CN105037646A - Polymer nano / micro particle additive and preparation method thereof - Google Patents
Polymer nano / micro particle additive and preparation method thereof Download PDFInfo
- Publication number
- CN105037646A CN105037646A CN201510422642.5A CN201510422642A CN105037646A CN 105037646 A CN105037646 A CN 105037646A CN 201510422642 A CN201510422642 A CN 201510422642A CN 105037646 A CN105037646 A CN 105037646A
- Authority
- CN
- China
- Prior art keywords
- group
- monomer
- functional
- acid
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A polymer nano / micro particle additive is prepared from a main monomer and functional monomers by copolymerization. The functional monomers contain carboxylic group, sulfate group, sulfonate group, phosphate group, phosphite group, silane functional group, silicon hydroxyl functional group, and quaternary amine, quaternary phosphonium and tertiary sulfur functional groups; and the polymer nano / micro particle additive is a dry powder, or an aqueous dispersion. Under certain circumstances, the polymer does not contain main monomer but necessarily contains the above functional monomers. By introducing functional groups or anaphase modification, the polymer nano / micro particles have the effects of promoting hydration and nucleation of cement and greatly improving the early hydration rate of cement, so as to achieve improve the early strength of the cement-based materials and improve the toughness of cement-based materials.
Description
Technical field
The invention belongs to cement-based material admixture technical field, particularly a kind of polymer nanocomposite/micron particle admixture for improving cement-based material early strength and preparation method thereof.
Background technology
Improve the early strength of cement-based material (comprising mortar, concrete), accelerate gain in strength, be the gordian technique requirement in some civil engineering works always.As: in concrete prefabricated components preparation process, early strength increases the Rapid Circulation use being conducive to template fast, enhances productivity; The quick growth of used cement-based material intensity is required in engineering first-aid repair, road repair engineering; Winter low temperature construction then needs to adopt special concrete admixture to carry out accelerate concrete strength development.Traditional technical measures in concrete (or mortar), add a small amount of hardening accelerator to accelerate the development of cement concrete early strength.Conventional hardening accelerator comprises inorganic salts material as sodium-chlor, calcium chloride, vitriol, nitrate etc.; And organic hardening accelerator comprises trolamine, tri-isopropanolamine etc.These hardening accelerator all can effectively improve cement concrete early strength, but an one common shortcoming can reduce mortar or concrete later strength exactly to some extent.This shortcoming, greatly limit the widespread use of hardening accelerator in concrete.
Research in recent years shows that some nanometers or micron-sized particle join in cement-based material, can promote the nucleation rate at hydrated cementitious initial stage, greatly improve the extent of hydration during early stage hydrated cementitious, thus significantly improve the early strength of cement-based material.This class particle is called nucleation accelerating agent, is called for short nucleator.The particle mainly inorganic particulate having this type of nucleogenesis had been found that, comprises TiO
2, SiO
2, CaCO
3deng nanoparticle, and the nanometer of hydrated calcium silicate (CSH) gel or the particle etc. of micron-scale.An advantage of these nucleator particles is exactly under the prerequisite significantly improving cement-based material early strength, does not reduce the later strength or final strength that even improve cement concrete.
Multiple polymers latex or rubber powder widely use in various cement-based material.Comprise styrene-butadiene latex, esters of acrylic acid latex and ethylene-vinyl acetate copolymer latex or rubber powder etc.The use of these polymer latexs, effectively can improve the toughness of cement concrete, folding strength, cohesive strength, splitting resistance, wear resistance and impermeability.Greatly improve mechanical property and the endurance quality of cement-based material.But the engineering problem of a facing is exactly various polymer latex or rubber powder, has all to some extent delay restraining effect to hydrated cementitious.
Summary of the invention
The object of the invention is the above-mentioned defect in order to overcome prior art, a kind of organic polymer nano/micrometre particle of synthesis is provided, function functional group or the modification in later stage is introduced by copolymerization, this type of polymer particles is made to have similar promotion hydrated cementitious nucleogenesis, greatly improve cement early hydration speed, thus reach the function improving cement-based material early strength, and improve the toughness of cement-based material.
The invention provides a kind of polymer nanocomposite/micron particle admixture, it is characterized in that, described polymkeric substance is obtained by copolymerization by main monomer and functional monomer; Described functional monomer contains hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group; Silane functional, silicone hydroxyl functional group; Quaternary amine, quaternary phosphine, Shu Liu functional group; Described polymer nanocomposite/micron particle admixture is the state of dried powder, or the state of aqueous liquid dispersion.
Further, described main monomer is one or more in the polyether macromonomer such as vinylbenzene, acrylamide, N,N-DMAA, vinyl pyrrolidone, ethene, acrylate, divinyl, vinylchlorid, vinyl acetate, isoprene, isopentene group Soxylat A 25-7 (TPEG), isobutyl-Soxylat A 25-7 (HPEG), allyl polyethenoxy ether (APEG), methacrylic acid polyethylene glycol methyl esters;
Further, described acrylate is ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, dodecylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, aliphatic acrylate, octadecyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, lauryl methacrylate, methacrylic acid cetyl ester, octadecyl methacrylate, dimethylaminoethyl methacrylate, one or more in n octyl methacrylate.
Further, described containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, the monomer of phosphite group is selected from but is not limited to following monomer: (methyl) vinylformic acid, methylene-succinic acid, equisetic acid, maleic anhydride, 2-acrylamide-2-methyl propane sulfonic (AMPS), Sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3-allyloxy-2-hydroxyl-1-propanesulfonate (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, methacrylic acid phosphoric acid glycol ester or isopropyl alkenyl phosphoric acid, end group is the isopentene group Soxylat A 25-7 of phosphonic functional groups, end group is the isobutyl-Soxylat A 25-7 of phosphonic functional groups, end group is the allyl polyethenoxy ether (APEG) of phosphonic functional groups, end group is the methacrylic acid polyethylene glycol methyl esters of phosphonic functional groups.
Further, the described monomer containing silane functional or silicone hydroxyl functional group is selected from but is not limited to following monomer: vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl, acryloxypropyl Trimethoxy silane, vinyl silane triisopropoxide, Y-methacryloxypropyl three isopropoxy silane or propenyl Trimethoxy silane.
Further, the described monomer containing quaternary amine, quaternary phosphine, Shu Liu functional group is selected from but is not limited to following monomer: diallyldimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 2-(acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3-trimethoxy silicon propyl group) ammonium chloride.
Further, the described monomer containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group, silane functional or silicone hydroxyl functional group, quaternary amine, quaternary phosphine, Shu Liu functional group also homopolymerization can obtain this nano/micrometre particle.
The present invention also provides the preparation method of above-mentioned polymer nanocomposite/micron particle admixture, it is characterized in that, main monomer and functional monomer is directly obtained by aqueous solution polymerization, letex polymerization, micro-emulsion polymerization, mini-emulsion polymerization or suspension polymerization; Or main monomer and functional monomer are polymerized in organic solvent, after polymerization by add water or other material formed phase reversion obtain; Or after the multipolymer containing main monomer and functional monomer is dissolved in solvent, in aqueous phase, dispersion and emulsion obtains; Described functional monomer contains hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group; Or silane functional, silicone hydroxyl functional group; Or quaternary amine, quaternary phosphine, Shu Liu functional group.
Further, described main monomer is one or more in the polyether macromonomer such as vinylbenzene, acrylamide, N,N-DMAA, vinyl pyrrolidone, ethene, acrylate, divinyl, vinylchlorid, vinyl acetate, isoprene, isopentene group Soxylat A 25-7 (TPEG), isobutyl-Soxylat A 25-7 (HPEG), allyl polyethenoxy ether (APEG), methacrylic acid polyethylene glycol methyl esters.
Further, described acrylic ester monomer is ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, dodecylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, aliphatic acrylate, octadecyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, lauryl methacrylate, methacrylic acid cetyl ester, octadecyl methacrylate, dimethylaminoethyl methacrylate, one or more in n octyl methacrylate.
Further, described containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, the monomer of phosphite group is selected from but is not limited to following monomer: (methyl) vinylformic acid, methylene-succinic acid, equisetic acid, maleic anhydride, 2-acrylamide-2-methyl propane sulfonic (AMPS), Sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3-allyloxy-2-hydroxyl-1-propanesulfonate (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, methacrylic acid phosphoric acid glycol ester or isopropyl alkenyl phosphoric acid, end group is the isopentene group Soxylat A 25-7 of phosphonic functional groups, end group is the isobutyl-Soxylat A 25-7 of phosphonic functional groups, end group is the allyl polyethenoxy ether (APEG) of phosphonic functional groups, end group is the methacrylic acid polyethylene glycol methyl esters of phosphonic functional groups.
Further, the described monomer containing silane functional or silicone hydroxyl functional group is selected from but is not limited to following monomer: vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl, acryloxypropyl Trimethoxy silane, vinyl silane triisopropoxide, γ-methacryloxypropyl three isopropoxy silane or propenyl Trimethoxy silane.
Further, the described monomer containing quaternary amine, quaternary phosphine, Shu Liu functional group is selected from but is not limited to following monomer: diallyldimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 2-(acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3-trimethoxy silicon propyl group) ammonium chloride.
Further, by resulting polymers and cationic colloidal silica, TiO
2colloidal sol, Al
2o
3colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle generation physical adsorption or Chemical bond.
Further, by sol particles, cationic colloidal silica, the TiO of resulting polymers and silicate
2colloidal sol, Al
2o
3colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle generation physical adsorption or Chemical bond.
Further, by resulting polymers and silicon sol, water glass, the TiO in negative electricity type
2colloidal sol, Al
2o
3colloidal sol or calcium carbonate nano particle generation physical adsorption or Chemical bond.
Polymer nanocomposite of the present invention/micron particle admixture is being incorporated in cement-based material, when volume is 0.2%-5% (amount of solid of thing of the present invention is converted into the per-cent of the quality of cement), the function of cement-based material early strength can be improved, do not reduce the later strength or final strength that even improve cement-based material.Meanwhile, under the prerequisite improving early strength, reach to have like polymer latex or rubber powder and improve cement-based material toughness, impervious effect.
Embodiment
The main raw of polymer nanocomposite of the present invention/micron particle admixture is: polystyrene, polyolefins polymer, acrylic acid esters co-polymer, cinnamic acrylic ester analog copolymer, butadiene-styrene analog copolymer, ethylene-vinyl acetate analog copolymer, chloroprene rubber class, natural rubber class, epoxy resin latex class etc.
Corresponding main monomer is but is not limited to vinylbenzene, acrylamide, N,N-DMAA, vinyl pyrrolidone, ethene, divinyl, vinylchlorid, vinyl acetate, isoprene, isopentene group Soxylat A 25-7 (TPEG), isobutyl-Soxylat A 25-7 (HPEG), allyl polyethenoxy ether (APEG), the polyether macromonomer such as methacrylic acid polyethylene glycol methyl esters, ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, dodecylacrylate, aliphatic acrylate, octadecyl acrylate, ethyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid-2-ethylamino ester, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, lauryl methacrylate, methacrylic acid cetyl ester, methacrylic acid octadecyl, dimethylaminoethyl methacrylate, n octyl methacrylate etc.
The hydroxy-acid group in functional functional group to be introduced by polymer nanocomposite of the present invention/micron particle admixture on surface by copolymerization, sulfate groups, sulfonate group, phosphate groups, phosphite group can from following but be not limited to following monomer: (methyl) vinylformic acid, methylene-succinic acid, equisetic acid, maleic anhydride, 2-acrylamide-2-methyl propane sulfonic (AMPS), Sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3-allyloxy-2-hydroxyl-1-propanesulfonate (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, methacrylic acid phosphoric acid glycol ester, isopropyl alkenyl phosphoric acid, end group is the isopentene group Soxylat A 25-7 of phosphonic functional groups, end group is the isobutyl-Soxylat A 25-7 of phosphonic functional groups, end group is the allyl polyethenoxy ether (APEG) of phosphonic functional groups, end group is the methacrylic acid polyethylene glycol methyl esters of phosphonic functional groups.
The silane functional in functional functional group to be introduced by polymer nanocomposite of the present invention/micron particle admixture on surface by copolymerization, silicone hydroxyl functional group can from following but be not limited to following monomer: vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl, acryloxypropyl Trimethoxy silane, vinyl silane triisopropoxide, γ-methacryloxypropyl three isopropoxy silane, propenyl Trimethoxy silane etc.
Polymer nanocomposite of the present invention/micron particle admixture introduced on surface by copolymerization quaternary amine, quaternary phosphine, Shu Liu functional group can from following but be not limited to following monomer: diallyldimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 2-(acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3-trimethoxy silicon propyl group) ammonium chloride etc.
The above-mentioned monomer containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group, silane functional or silicone hydroxyl functional group, quaternary amine, quaternary phosphine, Shu Liu functional group also homopolymerization can obtain this nano/micrometre particle.Polymer nanocomposite of the present invention/micron particle admixture is that main monomer and functional monomer are directly obtained by aqueous solution polymerization, letex polymerization, micro-emulsion polymerization, mini-emulsion polymerization, suspension polymerization copolymerization, or after the multipolymer containing main monomer and functional monomer is dissolved in solvent, in aqueous phase, dispersion and emulsion obtains.Letex polymerization wherein can adopt the method for conventional emulsion polymerization or seeded emulsion polymerization to prepare.First will add a certain amount of emulsifier solution in reaction vessel, or seed emulsion, after being heated to temperature of reaction, add a small amount of monomer (as 10%) and initiator carries out prepolymerization 30min.Then pre-emulsification monomer and initiator were added drop-wise to continuously in reaction vessel in 2-6 hour, after dropwising, add redox initiator again to react again after for some time, residual monomer quantity is dropped to minimum, finally namely obtain organic polymer nano/micrometre particle or preliminary particle.
Its primary process of aqueous polymer method is in the there-necked flask that thermometer, agitator, reflux exchanger are housed, and adds portions of de-ionized water, starts stirring, and logical water of condensation, rises to 40 ~ 90 DEG C, initiator and monomer are added drop-wise to respectively in flask by temperature.React certain hour again after to be triggered dose and monomer dropping and namely obtain machine high molecular nanometer (micron) particle or preliminary particle.
Conventional emulsion polymerization method (single stage method) comprises the following steps:
1. first will add a certain amount of emulsifier solution in reaction vessel,
2., after being heated to temperature of reaction (40-95 DEG C), add a small amount of monomer (as 5-10%) and initiator carries out prepolymerization 30min.
3. then pre-emulsification monomer and initiator were added drop-wise to continuously in reaction vessel in 2-6 hour, after dropwising, add redox initiator again to react again after for some time, residual monomer quantity is dropped to minimum, finally namely obtain machine high molecular nanometer/micron particle or preliminary particle.
Seed emulsion polymerization (two step method) comprises the following steps:
1 preparation latex seed
Take each component by the composition of above-mentioned monomer and usage ratio, join in header tank that band stirs, then add emulsifying agent and water, high-speed stirring 30-40 minute, namely obtain the pre-emulsion of monomer.First by the monomer pre-emulsion of 5-10%, join thermometer, well heater, agitator, filling tube and header tank are housed reactor in, when to be slowly warming up to temperature be 80 DEG C-90 DEG C, add initiator, after several minutes, there is faint blue light in emulsion, then stirs 5-10 minute, namely forms latex seed.
2 prepare polymer latex
Monomer pre-emulsion and initiator were added drop-wise in reactor continuously at 2-4 hour, react with latex seed, temperature of reaction remains on 85 DEG C-90 DEG C, after completion of the reaction, be incubated after 1 hour, drip redox initiator more simultaneously, after dropwising, be incubated after 1 hour, cool to less than 50 DEG C, add aqueous sodium hydroxide solution, the pH value of regulation system is 7-8, namely obtains machine high molecular nanometer/micron particle or preliminary particle.
Polymer nanocomposite of the present invention/micron particle admixture can also adopt the letex polymerization of self-emulsifying form to prepare, and the difference of its more general letex polymerization is not need additionally to add emulsifying agent.Its general process for first a certain amount of deionized water will be added in reaction vessel, after being heated to temperature of reaction.Then respectively oiliness monomer, aqueous monomers, initiator were added drop-wise to continuously in reaction vessel in 2-6 hour, after dropwising, add redox initiator again to react again after for some time, residual monomer quantity is dropped to minimum, finally namely obtain organic polymer nano/micrometre particle or preliminary particle dispersion.
Polymer nanocomposite of the present invention/micron particle admixture also can adopt micro-emulsion polymerization to prepare, its primary process is according to a certain ratio by monomer (comprising main monomer and function monomer), emulsifying agent, assistant for emulsifying agent, water is placed in round-bottomed flask, heat while stirring, , become after clear until system and add appropriate initiator (also can pass through light-initiated), fill nitrogen deoxygenation about 20 minutes, be warming up to 30-90 DEG C, under agitation constant temperature carries out polyreaction, regularly sample in polymerization process, its transformation efficiency is surveyed by weighting method, after transformation efficiency makes it, lower the temperature and obtain required particle aqueous liquid dispersion.
Polymer nanocomposite of the present invention/micron particle admixture can also adopt mini-emulsion polymerization to prepare, its primary process is for first co-stabilizer (as n-Hexadecane, hexadecanol etc.) being dissolved in monomer (comprising main monomer and function monomer) forms oil phase, by high speed shear or ultrasonic disperse, oil-soluble monomer is dispersed in aqueous phase, form pre-emulsified monomer emulsion, under agitation, temperature of reaction is warming up to and deoxygenation.After intensification and deoxygenation terminate, add initiator initiated polymerization, regularly sample in polymerization process, survey its transformation efficiency by weighting method, after transformation efficiency makes it, lower the temperature and obtain required particle aqueous liquid dispersion.
Polymer nanocomposite of the present invention/micron particle admixture can also adopt suspension polymerization to prepare, its primary process is in the there-necked flask that thermometer, agitator, reflux exchanger are housed, add deionized water, dispersion agent (as polyvinyl alcohol), start stirring, logical water of condensation, temperature is risen to 40 ~ 90 DEG C, dispersion agent is dissolved; Cool the temperature to 30 ~ 80 DEG C again, treat lather collapse on the water surface; Being joined by the monomer mixture being dissolved with initiator is dissolved with in the aqueous phase of dispersion agent; Under agitation make bath temperature progressively be raised to 80 ~ 85 DEG C and carry out suspension polymerization.After reaction 2h, available suction pipe is drawn a small amount of material and is observed in surperficial device, embrittlement as hardening in particle, can stop heating, withdraw from well heater, stir, with cold water, polymerization system is cooled to room temperature; Stop stirring, take off there-necked flask, product Büchner funnel suction filtration, and with hot water wash several, finally dry in air dry oven and obtain required particle.
Polymer nanocomposite of the present invention/high eyebrow particle admixture also can adopt by after polymkeric substance is dissolved in solvent, in aqueous phase, dispersion and emulsion obtains, its general process is: polymkeric substance and solvent are joined in flask, start stirring, be warmed up to 30-90 DEG C, after thing to be polymerized dissolves completely, violent stirring, the deionized water dripped containing acid or alkali (if general function functional group is cationic, adds acid, otherwise then add alkali) and emulsifying agent, until finally become aqueous dispersions, after dropwising, namely insulated and stirred more than half an hour obtains required particle dispersion again.
Polymer nano-particle admixture of the present invention can also adopt and be polymerized in organic solvent system, then adding water, it is obtained that phase reversion occurs, its general process is: monomer (comprising main monomer and function monomer), solvent and initiator join in flask, start stirring, logical nitrogen is after 20 minutes, be warmed up to 30-90 DEG C, regularly sample in polymerization process, its transformation efficiency is surveyed by weighting method, after transformation efficiency makes it, cool to 30-70 DEG C, violent stirring, the deionized water dripped containing acid or alkali (if general function functional group is cationic, adds acid, otherwise then add alkali), there is phase reversion gradually in solution, until finally become aqueous dispersions, after dropwising, namely insulated and stirred more than half an hour obtains required particle aqueous liquid dispersion again.
If the polymer nanocomposite that aforesaid method obtains/micron particle admixture surface-functional functional group is silane functional, silicone hydroxyl functional group, then there is the effect promoting cement heterogeneous nucleation, directly can be used as early strong nucleator, also can also add sol particles, cationic colloidal silica, the TiO of silicate inside above-mentioned particle
2colloidal sol, Al
2o
3colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle, can there is the surface of physical adsorption at organic polymer nano/micrometre particle in the latter, and then the effect of improvement and cement heterogeneous nucleation.
The surface-functional functional group of the polymer nanocomposite that aforesaid method obtains/micron particle admixture, then can at later stage and cationic colloidal silica, TiO if containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group
2colloidal sol, Al
2o
3colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle generation physical adsorption thus there is the effect of cement heterogeneous nucleation.
The surface-functional functional group of the polymer nanocomposite that aforesaid method obtains/micron particle admixture, thus can with silicon sol, water glass, the TiO in negative electricity type if containing quaternary amine, quaternary phosphine group
2, colloidal sol, Al
2o
3colloidal sol or calcium carbonate nano particle generation physical adsorption and then the effect had cement heterogeneous nucleation.
Below in conjunction with embodiment, the present invention is described in more detail.
Synthesis example 1
2kg γ-methacryloxypropyl is added in a header tank, 8kg vinyl pyrrolidone is added in another header tank, in the 3rd header tank, add ammonium persulphate 0.7kg, deionized water 20kg simultaneously, drip component as initiator.
In reactor, drop into 80kg deionized water, 70kgTPEG (isopentene group Soxylat A 25-7, molecular weight 2400), is warmed up to 80 degree, starts to drip above-mentioned three components.Wherein the first two component drips three hours, initiator component drips three and a half hours, drip off rear insulation 30 minutes, drip the solution A of 0.1 kilogram of tertbutyl peroxide and 5 kg of water composition, the solution B of 0.05 kilogram of Sulfothiorine and 5 kilograms of deionized water compositions, time for adding is after 2 hours simultaneously, be incubated half an hour again, be cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains stable transparent nanometer polymer solution.
Synthesis example 2
In a header tank, add 5kg deionized water, 8kg vinyl pyrrolidone (NVP), adds Sodium Persulfate 1.1kg in another header tank, deionized water 10kg, drips component as initiator.
In reactor, drop into deionized water 50kg, 50kg end group is the TPEG (isopentene group Soxylat A 25-7, molecular weight 1000) of phosphonic functional groups, is warmed up to 90 degree, starts to drip above-mentioned two components.Wherein front component drips three hours, initiator component drips three and a half hours, drip off rear insulation 30 minutes, temperature is dropped to 85 degree, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 5 kg of water composition simultaneously, the solution B of 0.25 kilogram of Sulfothiorine and 5 kilograms of deionized water compositions, time for adding after 2 hours, then is incubated half an hour, is cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains the nanometer polymer solution of stable transparent.
Synthesis example 3
90kg deionized water is added in a header tank, 5kg acrylamide, 17kg end group is HPEG (the isobutenyl Soxylat A 25-7 of phosphonic functional groups, molecular weight 4000), 68kg vinylbenzene is added in another header tank, in the 3rd header tank, add Sodium Persulfate 1.1kg, deionized water 110kg simultaneously, drip component as initiator.
In reactor, drop into deionized water 70kg, be warmed up to 90 degree, start to drip above-mentioned three components.Wherein front two components drip three hours, initiator component drips three and a half hours, drip off rear insulation 30 minutes, temperature is dropped to 85 degree, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 20 kg of water composition simultaneously, the solution B of 0.25 kilogram of Sulfothiorine and 12 kilograms of deionized water compositions, time for adding after 2 hours, then is incubated half an hour, is cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 4
200 grams of silicon sol (30% concentration) are put in there-necked flask, the solution of 4.5 grams of gamma-methyl allyl acyloxypropyl trimethoxysilanes and 5.5 grams of ethanol is dripped in 1 hour at normal temperatures, drip off rear placement 24 hours, obtain a silane-modified silicon sol A.
Deionized water 88g is dropped in flask, 6.8 grams of above-mentioned modification liquid A, vinylbenzene 20 grams, with nitric acid adjustment pH value to 3, rapid stirring became pre-emulsion after 10 minutes, added 0.13 gram of Sodium Persulfate, was warmed up to 85 DEG C, react 4 hours, cool to normal temperature and namely obtain stable milky nanometer polymer latex.
Synthesis example 5
90kg deionized water is dropped in reactor, 70kg end group is TPEG (the isopentene group Soxylat A 25-7 of phosphate group, molecular weight 800), be warmed up to 80 degree, start to drip initiator component (0.7kg ammonium persulphate is dissolved in 10 kilograms of deionized waters) and drip two hours, drip off rear insulation 30 minutes, be cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains stable nanometer polymer solution.
Synthesis example 6
90kg deionized water is added in the header tank that band stirs, 10kg sodium lauryl sulphate, 5kgOP-10 emulsifying agent, 190kg vinylbenzene, 2kg acrylamide, 2kg gamma-methyl allyl acyloxypropyl trimethoxysilane, 0.4 gram of lauryl mercaptan, stirs pre-emulsification half an hour at normal temperatures as pre-emulsion.In another header tank, add Potassium Persulphate 1.1kg, deionized water 110kg, as initiator simultaneously.
Deionized water 70kg is dropped in reactor, be warmed up to 90 degree, add 5% of above-mentioned pre-emulsion total mass, 10% of above-mentioned initiator total mass, react after 20 to 30 minutes, occur after faint blueness until system, add 5kgCOPS-1 (French Rhodia produces), drip remaining pre-emulsion and initiator simultaneously, drip process lasts 4 hours.Drip off rear insulation 30 minutes, temperature is dropped to 85 DEG C, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 20 kg of water composition, the solution B of 0.25 kilogram of rongalite and 12 kilograms of deionized water compositions, time for adding is after 2 hours simultaneously, be incubated half an hour again, be cooled to less than 50 DEG C, drip the NaOH aqueous solution that massfraction is 20%, pH value is transferred between 7.5 ~ 8, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 7
90kg deionized water is added in a header tank, 5kg hydroxyethyl methylacrylate, 17kgTPEG (isopentene group Soxylat A 25-7, molecular weight 2400), in another header tank, add 68kg vinylbenzene, 1kg vinyltriethoxysilane, in the 3rd header tank, add Sodium Persulfate 1.1kg simultaneously, deionized water 110kg, drips component as initiator.
In reactor, drop into deionized water 70kg, be warmed up to 90 degree, start to drip above-mentioned three components.Wherein front two components drip three hours, initiator component drips three and a half hours, drip off rear insulation 30 minutes, temperature is dropped to 85 degree, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 20 kg of water composition simultaneously, the solution B of 0.25 kilogram of Sulfothiorine and 12 kilograms of deionized water compositions, time for adding after 2 hours, then is incubated half an hour, is cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 8
90kg deionized water is added in the header tank that band stirs, 10kg sodium lauryl sulphate, 5kgOP-10 emulsifying agent, 190kg vinylbenzene, 6kg methacrylic acid, 14kg2-acrylamide-2-methyl propane sulfonic (AMPS), 4kg Hydroxyethyl acrylate, 0.4 gram of lauryl mercaptan, stirs pre-emulsification half an hour at normal temperatures as pre-emulsion.In another header tank, add Potassium Persulphate 1.1kg, deionized water 110kg, as initiator simultaneously.
Deionized water 70kg is dropped in reactor, be warmed up to 90 degree, add 5% of above-mentioned pre-emulsion total mass, 10% of above-mentioned initiator total mass, react after 20 to 30 minutes, occur after faint blueness until system, add 5kgCOPS-1 (French Rhodia produces), drip remaining pre-emulsion and initiator simultaneously, drip process lasts 4 hours.Drip off rear insulation 30 minutes, temperature is dropped to 85 degree, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 20 kg of water composition, the solution B of 0.25 kilogram of rongalite and 12 kilograms of deionized water compositions, time for adding is after 2 hours simultaneously, be incubated half an hour again, be cooled to less than 50 degree, drip the NaOH aqueous solution that massfraction is 20%, pH value is transferred between 7.5 ~ 8, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 9
90kg deionized water is added in a header tank, 50kg Sodium styrene sulfonate (SSS), 14kgTPEG (isopentene group Soxylat A 25-7, molecular weight 2400), 40kg vinylbenzene is added in another header tank, in the 3rd header tank, add Sodium Persulfate 1.1kg, deionized water 110kg simultaneously, drip component as initiator.
In reactor, drop into deionized water 70kg, be warmed up to 90 degree, start to drip above-mentioned three components.Wherein front two components drip three hours, initiator component drips three and a half hours, drip off rear insulation 30 minutes, temperature is dropped to 85 degree, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 20 kg of water composition simultaneously, the solution B of 0.25 kilogram of Sulfothiorine and 12 kilograms of deionized water compositions, time for adding after 2 hours, then is incubated half an hour, is cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 10
90kg deionized water is added in a header tank, 50kg vinyl phosphonate, 17kgTPEG (isopentene group Soxylat A 25-7, molecular weight 2400), 38kg vinylbenzene is added in another header tank, in the 3rd header tank, add Sodium Persulfate 1.1kg, deionized water 110kg simultaneously, drip component as initiator.
In reactor, drop into deionized water 70kg, be warmed up to 90 degree, start to drip above-mentioned three components.Wherein front two components drip three hours, initiator component drips three and a half hours, drip off rear insulation 30 minutes, temperature is dropped to 85 degree, drip the solution A of 0.42 kilogram of tertbutyl peroxide and 20 kg of water composition simultaneously, the solution B of 0.25 kilogram of Sulfothiorine and 12 kilograms of deionized water compositions, time for adding after 2 hours, then is incubated half an hour, is cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 11
Add 180kg deionized water in a kettle., the polyvinyl alcohol KH-20 (Japanese synthetic chemistry company) of 3kg, after dissolving completely at 90 DEG C, add emulsifier sodium lauryl sulfate 3kg again, 120kg vinyl acetate and 80kg tertiary ethylene carbonate, 10kg isobutyl-Soxylat A 25-7 (HPEG), 5kg vinylformic acid, then the sodium bicarbonate aqueous solution that 10kg massfraction is 5% is added, reflux condensation mode, unlatching polymeric kettle stirs, emulsification 30min, then the persulfate aqueous solution that 20kg massfraction is 5% is added, react 5h under 90 degree after, cooling adds water and makes solid content reach 40%, discharging.
Synthesis example 12
Add 130kg deionized water in a kettle., the polyvinyl alcohol KH-20 (Japanese synthetic chemistry company) of 2kg, after dissolving completely at 90 DEG C, add 4kgOP-10 emulsifying agent again, 100kg vinyl acetate and 0.3kg sodium bicarbonate, 4kg2-acrylamide-2-methyl propane sulfonic (AMPS), 0.2kg ammonium persulphate, respectively replaces three times with nitrogen and ethylene gas after closing lid and (is 15kg/cm
2pressure).Pass into ethene (pressure 35kg/cm
2) start stirring, after 15 minutes, ethylene pressure is risen to 50kg/cm
2, be warming up to 80 degree, maintain 8 hours, then be warming up to 85 degree, maintain 1 hour, cooling discharging.
Synthesis example 13
In order successively by 0.75kg disproportionated rosin soap, 0.28kg potassium stearate, 0.03kg Repone K, 0.35kg tert-dodecyl mercaptan, 140kg deionized water, adding massfraction is that the pH value of the potassium hydroxide aqueous solution adjustment system of 5% is to 9 ~ 10, then 30kg vinylbenzene is added, 3kg isopentene group Soxylat A 25-7 (TPEG, molecular weight 2400), 20kg2-acrylamide-2-methyl propane sulfonic (AMPS), 0.85kg Potassium Persulphate adds in reactor, sealing, vacuumize, keep half an hour, removing air, then 70kg divinylic monomer is added by test tank.Open and stir, be warmed up to 65 DEG C ~ 70 DEG C, react 15 hours, namely cooling discharge obtains stable nanometer polymer latex.
Synthesis example 14
90kg deionized water is added in the header tank that band stirs, 10kg cetyl trimethylammonium bromide, 5kgOP-10 emulsifying agent, 190kg vinylbenzene, 14kgN, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 4kg Hydroxyethyl acrylate, 0.4 gram of lauryl mercaptan, stirs pre-emulsification half an hour at normal temperatures as pre-emulsion.In another header tank, add 1.1kg azo-bis-isobutyrate hydrochloride, deionized water 110kg, as initiator simultaneously.
In reactor, drop into deionized water 70kg, be warmed up to 90 degree, add 5% of above-mentioned pre-emulsion total mass, 10% of above-mentioned initiator total mass, reacted after 20 to 30 minutes, occurred after faint blueness until system, drip remaining pre-emulsion and initiator simultaneously, drip process lasts 4 hours.Drip off rear insulation 1 hour, moisturizing is adjusted to 40% solid content, namely obtains stable translucent nanometer polymer latex.
Synthesis example 15
90kg deionized water is added in a header tank, 50kg diallyldimethylammonium chloride, 17kgTPEG (isopentene group Soxylat A 25-7, molecular weight 2400), 38kg vinylbenzene is added in another header tank, in the 3rd header tank, add azo-bis-isobutyrate hydrochloride 1.1kg, deionized water 110kg simultaneously, drip component as initiator.
In reactor, drop into deionized water 70kg, be warmed up to 90 degree, start to drip above-mentioned three components.Wherein front two components drip three hours, and initiator component drips three and a half hours, and drip off rear insulation 2 hours, be cooled to less than 50 degree, moisturizing is adjusted to 40% solid content, namely obtain stable translucent nanometer polymer latex.
Synthesis example 16
Deionized water 700kg is dropped in reactor, 10kg sodium lauryl sulphate, 0.2kg sodium bicarbonate, 5kgOP-10 emulsifying agent, 140kg vinylbenzene, 2kg methacrylic acid, 3kg2-acrylamide-2-methyl propane sulfonic (AMPS), 2kg gamma-methyl allyl acyloxypropyl trimethoxysilane, 1kg Pentyl alcohol, after stirring system becomes clear, , fill nitrogen deoxygenation about 20 minutes, be heated to 80 degree, add ammonium persulphate 1.1kg, keep temperature 4 hours, be warmed to 45 degree, drip the NaOH aqueous solution that massfraction is 20%, pH value is transferred between 7.5 ~ 8, moisturizing is adjusted to 15% solid content, namely stable transparent nanometer polymer solution is obtained.
Synthesis example 17
2kg hexadecanol is dissolved in 90kg vinylbenzene, 2kg gamma-methyl allyl acyloxypropyl trimethoxysilane, 2kg methacrylic acid, oily solution is made in 3kg2-acrylamide-2-methyl propane sulfonic (AMPS), 3kg sodium lauryl sulphate, 2kgOP-10 is dissolved in 300kg deionized water and makes the aqueous solution, in container, above-mentioned oily liquid and the aqueous solution are mixed, namely powerful magnetic agitation pre-emulsification after 30 minutes, then obtains miniemulsion in ultrasonic 30 minutes by ultrasonic apparatus.
Miniemulsion is poured in the reactor of band condensation and stirring, fill nitrogen deoxygenation about 20 minutes, be heated to 80 degree, add ammonium persulfate solution (1.1kg ammonium persulphate is dissolved in 100 kilograms of deionized waters), keep temperature 4 hours, be warmed to 45 degree, drip the NaOH aqueous solution that massfraction is 20%, pH value is transferred between 7.5 ~ 8, and moisturizing is adjusted to 20% solid content, namely obtains stable nanometer polymer emulsion.
Synthesis example 18
Thermometer is being housed, agitator, in the suspension polymerization still of reflux exchanger, add deionized water 200kg, polyvinyl alcohol (trade mark is 1788) 2kg starts stirring, logical water of condensation, temperature is risen to 90 DEG C, make polyvinyl alcohol dissolution, cool to 80 degree, add 180kg vinylbenzene, 4kg methacrylic acid, 15kg2-acrylamide-2-methyl propane sulfonic (AMPS), 1kg vinyltriethoxysilane, 3kg Hydroxyethyl acrylate and 0.2 gram of lauryl mercaptan, stir after 5 minutes, add ammonium persulfate solution (1.2kgAPS is dissolved in 20kg water), react under 80 degree after 4 hours, stop heating, stir while polymerization system is cooled to room temperature with cold water, stop stirring, product polyester fiber cloth filters, and finally dries under 60 degree in air dry oven and obtains required particle.
Synthesis example 19
By the multipolymer of 150 grams of phenylethylene-maleic anhydrides, (maleic anhydride content is 10%, number-average molecular weight is about 50,000), add 150 grams of acetone, after being heated to 50 degree of stirring and dissolving, drip the solution containing 2 grams of sodium lauryl sulphate, 1 gram of OP-10,12 grams of NaOH and 200 gram deionized waters, stir 1 hour again after dropwising, namely cooling discharge obtains stable nanometer polymer emulsion.
Synthesis example 20
90kg acetone is added in reactor, 10kg2-acrylamide-2-methyl propane sulfonic (AMPS), 12kgTPEG (isopentene group Soxylat A 25-7, molecular weight 2400), 38kg vinylbenzene, 1kg vinyltriethoxysilane, logical nitrogen is after 30 minutes, add the Diisopropyl azodicarboxylate of 0.6kg, in the little reaction of reflux temperature after 4 hours, cool to 40 degree, drip the solution containing 2kgNaOH and 200kg deionized water, stir 1 hour again after dropwising, namely cooling discharge obtains stable nanometer polymer emulsion.Synthesis example 21
90kg Virahol is added in reactor, 15kgN, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 7kgTPEG (isobutenyl Soxylat A 25-7, molecular weight 2400), 34kg vinylbenzene, logical nitrogen is after 30 minutes, add the Diisopropyl azodicarboxylate of 0.6kg, after 4 hours, cool to 40 degree in the little reaction of reflux temperature, drip the solution containing 1kg acetic acid and 200kg deionized water, stir 1 hour again after dropwising, namely cooling discharge obtains stable nanometer polymer emulsion.
The basic parameter of the organic polymer nano/micrometre particle obtained at synthesis example 1-21 is as in table 1.
The basic parameter of the organic polymer nano/micrometre particle that table 1 synthesis example 1-21 obtains
Preparation example 1
Get the polymers soln of 20 grams of synthesis examples 1,100 grams of silicon sol solutions (mass concentration is 30%) are added drop-wise to inner under the state stirred, place after 10 hours, instill 10 grams of calcium nitrate aqueous solutions (10%wt) again, stir again after dropwising and within 30 minutes, namely obtain final nanometer organic filler.
Preparation example 2
Get the polymers soln of 100 grams of synthesis examples 2, under the state stirred, instillation 10 grams of calcium nitrate aqueous solutions (10%wt), stir after dropwising again and within 30 minutes, namely obtain final nanometer organic filler.
Preparation example 3
Get the polymer dispersion liquid of 100 grams of synthesis examples 3, under the state stirred, instillation 10 grams of calcium nitrate aqueous solutions (10%wt), stir after dropwising again and within 30 minutes, namely obtain final nanometer organic filler.
Preparation example 4
Get the polymer emulsion of 100 grams of synthesis examples 4, under the state stirred, instillation 10 grams of calcium nitrate aqueous solutions (10%wt), stir after dropwising again and within 30 minutes, namely obtain final nanometer organic filler.
Preparation example 6
Get the nano rubber latex of 100 grams of synthesis examples 8, under the state stirred, instillation 10 grams of calcium nitrate aqueous solutions (10%wt), stir after dropwising again and within 30 minutes, namely obtain final nanometer organic filler.
Preparation example 7 and 8
For the nanometer polymer emulsion that synthesis example 9 and 10 obtains, carry out the step identical with preparation example 2, difference is to substitute nitrocalcite with isocyatic aluminum nitrate.
Preparation example 9 and 10
For the nanometer polymer emulsion that synthesis example 11 and 12 obtains, carry out the step identical with preparation example 2, difference is to substitute isocyatic nitrocalcite with Al2O3 colloidal sol.
Preparation example 11
For the nanometer polymer emulsion that synthesis example 13 obtains, carry out the step identical with preparation example 2, difference is to substitute nitrocalcite with isocyatic silicon sol.
Preparation example 12
Get the nano rubber latex of 100 grams of synthesis examples 14, under the state stirred, instillation 5 grams of concentration are the silicon sol of 30%wt, stir again and within 30 minutes, namely obtain final nanometer organic filler after dropwising.
Preparation example 13
Get the nano rubber latex of 100 grams of synthesis examples 15, under the state stirred, instillation 5 grams of concentration are the TiO2 colloidal sol of 30%wt, stir again and within 30 minutes, namely obtain final nanometer organic filler after dropwising.
Preparation example 14
Get the nano rubber latex of 100 grams of synthesis examples 6, under the state stirred, instillation 10 grams of calcium nitrate aqueous solutions (10%wt), stir after dropwising again and within 30 minutes, namely obtain final nanometer organic filler.
Preparation example 15
For the nanometer polymer emulsion that synthesis example 17 obtains, carry out the step identical with preparation example 2, difference is to substitute nitrocalcite with isocyatic aluminum nitrate.
Preparation example 16
For the nanometer polymer emulsion that synthesis example 14 obtains, carry out the step identical with preparation example 2, difference is to substitute nitrocalcite with isocyatic Al2O3 colloidal sol.
Preparation example 17
Get the nano rubber latex of 100 grams of synthesis examples 21, under the state stirred, instillation 5 grams of concentration are the sodium silicate solution of 10%wt, stir again and within 30 minutes, namely obtain final nanometer organic filler after dropwising.
Test example
Mortar is tested
Use reference cement, standard sand, polycarboxylate water-reducer (trade mark MP-103, Beijing Ma Pu novel material company limited provides), water cement ratio 0.38, husky gray scale 3,0.2% of the solid water mixing mud of water reducer folding.All preparation examples and synthesis example volume are 1% of cement, comparative example calcium chloride, and SODIUMNITRATE mixes 1%, trolamine volume position 0.05%.Anti-folding and ultimate compression strength the results are shown in following table:
Table 2 preparation example and synthesis example join the impact on intensity in mortar
Concrete test
Use PO42.5 cement (cement mill, Beijing provides), river sand (silt content 2.8%), polycarboxylate water-reducer (trade mark MP-103, Beijing Ma Pu novel material company limited provides), water cement ratio 0.44, husky gray scale 3,0.2% of the solid water mixing mud of water reducer folding.All preparation examples and synthesis example volume are 1% of cement, comparative example calcium chloride, and SODIUMNITRATE mixes 1%, trolamine volume position 0.05%.Concrete mix (kg/m3)
| Cement | Sand | Stone | Water | Polycarboxylate water-reducer (the solid volume of folding) | Hardening accelerator (the solid volume of folding) |
| 380 | 830 | 1050 | 170 | 0.2％ | 1％ |
Intensity results sees the following form:
Table 3 preparation example and synthesis example join the impact on intensity in concrete
As can be seen from above, polymer nanocomposite of the present invention/micron particle admixture can improve mortar and concrete early anti pressured intension, can also improve resistance to compression and the folding strength of 28 days.
Above-mentioned exemplary embodiment to be described, to should not be construed as and limit the invention.Although disclosed multiple exemplary embodiment, those skilled in the art have been readily appreciated that various deformation possible in exemplary embodiment, and inherently do not depart from novel teachings of the present invention and advantage.Therefore, being included in as defined by the following claims in scope of the present invention of all these Amoebidas.Be understandable that, aforementioned is explanation to various exemplary embodiment, and be not the specific embodiments of limit publicity, the distortion of disclosed embodiment and other exemplary embodiment, object is contained in the scope of claims.
Claims (16)
1. polymer nanocomposite/micron particle admixture, is characterized in that, described polymkeric substance is obtained by copolymerization by main monomer and functional monomer; Described functional monomer contains hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group; Silane functional, silicone hydroxyl functional group; Quaternary amine, quaternary phosphine, Shu Liu functional group; Described polymer nanocomposite/micron particle admixture is the state of dried powder, or the state of aqueous liquid dispersion.
2. polymer nanocomposite according to claim 1/micron particle admixture, it is characterized in that, described main monomer is one or more in vinylbenzene, acrylamide, N,N-DMAA, vinyl pyrrolidone, ethene, acrylate, divinyl, vinylchlorid, vinyl acetate, isoprene, isopentene group Soxylat A 25-7 (TPEG), isobutyl-Soxylat A 25-7 (HPEG), allyl polyethenoxy ether (APEG), methacrylic acid polyethylene glycol methyl esters.
3. polymer nanocomposite according to claim 2/micron particle admixture, it is characterized in that, described acrylate is ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, dodecylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, aliphatic acrylate, octadecyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, lauryl methacrylate, methacrylic acid cetyl ester, octadecyl methacrylate, dimethylaminoethyl methacrylate, one or more in n octyl methacrylate.
4. polymer nanocomposite according to claim 1/micron particle admixture, is characterized in that, described containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, the monomer of phosphite group is selected from but is not limited to following monomer: (methyl) vinylformic acid, methylene-succinic acid, equisetic acid, maleic anhydride, 2-acrylamide-2-methyl propane sulfonic (AMPS), Sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3-allyloxy-2-hydroxyl-1-propanesulfonate (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, methacrylic acid phosphoric acid glycol ester or isopropyl alkenyl phosphoric acid, end group is the isopentene group Soxylat A 25-7 of phosphonic functional groups, end group is the isobutyl-Soxylat A 25-7 of phosphonic functional groups, end group is the allyl polyethenoxy ether (APEG) of phosphonic functional groups, end group is the methacrylic acid polyethylene glycol methyl esters of phosphonic functional groups.
5. polymer nanocomposite according to claim 1/micron particle admixture, it is characterized in that, the described monomer containing silane functional or silicone hydroxyl functional group is selected from but is not limited to following monomer: vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl, acryloxypropyl Trimethoxy silane, vinyl silane triisopropoxide, Y-methacryloxypropyl three isopropoxy silane or propenyl Trimethoxy silane.
6. polymer nanocomposite according to claim 1/micron particle admixture, it is characterized in that, the described monomer containing quaternary amine, quaternary phosphine, Shu Liu functional group is selected from but is not limited to following monomer: diallyldimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 2-(acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3-trimethoxy silicon propyl group) ammonium chloride.
7. polymer nanocomposite according to claim 1/micron particle admixture, it is characterized in that, the described monomer containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group, silane functional or silicone hydroxyl functional group, quaternary amine, quaternary phosphine, Shu Liu functional group also homopolymerization can obtain this nano/micrometre particle.
8. the preparation method of the polymer nanocomposite according to claim 1-7 any one/micron particle admixture, it is characterized in that, main monomer and functional monomer are directly obtained by aqueous solution polymerization, letex polymerization, micro-emulsion polymerization, mini-emulsion polymerization or suspension polymerization; Or main monomer and functional monomer are polymerized in organic solvent, after polymerization by add water or other material formed phase reversion obtain; Or after the multipolymer containing main monomer and functional monomer is dissolved in solvent, in aqueous phase, dispersion and emulsion obtains; Described functional monomer contains hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group; Or silane functional, silicone hydroxyl functional group; Or quaternary amine, quaternary phosphine, Shu Liu functional group.
9. the preparation method of polymer nanocomposite according to claim 8/micron particle admixture, it is characterized in that, described main monomer is one or more in vinylbenzene, acrylamide, N,N-DMAA, vinyl pyrrolidone, ethene, acrylate, divinyl, vinylchlorid, vinyl acetate, isoprene, isopentene group Soxylat A 25-7 (TPEG), isobutyl-Soxylat A 25-7 (HPEG), allyl polyethenoxy ether (APEG), methacrylic acid polyethylene glycol methyl esters.
10. the preparation method of polymer nanocomposite according to claim 9/micron particle admixture, it is characterized in that, described acrylic ester monomer is ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, dodecylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, aliphatic acrylate, octadecyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, lauryl methacrylate, methacrylic acid cetyl ester, octadecyl methacrylate, dimethylaminoethyl methacrylate, one or more in n octyl methacrylate.
The preparation method of 11. polymer nanocomposite according to claim 8/micron particle admixtures, is characterized in that, described containing hydroxy-acid group, sulfate groups, sulfonate group, phosphate groups, the monomer of phosphite group is selected from but is not limited to following monomer: (methyl) vinylformic acid, methylene-succinic acid, equisetic acid, maleic anhydride, 2-acrylamide-2-methyl propane sulfonic (AMPS), Sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3-allyloxy-2-hydroxyl-1-propanesulfonate (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, methacrylic acid phosphoric acid glycol ester or isopropyl alkenyl phosphoric acid, end group is the isopentene group Soxylat A 25-7 of phosphonic functional groups, end group is the isobutyl-Soxylat A 25-7 of phosphonic functional groups, end group is the allyl polyethenoxy ether (APEG) of phosphonic functional groups, end group is the methacrylic acid polyethylene glycol methyl esters of phosphonic functional groups.
The preparation method of 12. polymer nanocomposite according to claim 8/micron particle admixtures, it is characterized in that, the described monomer containing silane functional or silicone hydroxyl functional group is selected from but is not limited to following monomer: vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl, acryloxypropyl Trimethoxy silane, vinyl silane triisopropoxide, γ-methacryloxypropyl three isopropoxy silane or propenyl Trimethoxy silane.
The preparation method of 13. polymer nanocomposite according to claim 7/micron particle admixtures, it is characterized in that, the described monomer containing quaternary amine, quaternary phosphine, Shu Liu functional group is selected from but is not limited to following monomer: diallyldimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N-trimethylammonium-3-(2-methallyl amido)-1-chlorination third ammonium, 2-(acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3-trimethoxy silicon propyl group) ammonium chloride.
The preparation method of 14. polymer nanocomposite according to claim 11/micron particle admixtures, is characterized in that, by resulting polymers and cationic colloidal silica, TiO
2colloidal sol, Al
2o
3colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle generation physical adsorption or Chemical bond.
The preparation method of 15. polymer nanocomposite according to claim 12/micron particle admixtures, is characterized in that, by sol particles, cationic colloidal silica, the TiO of resulting polymers and silicate
2colloidal sol, Al
2o
3colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle generation physical adsorption or Chemical bond.
The preparation method of 16. polymer nanocomposite according to claim 12/micron particle admixtures, is characterized in that, by resulting polymers and silicon sol, water glass, the TiO in negative electricity type
2colloidal sol, Al
2o
3colloidal sol or calcium carbonate nano particle generation physical adsorption or Chemical bond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510422642.5A CN105037646B (en) | 2015-07-17 | 2015-07-17 | A kind of polymer nanocomposite/micro particles additive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510422642.5A CN105037646B (en) | 2015-07-17 | 2015-07-17 | A kind of polymer nanocomposite/micro particles additive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105037646A true CN105037646A (en) | 2015-11-11 |
| CN105037646B CN105037646B (en) | 2018-05-29 |
Family
ID=54444647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510422642.5A Active CN105037646B (en) | 2015-07-17 | 2015-07-17 | A kind of polymer nanocomposite/micro particles additive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105037646B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008848A (en) * | 2016-05-24 | 2016-10-12 | 中国日用化学工业研究院 | Comb type macromolecular dispersant and preparation method thereof |
| CN106432628A (en) * | 2016-09-13 | 2017-02-22 | 科之杰新材料集团有限公司 | Low-sensitivity anti-mud ether-ester copolymerized polycarboxylic acid water reducing agent and preparation method thereof |
| CN106565159A (en) * | 2016-10-25 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | High-performance cement mortar and preparation method thereof |
| CN106565179A (en) * | 2016-11-14 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | Polymer-modified cement based on nano silicate particles and carbon nanotubes |
| CN106947036A (en) * | 2016-01-06 | 2017-07-14 | 南京金斯瑞生物科技有限公司 | A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion and preparation method thereof |
| CN108483980A (en) * | 2018-04-12 | 2018-09-04 | 清华大学 | The preparation method of nano-carbon material-polymer-silicate composite micro-nano particle nucleation agent |
| CN109265123A (en) * | 2018-11-27 | 2019-01-25 | 襄阳华壁新型建材有限公司 | A kind of coal ash autoclaved air-entrained concrete building block and its production method |
| CN112812215A (en) * | 2018-10-10 | 2021-05-18 | 刘鹏 | Preparation method of high-molecular debonder with good grinding-aiding effect for ceramic slurry |
| CN113060962A (en) * | 2021-03-18 | 2021-07-02 | 西南石油大学 | Oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer well cementation and preparation method thereof |
| CN114591646A (en) * | 2022-03-04 | 2022-06-07 | 广东台实实业有限公司 | Wetting dispersant for water-based paint and preparation method thereof |
| CN114891466A (en) * | 2022-06-14 | 2022-08-12 | 广东泰强化工实业有限公司 | Preparation method of single-component high-performance modified chloroprene water-based emulsion spray adhesive |
| CN115073654A (en) * | 2022-06-21 | 2022-09-20 | 清华大学 | Additive for inhibiting cement hydration, preparation method and application thereof |
| CN115806648A (en) * | 2022-12-28 | 2023-03-17 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer prepared from viscosity-reducing macromonomer and preparation method thereof |
| CN116535146A (en) * | 2023-05-24 | 2023-08-04 | 天津大学 | Self-repairing agent for well cementation cement suitable for high-mineralization water environment |
| WO2024064583A1 (en) * | 2022-09-20 | 2024-03-28 | Rohm And Haas Company | Method for preparing a microbe resistant styrenic latex |
| CN114891466B (en) * | 2022-06-14 | 2024-04-26 | 广东泰强科技实业有限公司 | Preparation method of single-component high-performance modified chlorine Ding Shuiji type emulsion spray adhesive |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304901A (en) * | 2000-12-20 | 2001-07-25 | 张新 | Disperser of synthetic fibre and its preparing process |
| CN102351999A (en) * | 2011-07-15 | 2012-02-15 | 清华大学 | Method for preparing nanoparticle water reducing agent |
| CN102911320A (en) * | 2012-07-21 | 2013-02-06 | 北京工业大学 | Method for preparing powder polycarboxylic acid superplasticizer |
| CN103012694A (en) * | 2012-09-13 | 2013-04-03 | 北京工业大学 | Preparation method of polyester type pure solid polycarboxylic acid high-performance water reducing agent |
| CN104725573A (en) * | 2014-10-11 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Superplasticizer for facilitating cement hydration, preparation method thereof and application |
-
2015
- 2015-07-17 CN CN201510422642.5A patent/CN105037646B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304901A (en) * | 2000-12-20 | 2001-07-25 | 张新 | Disperser of synthetic fibre and its preparing process |
| CN102351999A (en) * | 2011-07-15 | 2012-02-15 | 清华大学 | Method for preparing nanoparticle water reducing agent |
| CN102911320A (en) * | 2012-07-21 | 2013-02-06 | 北京工业大学 | Method for preparing powder polycarboxylic acid superplasticizer |
| CN103012694A (en) * | 2012-09-13 | 2013-04-03 | 北京工业大学 | Preparation method of polyester type pure solid polycarboxylic acid high-performance water reducing agent |
| CN104725573A (en) * | 2014-10-11 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Superplasticizer for facilitating cement hydration, preparation method thereof and application |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947036A (en) * | 2016-01-06 | 2017-07-14 | 南京金斯瑞生物科技有限公司 | A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion and preparation method thereof |
| CN106947036B (en) * | 2016-01-06 | 2019-09-20 | 南京金斯瑞生物科技有限公司 | A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether lotion and preparation method thereof |
| CN106008848A (en) * | 2016-05-24 | 2016-10-12 | 中国日用化学工业研究院 | Comb type macromolecular dispersant and preparation method thereof |
| CN106432628A (en) * | 2016-09-13 | 2017-02-22 | 科之杰新材料集团有限公司 | Low-sensitivity anti-mud ether-ester copolymerized polycarboxylic acid water reducing agent and preparation method thereof |
| CN106432628B (en) * | 2016-09-13 | 2018-06-26 | 科之杰新材料集团有限公司 | A kind of muting sensitive induction reactance mud ether-ether copoly type polycarboxylate water-reducer and preparation method thereof |
| CN106565159A (en) * | 2016-10-25 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | High-performance cement mortar and preparation method thereof |
| CN106565179A (en) * | 2016-11-14 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | Polymer-modified cement based on nano silicate particles and carbon nanotubes |
| CN108483980A (en) * | 2018-04-12 | 2018-09-04 | 清华大学 | The preparation method of nano-carbon material-polymer-silicate composite micro-nano particle nucleation agent |
| CN108483980B (en) * | 2018-04-12 | 2021-01-26 | 清华大学 | Preparation method of nano carbon material-polymer-silicate composite micro-nano particle nucleating agent |
| CN112812215A (en) * | 2018-10-10 | 2021-05-18 | 刘鹏 | Preparation method of high-molecular debonder with good grinding-aiding effect for ceramic slurry |
| CN109265123A (en) * | 2018-11-27 | 2019-01-25 | 襄阳华壁新型建材有限公司 | A kind of coal ash autoclaved air-entrained concrete building block and its production method |
| CN109265123B (en) * | 2018-11-27 | 2021-03-30 | 襄阳华壁新型建材有限公司 | Fly ash autoclaved aerated concrete block and production method thereof |
| CN113060962A (en) * | 2021-03-18 | 2021-07-02 | 西南石油大学 | Oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer well cementation and preparation method thereof |
| CN113060962B (en) * | 2021-03-18 | 2022-03-18 | 西南石油大学 | Oil well cement corrosion-resistant early strength agent suitable for salt-gypsum layer well cementation and preparation method thereof |
| CN114591646A (en) * | 2022-03-04 | 2022-06-07 | 广东台实实业有限公司 | Wetting dispersant for water-based paint and preparation method thereof |
| CN114891466A (en) * | 2022-06-14 | 2022-08-12 | 广东泰强化工实业有限公司 | Preparation method of single-component high-performance modified chloroprene water-based emulsion spray adhesive |
| CN114891466B (en) * | 2022-06-14 | 2024-04-26 | 广东泰强科技实业有限公司 | Preparation method of single-component high-performance modified chlorine Ding Shuiji type emulsion spray adhesive |
| CN115073654A (en) * | 2022-06-21 | 2022-09-20 | 清华大学 | Additive for inhibiting cement hydration, preparation method and application thereof |
| CN115073654B (en) * | 2022-06-21 | 2023-11-10 | 清华大学 | Additive for inhibiting cement hydration, preparation method and application thereof |
| WO2024064583A1 (en) * | 2022-09-20 | 2024-03-28 | Rohm And Haas Company | Method for preparing a microbe resistant styrenic latex |
| CN115806648A (en) * | 2022-12-28 | 2023-03-17 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer prepared from viscosity-reducing macromonomer and preparation method thereof |
| CN115806648B (en) * | 2022-12-28 | 2024-02-13 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer prepared from viscosity reducing macromonomer and preparation method thereof |
| CN116535146A (en) * | 2023-05-24 | 2023-08-04 | 天津大学 | Self-repairing agent for well cementation cement suitable for high-mineralization water environment |
| CN116535146B (en) * | 2023-05-24 | 2023-11-24 | 天津大学 | Self-repairing agent for well cementation cement suitable for high-mineralization water environment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105037646B (en) | 2018-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105037646A (en) | Polymer nano / micro particle additive and preparation method thereof | |
| CN105110687B (en) | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN103342782B (en) | Organosilicone modified acrylate emulsion, preparation method thereof and water-based artificial stone prepared from organosilicone modified acrylate emulsion | |
| CN104609759B (en) | Additive capable of improving bending strength and tensile strength of cement base material and its preparation method | |
| CN103922638B (en) | Preparation method of mortar concrete waterproof agent | |
| CN103864340B (en) | A kind of mortar concrete waterproofing agent | |
| CN106220791A (en) | The polycarboxylate water-reducer of a kind of phosphorous acidic group and preparation method | |
| CN109455971B (en) | Preparation method of powdery carboxylic acid water reducing agent | |
| WO2017114375A1 (en) | Cement-based material reinforcing agent, and preparation method therefor and applications thereof | |
| CN106700372B (en) | Application and its composite material and preparation method of the methylacryoyloxyethyl Dodecydimethylammonium bronides in dispersed silicon dioxide | |
| CN106587706A (en) | High self-compaction and reciprocity polycarboxylic acid water reducing agent composition for concrete | |
| CN106674439A (en) | Low and slow coagulating hyperbranched polycarboxylic acid super-plasticizer, preparation method and application thereof | |
| CN104649608A (en) | Additive for improving early strength of cement based material as well as preparation method and application of additive | |
| CN106432584A (en) | Synthesis of imidazole latent epoxy curing accelerator having toughening effect and application of accelerator in epoxy modification | |
| JP6092257B2 (en) | Aqueous dispersion | |
| CN112851889A (en) | Preparation method of graphene oxide modified TPEG type polycarboxylate superplasticizer | |
| WO2019218607A1 (en) | Method for synthesizing magadiite/pmma nano composite microspheres by using ph value regulation in pickering emulsion | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN114437299A (en) | Anti-mud polycarboxylate superplasticizer mother liquor | |
| SG171999A1 (en) | Semi-continuously operated method for producing copolymers | |
| CN1974619A (en) | Prepn and application of reactive polyacrylate microgel | |
| CN106749981B (en) | It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed | |
| CN106279564A (en) | One not chloride ion-containing amphoteric high performance water reducing agent of polyocarboxy acid and preparation method thereof | |
| CN104829792B (en) | A kind of preparation method of polyether-modified polycarboxylic acids grinding aid | |
| CN107200819A (en) | A kind of siliceous synthetic method of polycarboxylate water-reducer and products thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180719 Address after: 030082 Shanxi Shanxi Taiyuan comprehensive reform demonstration zone Taiyuan campus 306 Changzhi Road Fire Patentee after: Shanxi Jai Jiawei Technology Co.,Ltd. Address before: 100084 Beijing City, Haidian District, Haidian District, 100084 mailbox Patentee before: Tsinghua University |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 101303 no.259, jinmayuan 2nd Street, Gaoliying Town, Shunyi District, Beijing Patentee after: Beijing Shuimu Jiawei Technology Co.,Ltd. Address before: 030082 No. 306 Fire, Changzhi Road, Taiyuan Xuefu Park, Shanxi Comprehensive Reform Demonstration Zone Patentee before: Shanxi Jai Jiawei Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190911 Address after: 101303 no.259, jinmayuan 2nd Street, Gaoliying Town, Shunyi District, Beijing Co-patentee after: SHANXI JIAWEI NEW MATERIAL CO.,LTD. Patentee after: Beijing Shuimu Jiawei Technology Co.,Ltd. Address before: 101303 no.259, jinmayuan 2nd Street, Gaoliying Town, Shunyi District, Beijing Patentee before: Beijing Shuimu Jiawei Technology Co.,Ltd. |