CN105273121A - Preparation method of fluorine-containing polyvinylidene chloride emulsion for coating - Google Patents
Preparation method of fluorine-containing polyvinylidene chloride emulsion for coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a fluorine-containing polyvinylidene chloride emulsion for a coating. The preparation method comprises the following steps of (1) preparing for reaction raw materials for later use; (2) preparing a seed emulsion; (3) preparing a vinylidene chloride copolymer solution; and (4) preparing the fluorine-containing polyvinylidene chloride emulsion to obtain the fluorine-containing polyvinylidene chloride emulsion for the coating. The preparation method has the characteristics of simple process, easily-controlled reaction condition, good emulsion stability, environment friendliness and the like; and the obtained fluorine-containing polyvinylidene chloride emulsion has the advantages of good adhesive force, good oxygen and water resistance, good chemical stability and good stain resistance and is particularly suitable for outdoor high-grade building exterior wall coatings, wood coatings and the like with relatively high requirements for water resistance and weather resistance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the preparation method of a kind of coating with fluorine-containing polyvinylidene emulsions.
Background technology
Acrylate polymer emulsion has good photostabilization, resistance to acids and bases and the bonding force good with base material because of it, and becomes the main film forming substance of outdoor architecture exterior coating, woodwork coating.But acrylate polymer emulsion is mixed with the water tolerance of latex coating, oil-proofness is poor, do not bear dirty simultaneously, temperature tolerance is poor, weathering resistance is difficult to the application meeting outdoor architecture exterior coating, woodwork coating, needs to safeguard every year, adds maintenance cost.Therefore, release aqueous fluoropolymer emulsion both at home and abroad successively and be used for outdoor architecture exterior coating, the main film forming substance of woodwork coating, it has excellent weathering resistance, contamination resistance and water tolerance, reduce maintenance cost, as CN103864996A discloses a kind of silicon-fluorin acrylic acid ternary polymerization latex and preparation method thereof, by organosilicon, the copolymerization after nucleocapsid reaction and coordination reaction of organic fluorine and acrylic copolymer forms, define nucleocapsid material, three's advantage is had concurrently in one after copolymerization, there is excellent weathering resistance, weather resistance, water tolerance and pollution resistance, energy dirt-resistant self-cleaning, permanent maintenance is attractive in appearance, can directly use as coating or as the intermediates of different coating for preparing the coating of different purposes.But the organic fluorine prepolymer solid content that this kind of method uses is comparatively large, preparation difficulty is comparatively large, and cost is higher.
Polyvinylidene dichloride is because of its molecular structure symmetry, repeating unit is little, close structure, packing density is high, be a kind of difficulty combustion, nontoxic, tasteless, barrier property is good, oil resistant, chemicals-resistant, the macromolecular material that fast light, transparent and printing performance is good, physical strength is higher, copolymer emulsion is especially widely used in wrapping material with its excellent barrier property, directly can be coated with on plastics and paper, be prepared into composite package film, for packaging and the metal primer of food, medicine, military supplies, pharmaceutical chemicals etc.
As CN103059192A discloses a kind of polyvinylidene dichloride copolymer latex for inner, external wall coating and method for making thereof and application, this PVDC copolymer latex by containing the mix monomer of a certain amount of vinylidene chloride, vinylchlorid and acrylate, auxiliary agent, initiator, to obtain through a polymerization containing the emulsifying agent of Sodium dodecylbenzene sulfonate and OP-10 or OP-4.This PVDC latex makes stable system, can 30 DEG C, place under RH70% 24 months not breakdown of emulsion, without precipitation, do not destroyed by calcium ions and magnesium ions during use; With its obtained inner, external wall coating there is environmental protection, waterproof, protection against the tide (anti-mildew), flame retardant resistance meet the features such as UL94 standard V-0 grade, but its chemical stability and weathering resistance poor.
And for example CN1120847A discloses a kind of lower homologue (methyl) Perfluoroalkyl acrylate and vinylidene chloride and (methyl) alkyl acrylate and optional N hydroxymethyl acrylamide, the multipolymer of (methyl) acrylic acid hydroxy alkyl ester and/or (methyl) vinylformic acid alkoxy ester, fabric height waterproof can be given under mild conditions, resistance to alcohol and oil-proofness, this invention adopts " step " to synthesize above-mentioned fluorinated acrylate polymer, the fluorochemical monomer content used is higher than vinylidene chloride monomer and acrylate monomer, be difficult to ensure, with base material, there is good associativity, simultaneously, to obtain latex particle size larger, poor chemical stability, the product obtained is for fabric.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide that a kind of sticking power is high, resistance oxygen water preventing ability is good, the preparation method of chemical stability and the excellent fluorine-containing polyvinylidene emulsions of coating of resistance to soiling.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of coating preparation method of fluorine-containing polyvinylidene emulsions, comprises the following steps:
(1) ready reaction raw material for standby
By weight, reaction raw materials consists of: deionized water 40 ~ 73 parts, vinylidene 20 ~ 32 parts, acrylic monomer 3.4 ~ 8 parts, perfluor alkyl ethyl acrylate monomer 7 ~ 20 parts, initiator 0.15 ~ 0.3 part, pH value regulator 0.5 ~ 3 part, emulsifying agent 5 ~ 15 parts;
(2) seed emulsion preparation
By deionized water 37 ~ 70 parts, emulsifying agent 2 ~ 6 parts, pH value regulator 0.5 ~ 3 part adds in reactor, then at 10 ~ 25 DEG C, under 50 ~ 200rpm mixing speed, add acrylic monomer 0.5 ~ 1 part, vinylidene 1 ~ 3 part, emulsification 10 ~ 20min, then under 50 ~ 150rpm rotating speed, 40 ~ 80 DEG C are warming up to, add the mixing liquid of initiator 0.05 ~ 0.1 part and 1 part of deionized water composition, reaction 10 ~ 20min, obtained seed emulsion;
(3) vinylidene chloride copolymer emulsion preparation
Under 50 ~ 150rpm rotating speed and 40 ~ 80 DEG C of temperature, to drip mixing liquid, the perfluor alkyl ethyl acrylate monomer 1 ~ 5 part of the mixing liquid of emulsifying agent 1 ~ 3 part and initiator 0.05 ~ 0.1 part and deionized water 1 part composition, acrylic monomer 1.2 ~ 3 parts and vinylidene 15 ~ 24 parts at the uniform velocity respectively in the seed emulsion that step (2) obtains, dropwise at 0.5 ~ 2.5h, after dropwising, insulation 0.5 ~ 2h, obtains vinylidene chloride copolymer emulsion;
(4) fluorine-containing polyvinylidene emulsions preparation
Under 50 ~ 150rpm rotating speed and 40 ~ 80 DEG C of temperature, to drip mixing liquid, the perfluor alkyl ethyl acrylate monomer 6 ~ 17 parts of the mixing liquid of emulsifying agent 1 ~ 6 part and initiator 0.05 ~ 0.1 part and deionized water 1 part composition, acrylic monomer 1.7 ~ 4 parts and vinylidene 4 ~ 5 parts at the uniform velocity respectively in above-mentioned vinylidene chloride copolymer emulsion, dropwise at 1.5 ~ 2.5h, after dropwising, insulation 0.5 ~ 1h, be warming up to 80 ~ 95 DEG C, vacuumize to take off and analyse 1 ~ 3h, obtain the fluorine-containing polyvinylidene emulsions of coating.
Described acrylic monomer is preferably two or more the mixture in methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, octadecyl acrylate.
Described perfluor alkyl ethyl acrylate monomer is preferably the mixture of one or more in perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethyl propylene acid esters, perfluoro decyl ethyl propylene acid esters.
Described emulsifying agent is preferably the mixture of two kinds in sodium lauryl sulphate, Witco 1298 Soft Acid, Sodium dodecylbenzene sulfonate, dodecyl diphenyl oxide sodium sulfonate, perfluoro hexyl novalgin, perfluorobutyl potassium, perfluorohexylethyl sulfonic acid sodium, perfluor sodium nonylbenzenesulfonate, fatty alcohol-polyoxyethylene ether, polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol ether.
Described pH value regulator is preferably the mixture of two kinds in sodium bicarbonate, bicarbonate of ammonia, SODIUM PHOSPHATE, MONOBASIC, sodium hydrogen phosphate.
Described initiator is preferably one or both the mixture in ammonium persulphate, Potassium Persulphate, rongalite, sodium bisulfite, tertbutyl peroxide, formaldehyde sodium sulfoxylate.
The method of the present invention's employing " semi-continuous polymerzation " prepares the polyvinylidene emulsions that acrylic polymers, vinylidene chloride copolymer and fluoro-acrylate copolymer are three kinds of main micelle mixed structures; product solid content is 30% ~ 60%; sticking power is high, resistance oxygen water preventing ability is good, chemical stability and resistance to soiling excellent, be specially adapted to water tolerance and weathering resistance requires higher top-grade building exterior coating, woodwork coating etc.
Compared with prior art, the present invention has the following advantages:
1, present method has technique simply, and reaction conditions is easy to control, good emulsion stability, the features such as environmental friendliness.
2, owing to introducing acrylic monomer and perfluor alkyl ethyl acrylate monomer in polyvinylidene emulsions, molecular interaction is formed in latex particle inside, consistency is better, the fluorine-containing polyvinylidene emulsions obtained, except keeping advantage that the resistance oxygen water preventing ability of polyvinylidene dichloride is good, also has the advantage that sticking power is good, chemical stability is good and resistance to soiling is good.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
A coating preparation method for fluorine-containing polyvinylidene emulsions, comprises the following steps:
(1) ready reaction raw material for standby
Composition of raw materials is as follows:
Deionized water: 73kg
Emulsifying agent: sodium lauryl sulphate 2.5kg, polyoxyethylene nonylphenol ether (NP-10): 2.5kg
PH value regulator: sodium bicarbonate 0.5kg,
Acrylic monomer: methyl methacrylate 2.68kg, methyl acrylate 0.6kg, methacrylic acid 0.12kg
Vinylidene: 20kg
Initiator: tertbutyl peroxide 0.075kg, formaldehyde sodium sulfoxylate 0.075kg
Perfluor alkyl ethyl acrylate monomer: perfluoro hexyl ethyl propylene acid esters 7kg
(2) seed emulsion is prepared
By deionized water 70kg, emulsifying agent (sodium lauryl sulphate 1kg, polyoxyethylene nonylphenol ether 1kg), pH value regulator sodium bicarbonate 0.5kg adds in 150L reactor, then at 10 DEG C, under 50rpm mixing speed, slowly add acrylic monomer (the methyl methacrylate 0.28kg mixed, methyl acrylate 0.20kg, methacrylic acid 0.02kg) and vinylidene 1kg, emulsification 10min, after being warming up to 40 DEG C again under 50rpm mixing speed, add initiator (tertbutyl peroxide 0.025kg, formaldehyde sodium sulfoxylate 0.025kg) and the mixing liquid that forms with 1kg deionized water, reaction 10min, obtained seed emulsion,
(3) vinylidene chloride copolymer emulsion is prepared
At 50rpm mixing speed, at 40 DEG C, to drip emulsifying agent (sodium lauryl sulphate 1kg at the uniform velocity respectively in the seed emulsion that step (2) is obtained, polyoxyethylene nonylphenol ether 1kg) and initiator (tertbutyl peroxide 0.025kg, formaldehyde sodium sulfoxylate 0.025kg) and 1kg deionized water composition mixing liquid, acrylic monomer (methyl methacrylate 0.96kg, methyl acrylate 0.20kg, methacrylic acid 0.04kg) with the mixing liquid of vinylidene 15kg, perfluoro hexyl ethyl propylene acid esters 1kg, dropwise at 1.5h, after dropwising, insulation 1h, obtain vinylidene chloride copolymer emulsion,
(4) fluorine-containing polyvinylidene emulsions is prepared
At 50rpm mixing speed, at 40 DEG C, to drip emulsifying agent (sodium lauryl sulphate 0.5kg at the uniform velocity respectively in above-mentioned vinylidene chloride copolymer emulsion, polyoxyethylene nonylphenol ether 0.5kg) and initiator (tertbutyl peroxide 0.025kg, formaldehyde sodium sulfoxylate 0.025kg) and 1kg deionized water mixing liquid, acrylic monomer (methyl methacrylate 1.44kg, methyl acrylate 0.20kg, methacrylic acid 0.06kg) with the mixing liquid of vinylidene 4kg, perfluoro hexyl ethyl propylene acid esters 6kg, dropwise at 1.5h, after dropwising, insulation 0.5h, be warming up to 80 DEG C, vacuumize to take off and analyse 3h, obtain the fluorine-containing polyvinylidene emulsions of coating that solid content is 30%.The coating obtained by fluorine-containing polyvinylidene emulsions performance in table 1.
Embodiment 2
A coating preparation method for fluorine-containing polyvinylidene emulsions, comprises the following steps:
(1) ready reaction raw material for standby
Composition of raw materials is as follows:
Deionized water 43kg
Emulsifying agent: Witco 1298 Soft Acid 8kg, polyoxyethylene octylphenol ether (OP-10): 6kg, Sodium dodecylbenzene sulfonate 1kg,
PH value regulator: bicarbonate of ammonia 3kg
Acrylic monomer: methyl acrylate 6.3kg, butyl acrylate 1.35kg, vinylformic acid 0.35kg
Vinylidene: 32kg,
Initiator: ammonium persulphate 0.3kg
Perfluor alkyl ethyl acrylate monomer: perfluorooctylethyl group acrylate 20kg
(2) seed emulsion is prepared
By deionized water 40kg, emulsifying agent (Witco 1298 Soft Acid 4kg, polyoxyethylene octylphenol ether 2kg), pH value regulator bicarbonate of ammonia 3kg adds in reactor, then at 25 DEG C, under 200rpm mixing speed, slowly add acrylic monomer (the methyl acrylate 0.9kg mixed, butyl acrylate 0.05kg, vinylformic acid 0.05kg) and vinylidene 3kg, emulsification 20min, 80 DEG C are warming up to again under 150rpm mixing speed, add the mixing liquid that initiator ammonium persulfate 0.1kg and deionized water 1kg forms, reaction 20min, obtained seed emulsion,
(3) vinylidene chloride copolymer emulsion is prepared
At 150rpm mixing speed and 80 DEG C, to drip emulsifying agent (Sodium dodecylbenzene sulfonate 1kg at the uniform velocity respectively in the seed emulsion that step (2) is obtained, polyoxyethylene octylphenol ether 2kg) and the mixing liquid that forms of initiator ammonium persulfate 0.1kg and deionized water 1kg, acrylic monomer (methyl acrylate 1.8kg, butyl acrylate 1.1kg, vinylformic acid 0.1kg) with the mixing liquid of vinylidene 24kg, perfluorooctylethyl group acrylate 3kg, dropwise at 2.5h, after dropwising, insulation 0.5h, obtain vinylidene chloride copolymer emulsion,
(4) fluorine-containing polyvinylidene emulsions is prepared
At 150rpm mixing speed and 80 DEG C, to drip emulsifying agent (Witco 1298 Soft Acid 4kg at the uniform velocity respectively in above-mentioned vinylidene chloride copolymer emulsion, polyoxyethylene octylphenol ether 2kg) and the mixing liquid that forms of initiator ammonium persulfate 0.1kg and deionized water 1kg, acrylic monomer (methyl acrylate 3.6kg, butyl acrylate 0.2kg, vinylformic acid 0.2kg) with the mixing liquid of vinylidene 5kg, perfluorooctylethyl group acrylate 17kg, dropwise at 2.5h, after dropwising, insulation 1h, be warming up to 95 DEG C, vacuumize to take off and analyse 1h, obtain the fluorine-containing polyvinylidene emulsions of coating that solid content is 60%.The coating obtained by fluorine-containing polyvinylidene emulsions performance in table 1.
Embodiment 3
A coating preparation method for fluorine-containing polyvinylidene emulsions, comprises the following steps:
(1) ready reaction raw material for standby
Composition of raw materials is as follows:
Deionized water 63kg,
Emulsifying agent: dodecyl diphenyl oxide sodium sulfonate (2A1): 2kg, fatty alcohol-polyoxyethylene ether (TMN-10): 1kg, perfluorobutyl potassium 0.75kg, polyoxyethylene octylphenol ether (OP-10): 0.75kg, perfluorohexylethyl sulfonic acid sodium 1.5kg
PH value regulator: SODIUM PHOSPHATE, MONOBASIC 1kg
Acrylic monomer: methyl methacrylate 4.25kg, ethyl propenoate 0.5kg, vinylformic acid 0.25kg
Vinylidene: 25kg,
Initiator: Potassium Persulphate 0.1kg, rongalite 0.075kg
Perfluor alkyl ethyl acrylate monomer: perfluoro decyl ethyl propylene acid esters 5kg, perfluoro hexyl ethyl propylene acid esters 8kg
(2) seed emulsion is prepared
By deionized water 60kg, emulsifying agent (dodecyl diphenyl oxide sodium sulfonate 2kg, fatty alcohol-polyoxyethylene ether 1kg), pH value regulator SODIUM PHOSPHATE, MONOBASIC 1kg adds in 150L reactor, at 15 DEG C, under 100rpm mixing speed, slowly add acrylic monomer (the methyl methacrylate 0.85kg mixed, ethyl propenoate 0.1kg, vinylformic acid 0.05kg) and vinylidene 2kg, emulsification 15min, 60 DEG C are warming up to again under 150rpm mixing speed, add initiator (Potassium Persulphate 0.03kg, rongalite 0.02kg) and deionized water 1kg form mixing liquid, reaction 15min, obtained seed emulsion,
(3) vinylidene chloride copolymer emulsion is prepared
At 150rpm mixing speed and 60 DEG C, to drip emulsifying agent (perfluorobutyl potassium 0.75kg at the uniform velocity respectively in the seed emulsion that step (2) obtains, polyoxyethylene octylphenol ether 0.25kg) and initiator (Potassium Persulphate: 0.04kg, rongalite 0.035kg) and 1kg deionized water mixing liquid, acrylic monomer (methyl methacrylate 1.7kg, ethyl propenoate 0.2kg, vinylformic acid 0.1kg) with the mixing liquid of vinylidene 18kg, perfluoro decyl ethyl propylene acid esters 5kg, dropwise at 2h, after dropwising, insulation 0.75h, obtain vinylidene chloride copolymer emulsion,
(4) fluorine-containing polyvinylidene emulsions is prepared
At 150rpm mixing speed and 60 DEG C, to drip emulsifying agent (perfluorohexylethyl sulfonic acid sodium 1.5kg at the uniform velocity respectively in above-mentioned vinylidene chloride copolymer emulsion, polyoxyethylene nonylphenol ether 0.5kg) and initiator (Potassium Persulphate: 0.03kg, rongalite 0.02kg) and deionized water 1kg form mixing liquid, acrylic monomer (methyl methacrylate 1.7kg, ethyl propenoate 0.2kg, vinylformic acid 0.1kg) with the mixing liquid of vinylidene 5kg, perfluoro hexyl ethyl propylene acid esters 8kg, dropwise at 2h, after dropwising, insulation 0.75h, be warming up to 90 DEG C, vacuumize to take off and analyse 2h, obtain the fluorine-containing polyvinylidene emulsions of coating that solid content is 40%.The coating obtained by fluorine-containing polyvinylidene emulsions performance in table 1.
Embodiment 4
A coating preparation method for fluorine-containing polyvinylidene emulsions, comprises the following steps:
(1) ready reaction raw material for standby
Its composition of raw materials is as follows:
Deionized water: 40kg
Emulsifying agent: perfluoro hexyl novalgin 1kg, polyoxyethylene octylphenol ether (OP-10): 3kg, perfluor sodium nonylbenzenesulfonate 1kg
PH value regulator: sodium bicarbonate 0.5kg, bicarbonate of ammonia 0.5kg
Acrylic monomer: octadecyl acrylate 0.7kg, methyl acrylate 3.6kg, methyl methacrylate 2.5kg, butyl acrylate 0.1kg, vinylformic acid 0.1kg
Vinylidene: 30kg,
Initiator: ammonium persulphate 0.12kg, sodium bisulfite 0.105kg
Perfluor alkyl ethyl acrylate monomer: perfluoro butyl ethyl propylene acid esters 13kg
(2) seed emulsion is prepared
By deionized water 37kg, emulsifying agent (perfluoro hexyl novalgin 1kg, polyoxyethylene octylphenol ether 2kg), pH value regulator (sodium bicarbonate 0.5kg, bicarbonate of ammonia 0.5kg) add in 150L reactor, then at 20 DEG C, under 150rpm mixing speed, slowly add acrylic monomer (the methyl acrylate 0.9kg mixed, octadecyl acrylate 0.1kg) and vinylidene 2kg, emulsification 15min, 70 DEG C are warming up to again under 100rpm mixing speed, add initiator (ammonium persulphate 0.04kg, sodium bisulfite 0.035kg) and deionized water 1kg form mixing liquid, reaction 15min, obtained seed emulsion,
(3) vinylidene chloride copolymer emulsion is prepared
At 100rpm mixing speed and 70 DEG C, to drip emulsifying agent (perfluor sodium nonylbenzenesulfonate 0.5kg at the uniform velocity respectively in the seed emulsion that step (2) obtains, polyoxyethylene octylphenol ether 0.5kg) and initiator (ammonium persulphate 0.04kg, sodium bisulfite 0.035kg) and deionized water 1kg form mixing liquid, acrylic monomer (methyl acrylate 1.8kg, octadecyl acrylate 0.2kg) with the mixing liquid of vinylidene 24kg, perfluoro butyl ethyl propylene acid esters 2kg, dropwise at 2.5h, after dropwising, insulation 1.5h, obtain vinylidene chloride copolymer emulsion,
(4) fluorine-containing polyvinylidene emulsions is prepared
At 100rpm mixing speed and 70 DEG C, to drip emulsifying agent (perfluor sodium nonylbenzenesulfonate 0.5kg at the uniform velocity respectively in above-mentioned vinylidene chloride copolymer emulsion, polyoxyethylene octylphenol ether 0.5kg) and initiator (ammonium persulphate 0.04kg, sodium bisulfite 0.035kg) and deionized water 1kg form mixing liquid, acrylic monomer (methyl methacrylate 2.5kg, methyl acrylate 0.9kg, butyl acrylate 0.1kg, vinylformic acid 0.1kg, octadecyl acrylate 0.4kg) with the mixing liquid of vinylidene 4kg, perfluoro butyl ethyl propylene acid esters 11kg, dropwise at 1.5h, after dropwising, insulation 1h, be warming up to 85 DEG C, vacuumize to take off and analyse 2h, obtain the fluorine-containing polyvinylidene emulsions of coating that solid content is 50%.The coating obtained by fluorine-containing polyvinylidene emulsions performance in table 1.
Performance test:
The preparation of fluorine-containing polyvinylidene dichloride water-based latex: the coating that embodiment 1-4 is obtained with fluorine-containing polyvinylidene emulsions respectively under stirring at low speed, add film coalescence aid (diethylene glycol monoethyl ether) 0.01wt.%, defoamer surfynolDF-110D0.1wt.%, moistening flatting agent BYK-3070.1wt.% and thickening material ether of cellulose 0.2wt.%, after mixing, filter, obtain fluorine-containing polyvinylidene dichloride water-based latex, correlated performance is in table 1 after tested.
The fluorine-containing polyvinylidene emulsions performance of the coating that table 1 embodiment 1-4 obtains
Claims (6)
1. a coating preparation method for fluorine-containing polyvinylidene emulsions, is characterized in that comprising the following steps:
(1) ready reaction raw material for standby
By weight, reaction raw materials consists of: deionized water 40 ~ 73 parts, vinylidene 20 ~ 32 parts, acrylic monomer 3.4 ~ 8 parts, perfluor alkyl ethyl acrylate monomer 7 ~ 20 parts, initiator 0.15 ~ 0.3 part, pH value regulator 0.5 ~ 3 part, emulsifying agent 5 ~ 15 parts;
(2) seed emulsion preparation
By deionized water 37 ~ 70 parts, emulsifying agent 2 ~ 6 parts, pH value regulator 0.5 ~ 3 part adds in reactor, then at 10 ~ 25 DEG C, under 50 ~ 200rpm mixing speed, add acrylic monomer 0.5 ~ 1 part, vinylidene 1 ~ 3 part, emulsification 10 ~ 20min, then under 50 ~ 150rpm rotating speed, 40 ~ 80 DEG C are warming up to, add the mixing liquid of initiator 0.05 ~ 0.1 part and 1 part of deionized water composition, reaction 10 ~ 20min, obtained seed emulsion;
(3) vinylidene chloride copolymer emulsion preparation
Under 50 ~ 150rpm rotating speed and 40 ~ 80 DEG C of temperature, to drip mixing liquid, the perfluor alkyl ethyl acrylate monomer 1 ~ 5 part of the mixing liquid of emulsifying agent 1 ~ 3 part and initiator 0.05 ~ 0.1 part and deionized water 1 part composition, acrylic monomer 1.2 ~ 3 parts and vinylidene 15 ~ 24 parts at the uniform velocity respectively in the seed emulsion that step (2) obtains, dropwise at 0.5 ~ 2.5h, after dropwising, insulation 0.5 ~ 2h, obtains vinylidene chloride copolymer emulsion;
(4) fluorine-containing polyvinylidene emulsions preparation
Under 50 ~ 150rpm rotating speed and 40 ~ 80 DEG C of temperature, to drip mixing liquid, the perfluor alkyl ethyl acrylate monomer 6 ~ 17 parts of the mixing liquid of emulsifying agent 1 ~ 6 part and initiator 0.05 ~ 0.1 part and deionized water 1 part composition, acrylic monomer 1.7 ~ 4 parts and vinylidene 4 ~ 5 parts at the uniform velocity respectively in above-mentioned vinylidene chloride copolymer emulsion, dropwise at 1.5 ~ 2.5h, after dropwising, insulation 0.5 ~ 1h, be warming up to 80 ~ 95 DEG C, vacuumize to take off and analyse 1 ~ 3h, obtain the fluorine-containing polyvinylidene emulsions of coating.
2. the coating according to claim 1 preparation method of fluorine-containing polyvinylidene emulsions, is characterized in that described acrylic monomer is two or more the mixture in methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, octadecyl acrylate.
3. the coating according to claim 1 preparation method of fluorine-containing polyvinylidene emulsions, is characterized in that described perfluor alkyl ethyl acrylate monomer is the mixture of one or more in perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethyl propylene acid esters, perfluoro decyl ethyl propylene acid esters.
4. the coating according to claim 1 preparation method of fluorine-containing polyvinylidene emulsions, is characterized in that described emulsifying agent is the mixture of two kinds in sodium lauryl sulphate, Witco 1298 Soft Acid, Sodium dodecylbenzene sulfonate, dodecyl diphenyl oxide sodium sulfonate, perfluoro hexyl novalgin, perfluorobutyl potassium, perfluorohexylethyl sulfonic acid sodium, perfluor sodium nonylbenzenesulfonate, fatty alcohol-polyoxyethylene ether, polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol ether.
5. the coating according to claim 1 preparation method of fluorine-containing polyvinylidene emulsions, is characterized in that described pH value regulator is the mixture of two kinds in sodium bicarbonate, bicarbonate of ammonia, SODIUM PHOSPHATE, MONOBASIC, sodium hydrogen phosphate.
6. the coating according to claim 1 preparation method of fluorine-containing polyvinylidene emulsions, is characterized in that described initiator is one or both the mixture in ammonium persulphate, Potassium Persulphate, rongalite, sodium bisulfite, tertbutyl peroxide, formaldehyde sodium sulfoxylate.
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| CN109134736A (en) * | 2018-06-21 | 2019-01-04 | 安徽大学 | Aqueous polyvinylidene chloride-acrylate copolymer latex for heavy-duty anticorrosive paint and preparation method thereof |
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