dropwise under mechanical agitation (3000rpm) and goes
Ionized water obtains aqueous epoxy resin emulsion.
32 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier that 10g embodiments 10 are prepared, 200g epoxy resin E-51,2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
33 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier that 10g embodiments 11 are prepared, 200g epoxy resin E-44s, 2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
34 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier that 10g embodiments 12 are prepared, 200g epoxy resin E-20,2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
35 comparative examples of comparative example are related to the preparation of aqueous epoxy resin emulsion.
Nonionic emulsifier that 10g comparative examples 13 are prepared, 200g epoxy resin E-51,2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
36 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier that 10g embodiments 14 are prepared, 200g epoxy resin E-51,2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
37 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier that 10g embodiments 15 are prepared, 200g epoxy resin E-51,2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
38 the present embodiment of embodiment is related to the preparation of aqueous epoxy resin emulsion
Nonionic emulsifier that 10g embodiments 16 are prepared, 200g epoxy resin E-51,2g polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate is put into 1L beakers, is heated to 40 DEG C, and 114.15g deionized waters are added dropwise under mechanical agitation (3000rpm), obtain
To aqueous epoxy resin emulsion.
39 the present embodiment of embodiment is related to the preparation of water varnish coating
Under high velocity agitation, gained 100g water-base epoxy trees are added into example 17 in 0.3g Additol VXW 6393
In fat liquor, final water varnish coating component A is obtained.By 82.91g B components HGF-100 and component A mixed liquor obtained,
Varnish is made after stirring evenly.
40 the present embodiment of embodiment is related to the preparation of water varnish coating
Under high velocity agitation, gained 100g water-base epoxy trees are added into example 29 in 0.3g Additol VXW 6393
In fat liquor, final water varnish coating component A is obtained.By 82.91g B components HGF-100 and component A mixed liquor obtained,
Varnish is made after stirring evenly.
41 the present embodiment of embodiment is related to the preparation of water varnish coating
Under high velocity agitation, gained 100g water-base epoxy trees are added into example 32 in 0.3g Additol VXW 6393
In fat liquor, final water varnish coating component A is obtained.By 82.91g B components HGF-100 and component A mixed liquor obtained,
Varnish is made after stirring evenly.
42 the present embodiment of embodiment is related to the preparation of water varnish coating
Under high velocity agitation, gained 100g water-base epoxy trees are added into example 33 in 0.3g Additol VXW 6393
In fat liquor, final water varnish coating component A is obtained.By 71.58g B components HGF-100 and component A mixed liquor obtained,
Varnish is made after stirring evenly.
43 the present embodiment of embodiment is related to the preparation of water colour paint coating
Under high velocity agitation, by 0.75g Additol VXW 6208/60,0.67g Additol VXW 6393,13.5g
Gained is added into examples detailed above 17 in iron oxide red, 4.5g talcum powder, 6g barium sulfate, 6g ZAM+ and 0.6g HEUCORIN RZ
In 100g aqueous epoxy resin emulsions, final water colour paint coating component A is obtained.By 82.91g B components HGF-100 and it is made
Component A mixed liquor, after stirring evenly be made varnish.
44 the present embodiment of embodiment is related to the preparation of water colour paint coating
Under high velocity agitation, by 0.75g Additol VXW 6208/60,0.67g Additol VXW 6393,13.5g
Gained is added into examples detailed above 29 in iron oxide red, 4.5g talcum powder, 6g barium sulfate, 6g ZAM+ and 0.6g HEUCORIN RZ
In 100g aqueous epoxy resin emulsions, final water colour paint coating component A is obtained.By 82.91g B components HGF-100 and it is made
Component A mixed liquor, after stirring evenly be made varnish.
45 the present embodiment of embodiment is related to the preparation of water colour paint coating
Under high velocity agitation, by 0.75g Additol VXW 6208/60,0.67g Additol VXW 6393,13.5g
Gained is added into examples detailed above 32 in iron oxide red, 4.5g talcum powder, 6g barium sulfate, 6g ZAM+ and 0.6g HEUCORIN RZ
In 100g aqueous epoxy resin emulsions, final water colour paint coating component A is obtained.By 82.91g B components HGF-100 and it is made
Component A mixed liquor, after stirring evenly be made varnish.
46 the present embodiment of embodiment is related to the preparation of water colour paint coating
Under high velocity agitation, by 0.75g Additol VXW 6208/60,0.67g Additol VXW 6393,13.5g
Gained is added into examples detailed above 33 in iron oxide red, 4.5g talcum powder, 6g barium sulfate, 6g ZAM+ and 0.6g HEUCORIN RZ
In 100g aqueous epoxy resin emulsions, final water colour paint coating component A is obtained.By 71.58g B components HGF-100 and it is made
Component A mixed liquor, after stirring evenly be made varnish.
Aqueous epoxy resin emulsion grain size obtained by embodiment 17~38 is as shown in table 1.
1 embodiment particle size results of table
Varnish and colored paint made from embodiment 39~46, high-performance metal corrosion-inhibiting coating is obtained after solidification, works as coating
For thickness at 70 μm or so, anti-corrosion and mechanical property are as shown in table 2.The thickness of coating presses GB/T 6739-2006, and hardness presses GB/
T is measured.The adhesive force of coating presses GB 9286-1998, is measured using cross-hatching；The salt spray resistance of coating presses GB/T 1771-
1991 measure, and wherein colored paint is tested after scratching；The water resistance of coating is measured by GB/T 1733-1993；Coating
Resistant to liquid medium measured by GB/T 9274-1988.
The properties of table 2 varnish and colored paint coating
Claims (10)
1. a kind of method of solid acid catalysis synthesis nonionic emulsifier, which is characterized in that include the following steps：
(1) under inert gas protection, 1~16 mass parts acid anhydrides and 0.5~3 is added after 100 mass parts polyethylene glycol being melted
Mass parts solid acid catalyst, esterification is carried out at 50 DEG C~100 DEG C, and reaction obtains carboxylate solution after 1-3 hours；
(2) by carboxylate solution obtained by 100 mass parts steps (1) and 1~95 mass parts epoxy resin at 60 DEG C~170 DEG C into
Row reaction, reaction obtain the mixture of nonionic emulsifier and catalyst after 1-4 hours；
(3) mixture obtained by above-mentioned steps (2) is filtered while hot, liquid cooling to be filtered but obtains nonionic emulsifier afterwards.
2. a kind of method of solid acid catalysis synthesis nonionic emulsifier described in accordance with the claim 1, which is characterized in that institute
It is 1000~10000 to state molecular weight polyethylene glycol.
3. a kind of method of solid acid catalysis synthesis nonionic emulsifier described in accordance with the claim 1, which is characterized in that institute
It is one kind in phthalic anhydride, maleic anhydride to state acid anhydrides.
4. a kind of method of solid acid catalysis synthesis nonionic emulsifier described in accordance with the claim 1, which is characterized in that institute
It is liquid epoxies, one or more of the trade mark E44, E51, F51 to state epoxy resin.
5. a kind of method of solid acid catalysis synthesis nonionic emulsifier described in accordance with the claim 1, which is characterized in that institute
It is one or more of 3A molecular sieves, 4A molecular sieves, 5A molecular sieves to state catalyst.
6. special according to the method that a kind of solid acid catalysis of claim 1-5 any one of them synthesizes nonionic emulsifier
Sign is, whether general formula below is for the nonionic emulsifier obtained by bisphenol A type epoxy resin and maleic anhydride：
Wherein
R1=H or R.
7. a kind of preparation method of aqueous epoxy resin emulsion, which is characterized in that use any one of them sides claim 1-5
The nonionic emulsifier that method is prepared prepares aqueous epoxy resin emulsion, includes the following steps：
0.1~20 mass parts nonionic emulsifier, 100 mass parts epoxy resin and 0.1~20 mass parts ionic are emulsified
Agent after mixing, is added dropwise 50~100 mass parts deionized waters, is stirred at 40 DEG C~80 DEG C, obtains the aqueous ring
Oxygen resin emulsion.
8. a kind of preparation method of aqueous epoxy resin emulsion according to claim 7, which is characterized in that the ionic
Emulsifier is allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, allyloxy fatty alcohol polyoxyethylene ether, polyoxyethylene nonyl phenyl second
Alkene ether ammonium sulfate, AEO carboxylic acid sodium, more aromatic ring phosphate, dodecyl sodium sulfate, alkylbenzene ethoxylation
One or more mixtures in sulfate, alkyl ethylene oxide ether ammonium sulfate；Epoxy resin described in aqueous epoxy resin emulsion
It is one or more in E-01, E-03, E-06, E-12, E-14, E-20, E-31, E-35, E-42, E-44, E-51, E-55
Mixture.
9. a kind of preparation method of aqueous epoxy resin emulsion according to claim 7, which is characterized in that the stirring
Rotating speed is 400~5000rpm；The solid content of aqueous epoxy resin emulsion is 30%-80%.
10. a kind of water paint, which is characterized in that be prepared using claim 7-9 any one of them methods aqueous
Water paint prepared by epoxy resin latex, the varnish paint component A of preparation are grouped as by the group of following parts by weight：It is described aqueous
0.1-1 parts of antifoaming agent is added in 100 parts of epoxy resin latex；B component is the aqueous epoxy curing agent of modified aromatic amine；It uses
When component A and B component according to the ratio of epoxide equivalent and active hydrogen equivalent weight be 1：(0.8~1.2) is mixed；
Or the water paint prepared, prepared color paint coating component A are grouped as by the group of following parts by weight：The water-base epoxy
60~70 parts of resin emulsion, 8~10 parts of talcum powder, 10~15 parts of iron oxide red, 10~13 parts of trbasic zinc phosphate, wetting dispersing agent 0.3~1.2
Part, 0.1~1 part of antifoaming agent；B component is the aqueous epoxy curing agent of modified aromatic amine；Component A and B component are worked as according to epoxy
The ratio of amount and active hydrogen equivalent weight is 1：(0.8~1.2).
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