CN103059197B - Aqueous antiseptic metal undercoat polyvinyl dichloride (PVDC) copolymer emulsion and preparation method thereof and application - Google Patents
Aqueous antiseptic metal undercoat polyvinyl dichloride (PVDC) copolymer emulsion and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses an aqueous antiseptic metal undercoat polyvinyl dichloride (PVDC) copolymer emulsion and a preparation method thereof and application, and aims at solving the problems that an existing solvent type undercoat used for metal corrosion prevention is harmful to a human body and easily causes environmental pollution and the like. Vinylidene chloride, (methyl) acrylic esters, acrylonitrile and crylic acid are used as mixing monomers, seeded emulsion polymerization is adopted to obtain the aqueous antiseptic metal undercoat PVDC copolymer emulsion, the aqueous antiseptic metal undercoat PVDC copolymer emulsion is low in cost, simple in synthetic process, low in content of volatile organic compounds, environment-friendly, pollution-free, good in corrosion prevention performance of obtained metal undercoat, and capable of replacing the existing solvent type undercoat and being used for corrosion prevention of metal surface.
Description
Technical field
The present invention relates to a kind of PVDC copolymer emulsion, be specifically related to a kind of water-repellent preservation metal primer PVDC copolymer emulsion and its preparation method and application.
Background technology
At present conventional anti-corrosion of metal priming paint mostly is solvent bottom paint, and volatile organic content is high, and these volatile organic matters can evaporate in air when constructing, harmful and cause environmental pollution.Along with the raising of people's environmental consciousness, use priming paint replaces the cry of solvent bottom paint more and more higher, and relevant research and development also achieve continuous progress.CN01127425 application discloses a kind of water-based acrylic acid modified alcoholic acid amino baking paint, it utilizes vegetables oil, polyvalent alcohol, dibasic acid anhydride, eleostearic acid, vinylformic acid (ester) class monomer, aminoresin etc. to make acrylic acid modified alcoholic acid amino resin emulsion, again this emulsion is deployed into water-miscible paint, there is good water tolerance; But this water-miscible paint synthesis technique is comparatively complicated, synthesis cost is higher, improper large-scale industrial production and preservative property are bad; CN201110174160 application discloses a kind of antitheft door use alcohol acid amino priming paint and preparation method, it uses aqueous alkide resin and aminoresin as base-material, red iron oxide, toluidine red, composite zinc phosphate, composite iron-titanium powder and process white prepare as color stuffing, and cost is high, preservative property are bad.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the object of this invention is to provide a kind of water-repellent preservation metal primer PVDC copolymer emulsion, its volatile organic content is low, and cost is low, environment friendly and pollution-free, good stability, and obtained metal primer preservative property are good.Second object of the present invention is to provide the preparation method of this PVDC copolymer emulsion.3rd object of the present invention is to provide the application of this PVDC copolymer emulsion.
Water-repellent preservation metal primer PVDC copolymer emulsion of the present invention, it is made up of following feed composition by weight: (1) mix monomer 45-60 part, accounts for the vinylformic acid that the vinyl cyanide of mix monomer total amount 0.3 ~ 0.5 and weight percent account for mix monomer total amount 3 ~ 5% form by (methyl) acrylate that weight percent accounts for the vinylidene chloride of mix monomer total amount 90 ~ 92%, weight percent accounts for mix monomer total amount 4 ~ 4.5%, weight percent; (2) seeding polymerization emulsifying agent: Sodium dodecylbenzene sulfonate 0.06 ~ 0.08 part and OP-100.14-0.16 part; (3) blending emulsifiers: AMPS 0.6 ~ 0.8 part and 2A-1 emulsifying agent 0.5 ~ 0.7 part; (4) initiator: tertbutyl peroxide 0.08 ~ 0.2 part and sodium formaldehyde sulphoxylate 0.075 ~ 0.175 part; (5) auxiliary agent: ammonium acetate 0.013 ~ 0.017 part and iron protochloride 0.0004 ~ 0.0006 part.Wherein, (methyl) acrylate be selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate one or more, be preferably (methyl) methyl acrylate.AMPS is the abbreviation of compound 2-acrylamide-2-methylpro panesulfonic acid, and 2A-1 emulsifying agent is alkyl diphenyl ether disulfonate.
The preparation method of water-repellent preservation metal primer PVDC copolymer emulsion of the present invention, comprising:
1. the preparation of raw material:
1) mix monomer preparation: vinylidene chloride, (methyl) acrylate and vinyl cyanide are mixed to get mix monomer by formula ratio;
2) initiator preparation: will soluble in waterly for tertbutyl peroxide obtain the tertbutyl peroxide aqueous solution, obtain the sodium formaldehyde sulphoxylate aqueous solution by soluble in water for sodium formaldehyde sulphoxylate;
3) blending emulsifiers preparation: add vinylformic acid after being mixed by AMPS and 2A-1 emulsifying agent, add water obtained blending emulsifiers;
2. seeding polymerization:
Water is added in reactor, add Sodium dodecylbenzene sulfonate, OP-10, ammonium acetate and iron protochloride, envelope still, gas displacement 3 times, vacuumizes, suck the mix monomer of formula ratio 5%, cold dispersion 0.5h, is warming up to 47 DEG C, adds the initiator solution prepared, adding speed is 8kg/48 hour, control temperature 55 DEG C; When Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
3. letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining mix monomer, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, adds the water vapor of 0.1MPa, desorption 2h after bottom valve is crack, filters and obtains copolymer emulsion.The solid content of copolymer emulsion is 45-60%.
The present invention also provides the application of PVDC copolymer emulsion in preparation water-repellent preservation metal primer.
The present invention also provides a kind of water-repellent preservation metal primer, and it comprises PVDC copolymer emulsion of the present invention.
The present invention uses vinylidene chloride, (methyl) acrylate, vinyl cyanide and vinylformic acid to be mix monomer, seeded emulsion polymerization is adopted to obtain water-repellent preservation metal primer PVDC copolymer emulsion, its cost is low, synthesis technique is simple, volatile organic content is low, environment friendly and pollution-free, obtained metal primer preservative property are good, and alternative existing solvent bottom paint is used for the anticorrosion of metallic surface.
Emulsion of the present invention adds reactive emulsifier in blending emulsifiers, improves emulsion intercalation method; Further, monomeric acrylic together added in letex polymerization stage and reactive emulsifier, due to vinylformic acid good water solubility, it is good to the parcel of emulsifying agent, obtained polymkeric substance even particle size distribution, good emulsion stability, deposits 2 years not breakdown of emulsion, effects without precipitation under can reaching normal temperature.
The present invention after letex polymerization completes, vacuumize before add microcrystalline wax, it can play the effect of froth breaking, improves vacuum desorption effect, reduces level of residual monomers; And microcrystalline wax can be recycled by filtration after adding.
Accompanying drawing explanation
Fig. 1 is seeded emulsion polymerization process flow sheet of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1:
1. preparation of raw material:
1) mix monomer preparation: vinylidene chloride 92kg, methyl methacrylate 4kg, vinyl cyanide 0.5kg are mixed to get mix monomer;
2) initiator preparation: tertbutyl peroxide 160g is dissolved in 8kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 160g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: AMPS 1.2kg, 2A-1 emulsifying agent 1kg is mixed, adds vinylformic acid 3.5kg, add water and obtain blending emulsifiers to 20kg;
2. seeding polymerization:
Add water 64kg in reactor, add Sodium dodecylbenzene sulfonate 120g, OP-10280g, Glacial acetic acid 30g, iron protochloride 1g, envelope still, gas displacement 3 times, vacuumizes, and sucks the mix monomer of formula ratio 5%, cold dispersion 0.5h, be warming up to 47 DEG C, pump into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex.
3. letex polymerization:
Pump into the blending emulsifiers prepared, remaining mix monomer to seed latex, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, adds the water vapor of 0.1MPa, desorption 2h after bottom valve is crack, filters the copolymer emulsion obtaining solid content 50%.The physical index of the water-repellent preservation metal primer PVDC copolymer emulsion obtained is:
Embodiment 2
1. preparation of raw material:
1) mix monomer preparation: vinylidene chloride 110.4kg, methyl acrylate 4.8kg, vinyl cyanide 0.6kg are mixed to get mix monomer; 2) initiator preparation: tertbutyl peroxide 220g is dissolved in 8kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 220g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: AMPS 1.5kg, 2A-1 emulsifying agent 1.2kg is mixed, adds vinylformic acid 4.2kg, add water and obtain blending emulsifiers to 20kg;
2. seeding polymerization:
Add water 44kg in reactor, add Sodium dodecylbenzene sulfonate 150g, OP-10300g, Glacial acetic acid 30g, iron protochloride 1g, envelope still, gas displacement 3 times, vacuumizes, and sucks the mix monomer of formula ratio 5%, cold dispersion 0.5h, be warming up to 47 DEG C, pump into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex.
3. letex polymerization:
Pump into the blending emulsifiers prepared, remaining mix monomer to seed latex, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, adds the water vapor of 0.1MPa, desorption 2h after bottom valve is crack, filters the copolymer emulsion obtaining solid content 60%.
Embodiment 3:
1. preparation of raw material:
1) mix monomer preparation: vinylidene chloride 92kg, butyl methacrylate 4kg, vinyl cyanide 0.5kg are mixed to get mix monomer;
2) initiator preparation: tertbutyl peroxide 160g is dissolved in 8Kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 160g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: AMPS 1.2kg, 2A-1 emulsifying agent 1kg is mixed, adds vinylformic acid 3.5kg, add water and obtain blending emulsifiers to 20kg;
2. seeding polymerization:
Add water 64kg in reactor, add Sodium dodecylbenzene sulfonate 120g, OP-10 280g, Glacial acetic acid 30g, iron protochloride 1g, envelope still, gas displacement 3 times, vacuumizes, and sucks the mix monomer of formula ratio 5%, cold dispersion 0.5h, be warming up to 47 DEG C, pump into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex.
3. letex polymerization:
Pump into the blending emulsifiers prepared, remaining mix monomer to seed latex, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, adds the water vapor of 0.1MPa, desorption 2h after bottom valve is crack, filters the copolymer emulsion obtaining solid content 50%.
Claims (2)
1. a water-repellent preservation metal primer preparation method for PVDC copolymer emulsion, is characterized in that,
Be made up of following feed composition by weight:
(1) mix monomer 45 ~ 60 parts, accounts for by (methyl) acrylate that weight percent accounts for the vinylidene chloride of mix monomer total amount 90 ~ 92%, weight percent accounts for mix monomer total amount 4 ~ 4.5%, weight percent the vinylformic acid that the vinyl cyanide of mix monomer total amount 0.3 ~ 0.5% and weight percent account for mix monomer total amount 3 ~ 5% and forms;
(2) seeding polymerization emulsifying agent: Sodium dodecylbenzene sulfonate 0.06 ~ 0.08 part and OP-10 0.14 ~ 0.16 part;
(3) mixing emulsifying agent: AMPS 0.6 ~ 0.8 part and 2A-1 emulsifying agent 0.5 ~ 0.7 part;
(4) initiator: tertbutyl peroxide 0.08 ~ 0.2 part and sodium formaldehyde sulphoxylate 0.075 ~ 0.175 part;
(5) auxiliary agent: ammonium acetate 0.013 ~ 0.017 part and iron protochloride 0.0004 ~ 0.0006 part;
Described (methyl) acrylate be selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate one or more;
Its step comprises:
(1) preparation of raw material:
1) pre-mixing monomer preparation: vinylidene chloride, (methyl) acrylate and vinyl cyanide are mixed to get pre-mixing monomer by formula ratio;
2) initiator preparation: will soluble in waterly for tertbutyl peroxide obtain the tertbutyl peroxide aqueous solution, obtain the sodium formaldehyde sulphoxylate aqueous solution by soluble in water for sodium formaldehyde sulphoxylate;
3) blending emulsifiers preparation: add vinylformic acid after being mixed by AMPS and 2A-1 emulsifying agent, add water obtained blending emulsifiers;
(2) seeding polymerization:
Water is added in reactor, add Sodium dodecylbenzene sulfonate, OP-10, ammonium acetate and iron protochloride, envelope still, gas displacement 3 times, vacuumizes, suck the pre-mixing monomer of formula ratio 5%, cold dispersion 0.5h, is warming up to 47 DEG C, adds the initiator solution prepared, adding speed is 8kg/48 hour, control temperature 55 DEG C; When Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex,
Described pre-mixing monomer is vinylidene chloride, (methyl) acrylate and vinyl cyanide;
(3) letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining pre-mixing monomer, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, adds the water vapor of 0.1MPa, desorption 2h after bottom valve is crack, filters and obtains copolymer emulsion.
2. the application of the preparation-obtained PVDC copolymer emulsion of preparation method according to claim 1, is characterized in that, for the preparation of water-repellent preservation metal primer.
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| CN103193918A (en) * | 2013-05-06 | 2013-07-10 | 南通瑞普埃尔生物工程有限公司 | Vinyl chloride-vinylidene chloride (VDC)/acrylic acid (AA)/methyl methacrylate (MMA)/acrylonitrile (AN) copolymerized polyvinyl dichloride (PVDC) emulsion and preparation method thereof |
| CN105176230A (en) * | 2015-09-23 | 2015-12-23 | 南通瑞普埃尔生物工程有限公司 | Green anticorrosive paint of tap water conveying buried pipeline and preparation method thereof |
| CN105153346A (en) * | 2015-09-29 | 2015-12-16 | 南通瑞普埃尔生物工程有限公司 | Special waterborne anti-corrosion emulsion for multi-component copolymerization rust converting primer and preparation method of emulsion |
| CN105294913B (en) * | 2015-11-25 | 2017-04-19 | 海南赛诺实业有限公司 | PVDC copolymerization emulsion for flame-retardant carpets, preparation method and applications thereof |
| CN105295587B (en) * | 2015-11-25 | 2017-11-10 | 海南赛诺实业有限公司 | A kind of metal works pack special PVDC latex and its preparation method and application |
| CN108884352B (en) * | 2016-03-18 | 2021-03-09 | 索尔维公司 | Water-based anticorrosion coating composition |
| CN106280745A (en) * | 2016-09-14 | 2017-01-04 | 四川力久云智知识产权运营有限公司 | A kind of anticorrosive coating of improvement |
| CN107151491B (en) * | 2017-05-08 | 2019-09-06 | 南京长江涂料有限公司 | A kind of aqueous rust transfer priming paint and preparation method thereof suitable for corroding steel surface |
| CN113563499B (en) * | 2021-07-28 | 2023-03-24 | 浙江衢州巨塑化工有限公司 | Polyvinylidene chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
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