CN103193924B - Phased film forming styrene-acrylic coating emulsion and preparation method - Google Patents

Abstract

The present invention relates to the preparation method of a kind of building inside and outside wall elastic coating copolymer in cinnamic acrylic ester system coating emulsion, described cinnamic acrylic ester system coating emulsion comprises the preparation method of cinnamic acrylic ester seed emulsion and the preparation method of coating emulsion, main composition comprises vinylbenzene, acrylate, silane coupling agent, emulsifying agent, initiator, defoamer, pH adjusting agent, molecular weight regulator and water.Inside and outside the surface effects that the present invention utilizes organic nano particle powerful and latex particle, the designability of distribution of polymer, combines seed emulsion polymerization with the phased membrane technique that diffuses into, achieves and obtain high performance coating emulsion with convenient source; Successfully solve the problems such as compact in paint film, mechanical property and resistance to outdoor aging.Coating emulsion of the present invention can be used as the filmogen of all kinds of Discussion on architecture wall emulsion paint, also can be used for anti-corrosion of metal priming paint, the preparation of the varnish of woodenware door and window etc.

Description

Phased film forming styrene-acrylic coating emulsion and preparation method

Technical field

The present invention relates to the preparation method of a kind of building inside and outside wall elastic coating copolymer in cinnamic acrylic ester system coating emulsion, be specifically related to a kind of cinnamic acrylic ester type coating emulsion of phased film forming, the coating prepared by emulsion and their preparation method, belong to building coating field.

Background technology

Copolymer in cinnamic acrylic ester system coating emulsion (being called for short: styrene-acrylic coating emulsion) is in occupation of the principal market of all kinds of building coating emulsion, and 2009, China's all kinds of styrene-acrylic coating emulsion consumed nearly 700,000 tons.The Performance and Cost Modeling of styrene-acrylic coating emulsion determines the main body of domestic construction coating quality.Nineteen ninety-five, since BASF Corp. of Germany takes the lead in that high-performance styrene-acrylic coating 296DS is introduced Chinese market, numerous domestic manufacturer starts competitively to research and develop high-performance styrene-acrylic coating emulsion.Regrettably, the styrene-acrylic coating emulsion of current domestic production, exist always and cannot solve water tolerance and color developing, equilibrium problem between pigment supporting capacity and paint film mechanical property, the more important thing is, the weathering resistance of the styrene-acrylic coating emulsion of domestic production is poor, improve weathering resistance often with MMA copolymerization, cause cost to increase substantially, user is difficult to accept.Along with China's rapid development of economy, the building coating consumption often average annual rate of increase with 15% increases progressively, 2009, China's Mainland consumes building coating 3,600,000 tons altogether, wherein consume nearly 900,000 tons of all kinds of coating emulsion, wherein high-performance styrene-acrylic coating emulsion consumes nearly 300,000 tons, and by 2011, Architectural Paint in China has broken through 4,500,000 tons, and within 2011, actual building coating consumption is 4,600,000 tons.Along with the standardization of China's architectural finish, high-performance styrene-acrylic coating emulsion has started the application being widely used in external wall of high-rise building, and can the weathering resistance how improving styrene-acrylic just become the technical bottleneck restricting and use at external wall of high-rise building.Therefore the eternal problem that high-end building coating emulsion is domestic coating emulsion factory is always developed.

Chinese patent CN102372960A discloses a kind of high resistant styrene-acrylic latex coating, and it is mainly made up according to weight proportion stirring of following raw materials according: 157 parts of benzene emulsions, 13 parts of dispersion agents, 80 parts of deionized waters, 15 parts of adipic dihydrazide, 2 parts of dispersion agents, 4 parts of defoamers, 11 parts of mould inhibitors, 23 parts of kaolin, 15 parts of titanium dioxides, 15 parts of dicalcium powders, 15 parts of film coalescence aid, 12 parts of polyethers thickening materials.

Chinese patent CN1872888A discloses the synthetic method of the cruel emulsion of a kind of vinylbenzene for building one vinylformic acid; this copolymer emulsion take water as medium; with vinylbenzene, (methyl) acrylate and (methyl) vinylformic acid for comonomer; and add emulsifying agent and initiator and carry out emulsion polymerization synthesis; the weight percent of each moiety is: water 40 ~ 55%; vinylbenzene 18 ~ 30%; (methyl) acrylate 18 ~ 30; (methyl) vinylformic acid 0.5 ~ 3%; emulsifying agent 0.5 ~ 4%; initiator 0.1 ~ 0.5%, protecting glue 0.1 ~ 0.5%.

Chinese patent CN1249111C discloses a kind of preparation method of modifying cinepazid emulsion, for polymerization single polymerization monomer with vinylbenzene, butyl acrylate, vinylformic acid, take organic fluorine as modified monomer, take compound emulsifying agent as the emulsifying agent of system, employing thermal decomposition initiating is initiator, after pre-treatment being carried out to organic fluorine with silane coupling agent, make catalyzer with undecyl Phenylsulfonic acid, adopt nucleocapsid process polymerisation to obtain modifying cinepazid emulsion.

Carried out many improvement to styrene-acrylic coating emulsion in prior art, but still it is little to there is pigment volume concentration (PVC), poor to pigment supporting capacity, the problems such as color developing difference and resistance to rainprint ability, weathering resistance is not significantly improved.

Summary of the invention

There is weather resistance difference in the present invention to solve current building inside and outside wall coating styrene-acrylic coating emulsion always, pigment volume concentration (PVC) is little, poor to pigment supporting capacity, for the purpose of the problems such as color developing difference and resistance to rainprint ability, tackle styrene-acrylic coating emulsion mutually and carry out brand-new design and systematic study.Utilize the controlled emulsion polymerization technology of seed to combine with phased film technique, provide styrene-acrylic coating of a kind of high-performance (weather-proof, super water-fast, resistant and high color development) and preparation method thereof.

Mostly conventional seeded emulsion polymerization is at the strict emulsifier that controls at below CMC, and need multistep monomer swell-polymerization just can complete, and initial seed is positioned at the innermost layer of emulsion particle, because often step is polymerized the emulsification dosage added all at below CMC, therefore size distribution is very narrow, but the particle diameter of final latex grain is all very large, generally all at more than 160nm, this is advantage for synthesis PVC plasticized modifier, but be exactly shortcoming for preparing coating emulsion, because the particle diameter of building coating emulsion is thinner, it is to the supporting capacity of pigment, better to the adhesive property of pigment and base material, this is because there is super surface effects equally in nano level organic polymer.

The present invention utilizes the design of the particle form of emulsion particle to be combined with phased membrane formation mechanism by seeded emulsion polymerization, solve resistance to soiling and be difficult to balanced problem with low temperature flexibility, specifically adopt the seed law strictly to control the composition of the particle diameter of final emulsion and the sheath polymers of final emulsion latex grain and hydrophilic size thereof.Seed emulsion particle diameter involved by the present invention is little, narrow distribution, and have moderate wetting ability, can ensure that the follow-up monomer dripping polymerization is all polymerized in the inside of each emulsion particle of seed emulsion, because of the very big absorption merit that the super surface effects of these superfine particles is brought, all follow-up monomers are carried out increase-volume with the function in black hole, polymerization, therefore sheath polymers be not follow-up monomer formed polymkeric substance but seed polymer, and when emulsion solid content is higher, sheath polymers starts to break, flexible polymer with fragment or size distribution on the top layer of final latex grain, and then improve the color developing of coating and reduce the film-forming temperature of coating.

For realizing object of the present invention, according to a first aspect of the invention, seed emulsion providing a kind of cinnamic acrylic ester type coating and preparation method thereof.According to a second aspect of the invention, cinnamic acrylic ester type emulsion and preparation method thereof is provided.

Technical scheme of the present invention is summarized as follows:

1. cinnamic acrylic ester type seed emulsion, this emulsion is by the vinylbenzene as monomer component, butyl acrylate, methyl methacrylate and ethyl propenoate, under the existence of the reactive emulsifier containing olefinic double bond (or containing carbon-to-carbon double bond) and anionic emulsifier sodium lauryl sulphate or Sodium dodecylbenzene sulfonate and water, carry out emulsion polymerization by interpolation water-soluble free radical initiator to prepare, wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), the ratio (by weight) of butyl acrylate (BA) is St:MMA:EA:BA=(7 ~ 25): (15 ~ 40): (10 ~ 30): (20 ~ 70 or 20 ~ 60), preferably (8 ~ 20): (25 ~ 35): (12 ~ 27): (30 ~ 40), be more preferably (8 ~ 20): (25 ~ 30): (15 ~ 25): (30 ~ 35).

Preferably, the consumption of anionic emulsifier sodium lauryl sulphate or Sodium dodecylbenzene sulfonate is 2 ~ 12wt% of monomer total amount, preferably 3 ~ 9wt%, more preferably 3.2 ~ 8wt%, further preferably 3.5 ~ 7wt%, more preferably 4 ~ 6wt%, such as 5wt%.Preferably, the consumption of reactive emulsifier is the 2-~ 2wt% of monomer total amount, preferably 3 ~ 9wt%, more preferably 3.2 ~ 8wt%, further preferably 3.5 ~ 7wt%, more preferably 4 ~ 6wt%, such as 5wt%.

Preferably, the consumption of radical initiator is 0.4 ~ 2.0wt% of monomer total amount, preferably 0.45 ~ 1.5wt%, preferably 0.45 ~ 1.0wt%, more preferably 0.5-0.9wt%, further preferred 0.55-0.85wt%, more preferably 0.6-0.8wt%, such as 0.7wt%.

Preferably, the ratio (by wt) of the relative usage of whole monomer and deionized water (DW) is 28 ~ 50:50 ~ 72, preferably 30 ~ 40:60 ~ 70, more preferably 32 ~ 37:63 ~ 68, wherein all the weight sum of monomer and deionized water (DW) is 100 weight parts.

2. according to the seed emulsion of above 1, the Hunk constant (Hansch) of the polymkeric substance wherein in seed emulsion is 2.25 ~ 3.10, is preferably 2.30 ~ 3.00; Preferably 2.35 ~ 2.90, be preferably 2.35 ~ 2.55 or 2.55 ~ 2.8; And/or this polymkeric substance has 5.0 ~ 10.0 DEG C, preferably 5.5 ~ 9.5 DEG C or 6.0 ~ 9.0 DEG C, the more preferably second-order transition temperature (Tg) of 6.5 ~ 8.5 DEG C or 7.0 ~ 8.0 DEG C.The amphipathic property size according to me formed after wherein Hunk (Hansch) constant reflects monomer polymerization.

3. the seed emulsion according to above 1 or 2, is characterized in that the solid content of described seed emulsion is at 20-60wt%, preferably between 25-58wt%, more preferably between 30-56wt%, more preferably between 35-45wt%, preferably between 40-53wt%, more preferably between 48 ~ 51wt%.More preferably, solid content also can be at 30-40wt%, preferably between 33-37wt%, and such as 35wt% or 36wt%.

4. according to any one seed emulsion in above 1 ~ 3, it is characterized in that: reactive emulsifier (or being called response type surfactant active) is selected from following one or two or more in these: allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6, 8, 10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propane sulfonic acid salt (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate (COPS-3), methoxy polyethylene glycol methacrylate-styrene polymer (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS), preferably, reactive emulsifier is selected from one or both in 3-allyloxy-2-hydroxyl-propyl sodium sulfonate (COPS-1) or 3-allyloxy-2-hydroxyl-propyl sodium phosphate salt (COPS-3).

The above initiator is radical initiator such as inorganic peracid salt initiators or organic peroxide evocating agent, oxidation-reduction trigger system.Preferably inorganic peracid salt initiators, is more preferably persulphate, in initiator system of ammonium persulfate, Potassium Persulphate, Sodium Persulfate any one or two or more.

5., according to any one seed emulsion in above 1 ~ 4, it is characterized in that: in described seed emulsion, also comprise neutralizing agent.Described neutralizing agent is the one in ammoniacal liquor or alkyl alcohol ammonia; Preferably ammoniacal liquor, the such as ammoniacal liquor of 25-28wt% concentration.

Further preferably, contain based on total reaction mixture weight 0.5 ~ 4% in seed emulsion, the preferably neutralizing agent (ammoniacal liquor as 25-28wt% concentration) of 1 ~ 3%, 1.5-2wt%.

6., according to any one seed emulsion in above 1-5, it is characterized in that: in described seed emulsion, also comprise sanitas and/or defoamer.

Described sanitas is one or more in Sodium Benzoate, daconil M, aminopropanol compound, preferably BIT-20 (BIT, Sol company of the U.S.); Further preferably, contain based on total reaction mixture weight 0 ~ 0.2% in seed emulsion, the preferably sanitas of 0.05 ~ 0.1%;

Described defoamer is silicone antifoam agent or fluorine richness silicone antifoam agent, is preferably one or more in water-based silicone oil, silicone emulsion; Be preferably WBA defoamer (Kening Co., Ltd of the U.S.) further; Further preferably, contain based on total reaction mixture weight 0 ~ 0.2% in seed emulsion, the preferably defoamer of 0.05 ~ 0.1%.

7., according to any one seed emulsion in above 1 ~ 6, it is characterized in that: the number average bead diameter of described seed emulsion is 25 ~ 40nm, preferably 27 ~ 38nm, or 30 ~ 35nm, preferred 31 ~ 34nm further, or 32 ~ 33nm, and/or, size distribution index is less than 0.12, is more preferably less than 0.10

8., according to any one seed emulsion in above 1 ~ 7, it is characterized in that: the minimum film-forming temperature (MFT) of described seed emulsion is 4 ~ 12 DEG C, preferably 5 ~ 10 DEG C, such as 6,7,8,9 DEG C.

9. prepare the method for the seed emulsion of any one in above 1 ~ 8, the method comprises the following steps:

(1) pre-emulsification: by 25 ~ 37 weight parts (preferred 27-35, more preferably 28-32) deionized water, 2 ~ 10 weight parts (preferred 3-8, preferably 4 ~ 6 or 4.5 ~ 5.0) anionic emulsifier sodium lauryl sulphate (SDS) or Sodium dodecylbenzene sulfonate (SDBS), 2 ~ 10 weight parts (preferred 3-8, preferably 4 ~ 6 or 5.0 ~-5.5 weight parts) the reactive emulsifier containing olefinic double bond (or containing carbon-to-carbon double bond) stir for some time (such as 10 ~ 20 minutes) after, drip 90-110 weight part (preferably 95 ~ 105 weight parts) by vinylbenzene, methyl methacrylate, the monomer mixture of ethyl propenoate and butyl acrylate composition, continue high-speed stirring emulsification (such as 0.5-1.5 hour), obtain pre-emulsion, the ratio (by weight) of wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), butyl acrylate (BA) is St:MMA:EA:BA=(7 ~ 25): (15 ~ 40): (10 ~ 30): (20 ~ 70 or 20 ~ 60), preferably (8 ~ 20): (25 ~ 35): (12 ~ 27): (30 ~ 40), are more preferably (8 ~ 20): (25 ~ 30): (15 ~ 25): (30 ~ 35),

(2) be polymerized: by 70 ~ 95 weight parts (preferably 75 ~ 90 weight parts, such as 80, 85 weight parts) deionized water, 0.7 ~ 3 weight part (preferred 0.8-2 weight part, such as 1.5 weight parts) rebasing anionic emulsifier sodium lauryl sulphate (SDS) or Sodium dodecylbenzene sulfonate (SDBS), under agitation, be warming up to 70 ~ 95 DEG C (preferably 80 ~ 88 DEG C, preferably 82 ~ 86 DEG C, or 84 ~ 85 DEG C), keep 1-10 minute (such as, treat that temperature punching is to the highest and stable several minutes, such as 1 ~ 4 minute, or after 2 ~ 3 minutes), drip pre-emulsion and the initiator solution (deionized water of the initiator+2-5 weight part of 0.20-0.50 weight part) of step (1) gained, during dropping, temperature of reaction controls at 80 ~ 92 DEG C (preferably 83 ~ 90 DEG C, preferably 86 ~ 88 DEG C), total time for adding controls at 60 ~ 130 minutes (preferably 80 ~ 110 minutes, preferably 90 ~ 100 minutes), dropping terminates rear insulation 40 ~ 80 minutes (preferably 50 ~ 70 minutes, such as 60 minutes),

(3) step 2 gained emulsion is cooled to 15-40 DEG C (preferably 20 ~ 35 DEG C), add 1-6 weight part (preferred 2-5, more preferably 3-4) anionic emulsifier sodium lauryl sulphate (SDS) or Sodium dodecylbenzene sulfonate (SDBS), optionally add the sanitas of 0 weight part or 0.01-0.3 weight part (such as 0.1-0.2 weight part) and/or the defoamer of 0 weight part or 0.01-0.3 weight part (such as 0.1-0.2 weight part), final reaction mixture neutralizing agent (such as ammoniacal liquor) neutralization (such as to pH value 8.0 ~ 8.50), then filter, obtain seed emulsion.

In addition, according to the method for above 9th, the preferred embodiment of the method is identical with the above condition defined for the preferred embodiment of seed emulsion.

10. the seed emulsion prepared by any one method in above 1-10, the Hunk constant (Hansch) of the polymkeric substance wherein in seed emulsion is 2.25-3.10, is preferably 2.30-3.00; Preferred 2.35-2.90, is preferably 2.35-2.55 or 2.55-2.8; And/or this polymkeric substance has 5.0 ~ 10.0 DEG C, preferably 5.5 ~ 9.5 DEG C or 6.0 ~ 9.0 DEG C, the more preferably second-order transition temperature (Tg) of 6.5 ~ 8.5 DEG C or 7.0 ~ 8.0 DEG C.

Preferably, the number average bead diameter of the seed emulsion described in above 10 is 28 ~ 40nm, preferably 29 ~ 38nm, or 30 ~ 36nm, preferred 31 ~ 34nm further, or 32 ~ 33nm, and/or, size distribution index (PDI) is less than 0.12, is more preferably less than 0.10

The method of 11. preparation (phased film forming) copolymer in cinnamic acrylic ester type coating emulsions (being called for short styrene-acrylic coating emulsion), the method comprises the following steps:

(1) pre-emulsification: add 14 ~ 37 weight parts (preferably 15 ~ 34 weight parts in pre-emulsification still, preferably 16 ~ 32 weight parts, more preferably 18 ~ 28 weight parts, such as 24,26 weight parts) deionized water, under whipped state, add 0.2 ~ 1.5 weight part (preferably 0.3 ~ 1.2 weight part, more preferably 0.4 ~ 1.1 weight part, such as 0.5,0.6,0.7,0.8,0.9,1.0 weight parts) the non-reactive emulsifying agent [C of the such as terminal hydroxy group sulfonation of 0.1 ~ 0.8 weight part (preferably 0.2 ~ 0.6 weight part) ₅-C ₁₀alkyl alcohol ethoxylates type emulsifying agent, if the alkyl alcohol ethoxylates (EO:15 ~ 20) of terminal hydroxy group sulfonation is (hereinafter referred to as emulsifying agent B or mixed emulsifier B, Shanghai official loyal to his sovereign Fine Chemical Co., Ltd), and/or 0.1 ~ 0.6 the siliceous emulsifying agent of weight part (preferably 0.2 ~ 0.5 weight part) (as S-240, Germany's Degussa)] with the reactive emulsifier containing olefinic double bond (or containing carbon-to-carbon double bond) of 0.2 ~ 1.2 weight part (preferably 0.4 ~ 1.0 weight part), through after a while after (such as 10 ~ 30 minutes), drip 100 weight parts by vinylbenzene (St), butyl acrylate (BA), vinylformic acid (AA), acrylamide (AM), the monomer mixture of 2-EHA (EHA) and cross-linking monomer composition, (such as 45 ~ 75 minutes high-speed stirring emulsification for some time, as 1 hour),

Wherein the relative usage (based on total monomer weight) of various monomer is:

Vinylbenzene (St) 52 ~ 72%, preferably 54 ~ 68%, more preferably 55 ~ 66%;

Butyl acrylate (BA) 10 ~ 24%, preferably 11 ~ 20%, more preferably 11.4 ~ 18%;

Vinylformic acid (AA) 1.2 ~ 5%, preferably 1.5 ~ 4.5%, 2.5 ~ 4%;

Acrylamide (AM) 1.2 ~ 5%, preferably 1.5 ~ 4.5%, preferably 2.5 ~ 4%;

2-EHA (EHA) 12 ~ 22%, preferably 13 ~ 18%, more preferably 14 ~ 17%;

Cross-linking monomer 0.5 ~ 1.2%, preferably 0.6 ~ 1.0%, more preferably 0.7 ~ 0.9%;

Or the relative usage (wherein the consumption sum of various monomer is 100 weight parts) of various monomer is:

Vinylbenzene (St) 52 ~ 72 weight part, preferably 54 ~ 68 weight parts, more preferably 55 ~ 66 weight parts;

Butyl acrylate (BA) 10 ~ 24 weight part, preferably 11 ~ 20 weight parts, more preferably 11.4 ~ 18 weight parts;

Vinylformic acid (AA) 1.2 ~ 5 weight part, preferably 1.5 ~ 4.5 weight parts, 2.5 ~ 4 weight parts;

Acrylamide (AM) 1.2 ~ 5 weight part, preferably 1.5 ~ 4.5 weight parts, preferably 2.5 ~ 4 weight parts;

2-EHA (EHA) 12 ~ 22 weight part, preferably 13 ~ 18 weight parts, more preferably 14 ~ 17 weight parts;

Cross-linking monomer 0.5 ~ 1.5 weight part, preferably 0.6 ~ 1.2 weight part, more preferably 0.7 ~ 1.0 weight part;

(2) be polymerized: the deionized water adding 20 ~ 35 weight parts (preferably 25 ~ 30 weight parts) in polymerization reactor, with the buffer reagent (as hydrophosphate buffer reagent) of interpolation 0 or 0.1-0.3 weight part, stir, be warming up to 70-93 DEG C (preferably 84 ~ 92 DEG C, preferably 86 ~ 90 DEG C), add 5 ~ 32 weight parts (preferred 7-28 weight part, preferred 10-25 weight part, preferred 12-22 weight part, as 13, 14, 15, 16, 18, 20 weight parts) above 1 ~ 8 in the seed emulsion of seed emulsion described in any one or more 10, then at the temperature of 85-90 DEG C (87 ~ 89 DEG C), add rebasing initiator solution (persulphate of the deionized water+0.1-0.5 weight part of such as 2-5 weight part is as APS), after for some time (such as 3 ~ 8 minutes), start to drip step (1) gained pre-emulsion and initiator solution (persulphate of the deionized water+0.3-0.8 weight part of such as 5-6 weight part is as APS), time for adding controls 150 ~ 300 minutes (preferably 180 ~ 250 minutes), dropping temperature controls at 76 ~ 89 DEG C (preferably 80 ~ 88 DEG C), dropping terminates rear insulation 45 ~ 75 minutes (preferably 50 ~ 70 minutes), cool to again 62 ~ 72 DEG C (preferably 66 ~ 70 DEG C), add neutralizing agent (such as ammoniacal liquor),

(3) eliminate afterwards: under 60-70 DEG C (preferably 65 ~ 67 DEG C), initiator A is eliminated add the one of 0.2-0.5 weight part in step (2) gained emulsion after, 5 ~ 15 minutes (such as 10 minutes) eliminate initiator B after dripping the one of 0.2-0.5 weight part afterwards, time for adding controls at 15 ~ 45 minutes, preferably 20 ~ 40 minutes, such as 30 minutes, second time insulation is carried out after dropwising, soaking time is 30 minutes-3 hours (preferably 45 ~ 75 minutes, preferably 50 ~ 70 minutes, such as 60 minutes);

Wherein, the rear elimination initiator A of described 0.2 ~ 0.5 weight part is organic hydroperoxide (as the tertbutyl peroxide) aqueous solution (organic hydroperoxide (as tertbutyl peroxide) as deionized water+0.1 ~ 0.2 weight part of 0.1 ~ 0.3 weight part) of 0.2 ~ 0.5 weight part; The rear elimination initiator B of described 0.2 ~ 0.5 weight part is the aqueous solution (reductive agent (as sodium formaldehyde sulphoxylate and/or sodium bisulfite) as the deionized water+0.1-0.3 weight part of 0.1 ~ 0.2 weight part) of reductive agent (as sodium formaldehyde sulphoxylate and/or sodium bisulfite);

(4) be cooled to 15 ~ 40 DEG C (preferably 20 ~ 35 DEG C) after second time insulation, add emulsifying agent (the such as QM-1580 of 0.2 ~ 0.5 weight part, the loyal Fine Chemical Co., Ltd in Shanghai, LCN407, gram Lay benefactor department of Germany), optional (0 or 0.2 ~ 0.4 weight part) neutralizing agent (such as ammoniacal liquor) is added after stirring for some time (such as 15 ~ 30 minutes), (0 or 0.2 ~ 0.4 weight part) defoamer, (0 or 0.2 ~ 0.4 weight part) sanitas (as BIT-20), continue stirring again 45 ~ 75 minutes (preferably 50 ~ 70 minutes, such as 60 minutes),

(5) finally (such as using 500 mesh filter screens) is filtered, obtained phased film forming copolymer in cinnamic acrylic ester system coating emulsion.

Above-described " non-reactive emulsifying agent " be generally containing polyoxyethylene segment (PEO) containing the emulsifying agent of sodium group as emulsifying agent B, and/or the emulsifying agent (being called for short siliceous emulsifying agent) containing polysiloxane segment is as siliceous emulsifying agent S-240 (Dow corning company).The surface tension of siliceous emulsifying agent is generally between 2 ~ 20 dyne, preferably between 5 ~ 18 dyne.

The method of 12. preparation phased film forming copolymer in cinnamic acrylic ester system coating emulsions according to above 11 (being called for short styrene-acrylic coating emulsion), wherein said cross-linking monomer is vinyl three (C ₁-C ₃alkoxyl group) silane, preferably A151 (i.e. vinyltriethoxysilane).

13. methods according to above 11 or 12, in the pre-emulsion wherein formed in the step (1) or drip pre-emulsion in step (2) while or afterwards, also drip the molecular weight regulator of 0.5 ~ 8 weight part (preferably 1 ~ 7, more preferably 2 ~ 6).This conditioning agent is preferably TEXNOL (containing ester group and two secondary hydroxyls, Yi Shi Man) and/or vinylchlorid (VC).The TEXNOL of such as 1 ~ 2 weight part and/or the vinylchlorid of 1.5 ~ 2.5 weight parts.Because the saturation vapour pressure of vinylchlorid is higher, be generally 6kg/cm ²if when consumption is few, can directly be absorbed in styrene monomer.If consumption is large, then use the polymerization reactor of pressurization, such as autoclave.

14. according to the method in above 11 ~ 13 described in any one, wherein reactive emulsifier (or being called response type surfactant active) is selected from following one or two or more in these: allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6, 8, 10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propane sulfonic acid salt (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS), preferably, reactive emulsifier is selected from one or both in 3-allyloxy-2-hydroxyl-propyl sodium sulfonate (COPS-1) or 3-allyloxy-2-hydroxyl-propyl sodium phosphate salt (COPS-3).

15, according to the method in above 11-14 described in any one, wherein reactive emulsifier (or being called response type surfactant active) is selected from allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6, 8, 10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propane sulfonic acid salt (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or a kind of a kind of binding substances with being selected from NRS-10 or SE-10N in 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS), be more preferably a kind of a kind of binding substances with being selected from NRS-10 or SE-10N be selected from 3-allyloxy-2-hydroxyl-propyl sodium sulfonate (COPS-1) or 3-allyloxy-2-hydroxyl-propyl sodium phosphate salt (COPS-3).

16. according to the method preparing cinnamic acrylic ester type coating emulsion in above 11 ~ 15 described in any one, wherein the reactive emulsifier containing olefinic double bond (or containing carbon-to-carbon double bond) of 0.2 ~ 1.2 weight part (preferably 0.4 ~ 1.0) comprises NRS-10 or SE-10N of such as 0.1 ~ 0.6 weight part (preferably 0.2 ~ 0.5), with 0.1 ~ 0.6 weight part (preferably 0.2 ~ 0.5) be selected from allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6, 8, 10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propane sulfonic acid salt (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or the one in 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS)].

More preferably, the reactive emulsifier containing olefinic double bond (or containing carbon-to-carbon double bond) of 0.2 ~ 1.2 weight part (preferably 0.4 ~ 1.0) comprises the one be selected from NRS-10 or SE-10N being selected from one in 3-allyloxy-2-hydroxyl-propyl sodium sulfonate (COPS-1) or 3-allyloxy-2-hydroxyl-propyl sodium phosphate salt (COPS-3) and 0.1 ~ 0.6 weight part (preferably 0.2 ~ 0.5) of such as 0.1 ~ 0.6 weight part (preferably 0.2 ~ 0.5).

In the method preparing cinnamic acrylic ester type coating emulsion above, sanitas is preferably Alex251 or BIT-20; Further preferably, in styrene-acrylic coating emulsion, (or with the addition of) is contained based on total reaction mixture weight 0 ~ 0.2%, the preferably sanitas of 0.01 ~ 0.1%.Described defoamer is silicone antifoam agent or fluorine richness silicone antifoam agent, is preferably one or more in water-based silicone oil, silicone emulsion; Be preferably one or more in DF60 defoamer, Tego902W defoamer, WBA defoamer (Kening Co., Ltd of the U.S.) further; Further preferably, in cinnamic acrylic ester type coating emulsion, (or with the addition of) is contained based on total reaction mixture weight 0 ~ 5 ‰, the preferably defoamer of 1 ~ 4 ‰.

The 17. phased film forming copolymer in cinnamic acrylic ester system coating emulsions prepared by the method described in any one in above 11 ~ 16 (being called for short styrene-acrylic coating emulsion), the solid content of wherein said cinnamic acrylic ester type coating emulsion is between 35-60wt%, preferably between 40-55wt%, more preferably between 42 ~ 51wt%.

18. coating emulsions according to above 17, in wherein said cinnamic acrylic ester type coating emulsion, the number average particle size of particle is between 70 ~ 90nm, preferably 75 ~ 88nm, or between 80 ~ 86nm.The second-order transition temperature (Tg) of the polymkeric substance of this cinnamic acrylic ester type coating emulsion is 25 ~ 30 DEG C, preferably 26 ~ 28 DEG C.

19, cinnamic acrylic ester type coating, is characterized in that: described cinnamic acrylic ester type coating comprises following component:

Cinnamic acrylic ester type coating emulsion 100-400 weight part described in above 17 or 18, preferred 150-350, more preferably 200-300 weight part;

Filler 250-600 weight part, preferred 300-550 weight part, preferred 330-500 weight part, 350-450 weight part;

Pigment 0 or 0.5-150 weight part, preferred 10-130 weight part, more preferably 30-110 weight part, more preferably 50-100 weight;

Pigment dispersing agent 0 or 0.1-8 weight part, preferred 1-6 weight part;

Pigment wetting agent 0 or 0.05-2 weight part, preferred 0.1-1.5 weight part;

Defoamer 0 or 0.02-0.50 weight part, 0.05-0.30 weight part;

Thickening material 0 or 1-5 weight part, preferred 1.5-4 weight part;

PH adjusting agent 0 or 1-10 weight part, preferred 2-8 weight part, preferred 3-7 weight part;

Film coalescence aid 0 or 1-10 weight part, preferred 2-8 weight part, preferred 3-7 weight part;

Sanitas 0 or 0.1-3 weight part, preferred 0.5-2 weight part, preferred 0.8-1.5 weight part;

Mould inhibitor 0 or 0.1-3 weight part, preferred 0.5-2 weight part, preferred 0.8-1.5 weight part;

Water 160-400 weight part, preferred 200-350 weight part, more preferably 250-300 weight part.

20. according to the coating of above 19, and wherein said pigment is the one or two or more in titanium dioxide, ferric oxide, carbon black, toner pigment slurry or organic synthesis pigment; Or filler is the one or two or more in calcium carbonate, talcum powder, kaolin, wollastonite powder.

Described pigment dispersing agent is preferably polycarboxylate sodium's type dispersion agent, preferred SN-5040 (Japanese Nuo Puke Chemical Co., Ltd.);

Described pigment wetting agent is preferably PE-100 (Shenzhen Hai Chuan Chemical Co., Ltd.), and/or AF-10 (Dow Chemical);

Described defoamer be in liquid metal soap defoamer, silica anhydride defoamer, non-silicon defoaming agent any one or two or more, preferably in defoamer NXZ (Japanese Nuo Puke Chemical Co., Ltd.), SN-DEFOAMER345, DH-X2205 (Foshan Di Hui company) any one or two or more;

Described thickening material is preferably thickening material TT935 (Rhom and Hass of the U.S.) and/or ASE-60 (Rhom and Hass of the U.S.);

Described pH adjusting agent is preferably AMP-95 (2-amino-2-methyl-1-propanol, Dow Chemical).

Film coalescence aid is preferably TEXNOL.

The method of above 19 or 20 the described cinnamic acrylic ester type coating of 21. preparation, the method comprises the steps:

(1) with in the dispersing apparatus (as dispersion cylinder) of whipping device, add water, open and stir, add wetting agent, dispersion agent, pH adjusting agent, after stirring and dissolving, after improving the rotating speed (such as carrying to 1500 ~ 1800 revs/min) of whipping device, add filler and optional pigment carries out disperseing (jitter time is 30 ~ 50 minutes);

(2) by the slurry grinding after dispersion, fineness (mean particle size) reaches less than 20 microns or 20 microns;

(3) under low speed (such as 500 ~ 800 revs/min) agitation condition, cinnamic acrylic ester type coating emulsion described in above 17 or 18, defoamer, thickening material, pH adjusting agent, optional film coalescence aid, sanitas, mould inhibitor are dropped in dispersing apparatus, mixing and stirring, filters obtained described cinnamic acrylic ester type coating.

Cinnamic acrylic ester type coating described in more than 22. 19 or 20 is for preparing all kinds of Discussion on architecture wall emulsion paint, anti-corrosion of metal priming paint, the purposes of the varnish of woodenware door and window.

" optionally " expression is in this application with or without.

The particles size and distribution of seed emulsion, the wetting ability size of seed polymer and soft or hard final decision:

(1) determine the locus of polymerization of follow-up monomer and have follow-up monomer to form the position of polymkeric substance, the particle diameter of seed emulsion is less, and lipophilicity is stronger, and the polymerization probability of follow-up monomer in each emulsion particle of seed emulsion increases; Seeding polymerization is softer, and the compactness of final emulsion to the cohesive force of ground and film is better, and film-forming temperature is lower, and film coalescence aid add-on is less, and VOC content is lower;

(2) lipophilicity of seeded emulsion polymerization thing is too strong, causes final latex grain outermost layer polymer hydrophilicity to decline, causes the decline to pigment and base material wetting ability, thus causes the supporting capacity decline of emulsion to pigment and the decline of color developing;

(3) lipophilicity of seeded emulsion polymerization thing is too strong, also can cause occurring rear thickening behavior after adding associative thickener, and cause the Rheological Index of coating to improve, levelling property declines;

(4) lipophilicity of seeded emulsion polymerization thing is too strong, also can cause the rate of drying heterogeneity of paint film, finally cause the compactness of paint film to decline, cause water resistance to decline.Thus the water pollutions ability that bears dirty declines.

Hansch (Hunk) constant value of conventional monomer is as shown in table 1 below:

The Hunk constant (Hansch) of monomer commonly used by table 1

Therefore, from Hunk constant value and the glass transition temperature consideration of polymkeric substance, the present invention adopts vinylbenzene (St), butyl acrylate (BA), methyl methacrylate (MMA), ethyl propenoate (EA) as the comonomer component of preparation seed emulsion.

For coating emulsion, the rule of emulsifying agent is selected to be ensureing polymerization stability, stability in storage, under the prerequisite of salt stability, emulsifier is little as far as possible, therefore selects compatibilization effect good as far as possible, the emulsifying agent that micelle-forming concentration (CMC) value is little.The superfine particle diameter of seed emulsion determines all emulsifying agents must maximum compatibilization effect, only has sodium lauryl sulphate (SDS) and Sodium dodecylbenzene sulfonate (SDBS) to have this feature at present.Because the water tolerance of SDBS is better, therefore preferably SDBS and reactive emulsifier composite as polymeric emulsifiers.

In emulsion film forming process, hydrophilic small molecules material all with final minor amount of water, to coating surface diffusion under the effect of kapillary, then can be enriched in together in the later stage of drying process.Therefore the consumption of emulsifying agent is very important to the water tolerance of paint film.Along with the increase of emulsifier, the polymerization stability of the monomer compatibility that wetting ability is large decreases.This is that the outer field hydration layer of emulsion particle thickens because emulsification dosage increases, and hydrophilic monomer increases to micella internal diffusional resistance, caused by aqueous phase nucleation probability increases; And along with the increase of SDBS consumption, micellar concentration increases, but increase to a certain amount of rear free emulsification dosage increase, the chance causing new emulsion particle to generate increases, along with the increase of reactive emulsifier consumption, homogeneous nucleation probability increases, and generates the probability of new emulsion particle also in increase.

Described initiator can be inorganic radical-initiator (such as Potassium Persulphate, Sodium Persulfate or ammonium persulphate) or organic oxidation-reduction initiator (such as organo-peroxide (as tert-butyl peroxide)-organic reducing agent (as vitamins C)) or inorganic oxide-reduction initiator.Also can be the combination of the combination of two kinds of dissimilar initiators, such as inorganic radical-initiator and organic oxidation-reduction initiator.The preferred inorganic radical-initiator of the present invention, further preferably persulphate, one or more more preferably in ammonium persulphate (APS), Potassium Persulphate, Sodium Persulfate.

Preferably, described cross-linking monomer is vinylsiloxane, and with the increase of its consumption, the breaking tenacity of paint film increases, and extension at break reduces, and the contamination resistance of paint film is all always in the trend raised.Described vinylsiloxane can be one or more in A151, A171, A-174, preferably A151.

The polymerization stability of emulsion, mechanical stability and salt stability reduce gradually with the increase of amount ofthe cross-linking monomer, and scrubbing resistance ability, the stain resistant ability of paint film increase with it and increase.The consumption of cross-linking monomer has a significant impact the color developing improving coating.This is because, before film forming, the siloxane bond of A151 is not opened, the molecular weight of basic polymkeric substance and gel content and amount ofthe cross-linking monomer have nothing to do, but start crosslinking curing after film forming, active high silicone hydroxyl can with base material, pigment particles, react between polymkeric substance, not only increase the sticking power to base material, the water tolerance of gaseous state paint film, contamination resistance, and the color developing that improve paint film.

Described reactive emulsifier, the wettability of emulsion polymer to pigment itself and the water tolerance of paint film can be improved further, any one most preferably in allyloxy hydroxypropyl sulfonate (COPS-1), allyloxy hydroxypropyl sodium phosphate salt (COPS-3) of the present invention, and any one in NRS-10 or SE-10N.

Reactive emulsifier NRS-10 chemical constitution is for containing allylic extraordinary ether alcohol sulfate, and soap-free polymerization and the consumption of the control emulsion preferably of its polymerization activity seldom just play water-fast effect.The NRS-10 that the loyal Fine Chemical Co., Ltd in preferred Shanghai produces, the NRS-10 more environmental protection of its more Japanese ADK chemical production.

The emulsifying agent of described styrene-acrylic emulsion is preferably the compound of emulsifying agent B and reactive emulsifier.When emulsifying agent total amount is identical, the salt stability with the increase emulsion of emulsifying agent B ratio improves, and particle diameter becomes large.This is because emulsifying agent B has the Soxylat A 25-7 segment longer than NRS-10 or SE-10N; Particle diameter becomes large, is because Soxylat A 25-7 chain segment length, the hydration thickness of formation, caused by the particle diameter measured of light scattering method is higher.And, the scrub resistance of paint film, the color developing of coating all can improve along with the raising of reactive emulsifier consumption, this is because reactive emulsifier is finally on main polymer chain, reduce the interfacial effect of emulsifying agent and base material, what decrease emulsifying agent is rushed to phenomenon simultaneously, so far the initial whiting time of paint film postpones, and the wet adhesion of paint film improves; But the polymerization activity base of reactive emulsifier is allylic structure, exist active low always, be not suitable for the copolymerization of high-content, active high styrene monomer especially, therefore when reactive emulsifier amount is increased to a certain degree, because activity is low, the chance of homopolymerization increases, and not only polymerization stability declines, and the water-fast whiting of paint film, water-proof all can decline.Therefore reactive emulsifier should note the control of consumption in styrene-acrylic coating emulsion formula.

SIPPMERCOPS-1 is non-emulsified type reactive emulsifier the most classical in the world at present, for the mechanical stability of emulsion greatly can be improved in the letex polymerization of acrylate, emulsion is to the water tolerance of the supporting capacity of pigment and the color developing of paint film and paint film, but the price of Yin Qigao, it is its bottleneck used at coating emulsion of restriction always, this product domesticizes at present, and quality reaches the level of Luo Diya substantially, and price is the half of imported product.COPS-3 is also the another kind of non-emulsified type reactive emulsifier first developed by Rhodia, its chemical name is for being allyloxy di sodium, the difference of the two is the difference of phosphorus and sulphur, but the coordination ability of phosphorus atom is stronger, easier and pigment particles forms chelate bond, and linkage force is larger, should be stronger to the sticking power aspect of raising and base material.When utilizing described styrene-acrylic emulsion to prepare coating, along with the increase of non-emulsified type reactive emulsifier consumption, the saturated water absorption of paint film increases, and the initial whiting time is normal distribution trend, and wet adhesion increases, and scrubbing resistance ability increases; This is because along with the increase of non-emulsified type reactive emulsifier consumption, drying varniss speed reaches unanimity, caused by the compactness increase of paint film.Wet adhesion increase is because the powerful sequestering action of sulfonic group or phosphate, improves the dispersion moistening ability to pigment, improves caused by the binding ability to base material.The non-emulsified type reactive emulsifier being hydrophilic group with sodium phosphate group is to the sticking power improving paint film, water tolerance is better than the non-emulsified type reactive emulsifier with sodium sulfonate group, and the two is suitable to the color developing of coating, but the supporting capacity (representing with critical pigment volume concentration CPVC) of the pigment to raising emulsion, the reactive emulsifier of sodium sulfonate group is better.

Therefore, preferably, emulsifier is the 4.00 ~ 21.00wt ‰ of total monomer weight, preferably 6.00 ~ 20wt, ‰ or 8 ~ 18wt ‰, more preferably 10 ~ 16wt, ‰ or 12 ~ 14wt ‰, wherein emulsifying agent B consumption is the 1.00 ~ 6.00wt ‰ of total monomer weight, preferably 2.00 ~ 3.00wt ‰, NRS-10 or SE-10N consumption is the 1.00 ~ 6.00wt ‰ of total monomer weight, preferably 2.00 ~ 5.00wt ‰, more preferably 3.00 ~ 4.00wt ‰, polymerization stability now, the size of final emulsion and size distribution, viscosity and salt stability all meet the requirement of coating emulsion.The consumption of non-emulsified type reactive emulsifier COPS-1 or COPS-3 is at the 1.00 ~ 5.00wt ‰ of monomer total amount, preferably 2.00 ~ 3.00wt ‰.

Preferably, in described emulsifying agent, also comprise non ionic polymer type emulsifying agent, preferred siliceous emulsifying agent.The segmented copolymer of the preferred polysiloxane of described siliceous emulsifying agent and polyethers is totally nonionic, very little to grain diameter influence, but due to its surface tension extremely low, affect polymerization behavior.Further preferably, the surface tension of selected siliceous emulsifying agent is between 2 ~ 20 dyne, preferably between 5 ~ 18 dyne.Particularly preferably be, S-240 emulsifying agent (German Degussa company).The consumption of siliceous emulsifying agent has impact to polymerization stability, and with the increase of siliceous emulsifier, polymerization stability declines, and color developing strengthens, the performance of comprehensive polymerization stability and paint film, the Optimum of siliceous emulsifying agent 1 ~ 4 ‰, preferably 2 ‰ ~ 3.00 ‰.

Further preferably, the emulsifying agent that the preparation of styrene-acrylic coating emulsion is selected is the composite use of emulsifying agent B, NRS-10, COPS-3 and S-240, and consumption is respectively relative to monomer total amount: 1.00 ~ 6.00wt ‰, 1.00 ~ 5.00wt ‰, 1.00 ~ 4.00wt ‰.Be preferably 2.00 ~ 3.00wt ‰, 3.00 ~ 4.00wt ‰.

Described initiator, can be inorganic radical-initiator (such as Potassium Persulphate, Sodium Persulfate or ammonium persulphate), organic oxidation initiator (one or more in such as organo-peroxide (as tert-butyl peroxide), or organic reducing initiator (as sodium formaldehyde sulphoxylate, sodium bisulfite).

Described seed emulsion is any one seed emulsion of the invention described above.The particle diameter of emulsion is less, and its weathering resistance improves, and the character of seed emulsion itself has a strong impact on particle diameter and the size distribution of styrene-acrylic emulsion and finally emulsion polymer is in the distribution of emulsion particle, and these all affect the weather resistance of paint film.In the present invention, along with seed emulsion consumption increases, the seed polymer content of coating surface increases, and the styrene content of seed polymer is very little, and therefore weather resistance increases.And the inside particles of styrene-acrylic coating emulsion is the glassy phase of superfine particle diameter, when the ultraviolet in air is through paint film, a part is through the space of particle, and be then the excited molecular orbital(MO) of state of another part absorbed, and then the anti-ultraviolet ageing performance of raising paint film.This is that the tunnel effect of nanoparticle provides.But, the consumption of seed emulsion can not be too high, this is because seed emulsion consumption increases, particle diameter sharply diminishes, and causes the viscosity of emulsion sharply to increase, and not only gives the packaging of emulsion, taking-up, transfer causes difficulty, and the Rheological Index of the coating of the high emulsion content of final preparation increases, the levelling property of coating declines, and also can cause the degradation of part paint film.

For improving the performance of described styrene-acrylic coating emulsion, the auxiliary agent that emulsion preparation is conventional can also be added.

Preferably, also neutralizing agent is comprised in described styrene-acrylic coating emulsion, such as ammoniacal liquor, methylol ammonia, preferred ammoniacal liquor.In the present invention, ammoniacal liquor is usually with 20-40wt%, more general 22-35wt%, and especially the concentration of 25wt% uses.

Preferably, in described styrene-acrylic coating emulsion, sanitas can also be added, such as Sodium Benzoate, daconil M, aminopropanol compound, one or more in preferred Alex251, BIT-20 (Sol company of the U.S.).Further preferably, contain based on total reaction mixture weight 0 ~ 0.2% in styrene-acrylic coating emulsion, the preferably sanitas of 0 ~ 0.1%.

Preferably, can also add defoamer in described styrene-acrylic coating emulsion, described defoamer is silicone antifoam agent or fluorine richness silicone antifoam agent, one or more in preferred water-based silicone oil, silicone emulsion; One or more further preferably in DF60 defoamer, Tego902W defoamer, WBA defoamer (Kening Co., Ltd of the U.S.).Further preferably, contain based on total reaction mixture weight 0 ~ 5 ‰, the preferably defoamer of 1 ~ 4 ‰ in styrene-acrylic coating emulsion.

Color stuffing described in the present invention, specifically refers to pigment and filler.Wherein, the performance of pigment and the opacifying power of film, uniform coloring, tint retention and chalking resistance have substantial connection, one or more pigment can commonly used for this area, include but not limited to, titanium dioxide, ferric oxide, carbon black and various toner pigment slurry (such as phthalocyanine blue), more than fineness requirement 1200 order, preferably adopt the Rutile type Titanium Dioxide (R902) that du pont company produces.

Filler is a kind of non-coloring power or the pigment extender only having extremely less colored power, mainly play the adjustment of coating performance, the change of film performance and the further effect reducing filler cost, one or more fillers can commonly used for this area, include but not limited to as calcium carbonate, talcum powder, kaolin, wollastonite powder, more than fineness requirement 1200 order, preferably adopt in ultra-fine talcum powder (1200 order), heavy calcium carbonate (1200 order) or wollastonite powder (1200 order) any one or a few.The preferred Beijing Mei Yahua of the embodiment of the present invention becomes coarse whiting (1200 order), talcum powder (1200 order), the wollastonite powder (1200 order) of trade Co., Ltd.

Described dispersion agent is polycarboxylate sodium's type dispersion agent, the SN-5040 of preferred Japanese Nuo Puke Chemical Co., Ltd..

Described wetting agent, comprises pigment wetting agent and substrate wetting agents.Pigment wetting be pigment by the prerequisite of stable dispersion, the process that the gas that pigment wetting process is actually surface of pigments is replaced by base solution, the wetting ability of emulsion to pigment itself is very poor, so must use wetting agent.According to the color stuffing determined, select corresponding wetting dispersing agent, the Multi-purpose watch surface-active agent PE-100 of the preferred Shenzhen Hai Chuan Chemical Co., Ltd. of the present invention.

The present invention also comprises auxiliary film forming matter, auxiliary film forming matter can not film forming separately, just formed to be coated with in membrane process at coating and play auxiliary effect, as various auxiliary agents such as film coalescence aid, defoamer, frostproofer, neutralizing agent, sanitas, thickening materials, though their consumptions in coating are little, all there is obvious effect to the physicals such as water tolerance, ageing resistance, abrasion resistance of the storage of coating, construction and film.

Described molecular weight regulator is any one or a few in tertiary lauryl mercaptan (t-DM), n-dodecyl mercaptan (n-DM), thiohydracrylic acid butyl ester, thiohydracrylic acid monooctyl ester, secondary alcohol, vinylchlorid, TEXNOL.When using t-DM and n-DM, because its polarity differs comparatively large with acrylate copolymer, although molecular-weight adjusting effect is pretty good, the gloss of the coating of obtained emulsion preparation reduces, the molecular weight regulator of uncomfortable cooperation high-gloss paint emulsion; And consumption can not be too large, otherwise residual smell is very heavy, and this is still worthless for the clean taste coating of preparation.Use thiohydracrylic acid butyl ester, during thiohydracrylic acid monooctyl ester, the effect of Molecular regulator amount is suitable with t-DM and n-DM, also not delustring, but not only expensive, and still has bad smell to remain, and can exist equally and use t-DM and n-DM produced problem.Regulate the molecular weight effect of letex polymerization all be not as good as other molecular weight regulators with secondary alcohol, Virahol can be had, isopropylcarbinol for selectable at present, but taste is very large, is still not suitable as the molecular weight regulator of clean taste coating emulsion.Vinylchlorid is that a lipophilicity is fine, the polymerisable unsaturated vinyl monomer that chain transfer constant is maximum, after the monomer such as vinylbenzene, acrylate and chloroethylene copolymer, not only can improve the water tolerance of multipolymer, the compactness of paint film, sticking power etc., and the molecular weight reducing multipolymer can be had.But make with vinylchlorid the saturated vapor pressure that molecular-weight adjusting monomer should be noted vinylchlorid, the saturated vapor pressure of vinylchlorid is very high, generally at 6kg/cm ², when consumption is few, vinyl chloride monomer first can be absorbed in styrene monomer and cross in butyl acrylate, then together enter in pre-emulsification still by its absorption liquid, polymerization process afterwards just can carry out at ambient pressure.Therefore, preferred TEXNOL.TEXNOL is not only containing ester group but also containing the high boiling point organic compound of two secondary hydroxyls, not only those compatible is good together, and smell is very little and have certain molecular-weight adjusting effect in a part structure.Further preferably, TEXNOL and the composite use of vinyl chloride monomer.

Along with the increase of molecular weight regulator consumption, the molecular weight of polymkeric substance reduces, and the structural gel content of polymkeric substance reduces, the minimum film-forming temperature of emulsion, and the scrub performance of paint film and wet adhesion will improve; And the molecular weight of polymkeric substance reduces, the color developing of coating increases.Therefore, preferably, TEXNOL consumption is 1 ~ 4% of monomer total amount, and preferably 2 ~ 3%, VC consumptions are 1.00 ~ 4.50% of monomer total amount, preferably 1.50 ~ 4.00%, further preferably 2.50 ~ 3.50%.

Described defoamer can be liquid metal soap defoamer, as Japanese Nuo Puke Chemical Co., Ltd. defoamer NXZ; Can be silica anhydride defoamer, as SN-DEFOAMER345; Can be non-silicon defoaming agent, the such as DH-X2205 of Foshan Di Hui company.

Described neutralizing agent can be ammoniacal liquor or methylol ammonia, preferred ammoniacal liquor.

The associative thickener (TT935) of Rhom and Hass of the described thickening material preferred U.S., thickening material (ASE-60).

Interpolation sanitas, mould inhibitor that can also be optional in described coating.Described sanitas can be any one or a few in Sodium Benzoate, daconil M, aminopropanol compound.

The AMP-95 of the preferred Dow Chemical of described pH adjusting agent.

The invention still further relates to a kind of method preparing above-mentioned styrene-acrylic coating, the method comprises the steps:

(1) in dispersion cylinder, add water and open stirring, add wetting agent, dispersion agent, pH adjusting agent, after stirring and dissolving, improve rotating speed (such as carrying to 1500 ~ 1800 revs/min) and add color stuffing dispersion, disperse 30 ~ 50 minutes;

(2) by the slurry grinding after dispersion, fineness reaches less than 30 microns;

(3) under low speed (such as 500 ~ 800 revs/min) agitation condition, any one styrene-acrylic emulsion described in second aspect present invention, defoamer, thickening material, pH adjusting agent, molecular weight regulator, sanitas, mould inhibitor are dropped in dispersion cylinder, mixing and stirring, filters obtained styrene-acrylic coating.

Coating of the present invention can be used for the filmogen of all kinds of Discussion on architecture wall emulsion paint, also can be used for anti-corrosion of metal priming paint, the preparation of the varnish of woodenware door and window etc.

" optionally " expression is in this application with or without, such as, " optionally add " and represent interpolation or do not add.

Described in this application " water " is preferably " deionized water ".

The present invention utilizes the controlled emulsion polymerization technology of seed to combine with phased film technique, solves the technical bottleneck preparing high-performance building exterior wall styrene-acrylic coating emulsion.The present invention has the following advantages:

(1) seed emulsion controllable polymerization is combined with phased film technique, achieve the particle diameter to final emulsion, size distribution controls, achieve the distributed controll of polymkeric substance inside and outside emulsion particle and polymeric hydrophilic lipophilicity distributed controll.Seed emulsion used belongs to international pioneering in the design concept such as to quote of the wetting ability of seed polymer and lipophilicity, particles size and distribution and siliceous emulsifying agent; Finally reach seed emulsion and there is best amphipathic property, super surface effects.

(2) controlled for seed letex polymerization is combined with phased film technique, achieve and just can obtain with convenient source the target emulsion that over-all properties reaches advanced world standards.

(3) utilize the tunnel effect of organic nano particle, successfully enhance the ageing-resistant performance of styrene-acrylic coating emulsion;

(4) utilize seeded emulsion polymerization technology, successfully solve production process emulsion particle diameter and be difficult to control and the quality fluctuation problem that causes;

(5) utilize seeded emulsion polymerization technology, reduce the emulsifier of preparation fine grain size emulsion significantly, thus improve the water tolerance of paint film, contamination resistance;

(6) designability of distribution of polymer inside and outside the surface effects utilizing organic nano particle powerful and latex particle, seed emulsion polymerization is combined with the phased membrane technique that diffuses into, achieve with most convenient source (monomer, linking agent, emulsifying agent, auxiliary agent) coating emulsion of obtained high-performance (weather-proof, super water-fast, resistant and high color development);

(7) this seeded emulsion polymerization technology is different from prior seed letex polymerization, and the outside of seed polymer distribution objectives emulsion latex grain, successfully solves low surface energy emulsifying agent fast to the diffusion problem of coating surface;

(8) control to successfully solve the problems such as compact in paint film, mechanical property and resistance to outdoor aging by size and distribution.

(9) production process of intermediate raw material seed emulsion designed by the present invention and final styrene-acrylic coating emulsion and raw materials used production method, just reach discharging standards through simple improvement, is the method that an environment-protecting clean is produced.

In this application, described " styrene-acrylic " emulsion, coating refer to styrene-acrylate emulsion, coating, are to introduce the cinnamic acrylic emulsion system of hard monomer.

In this application, the monomer with lower glass transition temperatures (lower than 30 DEG C) is referred to as " soft monomer ", and the monomer with high glass-transition temperature (higher than 32 DEG C) is referred to as " hard monomer ".

In this application, the multipolymer with lower glass transition temperatures is referred to as " flexible polymer ", and the multipolymer with high glass-transition temperature is referred to as " hard polymer ".

Accompanying drawing explanation

Fig. 1 is the transmission electron microscope sectional view of the coating emulsion of the embodiment 10 prepared by seed emulsion adopting embodiment 5.

Wherein seeded emulsion polymerization thing is distributed in the outside of the particle of coating emulsion.

Embodiment

Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.

Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.

Embodiment illustrates:

1. the source of embodiment raw material and specification

(1) embodiment seed emulsion, styrene-acrylic emulsion raw materials source and specification

(2) styrene-acrylic coating prepare used additives and color stuffing source and specification

2. performance test standard

3. Main Analysis instrument, equipment

Embodiment

The preparation of I seed emulsion

(1) pre-emulsification adds the deionized water of metering in 5000ml there-necked flask, opens and stirs, add the emulsifying agent of metering, start to drip the monomer measured after 15min, continues high-speed stirring emulsification and is about 1h;

(2) polymerization adds deionized water in the 1000ml four-hole boiling flask with stirring, reflux exchanger, thermometer and constant pressure funnel, open and stir, add the rebasing emulsifying agent of metering, when being warming up to 85 DEG C, add the initiator solution of metering, rush extremely the highest until temperature and after stablizing 2 minutes, start drip pre-emulsion and drip initiator solution, during dropping, temperature controls at 86 ~ 88 DEG C, and total time for adding controls at 90 ~ 100 minutes; Dropping terminates rear insulation 1h;

(3) cool to less than the 40 DEG C emulsifying agents and sanitas and defoamer adding metering, finally with ammonia neutralization to pH value to 8.0 ~ 8.50, then filter, measure seed emulsion indices, comprise transformation efficiency, slag yield, particle diameter and size distribution, emulsion particle form.

The component formula (outside demonomerization ratio, other consumption is with parts by weight) of embodiment seed emulsion

The polymerization result of table 2 different monomers mix proportion scheme gained seed emulsion

Remarks: * monomer ratio: ST:MMA:EA:BA; * does not reach 100% because of glass effect transformation efficiency

1. polymerization temperature 88 DEG C, 2. SDBS amount is 5%, COPS-1 consumption of amount of monomer is 5.00% of amount of monomer; 3. APS consumption is 7.00 ‰ of amount of monomer

The data declaration of table 2: the Hunk constant along with mix monomer reduces and designs the reduction of Tg, and monomer conversion improves, and throw out reduces particle diameter and diminishes.

The preparation of II styrene-acrylic coating emulsion

(1) pre-emulsification: the deionized water (DW) adding metering in 5000ml there-necked flask, opens and stirs, add the emulsification emulsifying agent of metering, start to drip the monomer measured after 15min, continues high-speed stirring emulsification and is about 1h;

(2) be polymerized: in the 5000ml there-necked flask with stirring, reflux exchanger, thermometer and constant pressure funnel, add deionized water, open and stir, when being warming up to 86 ~ 90 DEG C, add the above-mentioned seed emulsion measured, when 88 DEG C, add metering component three, start after about 5 minutes to drip component one and component two, time for adding controls at 180 ~ 250 minutes, dropping temperature controls at 80 ~ 88 DEG C, dropping terminates rear insulation 1h, cools to 66 ~ 70 DEG C and adds neutralizing agent A, then carry out rear elimination;

(3) eliminate afterwards: at 65 ~ 67 DEG C, add component five, after 10 minutes, drip component six, time for adding 30 minutes, after dropwising, carry out second time insulation;

(4) be cooled to less than 40 DEG C after second time insulation, add component eight, stir and add component nine after 20 minutes, component ten, and component 11, then continue stirring 60 minutes;

(5) finally filter with 500 mesh filter screens, packaging, measure the properties of emulsion; Comprise transformation efficiency, slag yield, particle diameter and size distribution, emulsion particle form.

The component formula of styrene-acrylic coating emulsion (weight part, g)

The Hunk constant of the polymkeric substance of seed emulsion is equal to or less than 2.98pKa, much smaller than the Hunk constant (generally between 3.8 ~ 4.25pKa) of the polymerization mix monomer dripped when preparing coating emulsion subsequently, therefore seed polymer is finally at the skin of final styrene-acrylic emulsion latex grain.Fig. 1 is the Electronic Speculum figure of the styrene-acrylic emulsion adopting the seed emulsion of embodiment 5 to obtain, to prove the exactness of above-mentioned deduction.

As seen from Figure 1, compared with the follow-up monomer of styrene-acrylic emulsion, the vinylbenzene consumption of seed emulsion is few, seed polymer (below 20wt%) is in white, and follow-up dropping polymerization single polymerization monomer styrene content is up to 52%, and the color of follow-up dropping polymkeric substance is black, therefore ball center's part of Fig. 1 is that follow-up monomer polymerization is formed, and sheath polymers is formed by seed polymer, that is, seed polymer is finally distributed in the outside of emulsion particle.

The preparation of III styrene-acrylic coating

(1) prepare in Special dispersing cylinder at coating, add deionized water and open stirring, add pigment wetting agent (PE-100) successively, pigment dispersing agent (SN5040) and multifunctional assistant AMP-95, after stirring and dissolving, rotating speed is carried to 1500 ~ 1800 revs/min, adds color stuffing dispersion, disperse 40 minutes under this speed;

(2) by the slurry grinding after dispersion, fineness is allowed to reach less than 40 μm;

(3) under low speed (such as 500 ~ 800 revs/min) agitation condition, styrene-acrylic emulsion obtained for embodiment II is added in dispersion cylinder, appropriate defoamer, thickening material, AMP-95, TEXNOL are dropped into mixing and stirring simultaneously, filter obtained styrene-acrylic coating.

Styrene-acrylic coating composition is filled a prescription

Embodiment 1 ~ 3 and comparative example 1 are for measuring traditional performance and the mechanical property of coating; Embodiment 4 and comparative example 2 are for measuring color developing.

The paint film property of phenylpropyl alcohol plough coating is:

Remarks: 1-(5%CaCl ₂: 1:4,48h); 2-divides 5 grades, and 5 ★ are best.

Claims (21)

1. prepare the method for copolymer in cinnamic acrylic ester type coating emulsion, the method comprises the following steps:

(1) pre-emulsification: the deionized water adding 14 ~ 37 weight parts in pre-emulsification still, under whipped state, add the non-reactive emulsifying agent of 0.2 ~ 1.5 weight part and the reactive emulsifier containing olefinic double bond of 0.2 ~ 1.2 weight part, through after a period of time, drip the monomer mixture be made up of vinylbenzene (St), butyl acrylate (BA), vinylformic acid (AA), acrylamide (AM), 2-EHA (EHA) and cross-linking monomer of 100 weight parts, high-speed stirring emulsification for some time;

Wherein, based on total monomer weight, the relative usage of various monomer is:

Vinylbenzene (St) 52 ~ 72%;

Butyl acrylate (BA) 10 ~ 24%;

Vinylformic acid (AA) 1.2 ~ 5%;

Acrylamide (AM) 1.2 ~ 5%;

2-EHA (EHA) 12 ~ 22%;

Cross-linking monomer 0.5 ~ 1.2%;

(2) be polymerized: the water adding 20 ~ 35 weight parts in polymerization reactor, with the buffer reagent of interpolation 0 or 0.1 ~ 0.3 weight part, stir, be warming up to 70-93 DEG C, add the seed emulsion of 5 ~ 32 weight parts, then at 85-90 DEG C, rebasing initiator solution is added, after for some time, start to drip step (1) gained pre-emulsion and initiator solution, time for adding controls at 150 ~ 300 minutes, and dropping temperature controls at 76 ~ 89 DEG C, drips and terminates rear insulation for some time, cool to 62 ~ 72 DEG C again, add neutralizing agent;

(3) eliminate afterwards: at 60 ~ 70 DEG C, initiator A is eliminated add the one of 0.2 ~ 0.5 weight part in step (2) gained emulsion after, initiator B is eliminated dripped the one of 0.2 ~ 0.5 weight part after 5 ~ 15 minutes after, time for adding controls at 15 ~ 45 minutes, carry out second time insulation after dropwising, soaking time is 30 minutes-3 hours;

(4) be cooled to 15 ~ 40 DEG C after second time insulation, add the emulsifying agent of 0.2 ~ 0.5 weight part, after stirring for some time, add optional neutralizing agent, optional defoamer, optional sanitas, then continue to stir;

(5) finally filter, the copolymer in cinnamic acrylic ester type coating emulsion of obtained phased film forming,

Wherein, described seed emulsion is copolymer in cinnamic acrylic ester type seed emulsion, this emulsion is by the vinylbenzene as monomer component, butyl acrylate, methyl methacrylate and ethyl propenoate, under the existence of the reactive emulsifier containing olefinic double bond and anionic emulsifier sodium lauryl sulphate or Sodium dodecylbenzene sulfonate and water, carry out emulsion polymerization by interpolation radical initiator to prepare, wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), the weight ratio of butyl acrylate (BA) is St:MMA:EA:BA=(7 ~ 25): (15 ~ 40): (10 ~ 30): (20 ~ 70),

The number average bead diameter of wherein said seed emulsion is 25 ~ 40nm, and the Hunk constant of polymkeric substance in seed emulsion be 2.25 ~ 3.10 and/or this polymkeric substance there is the glass transition temperature Tg of 5.0 ~ 10.0 DEG C.

2. method according to claim 1, the Hunk constant (Hansch) of the polymkeric substance wherein in seed emulsion is 2.30 ~ 3.00; And/or this polymkeric substance has the glass transition temperature Tg of 5.5 ~ 9.5 DEG C.

3. method according to claim 1, is characterized in that the solid content of described seed emulsion is at 20-60wt%.

4. method according to claim 1, it is characterized in that: the reactive emulsifier in described seed emulsion is selected from following one or two or more in these: allyl group hydroxyalkylated sulfonic acid sodium, allyl group oxygen ethyl polyethylene-oxide (6) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (8) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (10) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (12) nonylplenyl ether ammonium sulfate, maleic anhydride derivative sodium sulfonate, 2-acrylamide-2-methylpro panesulfonic acid, 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate, 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate, methoxy polyethylene glycol methacrylate-styrene polymer, sodium vinyl sulfonate, 2-methyl-2-propylene-1-sodium sulfonate, or 2-acrylamido-2-methylbutane sodium sulfonate.

5. according to the method in Claims 1 to 4 described in any one, it is characterized in that: in described seed emulsion, also comprise neutralizing agent.

6. according to the method in Claims 1 to 4 described in any one, it is characterized in that: in described seed emulsion, also comprise sanitas and/or defoamer.

7. according to the method in Claims 1 to 4 described in any one, it is characterized in that: the number average bead diameter of described seed emulsion is 27 ~ 38nm, and/or size distribution index (PDI) is less than 0.12.

8. according to the method in Claims 1 to 4 described in any one, it is characterized in that: the minimum film-forming temperature (MFT) of described seed emulsion is 4 ~ 12 DEG C.

9. according to the method in Claims 1 to 4 described in any one, it is characterized in that: the weight ratio of the monomer component vinylbenzene (St) of described seed emulsion, methyl methacrylate (MMA), ethyl propenoate (EA), butyl acrylate (BA) is St:MMA:EA:BA=(8 ~ 20): (25 ~ 35): (12 ~ 27): (30 ~ 40).

10., according to the method in Claims 1 to 4 described in any one, it is characterized in that the solid content of described seed emulsion is between 30 ~ 50wt%.

11. methods according to any one of claim 1 ~ 4, the preparation of wherein said seed emulsion comprises the following steps:

(1) pre-emulsification: by the deionized water of 25 ~ 37 weight parts, the anionic emulsifier sodium lauryl sulphate (SDS) of 2 ~ 10 weight parts or Sodium dodecylbenzene sulfonate (SDBS), 2 ~ 10 weight parts containing olefinic double bond reactive emulsifier stirring and dissolving for some time after, drip the monomer mixture be made up of vinylbenzene, methyl methacrylate, ethyl propenoate and butyl acrylate of 90-110 weight part, continue high-speed stirring emulsification, obtain pre-emulsion; The weight ratio of wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), butyl acrylate (BA) is St:MMA:EA:BA=(7 ~ 25): (15 ~ 40): (10 ~ 30): (20 ~ 70);

(2) be polymerized: by the rebasing anionic emulsifier sodium lauryl sulphate (SDS) of the deionized water of 70 ~ 95 weight parts, 0.7 ~ 3 weight part or Sodium dodecylbenzene sulfonate (SDBS), under agitation, be warming up to 70 ~ 95 DEG C, keep 1 ~ 20 minute, drip pre-emulsion and the initiator solution of step (1) gained, during dropping, temperature of reaction controls at 80 ~ 92 DEG C, and total time for adding controls at 60 ~ 130 minutes; Dropping terminates rear insulation 40 ~ 80 minutes;

(3) step (2) gained emulsion is cooled to 15 ~ 40 DEG C, add anionic emulsifier sodium lauryl sulphate (SDS) or the Sodium dodecylbenzene sulfonate (SDBS) of 1 ~ 6 weight part, optionally add the sanitas of 0 weight part or 0.01-0.3 weight part and/or the defoamer of 0 weight part or 0.01-0.3 weight part, final reaction mixture neutralizing agent neutralizes, then filter, obtain seed emulsion.

12. methods according to claim 1, wherein said cross-linking monomer is vinyl three (C1-C3 alkoxyl group) silane.

13. methods according to claim 1, in the pre-emulsion wherein formed in the step (1) or drip pre-emulsion in step (2) while or afterwards, also drip the molecular weight regulator of 0.5-8 weight part.

14. methods according to claim 1, wherein in step (1) pre-emulsification, reactive emulsifier is selected from following one or more in these: allyl group hydroxyalkylated sulfonic acid sodium, allyl group oxygen ethyl polyethylene-oxide (6) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (8) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (10) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (12) nonylplenyl ether ammonium sulfate, maleic anhydride derivative sodium sulfonate, 2-acrylamide-2-methylpro panesulfonic acid, 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate, 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate, methoxy polyethylene glycol methacrylate-styrene polymer, sodium vinyl sulfonate, 2-methyl-2-propylene-1-sodium sulfonate, or 2-acrylamido-2-methylbutane sodium sulfonate.

15. methods according to claim 1, wherein in step (1) pre-emulsification, reactive emulsifier is selected from allyl group hydroxyalkylated sulfonic acid sodium, allyl group oxygen ethyl polyethylene-oxide (6) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (8) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (10) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (12) nonylplenyl ether ammonium sulfate, maleic anhydride derivative sodium sulfonate, 2-acrylamide-2-methylpro panesulfonic acid, 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate, 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate, methoxy polyethylene glycol methacrylate-styrene polymer, sodium vinyl sulfonate, 2-methyl-2-propylene-1-sodium sulfonate, or a kind of a kind of binding substances with being selected from NRS-10 or SE-10N in 2-acrylamido-2-methylbutane sodium sulfonate.

16. methods according to claim 1, wherein in step (1) pre-emulsification, the reactive emulsifier containing olefinic double bond of 0.2 ~ 1.2 weight part comprises NRS-10 or SE-10N of 0.1 ~ 0.6 weight part, with 0.1 ~ 0.6 weight part be selected from allyl group hydroxyalkylated sulfonic acid sodium, allyl group oxygen ethyl polyethylene-oxide (6) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (8) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (10) nonylplenyl ether ammonium sulfate, allyl group oxygen ethyl polyethylene-oxide (12) nonylplenyl ether ammonium sulfate, maleic anhydride derivative sodium sulfonate, 2-acrylamide-2-methylpro panesulfonic acid, 3-allyl group oxygen base-2-hydroxyl-propyl sodium sulfonate, 3-allyl group oxygen base-2-hydroxyl-propyl sodium phosphate, methoxy polyethylene glycol methacrylate-styrene polymer, sodium vinyl sulfonate, 2-methyl-2-propylene-1-sodium sulfonate, or the one in 2-acrylamido-2-methylbutane sodium sulfonate.

The 17. copolymer in cinnamic acrylic ester type coating emulsions prepared by the method in claim 1 ~ 16 described in any one, the solid content of wherein said copolymer in cinnamic acrylic ester type coating emulsion between 35-60wt%, and

In wherein said copolymer in cinnamic acrylic ester type coating emulsion, the number average particle size of particle is between 70 ~ 90nm.

18. phased film forming copolymer in cinnamic acrylic ester system latex coatings, is characterized in that: described coating comprises following component:

Copolymer in cinnamic acrylic ester type coating emulsion 100-400 weight part according to claim 17 above;

Filler 250-600 weight part;

Pigment 0 or 0.5-150 weight part;

Pigment dispersing agent 0 or 0.1-8 weight part;

Pigment wetting agent 0 or 0.05-2 weight part;

Defoamer 0 or 0.02-0.50 weight part;

Thickening material 0 or 1-5 weight part;

PH adjusting agent 0 or 1-10 weight part;

Film coalescence aid 0 or 1-10 weight part;

Sanitas 0 or 0.1-3 weight part;

Mould inhibitor 0 or 0.1-3 weight part;

Water 160-400 weight part.

19. coating according to claim 18, wherein said pigment is the one or two or more in titanium dioxide, ferric oxide, carbon black, toner pigment slurry or organic synthesis pigment; Or filler is the one or two or more in calcium carbonate, talcum powder, kaolin, wollastonite powder.

The method of the phased film forming copolymer in cinnamic acrylic ester system latex coating of 20. preparations described in claim 18 or 19, the method comprises the steps:

(1) with in the dispersing apparatus of whipping device, add water, open and stir, add pigment wetting agent, pigment dispersing agent, pH adjusting agent, after stirring and dissolving, after improving the rotating speed of whipping device, add filler and optional pigment disperses;

(2) by the slurry grinding after dispersion, fineness reaches less than 40 microns;

(3) under stirring at low speed condition, copolymer in cinnamic acrylic ester type coating emulsion according to claim 17, defoamer, thickening material, pH adjusting agent, optional film coalescence aid, sanitas, mould inhibitor are dropped in dispersing apparatus, mixing and stirring, filters obtained described phased film forming copolymer in cinnamic acrylic ester system latex coating.

21. phased film forming copolymer in cinnamic acrylic ester system latex coatings according to claim 18 or 19 are for preparing all kinds of Discussion on architecture wall emulsion paint, anti-corrosion of metal priming paint, the purposes of the varnish of woodenware door and window.