Summary of the invention
The present invention finishes in order to solve deficiency of the prior art, the purpose of this invention is to provide a kind of water as solvent, cost is low and can not pollute environment, saves the energy, the water-borne acrylic resin that forms at the aqueous phase emulsion free-radical polymerization.
A kind of water-borne acrylic resin of the present invention, its proportioning comprises: methyl methacrylate 24.5-33.15 part, butyl acrylate 16-25.5 part, N hydroxymethyl acrylamide 0.85-1.5 part, phosphate surfactant active 1.4-3 part, weight percent concentration are sodium polyacrylate 2-3 part of 40%, deionized water 48-52 part, ammonium persulphate 1.5-2.5 part, ammoniacal liquor 0.2-0.5 part and 0.1 part of formaldehyde vitriol and 0.1 part of ammonium persulphate of being used for end reaction.
A kind of water-borne acrylic resin of the present invention, because its proportioning comprises: methyl methacrylate 24.5-33.15 part, butyl acrylate 16-25.5 part, N hydroxymethyl acrylamide 0.85-1.5 part, phosphate surfactant active 1.4-3 part, weight percent concentration are sodium polyacrylate 2-3 part of 40%, deionized water 48-52 part, ammonium persulphate 1.5-2.5 part, ammoniacal liquor 0.2-0.5 part and 0.1 part of formaldehyde vitriol and 0.1 part of ammonium persulphate of being used for end reaction.In terms of existing technologies, owing to adopted the deionized water replace organic solvent, provide cost savings greatly, and owing to use deionized water as solvent, therefore evaporate in the atmosphere and can not cause any pollution atmosphere, belong to close environmental product, effectively saved resource, meet the overall development trend of current energy-saving and emission-reduction.
The present invention also provides simultaneously and has produced that the above-mentioned saving energy, cost are low, the preparation method of the water-borne acrylic resin of environmentally safe.
The preparation method of a kind of water-borne acrylic resin of the present invention may further comprise the steps:
A. mixing raw material: with 24.5-33.15 part methyl methacrylate, 16-25.5 part butyl acrylate and 0.85-1.5 part N hydroxymethyl acrylamide mix and stir becomes mix monomer; Half of 50 parts of deionized waters added 1.4-3 part phosphate surfactant active mixes and stirs and become the aqueous solution of tensio-active agent;
B. pre-emulsification: under agitation condition mix monomer is slowly added in the aqueous solution of tensio-active agent, 3/5 amount that adds 1.5-2.5 part ammonium persulphate simultaneously forms pre-emulsified monomer;
C. polyreaction: will remain 25 parts of deionized waters, 2 parts of concentration is that 40% sodium polyacrylate drops in the reactor, be warming up to 68 ℃-72 ℃ under the agitation condition, above-mentioned pre-emulsified monomer with 1/5 directly adds the reactor from header tank, when reaching 70 ℃, temperature in the reactor produces withdrawing fluid, after backflow finishes, to remain 4/5 pre-emulsified monomer splashed in the reactor with 2-3 hour, drip off back insulation 1 hour, mend the ammonium persulphate of residue 1/5 amount of 1.5-2.5 part ammonium persulphate amount that the B step adds, be incubated 1-1.5 hour, mend the ammonium persulphate of residue 1/5 amount of 1.5-2.5 part ammonium persulphate amount that the B step adds again, be incubated cooling after 1-1.5 hour, 0.1 part of formaldehyde vitriol of adding in the time of cooling, 0.1 part ammonium persulphate, temperature are reduced to and are added ammoniacal liquor after the room temperature to regulate pH value be 7.8-8.5;
D: filter and package: use vibratory screening apparatus to filter, package spare.
The preparation method of a kind of water soluble acrylic acid of the present invention can also be:
A. mixing raw material: with 30.65 parts of methyl methacrylates, 18.5 parts of butyl acrylates and 0.85 part of N hydroxymethyl acrylamide mix and stir becomes mix monomer; 25 parts of deionized waters are added 1.5 parts of phosphate surfactant actives to be mixed and stirs and become the aqueous solution of tensio-active agent;
B. pre-emulsification: under agitation condition mix monomer is slowly added in the aqueous solution of tensio-active agent, the ammonium persulphate that adds 1.5 parts simultaneously forms pre-emulsified monomer;
C. polyreaction: will remain 25 parts of deionized waters, 2 parts of concentration is that 40% sodium polyacrylate drops in the reactor, be warming up to 70 ℃ under the agitation condition, above-mentioned pre-emulsified monomer with 1/5 directly adds the reactor from header tank, when reaching 70 ℃, temperature in the reactor produces withdrawing fluid, after backflow finishes, to remain 4/5 pre-emulsified monomer with 2 hours and splash in the reactor, drip off back insulation 1 hour, mend 0.5 part ammonium persulphate, be incubated 1 hour, mend 0.5 part of ammonium persulphate again, be incubated cooling after 1 hour, add 0.1 part of formaldehyde vitriol in the time of cooling, 0.1 part ammonium persulphate, temperature are reduced to and are added ammoniacal liquor after the room temperature to regulate pH value be 7.8-8.5;
D: filter and package: use vibratory screening apparatus to filter, package spare.
By the preparation method of water-borne acrylic resin of the present invention, owing to adopt deionized water as solvent, each mixture generates water-borne acrylic resin at the aqueous phase emulsion free-radical polymerization, therefore saves the energy, reduces cost environmentally safe.
Further aim of the present invention provides and a kind ofly contains that above-mentioned cost is low, the water-based dip-coating vinylformic acid shop primer of the water-borne acrylic resin of environmentally safe.
The water-based dip-coating vinylformic acid shop primer that contains water-borne acrylic resin of the present invention, its prescription comprises: 15-20 part wet oxidation iron oxide red, 1-5 part water-based aluminium triphosphate, 8-16 part ST rust-stabilising pigment, 0.8-1.2 part sodium polyacrylate, 0.2-0.5 part sterilant, 1-2 part 968 water-based antirust agents, 2-2.5 part alcohol ester 12,35-50 part water-borne acrylic resin, 30-40 part deionized water.
The water-based dip-coating vinylformic acid shop primer that contains water-borne acrylic resin of the present invention, owing to adopt water-borne acrylic resin to replace the acrylic resin of original organic solvent diluting, the advantage that has in terms of existing technologies is after treating drying varniss as the deionized water of solvent, all evaporate in the atmosphere, to environment without any pollution, and because the cost of deionized water is lower than the cost of the organic solvent of present use, therefore the water-based dip-coating vinylformic acid shop primer of producing is saved the energy and has been reduced cost.
The present invention also provides the above-mentioned preparation method who contains the water-based dip-coating vinylformic acid shop primer of water-borne acrylic resin with above-mentioned advantage.
The preparation method who contains the water-based dip-coating vinylformic acid shop primer of water-borne acrylic resin of the present invention may further comprise the steps:
A: defibrination: 30-40 part deionized water, 15-20 part wet oxidation iron oxide red, 1-5 part water-based aluminium triphosphate, 8-16 part ST rust-stabilising pigment, 0.8-1.2 part sodium polyacrylate, drop into the material-compound tank high speed and disperseed 20-40 minute, be dispersed to fineness 40 μ m with sand mill, it is standby that formation water-based iron oxide red slurry is cooled to room temperature;
B: emulsion mixed solution preparation: 35-50 part water-borne acrylic resin, 1-2 part 968 water-based antirust agents, 0.2-0.5 part sterilant stirs in the input stirred pot, slowly adds 2-2.5 part alcohol ester 12 then, and stirring forms the emulsion mixed solution;
C: join lacquer: the water-based iron oxide red slurry that under agitation the A step is formed slowly adds in the emulsion mixed solution of B step, stirred 25-35 minute, with ammoniacal liquor accent pH value 7.8-8.5, viscosity for be coated with-4 glasss 23 ± 2 ℃ 25 seconds;
D: filter and package: filter and package with vibratory screening apparatus.
Use method of the present invention owing to use deionized water in the production process as solvent, therefore after treating drying varniss as the deionized water of solvent, all evaporate in the atmosphere, to environment without any pollution, and because the cost of deionized water is lower than the cost of the organic solvent of present use, therefore the water-based dip-coating vinylformic acid shop primer of producing is saved the energy and has been reduced cost.
Embodiment
Below water-borne acrylic resin of the present invention and preparation method thereof and water-based dip-coating vinylformic acid shop primer that contains water-borne acrylic resin and preparation method thereof are described in further detail.
Water-borne acrylic resin of the present invention, its proportioning comprises: methyl methacrylate 24.5-33.15 part, butyl acrylate 16-25.5 part, N hydroxymethyl acrylamide 0.85-1.5 part, phosphate surfactant active 1.4-3 part, weight percent concentration are sodium polyacrylate 2-3 part of 40%, deionized water 48-52 part, ammonium persulphate 1.5-2.5 part, ammoniacal liquor 0.2-0.5 part and 0.1 part of formaldehyde vitriol and 0.1 part of ammonium persulphate of being used for end reaction.Wherein, phosphate surfactant active specifically can be that the trade mark of the loyal Fine Chemical Co., Ltd in Shanghai production and sales is the inferior tensio-active agent of phosphoric acid of A103.Certainly can also be other phosphate surfactant active.The amount of ammoniacal liquor then is that the pH value according to the mixture that produces calculates the back and adds, and purpose is to regulate the pH value of final water-borne acrylic resin between the 7.8-8.5.In terms of existing technologies, owing to adopted the deionized water replace organic solvent, provide cost savings greatly, and owing to use deionized water as solvent, therefore evaporate in the atmosphere and can not cause any pollution atmosphere, belong to close environmental product, effectively saved resource, meet the overall development trend of current energy-saving and emission-reduction.
The preparation method of a kind of water-borne acrylic resin of the present invention may further comprise the steps:
A. mixing raw material: with 24.5-33.15 part methyl methacrylate, 16-25.5 part butyl acrylate and 0.85-1.5 part N hydroxymethyl acrylamide mix and stir becomes mix monomer; Half of 50 parts of deionized waters added 1.4-3 part phosphate surfactant active mixes and stirs and become the aqueous solution of tensio-active agent;
B. pre-emulsification: under agitation condition mix monomer is slowly added in the aqueous solution of tensio-active agent, 3/5 amount that adds 1.5-2.5 part ammonium persulphate simultaneously forms pre-emulsified monomer;
C. polyreaction: will remain 25 parts of deionized waters, 2 parts of concentration is that 40% sodium polyacrylate drops in the reactor, be warming up to 68 ℃-72 ℃ under the agitation condition, above-mentioned pre-emulsified monomer with 1/5 directly adds the reactor from header tank, when reaching 70 ℃, temperature in the reactor produces withdrawing fluid, after backflow finishes, to remain 4/5 pre-emulsified monomer splashed in the reactor with 2-3 hour, drip off back insulation 1 hour, mend the ammonium persulphate of residue 1/5 amount of 1.5-2.5 part ammonium persulphate amount that the B step adds, be incubated 1-1.5 hour, mend the ammonium persulphate of residue 1/5 amount of 1.5-2.5 part ammonium persulphate amount that the B step adds again, be incubated cooling after 1-1.5 hour, 0.1 part of formaldehyde vitriol of adding in the time of cooling, 0.1 part ammonium persulphate, temperature are reduced to and are added ammoniacal liquor after the room temperature to regulate pH value be 7.8-8.5;
D: filter and package: use vibratory screening apparatus to filter, package spare.
Wherein concentration is that percentage is weight percentage in 40% the sodium polyacrylate.And agitation condition choosing is warming up to 68 ℃-72 ℃, if temperature is lower than 68 ℃, the reaction that adds behind the pre-emulsified monomer of later stage is slower so, can not produce withdrawing fluid in the time of 70 ℃.And if temperature is higher than 72 ℃, monomer can volatilize so, and reaction discharges a large amount of heat, and reaction is violent, and the still that overflows takes place easily, produces dangerous.And the back of refluxing splashed into remaining pre-emulsified monomer in the reactor with 2-3 hour, if be lower than 2 hours duration of service, be exactly drip too fast so, will produce a large amount of heats, reaction is violent, to produce the still that overflows, relatively more dangerous, and if splash into too slow, promptly the time was above 3 hours, so the production cycle too long, reduce production efficiency.In addition, soaking time behind the adding ammonium persulphate is 1-1.5 hour, reaction so is not thorough if soaking time is lower than 1 hour, can not generate final water-borne acrylic resin, if and soaking time is too long, as surpassing 1.5 hours, though reaction is more thorough, but the production cycle is long, is unfavorable for enhancing productivity.And the effect that adds formaldehyde vitriol (being commonly called as rongalite) and a spot of ammonium persulphate during end reaction is feasible reacting completely.
In above-mentioned steps, be f if be used for 1.5-2.5 part ammonium persulphate measuring of primary reaction in the proportioning, the ammonium persulphate amount that adds in the B step is 0.6f so, is 0.2f and add volume of ammonium sulfate successively at twice respectively in the C step.In other words the B step be primary reaction 1.5-2.5 part ammonium persulphate amount 3/5, and in the C step, add half of ammonium persulphate amount of residue primary reaction in two steps respectively.The ammonium persulphate that also will add 0.1 part during end reaction, the amount of this ammonium persulphate are not included in 1.5-2.5 part ammonium persulphate, in proportioning are to calculate separately yet.The content that is the ammonium persulphate in the overall proportioning is between 1.6-2.6 part.
The proportioning of the water-borne acrylic resin of comparative optimization and preparation method are:
A. mixing raw material: with 30.65 parts of methyl methacrylates, 18.5 parts of butyl acrylates and 0.85 part of N hydroxymethyl acrylamide mix and stir becomes mix monomer; 25 parts of deionized waters are added 1.5 parts of phosphate surfactant actives to be mixed and stirs and become the aqueous solution of tensio-active agent;
B. pre-emulsification: under agitation condition mix monomer is slowly added in the aqueous solution of tensio-active agent, the ammonium persulphate that adds 1.5 parts simultaneously forms pre-emulsified monomer;
C. polyreaction: with the deionized water of residual content, 2-3 part concentration is that 40% sodium polyacrylate drops in the reactor, be warming up to 70 ℃ under the agitation condition, above-mentioned pre-emulsified monomer with 1/5 directly adds the reactor from header tank, when reaching 70 ℃, temperature in the reactor produces withdrawing fluid, after backflow finishes, to remain 4/5 pre-emulsified monomer with 2 hours and splash in the reactor, drip off back insulation 1 hour, mend 0.5 part ammonium persulphate, be incubated 1 hour, mend 0.5 part ammonium persulphate again, be incubated cooling after 1 hour, add 0.1 part of formaldehyde vitriol in the time of cooling, 0.1 part ammonium persulphate, temperature are reduced to and are added ammoniacal liquor after the room temperature to regulate pH value be 7.8-8.5;
D: filter and package: use vibratory screening apparatus to filter, package spare.
Because the water-borne acrylic resin that produces forms at the aqueous phase emulsion free-radical polymerization, deionized water is as solvent, deionized water substitutes organic solvent, not only save the energy, reduced cost, and can not produce toxic substance after the deionized water volatilization, and can not pollute atmosphere, belong to close environmental product.And employed steam heating reactor in the water-borne acrylic resin preparation process has the header tank and the vibratory screening apparatus of fractional column, reflux cooler, belt stirrer, and this reactor adopts and revolves the formula of saying, rotating speed is 100-120 rev/min.Such steam heating reactor is general in the market, can buy.
Embodiment: according to following proportioning table and above-mentioned preparation method, the water-borne acrylic resin performance comparison of manufacturing is as follows
Table 1 is produced the proportioning of water-borne acrylic resin
The water-based dip-coating vinylformic acid shop primer that contains water-borne acrylic resin of the present invention, its prescription comprises: 15-20 part wet oxidation iron oxide red, 1-5 part water-based aluminium triphosphate, 8-16 part ST rust-stabilising pigment, 0.8-1.2 part sodium polyacrylate, 0.2-0.5 part sterilant, 1-2 part 968 water-based antirust agents, 2-2.5 part alcohol ester 12,35-50 part water-borne acrylic resin, 30-40 part deionized water.Wherein, the water-borne acrylic resin of use is the manufacturings of aforesaid proportioning and method.The wet oxidation iron oxide red is meant the ferric oxide red colorant that wet method is made, and claims precipitator method iron oxide red again, is to be raw material with the ferrous salt, and ferrous salt and alkali reaction generate crystal seed, then iron filings is dissolved and are deposited in to gradually grow up on the crystal seed to be the iron oxide red particle.The ST rust-stabilising pigment is the product that can buy in the market, has many producers all to produce at present and sells the ST rust-stabilising pigment.Sterilant specifically can be that the trade mark of the modest chemical company of this moral of Shanghai hamming production and sales is the sterilant of MB-11.968 water-based antirust agents are No. 968 water-based antirust agents, and the trade mark that can adopt the production and sales of Japanese Kao company is 968 water-based antirust agents of MX-968.Alcohol ester 12 is meant alcohol ester-12 (film coalescence aid) chemical name: 2,2, and 4-trimethylammonium-1, the 3-pentanediol mono isobutyrate, its purposes is for being used as emulsion paint film coalescence aid (also claiming coalescing agent, flow agent).Owing to adopt water-borne acrylic resin to replace the acrylic resin of original organic solvent diluting, the advantage that has in terms of existing technologies is after treating drying varniss as the deionized water of solvent, all evaporate in the atmosphere, to environment without any pollution, and because the cost of deionized water is lower than the cost of the organic solvent of present use, therefore the water-based dip-coating vinylformic acid shop primer of producing is saved the energy and has been reduced cost.
The preparation method who contains the water-based dip-coating vinylformic acid shop primer of water-borne acrylic resin of the present invention may further comprise the steps:
A: defibrination: 30-40 part deionized water, 15-20 part wet oxidation iron oxide red, 1-5 part water-based aluminium triphosphate, 8-16 part ST rust-stabilising pigment, 0.8-1.2 part sodium polyacrylate, drop into the material-compound tank high speed and disperseed 20-40 minute, be dispersed to fineness 40 μ m with sand mill, it is standby that formation water-based iron oxide red slurry is cooled to room temperature;
B: emulsion mixed solution preparation: 35-50 part water-borne acrylic resin, 1-2 part 968 water-based antirust agents, 0.2-0.5 part sterilant stirs in the input stirred pot, slowly adds 2-2.5 part alcohol ester 12 then, and stirring forms the emulsion mixed solution;
C: join lacquer: the water-based iron oxide red slurry that under agitation the A step is formed slowly adds in the emulsion mixed solution of B step, stirred 25-35 minute, with ammoniacal liquor accent pH value 7.8-8.5, viscosity for be coated with-4 glasss 23 ± 2 ℃ 25 seconds;
D: filter and package: filter and package with vibratory screening apparatus.
Use method of the present invention owing to use deionized water in the production process as solvent, therefore after treating drying varniss as the deionized water of solvent, all evaporate in the atmosphere, to environment without any pollution, and because the cost of deionized water is lower than the cost of the organic solvent of present use, therefore the water-based dip-coating vinylformic acid shop primer of producing is saved the energy and has been reduced cost.
May further comprise the steps with the preparation method who further preferably contains the water-based dip-coating vinylformic acid shop primer of water-borne acrylic resin:
A: defibrination: 35 parts of deionized waters, 15 parts of wet oxidation iron oxide reds, 2 parts of water-based aluminium triphosphates, 8 parts of ST rust-stabilising pigments, 1 part of sodium polyacrylate drops into the material-compound tank high speed and disperseed 30 minutes, be dispersed to fineness 40u with sand mill, it is standby that formation water-based iron oxide red slurry is cooled to room temperature;
B: emulsion mixed solution preparation: 38 parts of water-borne acrylic resins, 1.5 parts of 968 water-based antirust agents, sterilant 0.2-0.5 part stirs in the input stirred pot, slowly adds 2 parts of alcohol esters 12 then, stirs.
C: join lacquer: the water-based iron oxide red slurry that under agitation the A step is formed slowly adds in the emulsion mixed solution that the B step forms, stirred 30 minutes, with ammoniacal liquor accent pH value 7.8-8.5, viscosity be coated with-4 glasss 23 ± 2 ℃ 25 seconds;
D: filter and package: filter and package with vibratory screening apparatus.
Use the water-based dip-coating vinylformic acid shop primer technical parameter such as the following table 2 that contain water-borne acrylic resin of aforesaid method production:
Table 2 technical parameter
Can draw the water-based dip-coating vinylformic acid shop primer of producing according to said ratio and preparation method that contains water-borne acrylic resin by last table, the performance of each side is all relatively good, and environmental sound, belongs to close environmental product.
Embodiment:
Except that the foregoing description, can also be that proportioning is following and contain the water-based dip-coating vinylformic acid shop primer of water-borne acrylic resin according to above-mentioned manufacture method manufacturing.
Table 3 contains the water-based dip-coating vinylformic acid shop primer proportioning table of water-borne acrylic resin
Table 3 dip-coating shop primer formula table
What use is 6# water-borne acrylic resin in the above-mentioned table 1.And the sodium polyacrylate of all uses herein is weight percent concentration is 40%.
Above-mentionedly only several specific embodiments among the present invention are illustrated, but can not be as protection scope of the present invention, every equivalence of having done according to the design spirit among the present invention changes or modifies, and all should think to fall into protection scope of the present invention.