CN105037646B - A kind of polymer nanocomposite/micro particles additive and preparation method thereof - Google Patents
A kind of polymer nanocomposite/micro particles additive and preparation method thereof Download PDFInfo
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Abstract
A kind of polymer nanocomposite/micro particles additive, the polymer are obtained by main monomer and functional monomer by combined polymerization；The functional monomer contains carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group；Silane functional, silicone hydroxyl functional group；Quaternary amine, quaternary phosphine, Shu Liu functional groups；The polymer nanocomposite/micro particles additive is the state of dried powder or the state of aqueous liquid dispersion.In some cases, the polymer can also not have main monomer, but must contain above-mentioned functional monomer.The polymer nano-particle additive of the present invention by introducing the modification of functional functional group or later stage in the copolymer, there are polymer nanocomposite/micro particles and promote hydrated cementitious nucleation, greatly improve cement early hydration rate, so as to reach the function of improving cement-based material early strength, and improve the toughness of cement-based material.
Description
Technical field
It is more particularly to a kind of to be used to improve cement-based material early stage the invention belongs to cement-based material additive technical field
The polymer nanocomposite of intensity/micro particles additive and preparation method thereof.
Background technology
It improves the early strength of cement-based material (including mortar, concrete), accelerate gain in strength, be always some buildings
Key technology requirement in engineering.Such as：In the prefabricated components preparation process of concrete, quick early strength growth is conducive to
The Rapid Circulation of template uses, and improves production efficiency；The cement matrix used in requirement in engineering first-aid repair, road repair engineering
Expect the rapid growth of intensity；Winter low temperature construction then needs using special concrete admixture concrete strength to be accelerated to send out
Exhibition.Traditional technical measures are the early strength agent that addition is a small amount of in concrete (or mortar) to accelerate cement concrete early strength
Development.Common early strength agent includes inorganic salts material such as sodium chloride, calcium chloride, sulfate, nitrate etc.；And organic early strength agent
Including triethanolamine, triisopropanolamine etc..These early strength agent can effectively improve cement concrete early strength, however one
It is a common disadvantage is that the later strength of mortar or concrete can be reduced to some extent.This shortcoming, greatly limits morning
Strong extensive use of the agent in concrete.
Research in recent years shows that some nanometers or micron-sized particle are added in cement-based material, can promote water
The nucleation rate at muddy water initial stage greatly improves the degree of hydration during early stage hydrated cementitious, so as to significantly improve cement matrix
The early strength of material.This kind of particle is known as nucleation accelerating agent, abbreviation nucleating agent.It has been found that the grain for having such nucleation
Son is mainly inorganic particulate, including TiO2,SiO2,CaCO3Wait nano-particles, and the nanometer of hydrated calcium silicate (CSH) gel or
Particle of micron-scale etc..One advantage of these nucleating agent particles is exactly to significantly improve the premise of cement-based material early strength
Under, the later strength or final strength for even improving cement concrete are not reduced.
Multiple polymers latex or rubber powder widely use in various cement-based materials.Including styrene-butadiene latex, propylene
Esters of gallic acid latex and ethylene-vinyl acetate copolymer latex or rubber powder etc..The use of these polymer emulsions can effectively improve
Toughness, flexural strength, adhesion strength, crack resistance, wearability and the impermeability of cement concrete.Substantially improve cement-based material
Mechanical property and endurance quality.However, the engineering problem of a facing is exactly various polymer emulsions or rubber powder, it is all different
Have to hydrated cementitious to degree and delay inhibitory action.
The content of the invention
The purpose of the invention is to overcome the drawbacks described above of the prior art, a kind of organic polymer of synthesis is provided and is received
Rice/micro particles introduce function functional group or the modification in later stage so that such polymer particles have by combined polymerization
Similar promotion hydrated cementitious nucleation, greatly improves cement early hydration rate, and cement-based material morning is improved so as to reach
The function of phase intensity, and improve the toughness of cement-based material.
The present invention provides a kind of polymer nanocomposite/micro particles additive, which is characterized in that the polymer is by main list
What body and functional monomer were obtained by combined polymerization；The functional monomer contains carboxylic acid group, sulfate groups, sulfonate radical
Group, phosphate groups, phosphite group；Silane functional, silicone hydroxyl functional group；Quaternary amine, quaternary phosphine, Shu Liu functional groups；Institute
It is the state of dried powder or the state of aqueous liquid dispersion to state polymer nanocomposite/micro particles additive.
Further, the main monomer be styrene, acrylamide, N,N-DMAA, vinyl pyrrolidone,
Ethylene, acrylate, butadiene, vinyl chloride, vinylacetate, isoprene, isopentene group polyoxyethylene ether (TPEG), isobutyl
The polyether macromonomers such as base polyoxyethylene ether (HPEG), allyl polyethenoxy ether (APEG), metering system acid polyethylene glycol methyl esters
One or more of；
Further, the acrylate is ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, propylene
The own ester of acid, dodecylacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, methacrylic acid
Hydroxypropyl acrylate, aliphatic acrylate, octadecyl acrylate, acrylic acid-2-ethyl caproite, acrylic acid -2- ethylaminos ester,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, lauryl
Base ester, methacrylic acid cetyl ester, octadecyl methacrylate, dimethylaminoethyl methacrylate, methyl-prop
One or more in olefin(e) acid n-octyl.
Further, it is described to contain carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group
Monomer be selected from but be not limited to following monomers：(methyl) acrylic acid, itaconic acid, aconitic acid, maleic anhydride, 2- acrylamides-
2- methyl propane sulfonic acids (AMPS), sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3- alkene
Propoxyl group -2- hydroxyl -1- propanesulfonates (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2- acryloyls
Amido -2- methylpropanephosphonic acids, metering system acid phosphoric acid glycol ester or isopropyl alkenyl phosphoric acid, the iso-amylene that end group is phosphonic functional groups
The pi-allyl polyoxy that base polyoxyethylene ether, end group are the isobutyl group polyoxyethylene ether of phosphonic functional groups, end group is phosphonic functional groups
Vinethene (APEG), the metering system acid polyethylene glycol methyl esters that end group is phosphonic functional groups.
Further, the monomer containing silane functional or silicone hydroxyl functional group is selected from but is not limited to following monomers：
Vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methyl-prop
Alkene monomethacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, acryloxypropyl trimethoxy
Silane, vinyl silane triisopropoxide, three isopropoxy silane of Y- methacryloxypropyls or acrylic trimethoxy
Silane.
Further, the monomer containing quaternary amine, quaternary phosphine, Shu Liu functional groups is selected from but is not limited to following monomers：Diene
Diallyidimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N- trimethyls -3- (2- methallyl acyls
Amino) the third ammonium of -1- chlorinations, 2- (acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3- trimethoxies
Silicon propyl) ammonium chloride.
Further, it is described to contain carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, phosphorous acid foundation
Group, silane functional or silicone hydroxyl functional group, quaternary amine, quaternary phosphine, Shu Liu functional groups monomer can also homopolymerization this nanometer/micro- is made
Rice corpuscles.
The present invention also provides the preparation methods of above-mentioned polymer nanocomposite/micro particles additive, which is characterized in that by main list
Body and functional monomer are directly made by aqueous solution polymerization, emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization or suspension polymerisation
；Or polymerize main monomer and functional monomer in organic solvent, by the way that water or other materials is added to be formed after polymerization
Phase reversal is made；Or by the way that the copolymer containing main monomer and functional monomer is dissolved in solvent after, in water phase disperse breast
Change and be made；The functional monomer contains carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, orthophosphite
Group；Or silane functional, silicone hydroxyl functional group；Or quaternary amine, quaternary phosphine, Shu Liu functional groups.
Further, the main monomer be styrene, acrylamide, N,N-DMAA, vinyl pyrrolidone,
Ethylene, acrylate, butadiene, vinyl chloride, vinylacetate, isoprene, isopentene group polyoxyethylene ether (TPEG), isobutyl
The polyether macromonomers such as base polyoxyethylene ether (HPEG), allyl polyethenoxy ether (APEG), metering system acid polyethylene glycol methyl esters
One or more of.
Further, the acrylic ester monomer is ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid penta
Ester, Hexyl 2-propenoate, dodecylacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, first
Base hydroxypropyl acrylate, aliphatic acrylate, octadecyl acrylate, acrylic acid-2-ethyl caproite, acrylic acid -2-
Ethylamino ester, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, metering system
Sour dodecyl ester, methacrylic acid cetyl ester, octadecyl methacrylate, dimethylaminoethyl second
One or more in ester, n octyl methacrylate.
Further, it is described to contain carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group
Monomer be selected from but be not limited to following monomers：(methyl) acrylic acid, itaconic acid, aconitic acid, maleic anhydride, 2- acrylamides-
2- methyl propane sulfonic acids (AMPS), sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3- alkene
Propoxyl group -2- hydroxyl -1- propanesulfonates (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2- acryloyls
Amido -2- methylpropanephosphonic acids, metering system acid phosphoric acid glycol ester or isopropyl alkenyl phosphoric acid, the iso-amylene that end group is phosphonic functional groups
The pi-allyl polyoxy that base polyoxyethylene ether, end group are the isobutyl group polyoxyethylene ether of phosphonic functional groups, end group is phosphonic functional groups
Vinethene (APEG), the metering system acid polyethylene glycol methyl esters that end group is phosphonic functional groups.
Further, the monomer containing silane functional or silicone hydroxyl functional group is selected from but is not limited to following monomers：
Vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methyl-prop
Alkene monomethacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, acryloxypropyl trimethoxy
Silane, vinyl silane triisopropoxide, three isopropoxy silane of γ-methacryloxypropyl or acrylic trimethoxy
Silane.
Further, the monomer containing quaternary amine, quaternary phosphine, Shu Liu functional groups is selected from but is not limited to following monomers：Diene
Diallyidimethylammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, N, N, N- trimethyls -3- (2- methallyl acyls
Amino) the third ammonium of -1- chlorinations, 2- (acryloyl-oxy) ethyl dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3- trimethoxies
Silicon propyl) ammonium chloride.
Further, by resulting polymers and cationic colloidal silica, TiO2Colloidal sol, Al2O3Colloidal sol, soluble calcium salt, aluminium salt or
Physical absorption or chemical bond occur for calcium carbonate nano particle.
Further, by the sol particles of resulting polymers and silicate, cationic colloidal silica, TiO2Colloidal sol, Al2O3Colloidal sol,
Physical absorption or chemical bond occur for soluble calcium salt, aluminium salt or calcium carbonate nano particle.
Further, by resulting polymers and Ludox, sodium metasilicate, the TiO in negative electricity type2Colloidal sol, Al2O3Colloidal sol or carbonic acid
Physical absorption or chemical bond occur for calcium nano-particle.
Polymer nanocomposite/micro particles additive of the present invention is being incorporated into cement-based material, volume 0.2%-5%
When (amount of solid of object of the present invention is converted into the percentage of the quality of cement), the function of cement-based material early strength can be improved,
The later strength or final strength for even improving cement-based material are not reduced.Meanwhile it on the premise of early strength is improved, reaches
Raising cement-based material toughness, impermeability to as there is polymer emulsion or rubber powder.
Specific embodiment
The main material of polymer nanocomposite/micro particles additive of the present invention is：Polystyrene, polyolefins high score
Son, acrylic acid esters co-polymer, cinnamic acrylic ester analog copolymer, butadiene-styrene analog copolymer, ethyl vinyl acetate second
Enester analog copolymer, neoprene class, natural rubber class, epoxy resin latex class etc..
Corresponding main monomer is but is not limited to styrene, acrylamide, N, N- dimethacrylamide, vinyl pyrrole
Alkanone, ethylene, butadiene, vinyl chloride, vinylacetate, isoprene, isopentene group polyoxyethylene ether (TPEG), isobutyl group gather
Polyether macromonomers, the propylene such as ethylene oxide ether (HPEG), allyl polyethenoxy ether (APEG), metering system acid polyethylene glycol methyl esters
Acetoacetic ester, propyl acrylate, butyl acrylate, amyl acrylate, Hexyl 2-propenoate, dodecylacrylate, acrylic acid ten
Six Arrcostabs, octadecyl acrylate, acrylic acid-2-ethyl caproite, hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl-prop
Olefin(e) acid hydroxyl ethyl ester, hydroxy propyl methacrylate, acrylic acid -2- ethylaminos ester, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, pentylmethacrylate, lauryl methacrylate, methacrylic acid cetyl ester, methyl
Octadecyl base, dimethylaminoethyl methacrylate, n octyl methacrylate etc..
Polymer nanocomposite/micro particles additive of the present invention is introduced by combined polymerization on surface in functional functional group
Carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group can come from following but do not limit to
In following monomers：(methyl) acrylic acid, itaconic acid, aconitic acid, maleic anhydride, 2- acrylamide-2-methyl propane sulfonics (AMPS),
Sodium styrene sulfonate (SSS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS), 3- allyloxy -2- hydroxyls -1- third
Sodium sulfonate (AHPS), vinylbenzenesulfonic acid sodium, vinyl phosphonate, styryl phosphonic acid, 2- acrylamido -2- methylpropanephosphonic acids,
Metering system acid phosphoric acid glycol ester, isopropyl alkenyl phosphoric acid, the isopentene group polyoxyethylene ether that end group is phosphonic functional groups, end group are
The isobutyl group polyoxyethylene ether of phosphonic functional groups, the allyl polyethenoxy ether that end group is phosphonic functional groups (APEG), end group are
The metering system acid polyethylene glycol methyl esters of phosphonic functional groups.
Polymer nanocomposite/micro particles additive of the present invention is introduced by combined polymerization on surface in functional functional group
Silane functional, silicone hydroxyl functional group can come from following but be not limited to following monomers：Vinyltriethoxysilane, second
Alkenyl trimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, gamma-methyl allyl acyloxypropyl trimethoxy silicon
Alkane, γ-methacryloxypropyl, acryloxypropyl trimethoxy silane, three isopropyl oxygen of vinyl
Base silane, three isopropoxy silane of γ-methacryloxypropyl, acrylic trimethoxy silane etc..
Quaternary amine, quaternary phosphines, the tertiary sulphur that polymer nanocomposite/micro particles additive of the present invention is introduced by combined polymerization on surface
Functional group can come from following but be not limited to following monomers：Diallyldimethylammonium chloride, (methyl) acryloyl-oxy second
Base trimethyl ammonium chloride, N, N, N- trimethyls -3- (2- methallyls acylamino-) third ammonium of -1- chlorinations, 2- (acryloyl-oxy) ethyl
Dimethylammonium chloride sulphur, methylacryoyloxyethyl dimethyl (3- trimethoxy silicon propyl) ammonium chloride etc..
It is above-mentioned to contain carboxylic acid group, sulfate groups, sulfonate group, phosphate groups, phosphite group, silane official
Can group or silicone hydroxyl functional group, quaternary amine, quaternary phosphine, Shu Liu functional groups monomer can also homopolymerization this nano/micrometre particle is made.This
The polymer nanocomposite of invention/micro particles additive be main monomer and functional monomer by aqueous solution polymerization, emulsion polymerization,
Micro-emulsion polymerization, mini-emulsion polymerization, suspension polymerisation copolymerization are directly obtained or by that will contain main monomer and functional monomer
After copolymer is dissolved in solvent, dispersion and emulsion is made in water phase.Conventional emulsion polymerization or seed can be used in emulsion polymerization therein
It is prepared by the method for emulsion polymerization.First a certain amount of emulsifier solution or seed emulsion will be added in reaction vessel, be heated to anti-
After answering temperature, add in a small amount of monomer (such as 10%) and initiator carries out prepolymerization 30min.Then by pre-emulsification monomer and initiator
It is continuously added drop-wise within 2-6 hour in reaction vessel, after being added dropwise, when adding redox initiator and reacting one section again
Between after, so that residual monomer quantity is preferably minimized, finally i.e. obtain organic polymer nano/micrometre particle or preliminary grain
Son.
Aqueous polymer method its basic process be equipped with thermometer, blender, reflux condenser three-necked flask in,
Portions of de-ionized water is added in, starts stirring, leads to condensed water, temperature is risen to 40~90 DEG C, initiator and monomer are added dropwise respectively
Into flask.Reacted again after to be triggered dose and monomer dropping certain time obtain machine high molecular nanometer (micron) particle or
Preliminary particle.
Conventional emulsion polymerization method (one-step method) comprises the following steps：
1. first a certain amount of emulsifier solution will be added in reaction vessel,
2. it after being heated to reaction temperature (40-95 DEG C), adds in a small amount of monomer (such as 5-10%) and initiator carries out prepolymerization
30min。
3. being then continuously added drop-wise to pre-emulsification monomer and initiator in reaction vessel within 2-6 hour, it is added dropwise
Afterwards, add after redox initiator reacts a period of time again, so that residual monomer quantity is preferably minimized, finally to obtain the final product
To machine high molecular nanometer/micro particles or preliminary particle.
Seed emulsion polymerization (two step method) comprises the following steps：
1 prepares latex seed
Each component is weighed by the composition and usage ratio of above-mentioned monomer, is added in the head tank with stirring, adds breast
Agent and water, high-speed stirred 30-40 minutes is to get to the pre-emulsion of monomer.First by the monomer pre-emulsion of 5-10%, dress is added to
In the reaction kettle for having thermometer, heater, blender, charge pipe and head tank, be slowly ramped to temperature for 80 DEG C -90 DEG C when,
Initiator is added in, after a few minutes, faint blue light occurs in lotion, is stirred for 5-10 minutes, that is, forms latex seed.
2 prepare polymer emulsion
Monomer pre-emulsion and initiator when 2-4 is small are continuously added drop-wise in reaction kettle, reacted with latex seed, reaction temperature
Degree be maintained at 85 DEG C -90 DEG C, after completion of the reaction, heat preservation 1 it is small when after, then simultaneously redox initiator is added dropwise, after being added dropwise,
Keep the temperature 1 it is small when after, cool to less than 50 DEG C, add in sodium hydrate aqueous solution, the pH value of regulation system is 7-8 to get to machine height
Molecule nano/micro particles or preliminary particle.
Polymer nanocomposite/micro particles additive of the present invention can also be made using the emulsion polymerization of self-emulsifying form
Standby, the difference of more general emulsion polymerization is additionally add in emulsifier.Its general process is first by reaction appearance
A certain amount of deionized water is added in device, after being heated to reaction temperature.Then respectively by oiliness monomer, aqueous monomers, initiator
It is continuously added drop-wise within 2-6 hour in reaction vessel, after being added dropwise, when adding redox initiator and reacting one section again
Between after, so that residual monomer quantity is preferably minimized, finally i.e. obtain organic polymer nano/micrometre particle or preliminary grain
Sub- dispersion liquid.
Polymer nanocomposite/micro particles additive of the present invention can also be prepared using micro-emulsion polymerization, substantially mistake
Journey is that monomer (including main monomer and function monomer), emulsifier, assistant for emulsifying agent, water are placed in round-bottomed flask according to a certain ratio,
It heats while stirring, suitable initiator (can also be by light-initiated), nitrogen charging deoxygenation are added in after system becomes clear
20 minutes or so, 30-90 DEG C is warming up to, constant temperature carries out polymerisation under stiring, is periodically sampled in polymerization process, uses gravimetric method
Its conversion ratio is surveyed, after conversion ratio makes it, is cooled down up to required particle aqueous liquid dispersion.
Polymer nanocomposite/micro particles additive of the present invention can also be prepared using mini-emulsion polymerization, substantially mistake
Journey forms oil phase for co-stabilizer (such as hexadecane, hexadecanol) is dissolved in monomer (including main monomer and function monomer) first,
By high speed shear or ultrasonic disperse, oil-soluble monomer is dispersed in water phase, forms pre-emulsified monomer emulsions, is being stirred
Under, it is warming up to reaction temperature and deoxygenation.After heating and deoxygenation, initiator initiated polymerization is added in, is determined in polymerization process
Phase samples, its conversion ratio is surveyed with gravimetric method, after conversion ratio makes it, cools down up to required particle aqueous dispersion
Liquid.
Polymer nanocomposite/micro particles additive of the present invention can also be prepared using suspension polymerisation, basic process
For equipped with thermometer, blender, reflux condenser three-necked flask in, add in deionized water, dispersant (such as polyvinyl alcohol),
Stirring is started, leads to condensed water, temperature is risen to 40~90 DEG C, dissolves dispersant；30~80 DEG C are cooled the temperature to again, treat the water surface
Upper lather collapse；It will be added to dissolved with the monomer mixture of initiator in the water phase dissolved with dispersant；Make water-bath temperature under stiring
Degree is progressively raised to 80~85 DEG C of progress suspension polymerisations.After reacting 2h, a small amount of material can be drawn with suction pipe and carried out in the device of surface
Observation if particle is hardened embrittlement, can stop heating, withdraw from heater, stir while being cooled to polymerization system with cold water
Room temperature；Stopping stirring, remove three-necked flask, product is filtered with Buchner funnel, and with hot water wash for several times, finally in air dry oven
Particle needed for middle drying.
Polymer nanocomposite/high eyebrow particle additive of the present invention also can be used after by dissolving a polymer in solvent,
Dispersion and emulsion is made in water phase, and general process is:Polymer and solvent are added in flask, stirring is started, is warming up to 30-
It is 90 DEG C, strong to stir after object to be polymerized is completely dissolved, the deionized water containing acid or alkali is added dropwise (if general function functional group is in
Cationic then adds in acid, on the contrary then add in alkali) and emulsifier, until eventually becoming aqueous dispersions, protected again after being added dropwise
Temperature stirring is more than half an hour up to required particle dispersion.
The polymer nano-particle additive of the present invention can also be used to be polymerize in organic solvent system, and then plus water is sent out
Raw phase reversal is made, and general process is:Monomer (including main monomer and function monomer), solvent and initiator are added to burning
In bottle, stirring is started, leads to nitrogen after twenty minutes, is warming up to 30-90 DEG C, is periodically sampled in polymerization process, its turn is surveyed with gravimetric method
Rate after conversion ratio makes it, cools to 30-70 DEG C, strong to stir, and the deionized water (one containing acid or alkali is added dropwise
As if function functional group in adding in acid if cationic, it is on the contrary then add in alkali), phase reversal gradually occurs for solution, until finally
Become aqueous dispersions, after being added dropwise again insulated and stirred it is more than half an hour up to required particle aqueous liquid dispersion.
If the polymer nanocomposite that the above method obtains/micro particles additive surface-functional functional group is silane-functional
Group, silicone hydroxyl functional group have then played an important role of promotion cement heterogeneous nucleation, can be used directly to as early strong nucleating agent,
Also sol particles, cationic colloidal silica, the TiO of silicate can also be added in inside above-mentioned particle2Colloidal sol, Al2O3Colloidal sol,
Physical absorption can occur for soluble calcium salt, aluminium salt or calcium carbonate nano particle, the latter in organic polymer nano/micrometre particle
Surface, and then improve the effect with cement heterogeneous nucleation.
The surface-functional functional group of the polymer nanocomposite that the above method obtains/micro particles additive is if contain carboxylic
Acid groups, sulfate groups, sulfonate group, phosphate groups, phosphite group, then can be molten in later stage and cationic silicon
Glue, TiO2Colloidal sol, Al2O3Physical absorption occurs for colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle so as to cement
The effect of heterogeneous nucleation.
The surface-functional functional group of the polymer nanocomposite that the above method obtains/micro particles additive is if contain season
Amine, quaternary phosphine groups, thus can be with the Ludox, sodium metasilicate, TiO in negative electricity type2, colloidal sol, Al2O3Colloidal sol or calcium carbonate nano
Particle occurs physical absorption and then plays an important role of to cement heterogeneous nucleation.
With reference to embodiment, the present invention is described in more detail.
Synthesis example 1
2kg γ-methacryloxypropyl is added in a head tank, in another head tank
In add in 8kg vinyl pyrrolidones, while in the 3rd head tank add in ammonium persulfate 0.7kg, deionized water 20kg, make
Component is added dropwise for initiator.
80kg deionized waters are put into reaction kettle, 70kgTPEG (isopentene group polyoxyethylene ether, molecular weight 2400) rises
Temperature to 80 degree starts that above three component is added dropwise.Wherein the first two component is added dropwise three hours, and it is small that initiator component is added dropwise three and half
When, 30 minutes are kept the temperature after dripping off, while 0.1 kilogram of tert-butyl hydroperoxide and the solution A of 5 kg of water composition is added dropwise, 0.05 is public
The solution B of jin sodium thiosulfate and 5 kilograms of deionized waters composition, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to 50
Below degree, solid content is adjusted to 40% to get to stable transparent nanometer polymer solution by moisturizing.
Synthesis example 2
5kg deionized waters, 8kg vinyl pyrrolidones (NVP), in another head tank are added in a head tank
Sodium peroxydisulfate 1.1kg, deionized water 10kg are added in, component is added dropwise as initiator.
TPEG (the isopentene group polyoxy second that deionized water 50kg, 50kg end group are phosphonic functional groups is put into reaction kettle
Alkene ether, molecular weight 1000), 90 degree are warming up to, starts that above-mentioned two component is added dropwise.Wherein preceding component is added dropwise three hours, initiator
Component is added dropwise three and a half hours, and 30 minutes are kept the temperature after dripping off, and temperature is dropped to 85 degree, while 0.42 kilogram of t-butyl peroxy is added dropwise
Change the solution B of the solution A of hydrogen and 5 kg of water composition, 0.25 kilogram of sodium thiosulfate and 5 kilograms of deionized waters composition, during dropwise addition
Between 2 it is small when after, then keep the temperature half an hour, be cooled to less than 50 degree, solid content is adjusted to 40% to get stable transparent is arrived by moisturizing
Nanometer polymer solution.
Synthesis example 3
90kg deionized waters, 5kg acrylamides are added in a head tank, 17kg end groups are the HPEG of phosphonic functional groups
(isobutenyl polyoxyethylene ether, molecular weight 4000) adds in 68kg styrene in another head tank, while in the 3rd height
Sodium peroxydisulfate 1.1kg, deionized water 110kg are added in the slot of position, component is added dropwise as initiator.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, starts that above three component is added dropwise.It is two groups wherein preceding
Divide and be added dropwise three hours, initiator component is added dropwise three and a half hours, keeps the temperature 30 minutes after dripping off, temperature is dropped to 85 degree, is dripped simultaneously
The solution A that 0.42 kilogram of tert-butyl hydroperoxide and 20 kg of water is added to form, 0.25 kilogram of sodium thiosulfate and 12 kilograms go from
The solution B of sub- water composition, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to less than 50 degree, moisturizing adjusts solid content
For 40% to get to stable translucent nanometer polymer latex.
Synthesis example 4
200 grams of Ludox (30% concentration) are put into three-necked flask, 4.5 grams of γ-methyl-props of interior dropwise addition when 1 is small at normal temperatures
The solution of alkene monomethacryloxypropyl trimethoxy silane and 5.5 grams of ethyl alcohol when placement 24 is small after dripping off, obtains a silane-modified silicon
Sol A.
The input deionized water 88g in flask, 6.8 grams of above-mentioned modification liquid A, 20 grams of styrene are arrived with nitric acid adjustment pH value
3, quick stirring into pre-emulsion, adds in 0.13 gram of sodium peroxydisulfate after ten minutes, is warming up to 85 DEG C, when reaction 4 is small, cools to room temperature
Obtain stable milky nanometer polymer latex.
Synthesis example 5
90kg deionized waters are put into reaction kettle, 70kg end groups are TPEG (the isopentene group polyoxyethylene of phosphate group
Ether, molecular weight 800), 80 degree are warming up to, starting dropwise addition initiator component, (0.7kg ammonium persulfates are dissolved in 10 kilograms of deionized waters
In) two hours are added dropwise, keep the temperature 30 minutes after dripping off, be cooled to less than 50 degree, moisturizing solid content be adjusted to 40% to get to
Stable nanometer polymer solution.
Synthesis example 6
90kg deionized waters, 10kg lauryl sodium sulfate, 5kg OP-10 emulsifications are added in the head tank with stirring
Agent, 190kg styrene, 2kg acrylamides, 2kg gamma-methyl allyl acyloxypropyl trimethoxysilanes, 0.4 gram of dodecyl sulphur
Alcohol stirs pre-emulsification half an hour as pre-emulsion at normal temperatures.Potassium peroxydisulfate 1.1kg is added in another head tank simultaneously,
Deionized water 110kg, as initiator.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, adds in the 5% of above-mentioned pre-emulsion gross mass, it is above-mentioned
The 10% of initiator gross mass after reacting 20 to 30 minutes, after occurring faint blueness after system, adds in 5kg COPS-1 (methods
Rhodia of state produces), while remaining pre-emulsion and initiator is added dropwise, dropwise addition process continue 4 it is small when.30 are kept the temperature after dripping off
Minute, temperature is dropped to 85 DEG C, while 0.42 kilogram of tert-butyl hydroperoxide and the solution A of 20 kg of water composition is added dropwise, 0.25
The solution B of kilogram rongalite and 12 kilograms of deionized water compositions, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to 50 DEG C
Hereinafter, the NaOH aqueous solutions that mass fraction is 20% are added dropwise, between pH value is transferred to 7.5~8, moisturizing is adjusted to solid content
40% to get to stable translucent nanometer polymer latex.
Synthesis example 7
90kg deionized waters, 5kg hydroxyethyl methacrylates, 17kgTPEG (isopentene groups are added in a head tank
Polyoxyethylene ether, molecular weight 2400), the addition 68kg styrene in another head tank, 1kg vinyltriethoxysilane,
Sodium peroxydisulfate 1.1kg, deionized water 110kg are added in the 3rd head tank simultaneously, component is added dropwise as initiator.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, starts that above three component is added dropwise.It is two groups wherein preceding
Divide and be added dropwise three hours, initiator component is added dropwise three and a half hours, keeps the temperature 30 minutes after dripping off, temperature is dropped to 85 degree, is dripped simultaneously
The solution A that 0.42 kilogram of tert-butyl hydroperoxide and 20 kg of water is added to form, 0.25 kilogram of sodium thiosulfate and 12 kilograms go from
The solution B of sub- water composition, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to less than 50 degree, moisturizing adjusts solid content
For 40% to get to stable translucent nanometer polymer latex.
Synthesis example 8
90kg deionized waters, 10kg lauryl sodium sulfate, 5kg OP-10 emulsifications are added in the head tank with stirring
Agent, 190kg styrene, 6kg methacrylic acids, 14kg 2- acrylamide-2-methyl propane sulfonics (AMPS), 4kg acrylic acid hydroxyl second
Ester, 0.4 gram of lauryl mercaptan stir pre-emulsification half an hour as pre-emulsion at normal temperatures.Simultaneously in another head tank
Add in potassium peroxydisulfate 1.1kg, deionized water 110kg, as initiator.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, adds in the 5% of above-mentioned pre-emulsion gross mass, it is above-mentioned
The 10% of initiator gross mass after reacting 20 to 30 minutes, after occurring faint blueness after system, adds in 5kg COPS-1 (methods
Rhodia of state produces), while remaining pre-emulsion and initiator is added dropwise, dropwise addition process continue 4 it is small when.30 are kept the temperature after dripping off
Minute, temperature is dropped to 85 degree, while 0.42 kilogram of tert-butyl hydroperoxide and the solution A of 20 kg of water composition is added dropwise, 0.25
The solution B of kilogram rongalite and 12 kilograms of deionized water compositions, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to 50 degree
Hereinafter, the NaOH aqueous solutions that mass fraction is 20% are added dropwise, between pH value is transferred to 7.5~8, moisturizing is adjusted to solid content
40% to get to stable translucent nanometer polymer latex.
Synthesis example 9
90kg deionized waters, 50kg sodium styrene sulfonate (SSS), 14kgTPEG (iso-amylene are added in a head tank
Base polyoxyethylene ether, molecular weight 2400), 40kg styrene is added in another head tank, while in the 3rd head tank
Sodium peroxydisulfate 1.1kg, deionized water 110kg are added in, component is added dropwise as initiator.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, starts that above three component is added dropwise.It is two groups wherein preceding
Divide and be added dropwise three hours, initiator component is added dropwise three and a half hours, keeps the temperature 30 minutes after dripping off, temperature is dropped to 85 degree, is dripped simultaneously
The solution A that 0.42 kilogram of tert-butyl hydroperoxide and 20 kg of water is added to form, 0.25 kilogram of sodium thiosulfate and 12 kilograms go from
The solution B of sub- water composition, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to less than 50 degree, moisturizing adjusts solid content
For 40% to get to stable translucent nanometer polymer latex.
Synthesis example 10
90kg deionized waters, 50kg vinyl phosphonates, 17kgTPEG (isopentene group polyoxy second are added in a head tank
Alkene ether, molecular weight 2400), 38kg styrene is added in another head tank, while over cure is added in the 3rd head tank
Component is added dropwise as initiator in sour sodium 1.1kg, deionized water 110kg.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, starts that above three component is added dropwise.It is two groups wherein preceding
Divide and be added dropwise three hours, initiator component is added dropwise three and a half hours, keeps the temperature 30 minutes after dripping off, temperature is dropped to 85 degree, is dripped simultaneously
The solution A that 0.42 kilogram of tert-butyl hydroperoxide and 20 kg of water is added to form, 0.25 kilogram of sodium thiosulfate and 12 kilograms go from
The solution B of sub- water composition, when time for adding 2 is small after, then keep the temperature half an hour, be cooled to less than 50 degree, moisturizing adjusts solid content
For 40% to get to stable translucent nanometer polymer latex.
Synthesis example 11
Addition 180kg deionized waters in a kettle, the polyvinyl alcohol KH-20 (synthesis chemical company of Japan) of 3kg, 90 DEG C
Under be completely dissolved after, add emulsifier sodium lauryl sulfate 3kg, 120kg vinyl acetate and 80kg tertiary ethylene carbonates,
Then it is water-soluble to add in the sodium acid carbonate that 10kg mass fractions are 5% for 10kg isobutyl groups polyoxyethylene ether (HPEG), 5kg acrylic acid
Liquid, reflux condensation mode open polymeric kettle stirring, emulsify 30min, and it is water-soluble then to add in the potassium peroxydisulfate that 20kg mass fractions are 5%
Liquid reacts 5h postcoolings under 90 degree and adds water that solid content is made to reach 40%, discharging.
Synthesis example 12
Addition 130kg deionized waters in a kettle, the polyvinyl alcohol KH-20 (synthesis chemical company of Japan) of 2kg, 90 DEG C
Under be completely dissolved after, add 4kg OP-10 emulsifiers, 100kg vinyl acetates and 0.3kg sodium acid carbonates, 4kg 2- propylene
Amide -2- methyl propane sulfonic acids (AMPS), 0.2kg ammonium persulfates, with nitrogen and ethylene gas, respectively displacement (is three times after closing lid
15kg/cm2Pressure).It is passed through ethylene (pressure 35kg/cm2) stirring is started, ethylene pressure is risen into 50kg/cm after 15 minutes2, rise
Temperature when maintenance 8 is small, then is warming up to 85 degree to 80 degree, when maintenance 1 is small, cooling discharging.
Synthesis example 13
In order successively by 0.75kg disproportionated rosin soaps, 0.28kg potassium stearates, 0.03kg potassium chloride, uncle 0.35kg 12
Carbon mercaptan, 140kg deionized waters add in the potassium hydroxide aqueous solution that mass fraction is 5% and adjust the pH value of system to 9~10,
Then 30kg styrene, 3kg isopentene groups polyoxyethylene ether (TPEG, molecular weight 2400), 20kg2- acrylamide -2- first are added in
Base propane sulfonic acid (AMPS), 0.85kg potassium peroxydisulfates are added in reaction kettle, and sealing vacuumizes, and is kept for half an hour, removes air, so
70kg divinylic monomers are added in by measuring tank afterwards.Stirring is opened, is warming up to 65 DEG C~70 DEG C, when reaction 15 is small, cooling discharge is
Obtain stable nanometer polymer latex.
Synthesis example 14
90kg deionized waters, 10kg cetyl trimethylammonium bromides, 5kg OP-10 are added in the head tank with stirring
Emulsifier, 190kg styrene, 14kg N, N, N- trimethyls -3- (2- methallyls acylamino-) third ammonium of -1- chlorinations, 4kg propylene
Sour hydroxyl ethyl ester, 0.4 gram of lauryl mercaptan stir pre-emulsification half an hour as pre-emulsion at normal temperatures.It is high at another simultaneously
1.1kg azo-bis-isobutyrate hydrochlorides, deionized water 110kg, as initiator are added in the slot of position.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, adds in the 5% of above-mentioned pre-emulsion gross mass, it is above-mentioned
After reacting 20 to 30 minutes, after occurring faint blueness after system, while remaining pre- breast is added dropwise in the 10% of initiator gross mass
Liquid and initiator, dropwise addition process continue 4 it is small when.When heat preservation 1 is small after dripping off, solid content is adjusted to 40% to get to steady by moisturizing
Fixed translucent nanometer polymer latex.
Synthesis example 15
90kg deionized waters, 50kg diallyldimethylammonium chlorides, 17kgTPEG (isoamyls are added in a head tank
Alkenyl polyoxyethylene ether, molecular weight 2400), 38kg styrene is added in another head tank, while in the 3rd head tank
In add in azo-bis-isobutyrate hydrochloride 1.1kg, deionized water 110kg, as initiator be added dropwise component.
Deionized water 70kg is put into reaction kettle, is warming up to 90 degree, starts that above three component is added dropwise.It is two groups wherein preceding
Divide and be added dropwise three hours, initiator component is added dropwise three and a half hours, when heat preservation 2 is small after dripping off, is cooled to less than 50 degree, moisturizing is admittedly
Content is adjusted to 40% to get to stable translucent nanometer polymer latex.
Synthesis example 16
Deionized water 700kg, 10kg lauryl sodium sulfate, 0.2kg sodium acid carbonates, 5kg OP- are put into reaction kettle
10 emulsifiers, 140kg styrene, 2kg methacrylic acids, 3kg 2- acrylamide-2-methyl propane sulfonics (AMPS), 2kg γ-first
Base acryloxypropyl trimethoxy silane, 1kg n-amyl alcohols, after stirring system becomes clear, 20 minutes left sides of nitrogen charging deoxygenation
The right side is heated to 80 degree, adds in ammonium persulfate 1.1kg, when keeping temperature 4 small, is warmed to 45 degree, and it is 20% that mass fraction, which is added dropwise,
NaOH aqueous solutions, between pH value is transferred to 7.5~8, solid content is adjusted to 15% to get to stable transparent nanometer by moisturizing
Polymer solution.
Synthesis example 17
2kg hexadecanols are dissolved in 90kg styrene, 2kg gamma-methyl allyl acyloxypropyl trimethoxysilanes, 2kg first
Oily solution is made in 3kg 2- acrylamide-2-methyl propane sulfonics (AMPS) in base acrylic acid, 3kg lauryl sodium sulfate,
2kgOP-10 is dissolved in 300kg deionized waters and aqueous solution is made, and above-mentioned oil-based liquid and aqueous solution are mixed in one in container
It rises, strength magnetic agitation pre-emulsification obtains miniemulsion in 30 minutes after 30 minutes, then with Ultrasound Instrument ultrasound.
Miniemulsion is poured into the reaction kettle with condensation and stirring, nitrogen charging deoxygenation 20 minutes or so is heated to 80 degree, adds in
Ammonium persulfate solution (1.1kg ammonium persulfates are dissolved in 100 kilograms of deionized waters) when keeping temperature 4 small, is warmed to 45 degree, drop
Add mass fraction be 20% NaOH aqueous solutions, between pH value is transferred to 7.5~8, moisturizing solid content be adjusted to 20% to get
To stable nanometer polymer emulsion.
Synthesis example 18
Equipped with thermometer, blender, reflux condenser suspension polymerization kettle in, add in deionized water 200kg, poly-
Vinyl alcohol (trade mark 1788) 2kg starts stirring, leads to condensed water, temperature is risen to 90 DEG C, polyvinyl alcohol is dissolved, cools to 80
Degree adds in 180kg styrene, 4kg methacrylic acids, 15kg 2- acrylamide-2-methyl propane sulfonics (AMPS), 1kg vinyl
Triethoxysilane, 3kg hydroxy-ethyl acrylates and 0.2 gram of lauryl mercaptan, stirring after five minutes, add in ammonium persulfate solution
(1.2kgAPS is dissolved in 20kg water), under 80 degree react 4 it is small when after, stop heating, stir while with cold water by polymerization
System is cooled to room temperature；Stop stirring, product is filtered with polyester fiber cloth, and finally drying is under 60 degree in air dry oven
Obtain required particle.
Synthesis example 19
By the copolymer of 150 grams of phenylethylene-maleic anhydrides, (maleic anhydride content 10%, number-average molecular weight are left for 50,000
It is right), 150 grams of acetone are added in, after being heated to 50 degree of stirring and dissolvings, are added dropwise containing 2 grams of lauryl sodium sulfate, 1 gram of OP-10,12
The solution of gram NaOH and 200 gram of deionized water, be stirred for after being added dropwise 1 it is small when, cooling discharge is up to the nanometer polymerization stablized
Object lotion.
Synthesis example 20
90kg acetone is added in reaction kettle, 10kg 2- acrylamide-2-methyl propane sulfonics (AMPS), 12kgTPEG is (different
Pentenyl polyoxyethylene ether, molecular weight 2400), 38kg styrene, 1kg vinyltriethoxysilane leads to nitrogen after 30 minutes,
Add in the azodiisobutyronitrile of 0.6kg, when the small reaction 4 of reflux temperature is small after, cool to 40 degree, be added dropwise containing 2kgNaOH and
The solution of 200kg deionized waters, be stirred for after being added dropwise 1 it is small when, cooling discharge up to stablize nanometer polymer emulsion.It closes
Into example 21
90kg isopropanols, 15kg N, N, N- trimethyls -3- (2- methallyls acylamino-) -1- chlorine are added in reaction kettle
Change the third ammonium, 7kgTPEG (isobutenyl polyoxyethylene ether, molecular weight 2400), 34kg styrene lead to nitrogen after 30 minutes, adds in
The azodiisobutyronitrile of 0.6kg, when the small reaction 4 of reflux temperature is small after, cool to 40 degree, be added dropwise and contain 1kg acetic acid and 200kg
The solution of deionized water, be stirred for after being added dropwise 1 it is small when, cooling discharge up to stablize nanometer polymer emulsion.
In the basic parameter of the organic polymer nano/micrometre particle obtained in synthesis example 1-21 such as table 1.
The basic parameter for the organic polymer nano/micrometre particle that 1 synthesis example 1-21 of table is obtained
Preparation example 1
The polymer solution of 20 grams of synthesis examples 1 is taken, 100 grams of silicon sol solutions are added drop-wise in the state of stirring, and (quality is dense
Spend in 30%), to place 10 it is small when after, then instill 10 grams of calcium nitrate aqueous solutions (10%wt), 30 points be stirred for after being added dropwise
Clock obtains final nanometer organic filler.
Preparation example 2
The polymer solution of 100 grams of synthesis examples 2 is taken, 10 grams of calcium nitrate aqueous solutions (10% are instilled in the state of stirring
Wt), it is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 3
The polymer dispersion liquid of 100 grams of synthesis examples 3 is taken, 10 grams of calcium nitrate aqueous solutions (10% are instilled in the state of stirring
Wt), it is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 4
The polymer emulsion of 100 grams of synthesis examples 4 is taken, 10 grams of calcium nitrate aqueous solutions (10% are instilled in the state of stirring
Wt), it is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 6
The nano rubber latex of 100 grams of synthesis examples 8 is taken, 10 grams of calcium nitrate aqueous solutions (10%wt) are instilled in the state of stirring,
It is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 7 and 8
For the nanometer polymer emulsion that synthesis example 9 and 10 obtains, the step identical with preparation example 2, difference are carried out
It is to substitute calcium nitrate with the aluminum nitrate of isoconcentration.
Preparation example 9 and 10
For the nanometer polymer emulsion that synthesis example 11 and 12 obtains, the step identical with preparation example 2, difference are carried out
It is the calcium nitrate that isoconcentration is substituted with Al2O3 colloidal sols.
Preparation example 11
For the nanometer polymer emulsion that synthesis example 13 obtains, the step identical with preparation example 2 is carried out, the difference is that
Calcium nitrate is substituted with the Ludox of isoconcentration.
Preparation example 12
The nano rubber latex of 100 grams of synthesis examples 14 is taken, the Ludox that 5 grams of concentration are 30%wt is instilled in the state of stirring,
It is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 13
The nano rubber latex of 100 grams of synthesis examples 15 is taken, it is molten that the TiO2 that 5 grams of concentration are 30%wt is instilled in the state of stirring
Glue is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 14
The nano rubber latex of 100 grams of synthesis examples 6 is taken, 10 grams of calcium nitrate aqueous solutions (10%wt) are instilled in the state of stirring,
It is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Preparation example 15
For the nanometer polymer emulsion that synthesis example 17 obtains, the step identical with preparation example 2 is carried out, the difference is that
Calcium nitrate is substituted with the aluminum nitrate of isoconcentration.
Preparation example 16
For the nanometer polymer emulsion that synthesis example 14 obtains, the step identical with preparation example 2 is carried out, the difference is that
Calcium nitrate is substituted with the Al2O3 colloidal sols of isoconcentration.
Preparation example 17
The nano rubber latex of 100 grams of synthesis examples 21 is taken, it is molten that the sodium metasilicate that 5 grams of concentration are 10%wt is instilled in the state of stirring
Liquid is stirred for obtaining within 30 minutes final nanometer organic filler after being added dropwise.
Test example
Mortar is tested
Using reference cement, normal sand, (trade mark MP-103, Beijing Ma Pu new materials Co., Ltd carry polycarboxylate water-reducer
For), the ratio of mud 0.38, husky gray scale 3, the 0.2% of the solid water mixing mud of water-reducing agent folding.All preparation examples and synthesis example volume are water
The 1% of mud, comparative example calcium chloride, sodium nitrate mix 1%, triethanolamine volume position 0.05%.Anti- folding and compression strength are the result is shown under
Table：
2 preparation example of table and synthesis example are added to the influence in mortar to intensity
Concrete test
PO42.5 cement (offer of Beijing cement plant), river sand (clay content 2.8%), polycarboxylate water-reducer (trade mark MP- are provided
103, Beijing Ma Pu new materials Co., Ltd provides), the ratio of mud 0.44, husky gray scale 3, the 0.2% of the solid water mixing mud of water-reducing agent folding.Institute
Some preparation examples and synthesis example volume are the 1% of cement, comparative example calcium chloride, and sodium nitrate mixes 1%, triethanolamine volume position
0.05%.Concrete mix (kg/m3)
| Cement | Sand | Stone | Water | Polycarboxylate water-reducer (the solid volume of folding) | Early strength agent (the solid volume of folding) |
| 380 | 830 | 1050 | 170 | 0.2% | 1% |
Intensity results see the table below：
3 preparation example of table and synthesis example are added to the influence in concrete to intensity
From the aforegoing it can be seen that polymer nanocomposite/micro particles additive of the present invention can improve the morning of mortar and concrete
Phase compression strength, moreover it is possible to improve resistance to compression and the flexural strength of 28 days.
It is above-mentioned to be illustrated for exemplary embodiment, it should not be construed as limiting the invention.Although it has disclosed
Multiple exemplary embodiments, those skilled in the art are readily appreciated that possible various deformation in exemplary embodiment, and do not have
There are the novel teachings and advantage for inherently deviateing the present invention.Therefore, all these Amoebidas are included in such as claim
In defined the scope of the present invention.It is understood that foregoing is the explanation to various exemplary embodiment, it is not limitation
Disclosed specific embodiments, the deformation of open embodiment and other exemplary embodiments, it is therefore an objective to which being contained in appended right will
In the scope asked.
Claims (3)
1. a kind of polymer nanocomposite/micro particles additive, which is characterized in that the polymer is by main monomer and functionality list
Body is obtained by combined polymerization；The main monomer is in vinyl pyrrolidone, ethylene, butadiene, vinyl chloride, isoprene
One or more, the functional monomer contains silane functional, silicone hydroxyl functional group；The polymer and TiO2It is molten
Glue, Al2O3Physical absorption or chemical bond occur for colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle；The polymer
Nano/micrometre particle additive is the state of dried powder or the state of aqueous liquid dispersion.
2. polymer nanocomposite according to claim 1/micro particles additive, which is characterized in that described to contain silane official
It can roll into a ball or the monomer of silicone hydroxyl functional group is selected from following monomers：Vinyltriethoxysilane, vinyltrimethoxysilane, second
Alkenyl three ('beta '-methoxy ethyoxyl) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxy
Propyl-triethoxysilicane, acryloxypropyl trimethoxy silane, vinyl silane triisopropoxide, γ-methacryl
Three isopropoxy silane of oxygroup propyl or acrylic trimethoxy silane.
3. the preparation method of polymer nanocomposite according to claim 1 or 2/micro particles additive, which is characterized in that institute
Polymer is stated directly to be made by aqueous solution polymerization by main monomer and functional monomer；Or existed by main monomer and functional monomer
It polymerize in organic solvent, by the way that water or other materials is added to form phase reversal and be made after polymerization；Or by the way that main list will be contained
After the copolymer of body and functional monomer is dissolved in solvent, dispersion and emulsion is made in water phase；By the polymer and TiO2Colloidal sol,
Al2O3Physical absorption or chemical bond occur for colloidal sol, soluble calcium salt, aluminium salt or calcium carbonate nano particle.
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| 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 |
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| 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 |
| 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 |
| 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 |
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