CN105384864A - Room temperature multiple self-crosslinking nano acrylate copolymer emulsion and preparation method and water-based woodenware paint using emulsion as base material - Google Patents

Room temperature multiple self-crosslinking nano acrylate copolymer emulsion and preparation method and water-based woodenware paint using emulsion as base material Download PDF

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CN105384864A
CN105384864A CN201510957083.8A CN201510957083A CN105384864A CN 105384864 A CN105384864 A CN 105384864A CN 201510957083 A CN201510957083 A CN 201510957083A CN 105384864 A CN105384864 A CN 105384864A
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emulsion
room temperature
self
monomer
crosslinking
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CN105384864B (en
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田海水
李成林
田海宁
王淑柳
孙志勇
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HENGSHUI XINGUANG CHEMICAL CO Ltd
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HENGSHUI XINGUANG CHEMICAL CO Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C08K9/00—Use of pretreated ingredients
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
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    • C08L2312/00—Crosslinking

Abstract

The invention discloses a room temperature multiple self-crosslinking nano acrylate copolymer emulsion and a preparation method thereof and water-based woodenware paint using the emulsion as a base material, preparation synthesis components of the room temperature multiple self-crosslinking nano acrylate copolymer emulsion include vinyl-unsaturated carboxylic acid, methacrylate, acrylate, styrene, a modified SiO2 and acrylate monomer dispersion liquid, a crosslinking monomer A, vinyl siloxane, a crosslinking monomer B and the like, and by use of three methods of introduction of three components of modified nano-SiO2, the cross linking monomers and the vinyl siloxane for crosslinking through the preparation of the room temperature multiple self-crosslinking nano acrylate copolymer emulsion, the three crosslinking methods are in mutual coordination, so that finally the water-based woodenware paint prepared from the emulsion as the base material forms a dense protective film, and has excellent water resistance, alcohol resistance, scratch resistance, high temperature after-tack resistance and relatively high hardness, and the paint film properties can be comparable to that of solvent-based furniture paint.

Description

A kind of room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion and preparation method thereof and the aqueous woodware paint being base-material with this emulsion
Technical field
The aqueous woodware paint that the present invention relates to a kind of emulsion and be base-material with this emulsion, the aqueous woodware paint particularly relating to the multiple self-crosslinking acrylic ester copolymer emulsion of a kind of room temperature and be base-material with this emulsion, belongs to environmental protection base Material Field.
Background technology
China is manufacture type big country, along with the swelling property of economy develops, the national outburst of the severe haze of environmental pollution and air is the serious threat compatriots environment of depending on for existence, and the VOC in coating and tackiness agent causes the crime of the serious haze of air to hang down chief culprit, is the most important thing causing haze.Although the over-all properties at present after wood lacquer Water-borne modification is still not as good as traditional solvent-thinned paint, but because it is pollution-free, Environmental Safety and meet national environmental protection policy, become the inevitable development trend of wood lacquer, especially in the end of the year 2014, China has promulgated that the new legislation of coating industry and new legislation are after coming into effect on February 1st, 2015, the Water-borne modification of water-borne coatings or coating has become the key of Enterprise's Sustainable Development, and former solvent based coating enterprise will progressively be eliminated.Numerous city is also corresponding has promulgated stricter regulation, solvent based coating and Solvent Adhesive are tightly controlled use, therefore develop excellent combination property, substitute the water-miscible paint resin of traditional solvent-borne wood lacquer and have boundless application prospect and social benefit.
The research and development of current aqueous woodware paint base resin material and application are still based on emulsified acrylic acid ester copolymer, compared with solvent wood coatings, water-borne wood coating all has a certain distance in coating film gloss degree, fullness ratio, hardness, scratch resistance and wear resistance etc., this is also the major reason always restricting water-borne wood coating development, therefore how to improve the gordian technique factor that the performances such as the hardness of emulsified acrylic acid ester copolymer, scratch resistance, wear resistance, gloss and rate of drying become current wood lacquer Water-borne modification.The emulsion that in patent CN201410238123, simple diacetone-acryloamide(DAA)/adipic dihydrazide cross-linking system is obtained, because dosage of crosslinking agent can not be too large, cause cross-linking density low, thus the hardness of the wood lacquer obtained with this type of emulsion only arrives HB level.Patent CN200910187305 relate to a kind of core-shell emulsion, wherein add aqueous woodware paint prepared by vinylsiloxane at shell, but final hardness also can only reach H level, far below the requirement of Wooden furniture paint to hardness.Even if the performance such as hardness, scratch resistance of the aqueous woodware paint acrylate copolymer emulsion that DSM N. V. leading in the world, the Dow Chemical Company are commercially available is also not as good as traditional solvent-borne type wood lacquer.
Due to Nano-meter SiO_2 2high reaction activity, high-specific surface area and excellence thixotropy, cause it to become paint field and apply maximum a kind of nano materials.Nano-meter SiO_2 2the hardness of organic polymer can be improved in coating, improve its wear resistance, scratch resistance, ultravioletlight screening performance and even thixotropy become industry common recognition.But how powder nanometer silicon-dioxide realizes good dispersion in water-borne coatings is a worldwide difficult problem always.Therefore, a lot of R&D institution is all in the exploitation being devoted to in-situ nano enhancement techniques, namely how in acrylic ester emulsion polymerization process, to produce nanometer titanium dioxide silicon structure on the spot, or how to prepare the developing direction that emulsion-type nano silicon composite dispersion becomes coating industry.Show after deliberation, in aqueous wood lacquer latex, introduce Nano-meter SiO_2 2preparation takes into account organic and nano-composite emulsion that is inorganic nature, realizes Nano-meter SiO_2 2good distribution in acrylic ester polymer, obtains high rigidity, high transparency, hydrophobic by force, the high heat-resisting wood protection material waiting excellent combination property.
The reasonable application of crosslinking technological in coating simultaneously is also a kind of powerful measure improving wood lacquer paint film over-all properties.Introduce in polymer molecular chain can be cross-linked function monomer later, after emulsion has adjusted pH value, add cross-linking monomer again, along with system pH reduces gradually, mutually merge between latex particle, function monomer generation self-crosslinking in cross-linking monomer and polymer molecular chain, the mode of this self-crosslinking considerably improves hardness of paint film, scratch resistance capability.If but apply unreasonable, the internal stress of paint film and base material can be caused to increase, not only loss of adhesion, water-resistant capacity also together with time decline.
Summary of the invention
For solving above technical problem, multiple self-crosslinking acrylic ester copolymer emulsion of a kind of room temperature and preparation method thereof is provided in the embodiment of the present invention, and with this acrylate copolymer emulsion for aqueous woodware paint prepared by base-material, finally obtain high rigidity, high transparency, hydrophobic by force, the high heat-resisting aqueous woodware paint waiting excellent combination property.
A kind of room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion provided in the embodiment of the present invention, it prepares synthesis by following weight part material:
Deionized water 40 ~ 50 parts; Emulsifying agent A0.1 ~ 1 part; Emulsifying agent B0.1 ~ 1 part; PH value buffer reagent 0.02 ~ 0.09 part; Initiator 0.3 part; Vinyl unsaturated carboxylic acid 0.3 ~ 0.9 part; Methacrylic ester 25 ~ 35 parts; Acrylate 4 ~ 6 parts; Vinylbenzene 4 ~ 6 parts; Modification SiO 2with the dispersion liquid 8 ~ 12 parts of acrylate monomer; Cross-linking monomer A0.3 ~ 1.0 part; Vinylsiloxane 0.1 ~ 0.9 part; Cross-linking monomer B0.3 ~ 1.0 part; Tertbutyl peroxide 0.04 part; Sodium bisulfite 0.04 part; Defoamer 0.05 part; Sanitas 0.05 part and ammoniacal liquor 1 part.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described modification SiO 2take tetraethoxy as silica precursor with the dispersion liquid of acrylate monomer, acrylate monomer is dispersion medium, dilute sulphuric acid is catalyzer, and γ-methacryloxypropyl trimethoxy silane is as active graft modification agent, and stirring at room temperature hydrolysis in 24 hours is obtained.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described cross-linking monomer A is selected from one or more in diacetone-acryloamide(DAA), glycidyl methacrylate, etheric acid methacrylic acid glycol ester; Described cross-linking monomer B selects the one in hexanodioic acid two hydrazine, carbon acid dihydrazide, careless acid dihydrazide, succinic acid hydrazide ii.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described vinylsiloxane is selected from the one in vinyltriethoxysilane, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described vinyl unsaturated carboxylic acid is selected from the one in vinylformic acid, methacrylic acid, methylene-succinic acid.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described methacrylic ester is selected from the one in butyl methacrylate, methyl methacrylate, Octyl methacrylate.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described acrylate is selected from the one in butyl acrylate, ethyl propenoate, Octyl acrylate.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described emulsifying agent A is anion surfactant, be selected from sodium laureth sulfate, alkylphenol polyoxyethylene ammonium sulfate, Witco 1298 Soft Acid, Witco 1298 Soft Acid ammonium, sodium laurate, ammonium laurate, sodium lauryl sulphate, ammonium lauryl sulfate, alkyl diphenyl ether disodium sulfonate salt, alkyl polyoxyethylene acyl sodium sulfonate, tributyl phenol sodium sulfonate of ethoxylated, one in allyl polyethenoxy ether derivative ammonium sulfate and allyl polyethenoxy ether ammonium sulfate, described emulsifying agent B is selected from the one in alkyl polyoxyethylene ether series environment-friendly type nonionic emulsifying agent, alkyl alcohol ethoxylates series, the mixture of alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene.
Preferably, above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, wherein, described pH value regulator is be selected from the one in sodium bicarbonate, bicarbonate of ammonia, SODIUM PHOSPHATE, MONOBASIC; Described initiator is be selected from the one in ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
Prepare the method for above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, comprise the steps:
(1) modification SiO is prepared 2with the dispersion liquid of acrylate monomer: in beaker, take emulsifying agent A and deionized water, stir with glass stick and fully dissolve, obtain emulsifier aqueous solution; Then take appropriate tetraethoxy, γ-methacryloxypropyl trimethoxy silane, be dissolved in the mix monomer of methyl methacrylate and butyl acrylate, obtain oil mixture; Then under the vigorous stirring of high-shear homogenizer, described oil mixture is dripped in above-mentioned emulsifier aqueous solution, and use dilute sulphuric acid adjust ph, continue high speed dispersion 30min, transfer in the ground Florence flask of band plug thereupon, at room temperature magnetic agitation 24 hours, makes it fully react, and obtains modification SiO 2with the dispersion liquid of acrylate monomer;
(2) nano-composite emulsion is prepared: add deionized water at four mouthfuls of round-bottomed flasks, then be placed in stirring in water bath and heat up, when temperature reaches 75 DEG C, the Potassium Persulphate getting 2/5 reaction consumption is dissolved in 5g deionized water, add round-bottomed flask, in 10min, at the uniform velocity drip the modification SiO of prepared by step (1) 1/5 subsequently 2enter round-bottomed flask with the dispersion liquid of acrylate monomer, when blue light appears in reaction solution in flask, the Potassium Persulphate of remaining 3/5 is dissolved in 5g deionized water, subsequently by itself and remaining modification SiO 2be added dropwise in round-bottomed flask with the dispersion liquid of acrylate monomer simultaneously, drip in about 3 hours, be then incubated 1 hour, obtained nano-composite emulsion;
(3) prepare monomer pre-emulsion: deionized water, emulsifying agent A, emulsifying agent B and vinyl unsaturated carboxylic acid, methacrylic ester, acrylate, vinylbenzene and linking agent A are dropped into monomer pre-emulsification tank successively, high-speed stirring emulsification forms monomer pre-emulsion in 1 hour;
(4) room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion is prepared: in polymeric kettle, add deionized water, nano-composite emulsion prepared by the step (2) of measuring, open and stir, be warming up to 80 DEG C-84 DEG C, after stablizing 15min, drip monomer pre-emulsion and the ammonium persulfate solution of preparation in step (3) simultaneously, in time being added drop-wise to residual monomer pre-emulsion 1/5, stop dripping; Add after vinylsiloxane monomer stirs 10min and continue to drip, control whole time for adding in 210min-240min, dropping temperature controls at 78 DEG C-82 DEG C; Under dropping temperature, 1 hour is incubated after dropwising; 60 DEG C-70 DEG C are cooled to after insulation, add the tertbutyl peroxide aqueous solution, drip aqueous solution of sodium bisulfite after 10min, time for adding is 30min, dropping temperature controls at 63 DEG C-67 DEG C, dropwise follow-up continuation of insurance temperature 30min, be finally cooled to less than 40 DEG C, regulate pH to 7-9 with ammoniacal liquor, the crosslinking agent B adding metering stirs 30min, after adding defoamer, sanitas again, filter with 200-500 mesh filter screen, preparation room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion.
With the aqueous woodware paint that above-mentioned room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion is prepared for base-material, the composition of this aqueous woodware paint comprises each component of following weight part:
Deionized water 16 parts; Emulsion 75 parts; Wetting agent 0.3 part; Flow agent 0.3 part; Dipropylene 4 parts; Dipropylene glycol methyl ether 4 parts; Thickening material 0.3 part; Defoamer 0.05 part; Sanitas 0.05 part; Dispersion agent 0.1 part; Scratching resistant 2.5 parts and Zinic stearas 5 parts.
Silicone hydroxyl condensation cross-linking technology combines with ketone hydrazine crosslinking technological by the present invention, and the introducing solved because of too much vinylsiloxane causes the remaining silicone hydroxyl too much problem that water tolerance declines, wet adhesion declines; The problem of the resistance to water-white ability that the introducing simultaneously solving too much diacetone-acryloamide(DAA) causes; The silicon-dioxide of the inner hydrolysis of micelle of room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion breast floats on surface on the procedure division of aqueous woodware paint film forming, due to the singularity of silicon, its existence can strengthen the hardness of aqueous woodware paint paint film, easily grinability; Preparing polymerizable self-cross linking monomer in nano acrylic ester copolymer emulsion breast process, polymer chain formation can be introduced there is elastic crosslinkable polymer, crosslinked elastomeric polymer i.e. easy distortion but also have good rebound resilience, so the self-crossing emulsion film of nano acrylic ester copolymer emulsion of the present invention has higher adhesion strength.
Relative to prior art, the present invention has following beneficial effect:
(1) in room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, Nano-meter SiO_2 is introduced 2preparation has organic and ACRYLIC EMULSION that is inorganic nature concurrently, then with this emulsion for aqueous woodware paint prepared by base-material, the wood lacquer paint film high rigidity finally obtained, high transparency, hydrophobic by force, high heat-resisting;
(2) in room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion polymerization process, cross-linking monomer is introduced, then with this emulsion for aqueous woodware paint prepared by base-material, occur further crosslinked in wood lacquer film process and form fine and close protective membrane, further increasing the hardness of wood lacquer paint film, water tolerance, resistance to alcohol, high temperature resistance after-tack and scratch resistant ability;
(3) vinylsiloxane is introduced in the later stage of room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion polymerization, then with this emulsion for aqueous woodware paint prepared by base-material, in wood lacquer film process, unhydrolysed part siloxane bond and pigment, base material and the siloxane bond condensation of self, improve the cross-linking density of wood lacquer paint film further;
(4) three kinds of cross-linking methods more than run through in the preparation of room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, three kinds of crosslinking technologicals are worked in coordination with mutually; finally with this emulsion for aqueous woodware paint prepared by base-material forms fine and close protective membrane; have excellent water-fast, resistance to alcohol, scratch resistance, high temperature resistance after-tack and higher hardness, paint film property can compare favourably with solvent-borne type furniture lacquer.
Embodiment
Below in conjunction with the form in the embodiment of the present invention and embodiment, carry out clear, complete description to the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The present invention with tetraethoxy (TS) for SiO 2precursor, acrylate (BA) monomer is dispersion medium, and γ-methacryloxypropyl trimethoxy silane (A174) is active graft modification agent, and obtained under dilute sulphuric acid catalysis take acrylate as the SiO of external phase 2/ acrylate monomer dispersion liquid (TM), then with this dispersion liquid for seed monomer carries out letex polymerization, obtained take polyacrylic ester as the nano-composite emulsion of carrier, and then using this nano-composite emulsion as seed, add the mix monomer of acrylate, methacrylic ester, vinylbenzene, cross-linking monomer, vinyl unsaturated carboxylic acid, just can obtain a kind of room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion through seeded emulsion polymerization; And with this acrylate copolymer emulsion for aqueous woodware paint prepared by base-material, finally obtain high rigidity, high transparency, and hydrophobic by force, the high heat-resisting aqueous woodware paint waiting excellent combination property.
Embodiment 1
Preparation room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, each amounts of components is as shown in table 1:
Table 1
(1) prepare monomer pre-emulsion: methacrylic acid, methyl methacrylate, butyl acrylate, vinylbenzene and linking agent A described in deionized water, emulsifying agent A, emulsifying agent B and table 1 are dropped into monomer pre-emulsification tank successively, high-speed stirring emulsification forms monomer pre-emulsion in 1 hour;
(2) room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion is prepared: add deionized water to polymeric kettle, the nano-composite emulsion of metering, open and stir, be warming up to 80 DEG C-84 DEG C, after stablizing 15min, drip monomer pre-emulsion and the ammonium persulfate solution of preparation in step (1) simultaneously, in time being added drop-wise to residual monomer pre-emulsion 1/5, stop dripping; Add after vinyltriethoxysilane monomer stirs 10min and continue to drip, control whole time for adding in 210min-240min, dropping temperature controls at 78 DEG C-82 DEG C; Under dropping temperature, 1 hour is incubated after dropwising; 60 DEG C-70 DEG C are cooled to after insulation, add the tertbutyl peroxide aqueous solution, drip aqueous solution of sodium bisulfite after 10min, time for adding is 30min, dropping temperature controls at 63 DEG C-67 DEG C, dropwise follow-up continuation of insurance temperature 30min, be finally cooled to less than 40 DEG C, regulate pH to 7-9 with ammoniacal liquor, the crosslinking agent B adding metering stirs 30min, after adding defoamer, sanitas again, filter with 200-500 mesh filter screen, preparation room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion.
The former room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion preparation method of embodiment 2-6 with embodiment 1, concrete raw material and consumption as shown in table 1.Wherein emulsifying agent A can also select one or more in sodium laureth sulfate, alkylphenol polyoxyethylene ammonium sulfate, Witco 1298 Soft Acid, Witco 1298 Soft Acid ammonium, sodium laurate, ammonium laurate, ammonium lauryl sulfate, alkyl diphenyl ether disodium sulfonate salt, tributyl phenol sodium sulfonate of ethoxylated, allyl polyethenoxy ether derivative ammonium sulfate and allyl polyethenoxy ether ammonium sulfate; Emulsifying agent B can also select in the mixture of alkyl polyoxyethylene ether series environment-friendly type nonionic emulsifying agent, alkyl alcohol ethoxylates series, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene one or several; Cross-linking monomer A can also select etheric acid methacrylic acid glycol ester; Described cross-linking monomer B can also select in carbon acid dihydrazide, careless acid dihydrazide one or both.
Wherein, needed for the preparation of nano-composite emulsion described in embodiment 1-6, the weight consumption of each component is as shown in table 2 below:
Table 2
MMA BA TS A174 Emulsifying agent A Deionized water PPS Deionized water
30.00 30.00 15.00 2.00 3.50 65.00 0.5 170
The preparation method of nano-composite emulsion is as follows:
(1) modification SiO is prepared 2with the dispersion liquid (TM) of acrylate monomer: in 100mL beaker, take emulsifying agent A3.50g and deionized water 65.00g, stir with glass stick and fully dissolve, obtain emulsifier aqueous solution; Then the tetraethoxy (TS) of 15.00g is taken, γ-the methacryloxypropyl trimethoxy silane (A174) of 2.00g is dissolved in the mix monomer of the methyl methacrylate (MMA) of 30.00g and the butyl acrylate (BA) of 30.00g, obtains oil mixture; Then under the vigorous stirring of high-shear homogenizer, described oil mixture is dripped in above-mentioned emulsifier aqueous solution, and use dilute sulphuric acid adjust ph, continue high speed dispersion 20min, transfer in the 150mL ground Florence flask of band plug thereupon, at room temperature magnetic agitation 24 hours, makes it fully react, and obtains preparation modification SiO 2dispersion liquid with acrylate monomer, is denoted as TM;
(2) nano-composite emulsion is prepared: add 160g deionized water at 250mL tetra-mouthfuls of round-bottomed flasks, then be placed in stirring in water bath and heat up, when temperature reaches 75 DEG C, the Potassium Persulphate (PPS) getting 2/5 is dissolved in 5g deionized water, add round-bottomed flask, in 10min, at the uniform velocity drip the modification SiO of 1/5 2with the dispersion liquid (TM) of acrylate monomer, when there is blue light in question response liquid, the PPS of remaining 3/5 is dissolved in 5g deionized water, subsequently itself and remaining TM are added dropwise in round-bottomed flask simultaneously, drip in about 3 hours, then be incubated 1 hour, form the nano-composite emulsion of slaking, this emulsion solid content about 20%.
Embodiment 7
With the multiple self-crosslinking acrylic ester copolymer emulsion of room temperature of above-described embodiment 1-6 synthesis for aqueous woodware paint prepared by base-material.The concrete component of described aqueous woodware paint and consumption as shown in table 3.
Table 3
(1) in a stirring tank, add the emulsion of the formula ratio that it is as shown in the table, dispersion agent, wetting agent, flow agent, scratching resistant, Zinic stearas join in above-mentioned stirring tank, stir 10min with rotating speed 900r/min, obtain uniform dispersion;
(2) in another stirring tank, get the film coalescence aid dipropylene glycol methyl ether (DPM) of formula ratio, dipropylene (DPnB), deionized water and thickening material RS-8W (polyurethane-modified class) join in stirring tank and stir 10min, obtain mixed solution;
(3) mixed solution in stirring tank in step (2) is slowly joined in step (1) stirring tank, with rotating speed 700r/min, add while stirring, stir 10min; Finally add defoamer, again stir 10min, obtain uniform aqueous woodware paint, filter and package.
Embodiment 8-12 preparation with room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion for base-material prepares the preparation method of aqueous woodware paint with embodiment 7, concrete raw material and consumption as shown in table 3.
Its performance test results parameter of room temperature prepared by embodiment of the present invention 1-6 multiple self-crosslinking nano acrylic ester copolymer emulsion is in table 4, and the aqueous woodware paint performance test results prepared for base material with this emulsion is as shown in table 5.
Table 4
Table 5
From table 4 and table 5, no matter the aqueous woodware paint adopting multiple self-crosslinking technology to prepare is pencil hardness, hardness should be abraded and all sell market product than now, simultaneously also sell market product than now good for the wear resisting property of paint film, fix the amount of seed emulsion in addition, the collocation of change cross-linking monomer A and B and vinylsiloxane, no matter how cross-linking monomer A and B changes, to arrange in pairs or groups the emulsion of synthesizing with γ-methacryloxypropyl trimethoxy silane, the hardness of final paint film is all at 3H, there is the water-fast of excellence simultaneously, resistance to boiling water scalds and does not whiten, resistance to alcohol does not whiten, wear resistance is high, antiblocking and higher gloss and fullness ratio, suitable with solvent-borne type furniture paint performance.

Claims (10)

1. a room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion, is characterized in that, prepares synthesis by following weight part material:
Deionized water 40 ~ 50 parts; Emulsifying agent A0.1 ~ 1 part; Emulsifying agent B0.1 ~ 1 part; PH value buffer reagent 0.02 ~ 0.09 part; Ammonium persulphate 0.3 part; Vinyl unsaturated carboxylic acid 0.3 ~ 0.9 part; Methacrylic ester 25 ~ 35 parts; Acrylate 4 ~ 6 parts; Vinylbenzene 4 ~ 6 parts; Modification SiO 2with the dispersion liquid 8 ~ 12 parts of acrylate monomer; Cross-linking monomer A0.3 ~ 1.0 part; Vinylsiloxane 0.5 ~ 0.9 part; Cross-linking monomer B0.3 ~ 1.0 part; Tertbutyl peroxide 0.04 part; Sodium bisulfite 0.04 part; Defoamer 0.05 part; Sanitas 0.05 part and ammoniacal liquor 1 part.
2. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, is characterized in that, described modification SiO 2take tetraethoxy as silica precursor with the dispersion liquid of acrylate monomer, acrylate monomer is dispersion medium, dilute sulphuric acid is catalyzer, and γ-methacryloxypropyl trimethoxy silane is as active graft modification agent, and stirring at room temperature hydrolysis in 24 hours is obtained.
3. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, it is characterized in that, described cross-linking monomer A is selected from the one in diacetone-acryloamide(DAA), glycidyl methacrylate, etheric acid methacrylic acid glycol ester; Described cross-linking monomer B selects the one in hexanodioic acid two hydrazine, carbon acid dihydrazide, careless acid dihydrazide, succinic acid hydrazide ii.
4. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, it is characterized in that, described vinylsiloxane is selected from the one in vinyltriethoxysilane, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane.
5. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, is characterized in that, described vinyl unsaturated carboxylic acid is selected from the one in vinylformic acid, methacrylic acid, methylene-succinic acid.
6. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, is characterized in that, described methacrylic ester is selected from the one in butyl methacrylate, methyl methacrylate, Octyl methacrylate.
7. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, is characterized in that, described acrylate is selected from the one in butyl acrylate, ethyl propenoate, Octyl acrylate.
8. room temperature according to claim 1 multiple self-crosslinking nano acrylic ester copolymer emulsion, it is characterized in that, described emulsifying agent A is anion surfactant, be selected from sodium laureth sulfate, sodium laurate, ammonium laurate, alkylphenol polyoxyethylene ammonium sulfate, Witco 1298 Soft Acid, Witco 1298 Soft Acid ammonium, sodium lauryl sulphate, ammonium lauryl sulfate, alkyl diphenyl ether disodium sulfonate salt, alkyl polyoxyethylene acyl sodium sulfonate, tributyl phenol sodium sulfonate of ethoxylated, one in allyl polyethenoxy ether derivative ammonium sulfate and allyl polyethenoxy ether ammonium sulfate, described emulsifying agent B is selected from the one in alkyl polyoxyethylene ether series environment-friendly type nonionic emulsifying agent, alkyl alcohol ethoxylates series, the mixture of alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene.
9. the method for the room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion of preparation according to any one of claim 1-8, is characterized in that, comprise the steps:
(1) modification SiO is prepared 2with the dispersion liquid of acrylate monomer: in beaker, take emulsifying agent A and deionized water, stir with glass stick and fully dissolve, obtain emulsifier aqueous solution; Then take appropriate tetraethoxy, γ-methacryloxypropyl trimethoxy silane, be dissolved in the mix monomer of methyl methacrylate and butyl acrylate, obtain oil mixture; Then under the vigorous stirring of high-shear homogenizer, described oil mixture is dripped in above-mentioned emulsifier aqueous solution, and use dilute sulphuric acid adjust ph, continue high speed dispersion 30min, transfer in the ground Florence flask of band plug thereupon, at room temperature magnetic agitation 24 hours, makes it fully react, and obtains modification SiO 2with the dispersion liquid of acrylate monomer;
(2) nano-composite emulsion is prepared: add deionized water at four mouthfuls of round-bottomed flasks, then be placed in stirring in water bath and heat up, when temperature reaches 75 DEG C, the Potassium Persulphate getting 2/5 reaction consumption is dissolved in 5g deionized water, add round-bottomed flask, in 10min, at the uniform velocity drip the modification SiO of prepared by step (1) 1/5 subsequently 2enter round-bottomed flask with the dispersion liquid of acrylate monomer, when blue light appears in reaction solution in flask, the Potassium Persulphate of remaining 3/5 is dissolved in 5g deionized water, subsequently by itself and remaining modification SiO 2be added dropwise in round-bottomed flask with the dispersion liquid of acrylate monomer simultaneously, drip in about 3 hours, be then incubated 1 hour, obtained nano-composite emulsion;
(3) prepare monomer pre-emulsion: deionized water, emulsifying agent A, emulsifying agent B and vinyl unsaturated carboxylic acid, methacrylic ester, acrylate, vinylbenzene and linking agent A are dropped into monomer pre-emulsification tank successively, high-speed stirring emulsification forms monomer pre-emulsion in 1 hour;
(4) room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion is prepared: in polymeric kettle, add deionized water, nano-composite emulsion prepared by the step (2) of measuring, open and stir, be warming up to 80 DEG C-84 DEG C, after stablizing 15min, drip monomer pre-emulsion and the ammonium persulfate solution of preparation in step (3) simultaneously, in time being added drop-wise to residual monomer pre-emulsion 1/5, stop dripping; Add after vinylsiloxane monomer stirs 10min and continue to drip, control whole time for adding in 210min-240min, dropping temperature controls at 78 DEG C-82 DEG C; Under dropping temperature, 1 hour is incubated after dropwising; 60 DEG C-70 DEG C are cooled to after insulation, add the tertbutyl peroxide aqueous solution, drip aqueous solution of sodium bisulfite after 10min, time for adding is 30min, dropping temperature controls at 63 DEG C-67 DEG C, dropwise follow-up continuation of insurance temperature 30min, be finally cooled to less than 40 DEG C, regulate pH to 7-9 with ammoniacal liquor, the crosslinking agent B adding metering stirs 30min, after adding defoamer, sanitas again, filter with 200-500 mesh filter screen, obtained room temperature multiple self-crosslinking nano acrylic ester copolymer emulsion.
10. with the aqueous woodware paint that the multiple self-crosslinking nano acrylic ester of the room temperature according to any one of claim 1-8 copolymer emulsion is prepared for base-material, it is characterized in that, the composition of this aqueous woodware paint comprises each component of following weight part:
Deionized water 16 parts; Emulsion 75 parts; Wetting agent 0.3 part; Flow agent 0.3 part; Dipropylene 4 parts; Dipropylene glycol methyl ether 4 parts; Thickening material 0.3 part; Defoamer 0.05 part; Sanitas 0.05 part; Dispersion agent 0.1 part; Scratching resistant 2.5 parts and Zinic stearas 5 parts.
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Pledgor: HENGSHUI XINGUANG NEW MATERIAL TECHNOLOGY Co.,Ltd.

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Denomination of invention: Room temperature multiple self crosslinking nano acrylate copolymer emulsion and preparation method thereof and waterborne wood paint based on the emulsion

Effective date of registration: 20210713

Granted publication date: 20190416

Pledgee: Renmin sub branch of Hengshui Bank Co., Ltd

Pledgor: HENGSHUI XINGUANG NEW MATERIAL TECHNOLOGY Co.,Ltd.

Registration number: Y2021130000015

PE01 Entry into force of the registration of the contract for pledge of patent right