CN104672403A - Environment-friendly silicon-acrylate emulsion and preparation method thereof - Google Patents
Environment-friendly silicon-acrylate emulsion and preparation method thereof Download PDFInfo
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- CN104672403A CN104672403A CN201510078512.4A CN201510078512A CN104672403A CN 104672403 A CN104672403 A CN 104672403A CN 201510078512 A CN201510078512 A CN 201510078512A CN 104672403 A CN104672403 A CN 104672403A
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Abstract
The invention discloses an environment-friendly silicon-acrylate emulsion with high color yield and high fastness, and a preparation method thereof. A few of existing silicon-acrylate emulsions are not environment-friendly, a few of existing silicon-acrylate emulsions are poor in fastness, a few of existing silicon-acrylate emulsions are light in color yield, and a few of existing silicon-acrylate emulsions are hard in hand feeling when being applied to textiles. The environment-friendly silicon-acrylate emulsion is formed by emulsion polymerization of an unsaturated acidic monomer, hydrocarbon unsaturated monomers, a double-bond type crosslinking monomer, an environment-friendly functional monomer, a complex monomer and a soft monomer under the action of an initiator, a polymerizable emulsifier, a modifier and a buffering agent in a water phase. According to the unsaturated acidic monomer, the emulsion stability and the coating (pigment) disperse capacity are improved; a good hand feeling can be realized by the hydrocarbon unsaturated monomers and the soft monomer; the brightening property of the polymer film can be greatly improved by the double-bond type crosslinking monomer and the complex monomer; and the fastness of the polymer film is improved by the environment-friendly functional monomer and the polymerizable emulsifier. The environment-friendly silicon-acrylate emulsion with high color yield and high fastness has excellent brightening property and softness and good fastness.
Description
Technical field
The present invention relates to chemical field, specifically a kind of high Dry Sack, high fastness environmental protection organosilicon crylic acid latex and preparation method thereof, can in the product such as application of paint stamp and coating.
Background technology
Acrylic ester emulsion wide material sources, with low cost, there is good film-forming property, intensity is high and cohesiveness is strong feature, and thermostability, photochemical stability and good in oxidation resistance, be thus widely used in the fields such as coating, tackiness agent, printing and dyeing, papermaking, leather; But acrylic ester emulsion has the shortcomings such as water tolerance, poor solvent resistance and low temperature become fragile, high temperature is clamminess.Organosilicon has excellent high temperature resistant, low-temperature performance, and the hydrophobicity of height, good ventilation property and superior weathering resistance, can improve the weak point of acrylic ester emulsion.Organic-silicon-modified acrylic ester emulsion is called as organosilicon crylic acid latex, has the advantage of acrylic ester emulsion and organic silicon emulsion concurrently, applies very extensive.
At present, domesticly in organosilicon crylic acid latex polymerization process, generally use low molecular weight emulsifier, still remain in emulsion after polymerization terminates.This emulsifying agent is normally attached to polymer beads sub-surface with physical adsorption way, reaches thermodynamic(al)equilibrium with its environment, thus stabilization of polymer particle, and do not participate in polyreaction directly.When environment exists certain stress, this thermodynamic(al)equilibrium can be destroyed, and emulsifier molecules desorb will occur, and result causes generation between polymer particle sticky also, makes the loss of stability of polymer latex.In latex film forming process, emulsifying agent residues among polymer solids with small molecules, easily moves to the surface of film, and this causes the water tolerance of coating and weathering resistance to be deteriorated to a certain extent.
For promoting the fastness of organosilicon crylic acid latex, mostly introduce n-methylolacrylamide or silicon-containing coupling reagents.Diazolidinyl Urea in the follow-up use of n-methylolacrylamide, inadequate environmental protection; And short chain vinylsiloxane hydrolytie polycondensation tendency in emulsion system is large, very easily produce gel, system technology stability and package stability is caused to reduce, also constrain the raising of silicone content simultaneously, improve limited to acrylic acid modified amplitude, therefore how to improve silicone content, reduce reactive silane hydrolytic crosslinking degree, obtaining high quality silicon acrylic emulsion just becomes popular research topic.Traditional solution between polymerization period, adds a large amount of emulsifying agent protected the polymkeric substance containing siloxanes; stablize with maintenance system; but a large amount of emulsifying agent is trapped in resin and the performances such as polymeric film gloss, sticking power, water tolerance, weathering resistance, scrub resistance can be caused again significantly to reduce; affect usability and ornamental, the emulsifying agent simultaneously in polymeric film also can slowly dissolve release and cause environmental pollution along with time lapse.Also the hydrolysis inhibitors such as similar BDO can be added, but this effect is also more limited, obtained emulsion long storage periods is poor, the introducing of BDO simultaneously also can reduce stability of emulsion and increase emulsion VOC (volatile organic matter), is unfavorable for environmental protection.
Publication number be CN103924458A patent discloses a kind of organosilicon crylic acid latex printing adhesive, relate to chemical technology field, key step is: 1) first purified water, the trimethyl carbinol and methyl alcohol are dropped in reactor and be uniformly mixed, be heated to 50-60 DEG C, obtained solution a is stand-by; 2) by nano titanium oxide, butyl acrylate, vegetable fibre, vinylformic acid and anionic ring-opening polymerization emulsion pass into solution a, stir, heat while stirring, reach 80-90 DEG C of insulation 2 hours to temperature, obtained solution b is stand-by; 3) hydrogen silicone oil, emulsifying agent and vinyl silicone oil are dropped in solution b, stir, stirring velocity remains on 3500r/min, and stir 30 minutes, obtained solution c is stand-by; 4) temperature of solution c controlled, at 40-45 DEG C, then to drip dimethyl formamide, dripped in 0.5 hour and terminate, be cooled to room temperature, obtained solution d is stand-by; 5) pH value of solution d is reconciled with ammoniacal liquor to neutral, discharging of coming, obtained tackiness agent.This invention introduces the materials such as the trimethyl carbinol, methyl alcohol, dimethyl formamide, be unfavorable for the environmental protection of textiles.
Publication number be CN103333284A patent discloses a kind of organosilicon crylic acid latex and the application as fabric finishing agent thereof, it is made up of the raw material of following weight proportion: 24 ~ 30 parts of butyl acrylates, 6 ~ 14 parts of methyl methacrylates, 0.15 ~ 1.0 part of initiator, 42.9 ~ 67.7 parts of deionized waters, 1.2 ~ 6 parts of compound emulsifying agents, 0.3 ~ 0.6 part of pH buffer reagent, 1 ~ 5 part of vinyltriethoxysilane and 0.1 ~ 0.3 part of ammoniacal liquor.The organosilicon crylic acid latex composition of this invention is simple, and organosilane monomer consumption is little, and emulsion solid content is higher but viscosity is lower, easy to use; As fabric finishing agent, fabric can be made to keep obtaining weightening finish, wrinkle resistance preferably under whiteness and powerful prerequisite, and in arrangement, preserve and the formaldehydeless release of use procedure, there is Be very effective, environmental protection, feature that cost is low.But due to the existence of free emulsifying agent and vinyltriethoxysilane, be difficult to the fastness (especially wet fastness) promoting polymeric film, can emulsion long-term stability also exist some problems.
Publication number is the preparation method that the patent of CN1431234 relates to without the hud typed organosilicon crylic acid latex of soap nano level.In preparation process, use reactive emulsifier, first the pure third core emulsion of nano level that obtained film forming properties is good, then active organosilicon compound and (methyl) acrylate generation shell emulsion is added, again under organic tin compound or titanic acid ester exist, complete the chemical bonding of silanol base three-dimensional, for the decoration of exterior wall of high-end residential community, villa, industrial building.But this emulsion be used for textiles then can feel very hard, the environmental protection of the heavy metal catalyst simultaneously introduced to textiles is fatal.
Summary of the invention
Technical problem to be solved by this invention overcomes the defect that above-mentioned prior art exists, provide a kind of cost low, color depth, soft type environmental protection organosilicon crylic acid latex that fastness is high.
For achieving the above object, the technical solution adopted in the present invention is: a kind of environmental protection organosilicon crylic acid latex, it is characterized in that, it is by unsaturated acid monomer, hydro carbons unsaturated monomer, double bond type cross-linking monomer, environment-protection functional monomer, complexing monomer and soft monomer are at initiator, polymerisable emulsifier, in aqueous phase, carry out letex polymerization under conditioning agent and buffer reagent effect to form, raw material dosage is counted by weight, it consists of: unsaturated acid monomer 2-12 part, hydro carbons unsaturated monomer 16-40 part, double bond type cross-linking monomer 4-20 part, environment-protection functional monomer 4-20 part, complexing monomer 20-28 part, soft monomer 20-28 part, initiator amount is 0.5-1.5 part, conditioning agent consumption is 0.2-0.6 part, buffer reagent consumption is 0.1-0.2 part, polymerisable emulsifier consumption is 1-3 part, deionized water consumption is 300-400 part,
Described complexing monomer is vinyl pyrrolidone (NVP), and described environment-protection functional monomer is the combination of unsaturated compound methacrylic ester with one or more functional group or acrylate functional monomer and silane coupling agent.
The present invention introduces unsaturated acid monomer in the component of multipolymer, can make polymer macromolecule in water, be ionized into carboxyl negative ion, and then originally curling molecular chain is extended in water, viscosity increases thereupon, has good water-soluble and dispersed simultaneously.Hydro carbons unsaturated monomer can make the molecular weight of polymkeric substance increase, and reduces its pressure permeability, to increase tinctorial yield.Double bond type cross-linking monomer can produce crosslinked action, thus makes polymkeric substance generate reticulated structure, significantly increases viscosity.The complexing monomer adopted can form the polymkeric substance with height " dissolving " ability, and this " dissolving " ability is because have high polar character and the amide group that can accept hydrogen bond in its molecular structure, has non-polar group again simultaneously.These two kinds of groups all have the ability of the corresponding group on " dissolving " small molecule component.The polymkeric substance that this ability makes complexing monomer be formed can with the compound formation solid-state complex of many materials, particularly hydroxyl, carboxyl, amino and other active hydrogen atom.These small-molecule substances are reduced by thermodynamic activity after complexing, and stability is improved.This molecular structure makes it with surfactivity, although its ability reducing surface or interfacial tension is less than low-molecular-weight surfactant, seepage force is also more weak, but its bulk shield ability formed the adsorption of solid surface and wetting ability the subject of knowledge and the object of knowledge, makes solids have excellent dispersion stabilization.It has the characteristic of macromolecular compound concurrently, so there is again the ability regulating dispersion or rheology of solution widely.In addition the hydrogen bond complex ability of it and many organic and inorganic compounds makes it have again excellent cohesion and stabilization, dispersed dye (pigment) effectively, promote utilization ratio, even if dyestuff (pigment) is less also can reach higher dye yield.
The present invention uses polymerisable emulsifier in the process of synthesis organosilicon crylic acid latex, compared with low molecular weight emulsifier, there is the emulsification group of hydrophilic and oleophilic simultaneously and can participate in radical polymerization functional group in the molecular structure of polymerisable emulsifier.In emulsion polymerization process, it not only plays emulsifying agent effect but also participate in the polyreaction of monomer and be attached on emulsion polymer molecular chain, be combined with covalent bonds instead of by physical adsorption with macromolecular chain, after reaction terminates, become a part for multipolymer, therefore to water, the stability of UV-light is improved greatly, after emulsion film forming, effectively can prevent the migration of emulsifying agent, the stability in storage of the organosilicon crylic acid latex obtained, Stability towards electrolytes, freeze-thaw stability, water tolerance, more excellent than with the organosilicon crylic acid latex of low molecular weight emulsifier synthesis of weathering resistance and tint retention.
For promoting the fastness of organosilicon crylic acid latex, and ensureing environmental protection (formaldehydeless, solvent-free), present invention employs the scheme of composite crosslinking, the effect that the crosslinking degree of two kinds of material compounds is used alone much larger than often kind.Environment-protection functional monomer used is be the combination of (methyl) acrylate functional monomer and silane coupling agent with the unsaturated compound of one or more functional group.
Further, described unsaturated acid monomer is preferably one in following compound or arbitrary combination: vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, fumaric acid.
Further, described hydro carbons unsaturated monomer is preferably one in following compounds or arbitrary combination: ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, dodecyl acrylate, lauryl methacrylate, octadecyl acrylate, stearyl methacrylate, vinyl cyanide, propenal, vinyl acetate, vinylbenzene, ethene, vinylchlorid, vinylidene chloride.
Further, described double bond type cross-linking monomer is preferably one in following compounds or arbitrary combination: Phthalic acid, diallyl ester, divinylbenzene, ethylene glycol diacrylate, triethylene glycol double methacrylate, poly(oxyethylene glycol) 400 double methacrylate, tri-propanediol diacrylate, Viscoat 295, methacrylate fourth diester, methylene-bisacrylamide.
Further, in described environment-protection functional monomer, described methacrylic ester is preferably any one in hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate; Described acrylate is preferably any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, glycidyl acrylate, glycidyl allyl ether;
Described silane coupling agent is preferably any one in methacryloxypropyl tripropoxy silane, methacryloxypropyl three isopropoxy silane, vinyl tripropoxy silane, vinyl silane triisopropoxide.Silane coupling agent is unsaturated three (different) npropoxysilane, and the overall steric hindrance of three (different) npropoxysilane is very large, (different) third oxygen again more than methoxyl group, oxyethyl group torpescence, so can emulsion-stabilizing be ensured.
Further, described soft monomer is preferably one in following compound or arbitrary combination: vinyl silicone oil, methacryloxypropyl alkyl silicone oil.
Further, described initiator is preferably one of following compounds: 1) water soluble persulfates, as: Potassium Persulphate, ammonium persulphate etc.; 2) oil soluble azo compound or organo-peroxide, as Diisopropyl azodicarboxylate (AIBN), azo 2,4-nitrile dimethyl, benzoyl peroxide (BPO) etc.; Described conditioning agent is preferably sulfur alcohol compound, as n-dodecyl mereaptan, acetic acid n-dodecyl mercaptan ester, succinic acid list-n-dodecyl mercaptan ester, oxalic acid two-n-dodecyl mercaptan ester etc.; Described buffer reagent is preferably one in water-soluble phosphoric acid hydrogen salt, dihydrogen phosphate, supercarbonate, carbonate or arbitrary combination.
Further, described polymerisable emulsifier is preferably one of following compounds or any several combination: Sodium styrene sulfonate, acrylamide stearic acid sodium salt, acrylic acid-2-ethyl sodium sulfonate, methacrylic acid-2-ethylsulfonic acid sodium, allyloxy hydroxypropyl azochlorosulfonate acid sodium, toxilic acid tetradecyl propyl sulfonic acid sodium, acrylamide ethylsulfonic acid ammonium, acrylamide dimethyl ethyl ammonium sulphonate, acrylamide ethylsulfonic acid sodium, acrylamide dimethyl ethyl sodium sulfonate.
Another object of the present invention is to the preparation method that above-mentioned high Dry Sack, high fastness environmental protection organosilicon crylic acid latex are provided, forming carrying out radical polymerization under various monomer, polymerisable emulsifier, conditioning agent, buffer reagent and initiator effect in aqueous phase;
Its concrete steps are as follows: at room temperature unsaturated acid monomer, hydro carbons unsaturated monomer, double bond type cross-linking monomer, environment-protection functional monomer, complexing monomer, soft monomer, polymerisable emulsifier, buffer reagent, conditioning agent and deionized water are placed in emulsification cup, then use high-shear emulsion machine pre-emulsification, form stable white pre-emulsion;
Above-mentioned white pre-emulsion being transferred to one is furnished with in the reactor of stirring, logical nitrogen, condensation and temperature measuring equipment; under nitrogen protection; stir, heat up; initiator is added at 50-80 DEG C; reacting after 5-15 minute, when there being blue light to occur, continuing insulation 2.5-3.5 hour; cooling, finally obtains the white emulsion with blue-fluorescence.
The present invention has following beneficial effect: 1, in the component of multipolymer, introduce unsaturated acid monomer, not only increase stability of emulsion, also improves the dispersive ability to coating (pigment), promotes apparent Dry Sack ability; 2, in the component of multipolymer, introduce hydro carbons unsaturated monomer, the feel of various style can be realized, also reduce the second-order transition temperature of multipolymer simultaneously, improve the film-forming properties for the treatment of solution; 3, in the component of multipolymer, introduce double bond type cross-linking monomer, promote the molecular weight of polymkeric substance, contribute to the vividness improving polymeric film; 4, in the component of multipolymer, introduce environment-protection functional monomer, the self-crosslinking of emulsion during film forming, can be realized, improve the fastness of the polymeric film processed, and formaldehydeless release; 5, in the component of multipolymer, introduce complexing monomer, greatly strengthen the interaction of polymer molecule and coating (pigment), promote dye yield; 6, introduce containing organosilyl soft monomer in the component of multipolymer, greatly put forward the flexibility of polymeric film; 7, in the component of multipolymer, use polymerisable emulsifier, emulsifying agent is chemically bonded to polymer surfaces, thoroughly eliminate free emulsifier surface migration, significantly improve every fastness (especially wet fastness) of polymeric film.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
At room temperature by unsaturated acid monomer 1.0-6.0 gram, hydro carbons unsaturated monomer 8.0-20.0 gram, double bond type cross-linking monomer 2.0-10.0 gram, environment-protection functional monomer 2.0-10.0 gram, complexing monomer 10.0-14.0 gram, soft monomer 10.0-14.0 gram, polymerisable emulsifier 0.5-1.5 gram, buffer reagent 0.05-0.1 gram, conditioning agent 0.1-0.3 gram is placed in emulsification cup with deionized water 150-200 gram, then use high-shear emulsion machine pre-emulsification 0.5 hour, form stable white pre-emulsion.
Above-mentioned pre-emulsion is transferred to one to be furnished with in the four-hole bottle of the device such as stirring, logical nitrogen, condensation, thermometric.Under nitrogen protection, stir, heat up, add initiator 0.25-0.75 gram, react after 5-15 minute at 50-80 DEG C, when there being obvious blue light to occur, continue insulation 2.5-3.5 hour, cooling, finally obtains the white emulsion with blue-fluorescence.
Embodiment 1
By 1.0 grams of vinylformic acid, 8.0 grams of β-dimethyl-aminoethylmethacrylates, 2.0 grams of Phthalic acid, diallyl esters, 1.0 grams of Propylene glycol monoacrylates and 1.0 grams of methacryloxypropyl tripropoxy silane, 10.0 gram vinyl pyrrolidone, 12.0 grams of vinyl silicone oils, 1.0 grams of acrylic acid-2-ethyl sodium sulfonates, 0.15 gram of n-dodecyl mereaptan, 0.05 gram of sodium bicarbonate, 150 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 50 DEG C, add ammonium persulphate 0.4 gram, react and have obvious blue light to occur after 15 minutes, can lower the temperature after 2.5 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 2
By 6.0 grams of toxilic acids, 12.0 grams of vinylbenzene, 5.0 grams of divinylbenzenes, 3.0 grams of hydroxyethyl methylacrylates and 3.0 grams of methacryloxypropyl tripropoxy silane, 14.0 gram vinyl pyrrolidone, 12.0 grams of vinyl silicone oils, 1.5 grams of Sodium styrene sulfonate, 0.3 gram of acetic acid n-dodecyl mercaptan ester, 0.1 gram of saleratus, 170 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 55 DEG C, add Potassium Persulphate 0.5 gram, react and have obvious blue light to occur after 12 minutes, can lower the temperature after 2.5 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 3
By 2.0 grams of vinylformic acid, 2.0 grams of methylene-succinic acids, 20.0 grams of (methyl) dodecyl acrylates, 5.0 grams of ethylene glycol diacrylates, 5.0 grams of glycidyl allyl ethers and 5.0 grams of methacryloxypropyl three isopropoxy silane, 12.0 gram vinyl pyrrolidone, 10.0 gram vinyl silicone oil, 0.5 gram of toxilic acid tetradecyl propyl sulfonic acid sodium, 0.1 gram of succinic acid list-n-dodecyl mercaptan ester, 0.06 gram of sodium carbonate, 200 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 60 DEG C, add AIBN 0.75 gram, react and have obvious blue light to occur after 11 minutes, can lower the temperature after 2.5 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 4
By 3 grams of fumaric acid, 14 grams of (methyl) octadecyl acrylates, 10.0 grams of triethylene glycol double methacrylates, 2.0 grams of glycidyl methacrylate and 2.0 grams of vinyl tripropoxy silane, 11 grams of vinyl pyrrolidones, 10 grams of methacryloxypropyl alkyl silicone oil, 1.2 grams of acrylamide dimethyl ethyl ammonium sulphonates, 0.2 gram of oxalic acid two-n-dodecyl mercaptan ester, 0.08 gram of salt of wormwood, 180 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 65 DEG C, add BPO 0.6 gram, react and have obvious blue light to occur after 10 minutes, can lower the temperature after 3.0 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 5
By 2.0 grams of methylene-succinic acids, 15 grams of vinyl cyanide, 7 grams of tri-propanediol diacrylates, 4.0 grams of hydroxyethyl methylacrylates and 4.0 grams of vinyl tripropoxy silane, 12.0 gram vinyl pyrrolidone, 14 grams of methacryloxypropyl alkyl silicone oil, 1.2 grams of allyloxy hydroxypropyl azochlorosulfonate acid sodiums, 0.2 gram of n-dodecyl mereaptan, 0.05 gram of sodium hydrogen phosphate, 155 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 70 DEG C, add azo 2,4-nitrile dimethyl 0.25 gram, react and have obvious blue light to occur after 10 minutes, can lower the temperature after 3.0 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 6
By 5 grams of methacrylic acids, 16 grams of vinyl acetates, 4.0 grams of polyoxyethylene glycol (400) double methacrylates, 2.5 grams of Rocryl 410s and 2.5 grams of vinyl silane triisopropoxides, 11.0 gram vinyl pyrrolidone, 12.0 grams of vinyl silicone oils, 0.75 gram of acrylamide ethylsulfonic acid sodium, 0.2 gram of n-dodecyl mereaptan, 0.07 gram of potassium hydrogen phosphate, 165 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 75 DEG C, add Potassium Persulphate 0.5 gram, react and have obvious blue light to occur after 9 minutes, can lower the temperature after 3.0 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 7
By 2.5 grams of vinylformic acid, 14.5 grams of Isooctyl acrylate monomers, 5.4 grams of Viscoat 295s, 4.0 grams of Propylene glycol monoacrylates and 2.0 grams of vinyl tripropoxy silane, 13.0 gram vinyl pyrrolidone, 12.8 grams of vinyl silicone oils, 1.2 grams of acrylamide stearic acid sodium salts, 0.2 gram of n-dodecyl mereaptan, 0.1 gram of SODIUM PHOSPHATE, MONOBASIC, 185 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 80 DEG C, add ammonium persulphate 0.55 gram, react and have obvious blue light to occur after 8 minutes, can lower the temperature after 3.5 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 8
By 2.5 grams of methacrylic acids, 16.2 gram butyl acrylate, 5.0 grams of methylene-bisacrylamides, 5 grams of glycidyl methacrylate and 2.5 grams of methacryloxypropyl three isopropoxy silane, vinyl pyrrolidone 10.0 grams, 14.0 gram vinyl silicone oil, 0.5 gram of Sodium styrene sulfonate, 0.5 gram of acrylamide stearic acid sodium salt, 0.1 gram of n-dodecyl mereaptan, 0.08 gram of potassium primary phosphate, 180 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 70 DEG C, add ammonium persulphate 0.50 gram, react and have obvious blue light to occur after 6 minutes, can lower the temperature after 3.5 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 9
By 2 grams of toxilic acids, 1 gram of methylene-succinic acid, 10 grams of propenal, 2.5 grams of two first class vinylformic acid fourth diester, 3.0 grams of hydroxyethyl methylacrylates and 3.0 grams of methacryloxypropyl three isopropoxy silane, 13.2 gram vinyl pyrrolidone, 12.2 gram vinyl silicone oil, 0.5 gram of Sodium styrene sulfonate, 1.0 grams of methacrylic acid-2-ethylsulfonic acid sodium, 0.3 gram of acetic acid n-dodecyl mercaptan ester, 0.09 gram of sodium bicarbonate, 170 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 70 DEG C, add Potassium Persulphate 0.45 gram, react and have obvious blue light to occur after 5 minutes, can lower the temperature after 3.0 hours in insulation, obtain the white emulsion with blue-fluorescence.
Embodiment 10
By 1.5 grams of vinylformic acid, 1.5 grams of methacrylic acids, 10 grams of ethene, 4.2 grams of methylene-bisacrylamides, 2 grams of Hydroxyethyl acrylates and 4 grams of vinyl silane triisopropoxides, 10.5 gram vinyl pyrrolidone, 10.2 grams of methacryloxypropyl alkyl silicone oil, 0.4 gram of acrylic acid-2-ethyl sodium sulfonate, 0.8 gram of acrylamide dimethyl ethyl ammonium sulphonate, 0.1 gram of n-dodecyl mereaptan, 0.08 gram of sodium bicarbonate, 195 grams of deionized waters are placed in emulsification cup, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 70 DEG C, add ammonium persulphate 0.70 gram, react and have obvious blue light to occur after 5 minutes, can lower the temperature after 3.0 hours in insulation, obtain the white emulsion with blue-fluorescence.
Following performance test (this product can be applied in the products such as stamp, coating and coating, and existing for stamp, the organosilicon crylic acid latex of synthesis is as pigment printing binding agent) is carried out to the product that above-described embodiment obtains:
1, printing technology
Fabric used: cotton poplin cloth
Treatment process: modulation mill base → stamp → oven dry (100 DEG C × 90s) → bake (160 DEG C × 90s) → performance evaluation
2, application performance test
2.1 dry, the wet fastness tests that rub
Adopt GB/T 3920-1997 standard to measure, dry, the wet fastness of rubbing of fabric is divided into 1-5 level, and rank is higher better.
2.2 dye yield tests
Test with Datacolor color measurement instrument.
Not increase Dry Sack, high fastness environmental protection organosilicon crylic acid latex treatment samples for standard specimen, to increase Dry Sack, high fastness environmental protection organosilicon crylic acid latex treatment samples for test comparison sample, Datacolor color measurement instrument is tested.Represent the color strength of fabric with K/S, K/S value is larger, and dye yield is darker.
2.3 hand valuation
Have with many people and enrich feel experience person to pass judgment on, be divided into 1-5 level, higher grade, and feel is more soft.
The application performance table of high Dry Sack of the present invention, high fastness environmental protection organosilicon crylic acid latex
| Sequence number | Unlubricated friction fastness | Wet fastness of rubbing | K/S | Feel |
| Standard specimen | 3-4 | 3 | 12.3 | 4 grades |
| Embodiment 1 | 3-4 | 3 | 15.2 | 4.5 level |
| Embodiment 2 | 4 | 3 | 14.3 | 3 grades |
| Embodiment 3 | 3-4 | 3 | 14.9 | 2.5 level |
| Embodiment 4 | 3 | 2-3 | 15.1 | 4.5 level |
| Embodiment 5 | 3-4 | 3 | 14.5 | 4 grades |
| Embodiment 6 | 2-3 | 3 | 14.2 | 4.5 level |
| Embodiment 7 | 4 | 3 | 15.4 | 4.5 level |
| Embodiment 8 | 4 | 3-4 | 15.8 | 5 grades |
| Embodiment 9 | 3 | 2-3 | 14.3 | 4.5 level |
| Embodiment 10 | 3 | 3 | 15.0 | 3.5 level |
Can find out from upper table, high Dry Sack of the present invention, high fastness environmental protection organosilicon crylic acid latex have the excellent dark function of increasing, height is done, the feel of wet rub fastness and softness.
The above is only preferred embodiment of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall within the scope of protection of the present invention.
Claims (10)
1. an environmental protection organosilicon crylic acid latex, it is characterized in that, it is by unsaturated acid monomer, hydro carbons unsaturated monomer, double bond type cross-linking monomer, environment-protection functional monomer, complexing monomer and soft monomer are at initiator, polymerisable emulsifier, in aqueous phase, carry out letex polymerization under conditioning agent and buffer reagent effect to form, raw material dosage is counted by weight, it consists of: unsaturated acid monomer 2-12 part, hydro carbons unsaturated monomer 16-40 part, double bond type cross-linking monomer 4-20 part, environment-protection functional monomer 4-20 part, complexing monomer 20-28 part, soft monomer 20-28 part, initiator amount is 0.5-1.5 part, conditioning agent consumption is 0.2-0.6 part, buffer reagent consumption is 0.1-0.2 part, polymerisable emulsifier consumption is 1-3 part, deionized water consumption is 300-400 part,
Described complexing monomer is vinyl pyrrolidone, and described environment-protection functional monomer is the combination of unsaturated compound methacrylic ester with one or more functional group or acrylate functional monomer and silane coupling agent.
2. environmental protection organosilicon crylic acid latex according to claim 1, is characterized in that, described unsaturated acid monomer is one in following compound or arbitrary combination: vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, fumaric acid.
3. environmental protection organosilicon crylic acid latex according to claim 1, it is characterized in that, described hydro carbons unsaturated monomer is one in following compounds or arbitrary combination: ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, dodecyl acrylate, lauryl methacrylate, octadecyl acrylate, stearyl methacrylate, vinyl cyanide, propenal, vinyl acetate, vinylbenzene, ethene, vinylchlorid, vinylidene chloride.
4. environmental protection organosilicon crylic acid latex according to claim 1, it is characterized in that, described double bond type cross-linking monomer is one in following compounds or arbitrary combination: Phthalic acid, diallyl ester, divinylbenzene, ethylene glycol diacrylate, triethylene glycol double methacrylate, poly(oxyethylene glycol) 400 double methacrylate, tri-propanediol diacrylate, Viscoat 295, methacrylate fourth diester, methylene-bisacrylamide.
5. environmental protection organosilicon crylic acid latex according to claim 1, is characterized in that, in described environment-protection functional monomer, described methacrylic ester is any one in hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate; Described acrylate is any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, glycidyl acrylate, glycidyl allyl ether;
Described silane coupling agent is any one in methacryloxypropyl tripropoxy silane, methacryloxypropyl three isopropoxy silane, vinyl tripropoxy silane, vinyl silane triisopropoxide.
6. environmental protection organosilicon crylic acid latex according to claim 1, is characterized in that, described soft monomer is one in following compound or arbitrary combination: vinyl silicone oil, methacryloxypropyl alkyl silicone oil.
7. environmental protection organosilicon crylic acid latex according to claim 1, is characterized in that, described initiator is one of following compounds: 1) water soluble persulfates; 2) oil soluble azo compound or organo-peroxide; Described conditioning agent is sulfur alcohol compound; Described buffer reagent is one in water-soluble phosphoric acid hydrogen salt, dihydrogen phosphate, supercarbonate, carbonate or arbitrary combination.
8. environmental protection organosilicon crylic acid latex according to claim 7, is characterized in that, described initiator is any one in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, azo 2,4-nitrile dimethyl, benzoyl peroxide; Described conditioning agent is one in n-dodecyl mereaptan, acetic acid n-dodecyl mercaptan ester, succinic acid list-n-dodecyl mercaptan ester, oxalic acid two-n-dodecyl mercaptan ester or arbitrary combination.
9. environmental protection organosilicon crylic acid latex according to claim 1, it is characterized in that, described polymerisable emulsifier is one of following compounds or any several combination: Sodium styrene sulfonate, acrylamide stearic acid sodium salt, acrylic acid-2-ethyl sodium sulfonate, methacrylic acid-2-ethylsulfonic acid sodium, allyloxy hydroxypropyl azochlorosulfonate acid sodium, toxilic acid tetradecyl propyl sulfonic acid sodium, acrylamide ethylsulfonic acid ammonium, acrylamide dimethyl ethyl ammonium sulphonate, acrylamide ethylsulfonic acid sodium, acrylamide dimethyl ethyl sodium sulfonate.
10. the preparation method of environmental protection organosilicon crylic acid latex described in any one of claim 1-9, is characterized in that, forms carrying out radical polymerization under various monomer, polymerisable emulsifier, conditioning agent, buffer reagent and initiator effect in aqueous phase;
Its concrete steps are as follows: at room temperature unsaturated acid monomer, hydro carbons unsaturated monomer, double bond type cross-linking monomer, environment-protection functional monomer, complexing monomer, soft monomer, polymerisable emulsifier, buffer reagent, conditioning agent and deionized water are placed in emulsification cup, then use high-shear emulsion machine pre-emulsification, form stable white pre-emulsion;
Above-mentioned white pre-emulsion being transferred to one is furnished with in the reactor of stirring, logical nitrogen, condensation and temperature measuring equipment; under nitrogen protection; stir, heat up; initiator is added at 50-80 DEG C; reacting after 5-15 minute, when there being blue light to occur, continuing insulation 2.5-3.5 hour; cooling, finally obtains the white emulsion with blue-fluorescence.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724329A (en) * | 2009-11-10 | 2010-06-09 | 上海漠王复合材料科技有限公司 | Environment-friendly encaustic tile coating and preparation method thereof |
| CN101735378A (en) * | 2009-11-24 | 2010-06-16 | 东莞市英科水墨有限公司 | Pure acrylic emulsion for waterborne preprinting gloss oil and preparation method thereof |
| CN101798369A (en) * | 2010-03-05 | 2010-08-11 | 北京高盟新材料股份有限公司 | Silicone-acrylic emulsion with high silicon content and preparation method thereof |
| CN102321209A (en) * | 2009-03-27 | 2012-01-18 | 广东德美精细化工股份有限公司 | Preparation method of non-phosphate high-molecular acidic prepolymer used for textile dyeing |
| CN102643380A (en) * | 2012-04-18 | 2012-08-22 | 上海维凯化学品有限公司 | Acrylate emulsion used for vacuum aluminum plating and laser embossing and preparation method thereof |
| CN102766233A (en) * | 2012-07-31 | 2012-11-07 | 浙江传化股份有限公司 | Disperse printing thickener and preparation method thereof |
| CN103602193A (en) * | 2013-11-29 | 2014-02-26 | 深圳市安品有机硅材料有限公司 | Priming paint for water-borne heavy anti-corrosion coating and preparation method thereof |
-
2015
- 2015-02-13 CN CN201510078512.4A patent/CN104672403B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321209A (en) * | 2009-03-27 | 2012-01-18 | 广东德美精细化工股份有限公司 | Preparation method of non-phosphate high-molecular acidic prepolymer used for textile dyeing |
| CN101724329A (en) * | 2009-11-10 | 2010-06-09 | 上海漠王复合材料科技有限公司 | Environment-friendly encaustic tile coating and preparation method thereof |
| CN101735378A (en) * | 2009-11-24 | 2010-06-16 | 东莞市英科水墨有限公司 | Pure acrylic emulsion for waterborne preprinting gloss oil and preparation method thereof |
| CN101798369A (en) * | 2010-03-05 | 2010-08-11 | 北京高盟新材料股份有限公司 | Silicone-acrylic emulsion with high silicon content and preparation method thereof |
| CN102643380A (en) * | 2012-04-18 | 2012-08-22 | 上海维凯化学品有限公司 | Acrylate emulsion used for vacuum aluminum plating and laser embossing and preparation method thereof |
| CN102766233A (en) * | 2012-07-31 | 2012-11-07 | 浙江传化股份有限公司 | Disperse printing thickener and preparation method thereof |
| CN103602193A (en) * | 2013-11-29 | 2014-02-26 | 深圳市安品有机硅材料有限公司 | Priming paint for water-borne heavy anti-corrosion coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 龚兴宇: "高性能高硅烷含量硅丙复合乳液的研究", 《高分子材料科学与工程》 * |
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