CN106675303A - Water-based polyurethane polyaniline anticorrosive paint and preparation method thereof - Google Patents
Water-based polyurethane polyaniline anticorrosive paint and preparation method thereof Download PDFInfo
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- CN106675303A CN106675303A CN201611162395.0A CN201611162395A CN106675303A CN 106675303 A CN106675303 A CN 106675303A CN 201611162395 A CN201611162395 A CN 201611162395A CN 106675303 A CN106675303 A CN 106675303A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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Abstract
The invention provides a water-based polyurethane polyaniline anticorrosive paint and a preparation method thereof. The preparation method comprises the following steps: carrying out reaction on aniline and p-phenylenediamine used as monomers by using hydrochloric acid as a dopant and ammonium persulfate as an oxidizer by microemulsion polymerization, and de-doping with ammonia water to obtain an aniline-p-phenylenediamine copolymer; carrying out reaction on polyester polyol, diisocyanate, a hydrophilic chain extender and an inner crosslinking agent used as raw materials by using a vinyl monomer as a continuous phase by in-situ emulsion polymerization to obtain a prepolymer-vinyl monomer mixture, carrying out vinyl termination neutralization, adding deionized water containing polymerizable surface-active monomers, dispersing at high speed to obtain a polyurethane dispersion solution, adding an initiator to polymerize the vinyl monomer, polyurethane and double-bond-containing surface-active monomer, and meanwhile, introducing an outer crosslinking agent to obtain a water-based polyurethane-acrylate composite emulsion; and by using the emulsion as a matrix, adding the aniline-p-phenylenediamine copolymer, a thickener, a defoaming agent and a film forming aid to obtain the anticorrosive paint. The paint is economical and environment-friendly.
Description
【Technical field】
The present invention relates to a kind of water-based anticorrosive paint preparing technical field, more particularly to a kind of aniline-p-phenylenediamine copolymerization
Thing/aqueous polyurethane-acrylate anticorrosive paint and preparation method thereof.
【Background technology】
The economic loss and environmental pollution that metal erosion is caused every year to society is increasingly serious, develops nuisanceless, high-performance
With the trend that Eco-power corrosion-inhibiting coating has become development.Polyaniline is the conduction that a kind of nontoxic, raw material is easy to get, has good stability
Macromolecule, with excellent antiseptic property, but because polyaniline molecule chain is rigid structure, and molecule interchain mutually pretends use
Power can cause the difficult processing of its indissoluble so as to which application is restricted, so people's trial carries out modification to its structure it is answered
With being improved, polyaniline derivative aniline-p-phenylenediamine copolymer is exactly one of which.At present, aniline-p-phenylenediamine copolymerization
Applied research report of the thing in terms of anti-corrosion is little.Because Polyaniline and its derivative aniline-p-phenylenediamine copolymer is to base material
Caking property it is poor, in a large number using pure polyaniline or aniline-p-phenylenediamine copolymer as corrosion-inhibiting coating from film combination property
It is economically all less desirable.So, people attempt polyaniline or aniline-p-phenylenediamine copolymer is strong with other adhesions
Resin alloy formed composite anticorrosion coating, improve painting with the interaction between other blend components or chemical bond using it
The antiseptic property of material.At present, blending resin has epoxy resin, alkyd resin, polyurethane, acrylate etc., wherein, great majority are
Oleaginous system, water-based system report is little, and water-based system reduces the content of organic volatile, saves ample resources, economical
Environmental protection.Water paint most widely used at present has polyacrylate dispersion (PA) and polyaminoester emulsion (PU), wherein, PU emulsions tool
There is safe and nontoxic, environmentally friendly, excellent filming performance, but the aspect Shortcomings such as stability, adhesive force, hardness, PA is newborn
The film property and chemical-resistant of liquid is poor, but film has excellent weatherability, color inhibition, resistance to water and mechanical performance.PU
Have with PA well complementary, can prepare that wearability is good, weatherability is good, hardness is high, resistance to water and mechanical property are good
PUA complex emulsions.
【The content of the invention】
For solve problems of the prior art, the invention provides a kind of aqueous polyurethane polyaniline anti-corrosive paint and
Its preparation method.The method of the present invention effectively increases the solid content of aqueous polyurethane emulsion, improves and applies film strength, water-fast
Property, hardness etc., preparation process is economic and environment-friendly.
To reach above-mentioned purpose, the key technology scheme of the present invention is：
A kind of aqueous polyurethane polyaniline anti-corrosive paint,
Described aqueous polyurethane polyaniline anti-corrosive paint is aniline-p-phenylenediamine copolymer/water-borne polyurethane-acrylate
Ester anticorrosive paint, including the raw material of following weight portion：
100 parts of aqueous polyurethane-acrylate composite emulsion, aniline -0.4~2 part of p-phenylenediamine copolymer, thickening agent
0.05~0.2 part, 0.1~0.5 part of defoamer, 3~10 parts of coalescents；
The preparation method of aniline-p-phenylenediamine copolymer is：
First 10-30 parts aniline of Jing second distillations and 10-35 parts p-phenylenediamine are added in reactor, is adjusted using acid solution
Section system pH is to 1-4, the mixed liquor of stir under the conditions of ice-water bath prepared aniline and p-phenylenediamine；Take 49-98 part oxygen
Agent is dissolved in aqueous acid, during above-mentioned mixed liquor is added drop-wise to while stirring, oxidant and aniline and p-phenylenediamine mix monomer
Mol ratio between 1:1 to 1:Between 2；And add 0.3-0.9 part nonionic surfactants as emulsifying agent, fill after dripping
Point reaction is poured out reactant, sucking filtration to terminating, and is first washed with distilled water to neutrality, then uses ammonia dedoping, then with distilling
Water washing, again with absolute ethanol washing, after being dried, that is, obtains eigenstate aniline-p-phenylenediamine copolymer to neutrality.
The acid is hydrochloric acid, acetic acid, phosphoric acid or DBSA；
The oxidant is Ammonium persulfate. or potassium peroxydisulfate；
The nonionic surfactant is OPEO.
A kind of preparation method of aqueous polyurethane polyaniline anti-corrosive paint, comprises the following steps：
Step 1) prepare aniline-p-phenylenediamine copolymer：
A. by weight, 10-30 parts aniline of Jing second distillations and 10-35 part p-phenylenediamine are added to equipped with pH first
It is worth in the reactor for the acidic aqueous solution of 1-4, stirs under the conditions of ice-water bath, and adds 0.3-0.9 part nonionic tables
Face activating agent；
B. 49-98 part oxidants are taken to be dissolved in acidic aqueous solution, are added drop-wise under agitation in the reaction system in step a,
React after dripping to terminating, reactant is poured out, sucking filtration is first washed with distilled water to neutrality, then use ammonia dedoping, then
Neutrality is washed with distilled water to, again with absolute ethanol washing, after dried, that is, eigenstate aniline-p-phenylenediamine is obtained common
Polymers；
Step 2) prepare aqueous polyurethane-acrylate composite emulsion：
C. by weight, 10~28 parts of inertia vinyl monomers, 5~15 parts of polyester polyols are added in dry reactor
Alcohol, 5~12 parts of diisocyanate, 1~2.8 part of anionic hydrophilic chain extender and 0.3~2 part of internal crosslinker, reaction temperature is constant
For 70~80 DEG C, the response time is 3~4 hours；
D. add the hydrophilic vinylic monomer of 3~5 parts of hydroxyls to be blocked, react 0.5~1 hour, system temperature
70~80 DEG C are maintained at, 1~4 part of bases salt forming agent is added, after neutralization reaction, are added and is contained 0.02~0.04 part of polymerizable surface
The mixed liquor of activated monomer and 75~85 parts of water, dispersed with stirring is uniform；
E. at 70~80 DEG C of constant temperature, 0.02~0.08 part of initiator is dissolved in into initiator water made by 0.2~0.8 part of water
Solution is added drop-wise in reactor, after dripping, by 1.5~4 especially cross-linking agent be added drop-wise in reactor simultaneously in 0.5 hour,
After completion of dropping, continue to be incubated 1 hour and then be down to room temperature, that is, aqueous polyurethane-acrylate composite emulsion is obtained；
Step 3) prepare anticorrosive paint：
100 parts of aqueous polyurethane-acrylate composite emulsion adds aniline-p-phenylenediamine copolymerization as matrix resin
0.4~2 part of thing, 0.05~0.2 part of thickening agent, 0.1~0.5 part of defoamer, 3~10 parts of coalescents, using physical blending process
Mix homogeneously, that is, obtain aniline-p-phenylenediamine copolymer/aqueous polyurethane-acrylate anticorrosive paint.
As a further improvement on the present invention, the acid is hydrochloric acid, acetic acid, phosphoric acid or DBSA；
The oxidant is Ammonium persulfate. or potassium peroxydisulfate；
The nonionic surfactant is OPEO.
As a further improvement on the present invention, the inertia vinyl monomer is acrylic acid methyl ester., butyl acrylate, methyl
Acrylic acid methyl ester., butyl methacrylate, styrene, n-octyl, Hexyl 2-propenoate, n octyl methacrylate, first
The mixture of one or more any proportionings in base Hexyl 2-propenoate.
As a further improvement on the present invention, the PEPA is polycaprolactone diols, PCDL
Or the own dihydroxylic alcohols of polyadipate.
As a further improvement on the present invention, the diisocyanate is isophorone diisocyanate, diphenyl methane
Diisocyanate or hexamethylene diisocyanate；
The anionic hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid；
The internal crosslinker is trimethylolpropane.
As a further improvement on the present invention, the vinyl monomer end-capping reagent is hydroxyethyl methylacrylate or acrylic acid
Hydroxyl ethyl ester；
The polymerizable surface active monomer is α-sodium olefin sulfonate or 1- propenyloxy group -2- hydroxypropanesulfonic acid sodium；
The bases salt forming agent is ammonia or triethylamine.
As a further improvement on the present invention, the initiator is Ammonium persulfate. or potassium peroxydisulfate；
The outside cross-linking agent is that γ-methacryloxypropyl trimethoxy silane and/or Glycidyl methacrylate are sweet
Grease.
As a further improvement on the present invention, the thickening agent is LS-112 or DL-80；
The defoamer is BYK-034, BYK-035 or BYK-037 of German BYK companies production；
The coalescents are lauryl alcohol ester or butyl glycol ether.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention is lived in the preparation process of aqueous polyurethane-acrylate composite emulsion by introducing polymerizable surface
Property monomer, effectively increase the solid content of emulsion, be cross-linked to form network structure using inside and outside, improve apply film strength, resistance to water,
Hardness etc..The specific present invention adopts microemulsion polymerization method, and with aniline, p-phenylenediamine as monomer, nonionic surfactant is
Emulsifying agent, acid is dopant, adds oxidant, Jing bases salt forming agent dedopings to obtain aniline-p-phenylenediamine copolymer.Using original
Position emulsion polymerization, with vinyl monomer as continuous phase, PEPA, diisocyanate, hydrophilic chain extender, internal crosslinker is
Raw material prepares base polyurethane prepolymer for use as and mixture of vinyl monomer, and Jing ethenyl blockings are neutralized, add the list of surface activity containing polymerizable
At a high speed dispersion obtains polyurethane dispersing liquid to the deionized water of body, and being subsequently adding initiator makes vinyl monomer with polyurethane and containing double
The surface active monomer polymerization of key, while introducing outside cross-linking agent obtains aqueous polyurethane-acrylate composite emulsion.With the emulsion
Based on, add a certain proportion of aniline-p-phenylenediamine copolymer, thickening agent, defoamer, coalescents, that is, obtain aniline-right
Phenylenediamine copolymer/aqueous polyurethane-acrylate anticorrosive paint.Due to Polyaniline and its derivative and copolymer have it is excellent
Antiseptic property, selection aqueous polyurethane-acrylate be base material, aniline-p-phenylenediamine copolymerization is prepared according to physical blending process
Thing/aqueous polyurethane-acrylate anticorrosive paint, it is economic and environment-friendly compared with simple polyaniline coating or solvent based coating.
Aqueous polyurethane polyaniline anti-corrosive paint solid content prepared by the present invention is high, applies film strength, resistance to water, hardness etc.
Excellent performance, it is economic and environment-friendly.
【Specific embodiment】
The present invention is described in further detail with reference to specific embodiment：(in parts by weight)
Embodiment 1：
100 parts of aqueous polyurethane-acrylate composite emulsion, aniline -0.4 part of p-phenylenediamine copolymer, thickening agent 0.1
Part, 0.3 part of defoamer, 5 parts of coalescents, high-speed stirred 5h obtains aniline-p-phenylenediamine copolymer/aqueous polyurethane-the third
Olefin(e) acid ester anticorrosive paint.
Wherein, the synthesis technique of aniline-p-phenylenediamine copolymer is as follows：
28 parts of aniline of Jing second distillations and 32 parts of p-phenylenediamine are added in the there-necked flask equipped with finite concentration acid,
After stirring under the conditions of ice-water bath, and add 0.3 portion of nonionic surfactant；Take 68 parts of oxidants be dissolved in it is certain density
In acidic aqueous solution, it is added drop-wise under stirring in reaction system, reacts after dripping in 1.5h and terminate after 4h, reactant is fallen
Go out, sucking filtration, be washed with distilled water to neutrality, then with certain density ammonia dedoping, be washed with distilled water to neutrality, then use
A small amount of absolute ethanol washing, is dried after 48h at 40 DEG C, that is, obtain eigenstate aniline-p-phenylenediamine copolymer.
The acid is acetic acid.The oxidant is potassium peroxydisulfate.
Wherein, the preparation technology of water-based polyurethane-acrylate emulsion is as follows：
A. first, 20 parts of inertia vinyl monomers, 10 parts of PEPAs, 8 part of two isocyanide are added in dry reactor
Acid esters, 1.5 parts of anionic hydrophilic chain extenders and 1 part of internal crosslinker, it is 80 DEG C that reaction temperature is constant, and the response time is 3 hours.
B. then, add the hydrophilic vinylic monomer of 3.5 parts of hydroxyls to be blocked, react 0.5 hour, system temperature
Remain 80 DEG C, add 1.5 parts of bases salt forming agents, after neutralization reaction 20 minutes, add containing 0.02 part of surface active monomer and
The mixed liquor of 75 parts of water, high-speed stirred is disperseed 5~7 minutes, and constant temperature is 80 DEG C.
C. it is last, at 80 DEG C of constant temperature, during initiator solution (0.03 part of initiator) is added drop-wise to into reactor, Deca
After 1.5 hours, will be added drop-wise in reactor simultaneously in 2 especially cross-linking agent 0.5 hour, after completion of dropping, continue to be incubated 1 hour so
After be down to room temperature, that is, the aqueous polyurethane-acrylate composite emulsion made.
The inertia vinyl monomer is the mixture of methacrylic acid monomer (MMA) and butyl acrylate (BA), wherein,
The mass ratio of MMA and BA is 4：1；The PEPA is polycaprolactone diols；The diisocyanate is isophorone
Diisocyanate；The anionic hydrophilic chain extender is dihydromethyl propionic acid；The internal crosslinker is trimethylolpropane；It is described
Vinyl monomer end-capping reagent is hydroxyethyl methylacrylate；The polymerizable surface active monomer is α-sodium olefin sulfonate；It is described
Bases salt forming agent is ammonia；The initiator is Ammonium persulfate.；The outside cross-linking agent is γ-methacryloxypropyl front three
TMOS (KH570) and glycidyl methacrylate (GMA)；The thickening agent is LS-112；The defoamer is
BYK-034；The coalescents are lauryl alcohol ester.
Embodiment 2：
Take 100 parts of aqueous polyurethane-acrylate composite emulsions, aniline-p-phenylenediamine copolymer 1 .2 parts, thickening agent
0.05 part, 0.1 part of defoamer, 3 parts of coalescents, high-speed stirred 5h obtains aniline-p-phenylenediamine copolymer/poly- ammonia of aqueouss
Ester-acrylate anticorrosive paint.
Wherein, the synthesis technique of aniline-p-phenylenediamine copolymer is as follows：
20 parts of aniline of Jing second distillations and 25 parts of p-phenylenediamine are added in the there-necked flask equipped with finite concentration acid,
Stir under the conditions of ice-water bath, and add 0.9 portion of nonionic surfactant；Take 50 parts of oxidants and be dissolved in certain density acid
Property aqueous solution in, be added drop-wise under stirring in reaction system, after dripping in 1.5h react 4h after terminate, reactant is poured out,
Sucking filtration, is washed with distilled water to neutrality, then with certain density ammonia dedoping, is washed with distilled water to neutrality, then with less
Amount absolute ethanol washing, is dried after 48h at 40 DEG C, that is, obtain eigenstate aniline-p-phenylenediamine copolymer.
The acid is hydrochloric acid.The oxidant is Ammonium persulfate..
Wherein, the preparation technology of water-based polyurethane-acrylate emulsion is as follows：
A. first, 15 parts of inertia vinyl monomers, 12 parts of PEPAs, 10 part of two isocyanide are added in dry reactor
Acid esters, 2 parts of anionic hydrophilic chain extenders and 1.5 parts of internal crosslinkers, it is 80 DEG C that reaction temperature is constant, and the response time is 3.5 hours.
B. then, add the hydrophilic vinylic monomer of 4 parts of hydroxyls to be blocked, react 0.7 hour, system temperature is protected
Hold as 80 DEG C, add 2 parts of bases salt forming agents, after neutralization reaction 25 minutes, add containing 0.03 part of surface active monomer and 80 parts
Water mixed liquor, high-speed stirred disperse 5~7 minutes, constant temperature be 80 DEG C.
C. it is last, at 80 DEG C of constant temperature, during initiator solution (0.06 part of initiator) is added drop-wise to into reactor, Deca
After 1.5 hours, by 3 especially cross-linking agent be added drop-wise in reactor simultaneously in 0.5 hour, after completion of dropping, continue to be incubated 1 hour
Then room temperature is down to, that is, aqueous polyurethane-acrylate composite emulsion is obtained.
The vinyl monomer is the mixture of methacrylic acid monomer (MMA) and butyl acrylate (BA), wherein, MMA
It is 3 with the mass ratio of BA：1；The PEPA is polyadipate and dihydroxylic alcohols；The diisocyanate is diphenyl methane
Diisocyanate；The anionic hydrophilic chain extender is dimethylolpropionic acid；The internal crosslinker is trimethylolpropane；It is described
Vinyl monomer end-capping reagent is 2-(Acryloyloxy)ethanol；The polymerizable surface active monomer is 1- propenyloxy group -2- hydroxy propanes
Sodium sulfonate；The bases salt forming agent is triethylamine；The initiator is potassium peroxydisulfate；The outside cross-linking agent is γ-metering system
Acryloxypropylethoxysilane trimethoxy silane (KH570) and glycidyl methacrylate (GMA)；The thickening agent is DL-80；Institute
Defoamer is stated for BYK-035；The coalescents are butyl glycol ether.
Embodiment 3：
Take 100 parts of aqueous polyurethane-acrylate composite emulsions, aniline -2 parts of p-phenylenediamine copolymer, thickening agent 0.2
Part, 0.5 part of defoamer, 10 parts of coalescents, high-speed stirred 5h, that is, obtain aniline-p-phenylenediamine copolymer/aqueous polyurethane-
Acrylate anticorrosive paint.
Wherein, the synthesis technique of aniline-p-phenylenediamine copolymer is as follows：
25 parts of aniline of Jing second distillations and 35 parts of p-phenylenediamine are added in the there-necked flask equipped with finite concentration acid,
Stir under the conditions of ice-water bath, and add 0.6 portion of nonionic surfactant；Take 98 parts of oxidants and be dissolved in certain density acid
In aqueous solution, it is added drop-wise under stirring in reaction system, reacts after dripping in 1.5h and terminate after 4h, reactant is poured out, takes out
Filter, is washed with distilled water to neutrality, then with certain density ammonia dedoping, is washed with distilled water to neutrality, then with a small amount of
Absolute ethanol washing, is dried after 48h at 40 DEG C, that is, obtain eigenstate aniline-p-phenylenediamine copolymer.
The acid is DBSA.The oxidant is Ammonium persulfate..
Wherein, the preparation technology of water-based polyurethane-acrylate emulsion is as follows：
A. first, add in dry reactor 28 parts of inertia vinyl monomers, 15 parts of PEPAs, 12 part two it is different
Cyanate, 2.8 parts of anionic hydrophilic chain extenders and 2 parts of internal crosslinkers, it is 80 DEG C that reaction temperature is constant, and the response time is 3.5 little
When.
B. then, add the hydrophilic vinylic monomer of 5 parts of hydroxyls to be blocked, react 1 hour, system temperature keeps
At 80 DEG C, 2.8 parts of bases salt forming agents are added, after neutralization reaction 30 minutes, add containing 0.04 part of surface active monomer and 85 parts
Water mixed liquor, high-speed stirred disperse 5~7 minutes, constant temperature be 80 DEG C.
C. it is last, at 80 DEG C of constant temperature, during initiator solution (0.08 part of initiator) is added drop-wise to into reactor, Deca
After 1.5 hours, by 3.5 especially cross-linking agent be added drop-wise in reactor simultaneously in 0.5 hour, after completion of dropping, continue to be incubated 1 little
Shi Ranhou is down to room temperature, that is, aqueous polyurethane-acrylate composite emulsion is obtained.
The vinyl monomer is the mixture of methacrylic acid monomer (MMA) and butyl acrylate (BA), wherein, MMA
It is 3.5 with the mass ratio of BA：1；The PEPA is PCDL；The diisocyanate is hexa-methylene two
Isocyanates；The anionic hydrophilic chain extender is dihydromethyl propionic acid；The internal crosslinker is trimethylolpropane；The second
Alkenyl monomer end-capping reagent is hydroxyethyl methylacrylate；The polymerizable surface active monomer is α-sodium olefin sulfonate；The alkali
Class salt forming agent is triethylamine；The initiator is Ammonium persulfate.；The outside cross-linking agent is γ-methacryloxypropyl front three
TMOS (KH570) and glycidyl methacrylate (GMA)；The thickening agent is DL-80；The defoamer is BYK-
038；The coalescents are lauryl alcohol ester.
The aniline that example 1-3 is obtained-p-phenylenediamine copolymer/aqueous polyurethane-acrylate anticorrosive paint is adopted respectively
It is coated on the tinplate of Jing polishings with the method for blade coating, and the performance to paint film is detected, as a result such as table 1.
Table 1
Embodiment 4：
Take 100 parts of aqueous polyurethane-acrylate composite emulsions, aniline -2 parts of p-phenylenediamine copolymer, thickening agent 0.2
Part, 0.5 part of defoamer, 10 parts of coalescents, high-speed stirred 5h, that is, obtain aniline-p-phenylenediamine copolymer/aqueous polyurethane-
Acrylate anticorrosive paint.
Wherein, the synthesis technique of aniline-p-phenylenediamine copolymer is as follows：
10 parts of aniline of Jing second distillations and 10 parts of p-phenylenediamine are added in the there-necked flask equipped with finite concentration acid,
After stirring under the conditions of ice-water bath, and add 0.5 portion of nonionic surfactant；Take 19 parts of oxidants be dissolved in it is certain density
In acidic aqueous solution, it is added drop-wise under stirring in reaction system, reacts after dripping in 1.5h and terminate after 4h, reactant is fallen
Go out, sucking filtration, be washed with distilled water to neutrality, then with certain density ammonia dedoping, be washed with distilled water to neutrality, then use
A small amount of absolute ethanol washing, is dried after 48h at 40 DEG C, that is, obtain eigenstate aniline-p-phenylenediamine copolymer.
The acid is DBSA.The oxidant is Ammonium persulfate..
Wherein, the preparation technology of water-based polyurethane-acrylate emulsion is as follows：
A. first, 10 parts of inertia vinyl monomers, 5 parts of PEPAs, 5 part of two Carbimide. are added in dry reactor
Ester, 1 part of anionic hydrophilic chain extender and 0.3 part of internal crosslinker, it is 80 DEG C that reaction temperature is constant, and the response time is 4 hours.
B. then, add the hydrophilic vinylic monomer of 3 parts of hydroxyls to be blocked, react 0.8 hour, system temperature is protected
Hold at 80 DEG C, add 1 part of bases salt forming agent, after neutralization reaction 30 minutes, add containing 0.04 part of surface active monomer and 75 parts
Water mixed liquor, high-speed stirred disperse 5~7 minutes, constant temperature be 80 DEG C.
C. it is last, at 80 DEG C of constant temperature, during initiator solution (0.02 part of initiator) is added drop-wise to into reactor, Deca
After 1.5 hours, will be added drop-wise in reactor simultaneously in 1.5 especially cross-linking agent 0.5 hour, after completion of dropping, continue to be incubated 1 hour
Then room temperature is down to, that is, aqueous polyurethane-acrylate composite emulsion is obtained.
The vinyl monomer is the mixture of acrylic acid methyl ester., butyl acrylate and methyl methacrylate；It is described poly-
Ester polyol is PCDL；The diisocyanate is hexamethylene diisocyanate；The anionic hydrophilic expands
Chain agent is dihydromethyl propionic acid；The internal crosslinker is trimethylolpropane；The vinyl monomer end-capping reagent is metering system
Sour hydroxyl ethyl ester；The polymerizable surface active monomer is α-sodium olefin sulfonate；The bases salt forming agent is triethylamine；The initiation
Agent is Ammonium persulfate.；The outside cross-linking agent is γ-methacryloxypropyl trimethoxy silane (KH570) and metering system
Acid glycidyl ester (GMA)；The thickening agent is DL-80；The defoamer is BYK-038；The coalescents are lauryl alcohol
Ester.
Embodiment 5：
100 parts of aqueous polyurethane-acrylate composite emulsion, aniline -0.4 part of p-phenylenediamine copolymer, thickening agent 0.1
Part, 0.3 part of defoamer, 5 parts of coalescents, high-speed stirred 5h obtains aniline-p-phenylenediamine copolymer/aqueous polyurethane-the third
Olefin(e) acid ester anticorrosive paint.
Wherein, the synthesis technique of aniline-p-phenylenediamine copolymer is as follows：
28 parts of aniline of Jing second distillations and 32 parts of p-phenylenediamine are added in the there-necked flask equipped with finite concentration acid,
Stir under the conditions of ice-water bath, and add 0.8 portion of nonionic surfactant；Take 68 parts of oxidants and be dissolved in certain density acid
Property aqueous solution in, be added drop-wise under stirring in reaction system, after dripping in 1.5h react 4h after terminate, reactant is poured out,
Sucking filtration, is washed with distilled water to neutrality, then with certain density ammonia dedoping, is washed with distilled water to neutrality, then with less
Amount absolute ethanol washing, is dried after 48h at 40 DEG C, that is, obtain eigenstate aniline-p-phenylenediamine copolymer.
The acid is hydrochloric acid.The oxidant is Ammonium persulfate..
Wherein, the preparation technology of water-based polyurethane-acrylate emulsion is as follows：
A. first, 10 parts of inertia vinyl monomers, 5 parts of PEPAs, 5 part of two Carbimide. are added in dry reactor
Ester, 1 part of anionic hydrophilic chain extender and 0.3 part of internal crosslinker, it is 80 DEG C that reaction temperature is constant, and the response time is 4 hours.
B. then, add the hydrophilic vinylic monomer of 3 parts of hydroxyls to be blocked, react 0.8 hour, system temperature is protected
Hold at 80 DEG C, add 4 parts of bases salt forming agents, after neutralization reaction 30 minutes, add containing 0.04 part of surface active monomer and 75 parts
Water mixed liquor, high-speed stirred disperse 5~7 minutes, constant temperature be 80 DEG C.
C. it is last, at 80 DEG C of constant temperature, during initiator solution (0.02 part of initiator) is added drop-wise to into reactor, Deca
After 1.5 hours, will be added drop-wise in reactor simultaneously in 4 especially cross-linking agent 0.5 hour, after completion of dropping, continue to be incubated 1 hour so
After be down to room temperature, that is, be obtained aqueous polyurethane-acrylate composite emulsion.
The vinyl monomer is butyl acrylate；The PEPA is polyadipate and dihydroxylic alcohols；Described two is different
Cyanate is methyl diphenylene diisocyanate；The anionic hydrophilic chain extender is dimethylolpropionic acid；The internal crosslinker
For trimethylolpropane；The vinyl monomer end-capping reagent is 2-(Acryloyloxy)ethanol；The polymerizable surface active monomer is 1-
Propenyloxy group -2- hydroxypropanesulfonic acid sodium；The bases salt forming agent is triethylamine；The initiator is potassium peroxydisulfate；It is described outer
Cross-linking agent is γ-methacryloxypropyl trimethoxy silane (KH570) and glycidyl methacrylate (GMA)；
The thickening agent is DL-80；The defoamer is BYK-035；The coalescents are butyl glycol ether.
Butyl acrylate in embodiment 5 can also be acrylic acid methyl ester., butyl acrylate, methyl methacrylate, first
In base butyl acrylate, styrene, n-octyl, Hexyl 2-propenoate, n octyl methacrylate, N-Hexyl methacrylate
One or more any proportionings mixture.
Above content is to combine specific preferred implementation further description made for the present invention, it is impossible to assert
The present invention specific embodiment be only limitted to this, for general technical staff of the technical field of the invention, not every
On the premise of present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention and be carried
Claims of friendship determine scope of patent protection.
Claims (10)
1. a kind of aqueous polyurethane polyaniline anti-corrosive paint, it is characterised in that：
Described aqueous polyurethane polyaniline anti-corrosive paint is anti-for aniline-p-phenylenediamine copolymer/aqueous polyurethane-acrylate
Rotten coating, including the raw material of following weight portion：
100 parts of aqueous polyurethane-acrylate composite emulsion, aniline -0.4~2 part of p-phenylenediamine copolymer, thickening agent 0.05~
0.2 part, 0.1~0.5 part of defoamer, 3~10 parts of coalescents；
The preparation method of described aniline-p-phenylenediamine copolymer is：
First 10-30 parts aniline of Jing second distillations and 10-35 parts p-phenylenediamine are added in reactor, is adjusted using acidic aqueous solution
Section system pH is to 1-4, the mixed liquor of stir under conditions of ice-water bath prepared aniline and p-phenylenediamine；Take 49-98 parts
Oxidant is dissolved in acidic aqueous solution, and during above-mentioned mixed liquor is added drop-wise to while stirring, oxidant mixes with aniline and p-phenylenediamine
The mol ratio of monomer is between 1:1 to 1:Between 2；And add 0.3-0.9 part nonionic surfactants as emulsifying agent, drip
Fully react to terminating afterwards, reactant is poured out, sucking filtration；Neutrality is first washed with distilled water to, ammonia dedoping is then used, then is used
Distilled water wash, again with absolute ethanol washing, after being dried, that is, obtains eigenstate aniline-p-phenylenediamine copolymer to neutrality.
2. a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 1, it is characterised in that：
The acid is hydrochloric acid, acetic acid, phosphoric acid or DBSA；
The oxidant is Ammonium persulfate. or potassium peroxydisulfate；
The nonionic surfactant is OPEO.
3. a kind of preparation method of aqueous polyurethane polyaniline anti-corrosive paint, it is characterised in that：Comprise the following steps：
Step 1) prepare aniline-p-phenylenediamine copolymer：
A. by weight, first 10-30 parts aniline of Jing second distillations and 10-35 part p-phenylenediamine are added to and are equipped with pH value
In the reactor of the acidic aqueous solution of 1-4, stir under the conditions of ice-water bath, and add 0.3-0.9 parts non-ionic surface to live
Property agent；
B. 49-98 part oxidants are taken to be dissolved in acidic aqueous solution, is added drop-wise under stirring in the reaction system in step a, dripped
After react to terminating, reactant is poured out, sucking filtration, be first washed with distilled water to neutrality, then use ammonia dedoping, then with distillation
Water washing, again with absolute ethanol washing, after dried, that is, obtains eigenstate aniline-p-phenylenediamine copolymer to neutrality；
Step 2) prepare aqueous polyurethane-acrylate composite emulsion：
C. by weight, 10~28 parts of inertia vinyl monomers, 5~15 parts of polyester polyols are added in dry reactor
Alcohol, 5~12 parts of diisocyanate, 1~2.8 part of anionic hydrophilic chain extender and 0.3~2 part of internal crosslinker, reaction temperature is constant
For 70~80 DEG C, the response time is 3~4 hours；
D. add the hydrophilic vinylic monomer of 3~5 parts of hydroxyls to be blocked, react 0.5~1 hour, system temperature keeps
At 70~80 DEG C, 1~4 part of bases salt forming agent is added, after neutralization reaction, add and contain 0.02~0.04 part of polymerizable surface activity
The mixed liquor of monomer and 75~85 parts of water, dispersed with stirring is uniform；
E. at 70~80 DEG C of constant temperature, 0.02~0.08 part of initiator is dissolved in into initiator solution made by 0.2~0.8 part of water
In being added drop-wise to reactor, after dripping, by 1.5~4 especially cross-linking agent be added drop-wise in reactor simultaneously in 0.5 hour, Deca
After finishing, continue to be incubated 1 hour and then be down to room temperature, that is, aqueous polyurethane-acrylate composite emulsion is obtained；
Step 3) prepare anticorrosive paint：
100 parts of aqueous polyurethane-acrylate composite emulsion adds aniline-p-phenylenediamine copolymer 0.4 as matrix resin
~2 parts, 0.05~0.2 part of thickening agent, 0.1~0.5 part of defoamer, 3~10 parts of coalescents are equal using physical blending process mixing
It is even, that is, obtain aniline-p-phenylenediamine copolymer/aqueous polyurethane-acrylate anticorrosive paint.
4. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：
The acid is hydrochloric acid, acetic acid, phosphoric acid or DBSA；
The oxidant is Ammonium persulfate. or potassium peroxydisulfate；
The nonionic surfactant is OPEO.
5. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：
The inertia vinyl monomer be acrylic acid methyl ester., butyl acrylate, methyl methacrylate, butyl methacrylate,
One or two in styrene, n-octyl, Hexyl 2-propenoate, n octyl methacrylate, N-Hexyl methacrylate
The mixture of any of the above proportioning.
6. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：Institute
PEPA is stated for the own dihydroxylic alcohols of polycaprolactone diols, PCDL or polyadipate.
7. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：
The diisocyanate is isophorone diisocyanate, methyl diphenylene diisocyanate or the Carbimide. of hexa-methylene two
Ester；
The anionic hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid；
The internal crosslinker is trimethylolpropane.
8. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：
The vinyl monomer end-capping reagent is hydroxyethyl methylacrylate or 2-(Acryloyloxy)ethanol；
The polymerizable surface active monomer is α-sodium olefin sulfonate or 1- propenyloxy group -2- hydroxypropanesulfonic acid sodium；
The bases salt forming agent is ammonia or triethylamine.
9. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：
The initiator is Ammonium persulfate. or potassium peroxydisulfate；
The outside cross-linking agent is γ-methacryloxypropyl trimethoxy silane and/or glycidyl methacrylate.
10. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：
The thickening agent is LS-112 or DL-80；
The defoamer is BYK-034, BYK-035 or BYK-037 of German BYK companies production；
The coalescents are lauryl alcohol ester or butyl glycol ether.
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