CN103360890B - Containing the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion - Google Patents
Containing the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion Download PDFInfo
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Abstract
The invention belongs to technical field of paint preparation, disclose a kind of organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion.This coating is made up of the component of following weight parts: inorganic silicate 100 parts; Long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion 1 ~ 50 part; 4 ~ 100 parts, water; Defoamer 0.5 ~ 5 part; Dispersion agent 0.5 ~ 5 part; Thickening material 0.5 ~ 5 part; Antifreezing agent 0.5 ~ 4 part; Film coalescence aid 0.5 ~ 5 part; Filler 40 ~ 100 parts.The invention also discloses its preparation method.Organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion of the present invention has the advantages such as water-fast, wear-resisting, acidproof, alkaline-resisting, anchor effect is good, film forming is stable.
Description
Technical field
The invention belongs to technical field of paint preparation, particularly one is containing the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion.
Background technology
Inorganic coating for internal and external wall uses inorganic silicate as film forming matter usually, and inorganic silicate has abundant raw material, the advantage such as with low cost, pollution-free, high temperature resistant and ageing-resistant.It has certain viscosity, stronger cohesive force and film forming ability, meets the requirement of Contemporary Architecture material energy-saving and environmental protection.But inorganic silicate because of water tolerance after film forming, sticking power, snappiness very poor, this causes, and inorganic coating for internal and external wall is not water-fastness, difference of hardness, easy to crackly comes off.
Compared with inorganic silicate, acrylic ester emulsion generally has good water-alkali resistance performance as filmogen, and the snappiness of film is very good, is used alone and there will not be film cracking and obscission, as the filmogen that a kind of building coating is commonly used, its application widely.But the shortcomings such as it also also exists poor water resistance, low temperature easily becomes fragile, weathering resistance is good not, affect its practical function.Therefore, software engineering researchers invent goes out organosilicon crylic acid latex, by silane coupling agent is introduced in acrylic ester emulsion, certain water tolerance, alkali resistance can be produced, but because silane coupling agent is easily cross-linked, cause organosilicon crylic acid latex to place property, productivity be unstable, and due to silane coupling agent silica chain shorter, so its water-alkali resistance effect is also not obvious.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion.The present invention by (methyl) acrylate polymer emulsion of long-chain siloxy vinylsiloxane modification is joined in coating, thus provides that a kind of cost is low, water-fast, the organic inorganic hybridization coating for internal and external wall of stain resistant, washability.
Another object of the present invention is the preparation method providing a kind of above-mentioned organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion.The method is modification (methyl) acrylate polymer emulsion being obtained by radical polymerization by long-chain siloxy vinylsiloxane, mixes, be mixed with coating for internal and external wall with filler, auxiliary agent etc.
Object of the present invention is realized by following proposal:
A kind of organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion, is made up of the component of following weight parts:
Inorganic silicate 100 parts
Long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion
Described long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion, has the structure as formula I:
Formula (I)
Wherein R
1, R
5, R
6hydrogen or methyl;
R
2-CH
2-or-COOCH
2cH
2cH
2-;
R
3, R
4be methoxyl group, oxyethyl group, hydroxyl or
R
7to be carbon number be 1 ~ 10 saturated alkane or hydrogen;
N
1, n
2, n
3, n
4, n
5it is the natural number can divided exactly by 4 in 4 ~ 2000.
Described long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion is prepared by following methods: 80 ~ 150 weight parts waters, 3 ~ 6 weight part anionic emulsifiers, 2 ~ 4 weight part nonionic emulsifying agents and 8 ~ 37.5 weight part octamethylcyclotetrasiloxanes are mixed, nitrogen protection, 70 ~ 90 DEG C of reaction 3 ~ 9h, add the siloxanes of 2.5 ~ 7.5 weight parts containing unsaturated double-bond, 75 ~ 90 DEG C of reaction 3 ~ 9h; Add 1 ~ 20 weight part (methyl) vinylformic acid, 7.8 ~ 50 weight parts (methyl) acrylate monomer and 0.5 ~ 3 weight part initiator, 70 ~ 90 DEG C of reaction 3 ~ 9h, obtain long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion.
Described anionic emulsifier refers to that atomic number of alkyl carbon is at the chain alkyl Phenylsulfonic acid of 8 ~ 25, is preferably Witco 1298 Soft Acid or cetyl benzenesulfonic acid.
Described nonionic emulsifying agent refers at least one in alkylphenol-polyethenoxy base ether, Voranol EP 2001, polyoxyethylene sorbitol acid anhydride oleic acid ester and polyoxyethylene sorbitol acid anhydride stearate.
The described siloxanes containing unsaturated double-bond refers at least one in allyltrimethoxysilanis, allyltriethoxysilane and gamma-methyl allyl acyloxypropyl trimethoxysilane.
At least one in the described different monooctyl ester of (methyl) acrylate monomer methacrylic acid, butyl acrylate, ethyl propenoate, n-propyl, Propenoic acid, 2-methyl, isobutyl ester, methyl methacrylate, methyl acrylate, vinylformic acid, β-dimethyl-aminoethylmethacrylate, n-BMA and glycidyl methacrylate.
Described inorganic silicate refers at least one in water glass and potassium silicate.
The degree Beaume of described inorganic silicate is 0.35, modulus is 1.5 ~ 5.6.
Described initiator refers to persulphate, is preferably ammonium persulphate or Potassium Persulphate.
Described defoamer refers to mineral oil defoaming agent or polysiloxane defoamer; Be preferably metallic soap of stearic acid, HT-610.
Described dispersion agent refers to acrylate, polyacrylate or carboxylic acid sodium salt; Be preferably HT-5050 or sodium polyacrylate.
Described thickening material refers at least one in Natvosol, methylcellulose gum, Vltra tears and Xylo-Mucine.
Described antifreezing agent refers at least one in propylene glycol, ethylene glycol and ethanol.
Described film coalescence aid refers at least one in Lauryl Alcohol ester, propylene glycol phenylate and phenylcarbinol.
Described filler refers at least one in talcum powder and light calcium carbonate.
Above-mentioned coating can also add titanium dioxide or colorant as required.The consumption of described titanium dioxide and colorant is 0 ~ 40 weight part.
The preparation method of the above-mentioned organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion, comprise following concrete steps: inorganic silicate 100 weight part, water 4 ~ 100 weight part, defoamer 0.5 ~ 5 weight part, dispersion agent 0.5 ~ 5 weight part, thickening material 0.5 ~ 5 weight part, antifreezing agent 0.5 ~ 4 weight part, film coalescence aid 0.5 ~ 5 weight part, filler 40 ~ 100 weight part closes dispersion, add the grinding of long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion 1 ~ 50 weight part more evenly, namely the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion is obtained.
Mechanism of the present invention is:
Long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion that the present invention uses is by introducing the organosilicon of long side chain, when (methyl) acrylic resin film forming, the organosilicon of long side chain is enriched in multipolymer surface, improve the water tolerance of coating, stain resistant, the coating therefore prepared has good performance.
The present invention, relative to prior art, has following advantage and beneficial effect:
Organic inorganic hybridization coating for internal and external wall of the present invention, owing to employing modification (methyl) acrylate polymer emulsion, has water-fast, wear-resisting, acidproof, alkaline-resisting, easy construction, anchor effect is good, film forming is stable, the advantage such as film forming excellent appearance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: containing the preparation of the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion
(1) preparation of long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion:
Agitator is being housed, thermometer, 110g deionized water is added in the reaction vessel of prolong and nitrogen access tube, 4g Witco 1298 Soft Acid (DBSA), 2g alkylphenol-polyethenoxy base ether (NP-9), 37.5g octamethylcyclotetrasiloxane (D4), pass into nitrogen, 9h is reacted at 70 DEG C, then 2.5g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH-570) is added, air cooling discharging after 70 DEG C of reaction 9h, then 2g methacrylic acid is added, 5.3g Isooctyl methacrylate, 2.5g Propenoic acid, 2-methyl, isobutyl ester, 0.5g ammonium persulphate (being dissolved in 10g deionized water), air cooling discharging after 70 DEG C of reaction 9h, obtain long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion.
(2) getting 100 weight part degree Beaume is 0.35, modulus is the sodium silicate aqueous solution of 1.5, 20 weight parts waters, 20 weight part titanium dioxides, 20 weight part talcum powder, 20 weight part light calcium carbonates, 0.5 weight part metallic soap of stearic acid, 1.5 weight part Natvosols, 0.5 weight part HT-5050, 0.5 parts by weight of propylene glycol, 1 weight part Lauryl Alcohol ester, put into high speed dispersor (model: GZ102.S, power: 120W) middle dispersion 60min, then skin grinder is gone to, add long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion that 2 weight part steps (1) prepare again, ground and mixed, namely the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion is obtained.
Embodiment 2: containing the preparation of the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion
(1) preparation of long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion:
Agitator is being housed, thermometer, 130g deionized water is added in the reaction vessel of prolong and nitrogen access tube, 5g Witco 1298 Soft Acid (DBSA), 2.5g alkylphenol-polyethenoxy base ether (NP-9), 25g octamethylcyclotetrasiloxane (D4), pass into nitrogen, 5h is reacted at 80 DEG C, then 6.0g allyltriethoxysilane is added, air cooling discharging after 80 DEG C of reaction 5h, then 10g methacrylic acid is added, 20.5g ethyl propenoate, 7.2g methyl acrylate, 1.8g Potassium Persulphate (being dissolved in 10g deionized water), air cooling discharging after 80 DEG C of reaction 5h, obtain long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion.
(2) getting 100 weight part degree Beaume is 0.35, modulus is the potassium silicate aqueous solution of 3.5, 50 weight parts waters, 20 weight part of pigment, 30 weight part talcum powder, 35 weight part light calcium carbonates, 2.5 weight part metallic soap of stearic acid, 3 weight part methylcellulose gum, 1.5 weight part HT-5050, 2.5 weight part ethylene glycol, 3.5 parts by weight of propylene glycol phenylates, put into high speed dispersor (as described in Example 1) dispersion 60min, then skin grinder is gone to, add long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion that 20 weight part steps (1) prepare again, ground and mixed, namely the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion is obtained.
Embodiment 3: containing the preparation of the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion
(1) preparation of long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion:
Agitator is being housed, thermometer, 150g deionized water is added in the reaction vessel of prolong and nitrogen access tube, 5g Witco 1298 Soft Acid (DBSA), 4g alkylphenol-polyethenoxy base ether (NP-9), 15g octamethylcyclotetrasiloxane (D4), pass into nitrogen, 3h is reacted at 90 DEG C, then 7.5g allyltrimethoxysilanis is added, air cooling discharging after 90 DEG C of reaction 3h, then 20g vinylformic acid is added, 38.5g n-propyl, 11.5g vinylformic acid, 3.0g Potassium Persulphate (being dissolved in 10g deionized water), air cooling discharging after 90 DEG C of reaction 3h, obtain long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion.
(2) getting 100 weight part degree Beaume is 0.35, modulus is the sodium silicate aqueous solution of 5.6, 100 weight parts waters, 40 weight part titanium dioxides, 40 weight part of pigment, 40 weight part talcum powder, 50 weight part light calcium carbonates, 5 weight part HT-610, 5 weight part Vltra tearss, 5 parts by weight of polypropylene acid sodium, 4 parts by weight of ethanol, 5 weight part phenylcarbinols, put into high speed dispersor (as described in Example 1) dispersion 60min, then skin grinder is gone to, add long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion that 50 weight part steps (1) prepare again, ground and mixed, namely the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion is obtained.
Embodiment 4: containing the performance measurement of the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion
What prepare embodiment 1 ~ 3 carries out performance measurement containing the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion, testing standard and the results are shown in Table 1.
The performance index of table 1 organic inorganic hybridized paint
Above all technical all higher than the requirement of national standard to acceptable end product, and to be better than on market sell the performance of coating products.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1., containing an organic inorganic hybridized paint for modification (methyl) acrylate polymer emulsion, it is characterized in that being made up of the component of following weight parts:
Described long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion, has the structure as formula I:
Wherein R
1, R
5, R
6hydrogen or methyl;
R
2-CH
2-or-COOCH
2cH
2cH
2-;
R
3, R
4be methoxyl group, oxyethyl group, hydroxyl or
R
7to be carbon number be 1 ~ 10 saturated alkane or hydrogen;
N
1, n
2, n
3, n
4, n
5it is the natural number can divided exactly by 4 in 4 ~ 2000;
Described inorganic silicate refers at least one in water glass and potassium silicate; The degree Beaume of described inorganic silicate is 0.35, modulus is 1.5 ~ 5.6.
2. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 1, it is characterized in that: described long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion is prepared by following methods: by 80 ~ 150 weight parts waters, 3 ~ 6 weight part anionic emulsifiers, 2 ~ 4 weight part nonionic emulsifying agents and the mixing of 8 ~ 37.5 weight part octamethylcyclotetrasiloxanes, nitrogen protection, 70 ~ 90 DEG C of reaction 3 ~ 9h, add the siloxanes of 2.5 ~ 7.5 weight parts containing unsaturated double-bond, 75 ~ 90 DEG C of reaction 3 ~ 9h, add 1 ~ 20 weight part (methyl) vinylformic acid, 7.8 ~ 50 weight parts (methyl) acrylate monomer and 0.5 ~ 3 weight part initiator, 70 ~ 90 DEG C of reaction 3 ~ 9h, obtain long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion.
3. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 2, is characterized in that: described anionic emulsifier refer to atomic number of alkyl carbon 8 ~ 25 chain alkyl Phenylsulfonic acid; Described nonionic emulsifying agent refers at least one in alkylphenol-polyethenoxy base ether, Voranol EP 2001, polyoxyethylene sorbitol acid anhydride oleic acid ester and polyoxyethylene sorbitol acid anhydride stearate; The described siloxanes containing unsaturated double-bond refers at least one in allyltrimethoxysilanis, allyltriethoxysilane and gamma-methyl allyl acyloxypropyl trimethoxysilane; At least one in the described different monooctyl ester of (methyl) acrylate monomer methacrylic acid, butyl acrylate, ethyl propenoate, n-propyl, Propenoic acid, 2-methyl, isobutyl ester, methyl methacrylate, methyl acrylate, vinylformic acid, β-dimethyl-aminoethylmethacrylate, n-BMA and glycidyl methacrylate.
4. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 2, is characterized in that: described initiator refers to persulphate; Described defoamer refers to mineral oil defoaming agent or polysiloxane defoamer.
5. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 1, is characterized in that: described dispersion agent refers to acrylate, polyacrylate or carboxylic acid sodium salt.
6. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 1, is characterized in that: described thickening material refers at least one in Natvosol, methylcellulose gum, Vltra tears and Xylo-Mucine.
7. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 1, is characterized in that: described antifreezing agent refers at least one in propylene glycol, ethylene glycol and ethanol; Described film coalescence aid refers at least one in Lauryl Alcohol ester, propylene glycol phenylate and phenylcarbinol; Described filler refers at least one in talcum powder and light calcium carbonate.
8. the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion according to claim 2, is characterized in that: described initiator refers to ammonium persulphate or Potassium Persulphate; Described dispersion agent refers to HT-5050 or sodium polyacrylate.
9. one kind contains the preparation method of the organic inorganic hybridized paint of modification (methyl) acrylate polymer emulsion according to any one of claim 1 ~ 8, it is characterized in that comprising following concrete steps: inorganic silicate 100 weight part, water 4 ~ 100 weight part, defoamer 0.5 ~ 5 weight part, dispersion agent 0.5 ~ 5 weight part, thickening material 0.5 ~ 5 weight part, antifreezing agent 0.5 ~ 4 weight part, film coalescence aid 0.5 ~ 5 weight part, filler 40 ~ 100 weight part blending dispersion, add the grinding of long-chain siloxy vinylsiloxane modification (methyl) acrylate polymer emulsion 1 ~ 50 weight part more evenly, namely the organic inorganic hybridized paint containing modification (methyl) acrylate polymer emulsion is obtained.
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| CN110023424A (en) * | 2016-10-20 | 2019-07-16 | 通用线缆技术公司 | Durable application composition and the coating formed by it |
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| WO2016161586A1 (en) * | 2015-04-09 | 2016-10-13 | Rhodia Operations | Water based composition comprising light diffusion particles and a siloxane-modified acrylic resin |
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