Styrene-acrylic Polymers

Benzene emulsion that a kind of building coating is used and preparation method thereof

Technical field

The present invention relates to a kind of emulsion, relate in particular to a kind of benzene emulsion, more specifically relate to the benzene emulsion that a kind of building coating is used, the invention still further relates to the preparation method of the benzene emulsion that a kind of above-mentioned this building coating uses.

Background technology

Building coating is kind maximum in China's coating industry, and China is also the large production of the first in the world, country of consumption, but the eco-environmental impact that coating produces is also the problem of a headache.Traditional solvent based coating, owing to containing a large amount of volatile organic solvents, in use enters atmosphere, and human body and environment are caused to very major injury, is progressively eliminated.Benzene emulsion is the emulsion of the monomer copolymerizations such as vinylbenzene, esters of acrylic acid, the benzene emulsion paint organic solvent content of being prepared using it as main film forming substance is low, little to environmental influence, and there are good weathering resistance, water tolerance, alkali resistance and tint retention, thereby are widely applied in interior exterior wall latex paint and other water-borne coatingss; But benzene emulsion often needs to add more emulsifying agent in preparation process, due to the serial emulsifying agent unique properties of alkylphenol polyoxyethylene (APEO), emulsifying capacity is strong, particularly can be at acid, stable existence in alkaline solution, and stronger to all kinds of SOLVENTS emulsifying capacity, stablizing that emulsion is synthesized is most important, and after resin, emulsion are synthesized, this kind of emulsifying agent affects again minimum to its end properties, therefore, APEO series emulsifying agent is one of frequent material using of the industries such as benzene emulsion, resin synthesize always, and the shared market share is quite large.But research discovery, APEO series emulsifying agent can not be ignored ecological harm, is mainly reflected in Mammals, hydrobiont and human body are existed to carcinogenic toxicity, and be difficult to the problem of degraded.

Along with the continuous reinforcement of people's environmental consciousness, also more and more stricter about the rules of material of construction, not only require material of construction performance brilliance, but also will there is good Environmental compatibility.Mainly with nonionic surface active agent, substitute APEO series emulsifying agent abroad at present, generally can be divided into two classes: the 1) multipolymer of the alkyl or aryl ester of polyoxyethylene or ether and oxyethane and propylene oxide, wherein alkyl or aryl ester or the ethers of polyoxyethylene, the carbonatoms of alkyl is approximately 8'9; 2) relative molecular mass is generally ' oxyethane and the multipolymer of propylene oxide, and wherein oxyethane component accounts for 40%'80%; The price of this two classes emulsifying agent is all relatively high, and still has larger gap on emulsifying property compared with APEO series emulsifying agent.Some Domestic enterprise replaces APEO series emulsifying agent take fatty alcohol-polyoxyethylene ether as main, but in use there are the following problems: 1) emulsifying property is poor; 2) stability in acid, alkali systems is not high, under the system particularly existing at solvent; 3) along with the rising of high temperature, its solubleness in water-soluble declines; 4) cruelly leaking the acetaldehyde and the superoxide that in air, in easy deterioration by oxidation, degradation process, produce knows from experience and causes compared with major injury people.Therefore, find a kind of novel green emulsifying agent and substitute the serial emulsifying agent of traditional alkylphenol polyoxyethylene (APEO), thereby obtain the benzene emulsion of real environmental protection, and then the green product of exploitation different kinds of building finishing material, the new direction that paint field develops now become.

Summary of the invention

For overcoming the problem of above existence, the object of this invention is to provide that a kind of stability is high, emulsifying capacity is high, and benzene emulsion nontoxic, non-environmental-pollution.

Another object of the present invention is to provide a kind of preparation method of above-mentioned benzene emulsion.

For realizing above object, benzene emulsion of the present invention comprises following each component and mass percent:

Vinylbenzene 15-25

Acrylic monomer 20-30

Small-molecular emulsifier 0.3-1.0

Initiator 0.1-0.5

Neutralizing agent 0.05-0.2

Macromolecule emulsifier 0.4-1.2

Deionized water surplus

Macromolecule emulsifier is wherein that the molecular weight that is polymerized through addition polymerization by 5-20 polyisobutene unit and 40-80 polyoxyethylene ether unit is 500-2,000 ten thousand the long side chain isomerism alkyl, polyether with micro-crosslinking structure, and small-molecular emulsifier is sodium lauryl sulphate, sodium laurylsulfonate, Witco Soft Acid, Sodium dodecylbenzene sulfonate, α sodium olefin sulfonate, fatty alcohol-polyoxyethylene ether, alkyl phenol ether sulfo-succinic acid ester sodium salt.

Above-mentioned molecular weight is the macromolecule emulsifier that the model produced in the preferred Shantou City Daqian High and New Technology Research Center Co., Ltd of 500-2,000 ten thousand the long side chain isomerism alkyl, polyether with micro-crosslinking structure is T-; Small-molecular emulsifier preferably sodium dodecyl sulfate.

Aforesaid propylene acids monomer is vinylformic acid, methacrylic acid, methyl acrylate, butyl acrylate, ethyl propenoate, Octyl acrylate, α-methacrylic acid, methyl methacrylate, butyl methacrylate, Isooctyl acrylate monomer, dodecyl acrylate, tetradecyl acrylate, octadecyl acrylate, vinylformic acid 20 diester, methacrylic acid, butyl methacrylate, β-dimethyl-aminoethylmethacrylate, Octyl methacrylate, one or more in Isooctyl methacrylate, preferably butyl acrylate, three kinds of monomer compositions of methyl acrylate and α-methacrylic acid, its mass ratio is 7.5:5:1.

The preferred Potassium Persulphate of above-mentioned initiator, ammonium persulphate, Sodium Persulfate or benzoyl peroxide.

Above-mentioned neutralizing agent is sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.

The preferred sodium bicarbonate of above-mentioned neutralizing agent, addition is 0.08-0.12%.

Benzene emulsion of the present invention, adopt the macromolecule emulsifier with special construction of water-soluble non-toxic, because this emulsifying agent emulsifying capacity is strong, stability in acid, alkali systems is high, jointly use with low molecule emulsifying agent, can produce synergy, can make to form the benzene emulsion that proterties is stable after vinylbenzene, acrylic ester monomer emulsification.Benzene emulsion of the present invention, water tolerance is strong, bonding strength is high, film is tough and tensile, pigment, filler are had compared with high-bearing capacity, and also nontoxic, pollution-free, the membrane-forming agent that is particularly suitable as high-quality building is used.

The present invention also provides a kind of preparation method of above-mentioned benzene emulsion, and the method adopts seeded emulsion polymerization method, in turn includes the following steps:

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(1) in pre-emulsification still, add successively 1/2-2/3 deionized water, initiator, 2/3-5/6 small-molecular emulsifier and all vinylbenzene, acrylic monomer, carry out pre-emulsification, obtain stable pre-emulsion;

(2) in reactor, add successively remaining deionized water, remaining small-molecular emulsifier, remaining initiator and macromolecule emulsifier, neutralizing agent, after stirring, obtain kettle base solution;

(3) reactor interlayer is warming up to 75-85 ', to the pre-emulsion that first adds 5% in kettle base solution, continues to stir, after there is blue light, constant temperature 10min, makes seed emulsion;

(4) continue slowly to drip remaining pre-emulsion in reactor, at 2.5-3 hour, be added dropwise to complete, continue constant temperature 1.5-2 hour, when dropping and constant temperature, system temperature maintains 82 ± 2 ';

(5) while being cooled to 40-50 ' after constant temperature, regulate pH value to 7-8, with 200 order filter sieve filtrations, obtain the benzene emulsion that solid content is 35-55%.

The preparation method of benzene emulsion of the present invention, adopts seeded emulsion polymerization method, and by order of addition, feeding quantity and the feed rate of the each component of strict control, the emulsion that makes to obtain has that stability is better, narrow diameter distribution, easy to control, and the high advantage of solid content.

Embodiment

Be specific embodiments of the invention below, these embodiment are just to the illustrating of benzene emulsion formula and preparation method, not in order to limit the scope of the invention.

One, benzene emulsion

1, the synthesizing formula of benzene emulsion

2, the preparation of benzene emulsion

1) by pre-emulsion formula, in pre-emulsification still, add successively deionized water, vinylbenzene, butyl acrylate, methyl acrylate, α-methacrylic acid, sodium lauryl sulphate, potassium sulfate, carry out pre-emulsification, obtain stable monomer pre-emulsion;

2) by kettle base solution formula, in reactor, add successively deionized water, sodium lauryl sulphate, T-, Potassium Persulphate, sodium bicarbonate, after stirring, obtain kettle base solution;

3) by be warming up to 80 ' of reactor interlayer, in kettle base solution, first add 5% pre-emulsion, continue to stir, after there is blue light, constant temperature 10min, makes seed emulsion;

4) continue slowly to drip remaining pre-emulsion in reactor, in 3 hours, be added dropwise to complete, continue constant temperature 1.5-2 hour, when dropping and constant temperature, system temperature maintains 82 ± 2 '.

5) while being cooled to 45 ' after constant temperature, regulate pH value to 7-8, with 200 order filter sieve filtrations, obtain solid content and be 46% benzene emulsion.

3, the performance test of benzene emulsion

Two, styrene-acrylic latex coating

Embodiment 1

1, formula

2, preparation

At high speed dispersor, add successively deionized water, thickening material AES-60,28% ammoniacal liquor, 10% Sodium hexametaphosphate 99, film coalescence aid CS-12, ethylene glycol, titanium dioxide, zinc sulfide white B311,325 order calcium carbonate, 400 order talcum powder, through high speed dispersion to fineness 30 μ m, the benzene emulsion, defoamer , the sanitas that under low speed, add successively again the present invention to make, stir, sand milling, filtration obtain coating finished product.

Embodiment 2

1, formula

2, preparation

At high speed dispersor, add successively deionized water, the 2%HEC aqueous solution, wilkinite, 10% Sodium hexametaphosphate 99, titanium dioxide, 800 order calcium carbonate, 800 order wollastonite powder, through high speed dispersion to fineness 30 μ m, the benzene emulsion, butyl glycol ether, 28% ammoniacal liquor, defoamer , the sanitas that under low speed, add successively again the present invention to make, stir, sand milling, filtration obtain coating finished product.

Embodiment 3

1, formula

2, preparation

At high speed dispersor, add successively the too white R-215 of deionized water, ethylene glycol, dispersion agent Hydropalat 100, wetting agent Hydropalat 436, defoamer Foamaster NXZ, sanitas Dehygant LFM, rutile, 800 order wollastonites, process white, through high speed dispersion to fineness 25 μ m, under low speed, add successively benzene emulsion, film coalescence aid Filmer C40, the thickening material HAS 660 that defoamer Foamaster 111, the present invention make to stir, sand milling, filtration obtain coating finished product again.

The styrene-acrylic latex coating that above-mentioned 3 embodiment makes, after testing, meet the relevant criterion of < < GB/T- resin latex dope > > and < < GB/T- exterior wall coating material of synthetic resin emulsion > >.

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