CN106117420B - A kind of modified cement mortar styrene-acrylic emulsion and preparation method thereof - Google Patents
A kind of modified cement mortar styrene-acrylic emulsion and preparation method thereof Download PDFInfo
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- CN106117420B CN106117420B CN201610595738.6A CN201610595738A CN106117420B CN 106117420 B CN106117420 B CN 106117420B CN 201610595738 A CN201610595738 A CN 201610595738A CN 106117420 B CN106117420 B CN 106117420B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The present invention relates to a kind of modified cement mortar styrene-acrylic emulsion and preparation method thereof, modified cement mortar is made of with styrene-acrylic emulsion the component of following components and parts by weight：Styrene 24~49, butyl acrylate 49~74, functional monomer 2~6, anion emulsifier 0.5~1, nonionic emulsifier 0.5~1.5, initiator 0.4~0.75, pH buffer 0.3~0.5, stabilizer 0~2, appropriate pH adjusting agent, water 100~150；Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7~8.Compared with prior art, the polymer emulsion that the present invention obtains can keep stablizing in cement mortar, and modified mortar is made to have better performance, and low Tg polymer emulsion is easily demulsified in cement mortar in being studied before solving the problems, such as.
Description
Technical field
The invention belongs to building material technical field, more particularly, to a kind of modified cement mortar styrene-acrylic emulsion and its system
Preparation Method.
Background technology
Ordinary cement sill bond strength is low, and brittleness is big, and impermeability, crack resistance, frost resistance are poor.For common cement-base
These shortcomings existing for material, people start to explore the property blended using polymer and cement to improve ordinary cement sill
Energy.After adding polymer material, many performances of cement-based material for example intensity, deformability, adhesive property, water resistance,
Endurance quality etc. can all have improvement, improved degree and polymer cement ratio (the ratio between the weight of solid polymer and cement weight), polymerize
Kind and performance of object etc. have much relations.
The research of polymer emulsion used in terms of the polymer cement waterproof paint is relatively more, the product of exploitation also phase
It is relatively abundanter for, and it is then fewer about polymer emulsion kind used in modified cement mortar, and be concentrated mainly on
The product of the world such as BASF, Tao Shi major company.Since in polymer cement waterproof paint, the dosage of cement and sand compares
It is few, therefore stability contradiction of the lotion in polymer cement waterproof paint does not protrude.And in Polymer-Modified Mortar, water
Mud and sand are key components, and mostly between the 1%-20% of cement quality, hydrated cementitious discharges anti-polymer emulsion volume
Shear agitation in number ion and mixed process can all cause the stability of polymer emulsion very big influence, especially exist
The glass transition temperature of polymer than it is relatively low when, this is particularly problematic, many lotions be used for modified cement mortar when also
There is phenomena such as lotion exosmoses, slurry is unstable, the quality of polymer-modified cement mortar has been seriously affected.In the market almost
There is no the domestic lotion kind of stay in grade, cement mortar in good standing and concrete modifying.
In recent years, some researchers have done some researchs to modified mortar with polymer emulsion.
Chinese patent CN101062850A discloses a kind of flexible acrylic ester emulsion for sand pulp, and mainly highlighting can carry
The adhesion strength of high cement products, but be not directed to polymer emulsion and mortar compatibility and polymer emulsion to mortar other
The influence of aspect of performance.
Chinese patent CN101386663A discloses a kind of multi-functional acrylic acid lotion, prepared by lotion claim can be with
Improve the performance of mortar, but waterproof is only prepared there is no the data that lotion can be used successfully in mortar in its content
The performance data of coating.
Chinese patent CN1587178A discloses a kind of polymer emulsion for cement-based material diminishing and its preparation side
Method, the polymer emulsion prepared have good diminishing efficiency, can be by reducing water consumption under conditions of fluidities are waited
To improve the flexural strength of mortar and adhesion strength, and reduce the water absorption rate of mortar.But polymerized monomer has been used and has largely been subtracted
Aqua polymerization macromer methoxyl polyethylene glycol methacrylate, methoxylation polypropylene glycol polyethylene glycol metering system
Acid esters, polyethylene glycol methacrylate-styrene polymer etc., these raw material are not only not as good as traditional emulsion polymerization is easy to get, but also valency with monomer
Lattice are relatively expensive, substantially increase the cost of polymer emulsion.And its emulsifier used is reactive emulsifier, it is domestic at present right
Limited in the exploitation of reactive emulsifier, price is high, less varieties, and for the good kind of application performance with regard to less, molecular structure is complicated,
Influence factor is more, and regularity is not strong, if polymerisation group reaction rate is too fast in emulsifier or slowly can all influence to polymerize excessively
Object emulsion intercalation method.In addition, it is mainly the lotion of a kind of water-reducing agent rather than cement mortar modification.
Chinese patent CN102718922A discloses a kind of preparation method of modified road concrete polyacrylate emulsion,
Obtained polyacrylate dispersion can preferably improve the performance of mortar.But the workability without handing over mortar (does not have
Illustrate how to ensure stability of the lotion in mortar), caking property, performances, the mortar formula prepared such as water resistance do not hand over
Generation, the performance for comprehensively comparing very much prepared lotion of having no idea.And technique used is core-shell emulsion polymerization technique, although nucleocapsid
Emulsion polymerization can be according to the latex particle for needing to design different structure of performance, but to the structural form of its emulsion particle
It can not accurately control.And there are many factor due to be designed and influence factor, and it is how accurate in large-scale production
The influence of control various factors be a very big challenge.
It is husky that Chinese patent CN101687952A discloses a kind of cement mortar admixture aqueous synthetic-resin emulsion, cement
It starches additive emulsibility aqueous synthetic-resin emulsion powder again and uses its cement mortar admixture, be 3 in aggregate-to-cement ratio, water
Gray scale is 0.7, and under conditions of polymer cement ratio is 0.1, the not high only 170mm of initial fluidity of mortar illustrates in the patent
The polymer emulsion and latex powder of announcement are in mortar and not bery stablize (so just using the so high ratio of mud), while so
The high ratio of mud can cause the degradation of other performances of mortar, although not providing the pressure-proof and snap-resistent of mortar in that patent
Etc. mechanical properties.
It can be seen that China's research for modified mortar polymer emulsion at present and not perfect, the polymerization developed
Also there are many problems for object lotion.And, it is most important that it is all not specifically mentioned and how to select in above publication
Monomer component can allow the lotion synthesized by it steadily to be used in mortar with when technique.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of modified cement mortars
With styrene-acrylic emulsion and preparation method thereof.
The problem of for background technology, the present inventor have carried out a large amount of experimental study.It was found that it influences
Styrene-acrylic emulsion is in cement mortar there are four the principal elements of stability：First, the influence of glass transition temperature, in identical polymerization
When technique and identical functional monomer, glass transition temperature difference is to stability of the polymer emulsion in cement slurry and most
Good stabilizer structure selection has very big influence；Secondly when glass transition temperature is identical, influence maximum is function
The selection of property monomer and its proportioning；Again, the stabilizer of suitable construction is selected, lotion is made to can be used for cement mortar；Finally, it polymerize
The control of technique also has a significant impact to stability of the lotion in cement mortar.By rationally adjusting more than influence factor, gather
It closes object lotion and just can be good in mortar use without consistency problem.
When the present invention proposes the lotion of synthesis different glass temperature Styrene-acrylic copolymer, rational functionality how is selected
Monomer component proportioning, emulsifier and stabilizer structure and the scheme of polymerization technique, it can be ensured that obtained polymer emulsion energy
It is enough to keep stablizing, and make modified mortar that there is better performance in cement mortar.
The purpose of the present invention can be achieved through the following technical solutions：
Technical solution one：Modified cement mortar styrene-acrylic emulsion is provided：
A kind of modified cement mortar styrene-acrylic emulsion, is made of the component of following components and parts by weight：
Preferably, the functional monomer is selected from acrylic acid, methacrylic acid, acrylamide, N- methylol acryloyls
It is one or more in amine, hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate or hydroxypropyl acrylate
Compounding.
Preferably, the anion emulsifier is selected from lauryl sodium sulfate, neopelex or alkylbenzene
One kind in ether disulfonate.
Preferably, the nonionic emulsifier is selected from alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween
In one kind；The one kind of the stabilizer in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween.
Preferably, the one kind of the initiator in ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
Preferably, the pH buffer is the sodium bicarbonate of a concentration of 10wt%, and pH adjusting agent is ammonium hydroxide, 5wt%
Sodium hydroxide or potassium hydroxide.
Preferred embodiment one：Modified cement mortar styrene-acrylic emulsion is made of the component of following components and parts by weight：
In the preferred embodiment, functional monomer is selected from 1-2 parts by weight of acrylic acid, 1-2 parts by weight N- methylol acryloyls
The compounding of amine, 1-2 weight parts of methacrylic acid hydroxyl ethyl esters；The nonionic emulsifier is selected from alkyl phenol polyoxyethylene ether or fat
One kind in fat alcohol polyoxyethylene ether；The stabilizer is in alkyl phenol polyoxyethylene ether or fatty alcohol polyoxyethylene ether
It is a kind of；The nonionic emulsifier and structure of the preferred water-wet side EO chain elements of stabilizer below 20.
In this preferred embodiment, the copolymer glass transition temperature being calculated according to FOX formula is at -30 DEG C~-10 DEG C
Between.
Preferred embodiment two：Modified cement mortar styrene-acrylic emulsion is made of the component of following components and parts by weight：
In this preferred embodiment, functional monomer is selected from 1 parts by weight of acrylic acid and 1 parts by weight N hydroxymethyl acrylamide
Compounding；The one kind of the nonionic emulsifier in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween；Institute
The one kind of the stabilizer stated in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween；The nonionic Emulsion
Agent and structure of the preferred water-wet side EO chain elements of stabilizer more than 40.
In this preferred embodiment, according to the copolymer glass transition temperature that FOX formula are calculated -10 DEG C~0 DEG C it
Between.
Preferred embodiment three：Modified cement mortar styrene-acrylic emulsion is made of the component of following components and parts by weight：
In this preferred embodiment, the functional monomer is selected from acrylic acid, methacrylic acid, acrylamide, N- methylols
One kind in acrylamide, hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate or hydroxypropyl acrylate
Or a variety of compoundings；The nonionic emulsifier is in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween
It is a kind of；The one kind of the stabilizer in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween.This is preferred real
It applies in mode, the copolymer glass transition temperature being calculated according to FOX formula is at 0 DEG C or more.
From preferred embodiment one to preferred embodiment three, the requirement in component formula to functional monomer and stabilizer is increasingly
It is low.It can cause preferred embodiment two and preferred embodiment three with the proportioning of the functional monomer in preferred embodiment one and stabilizer
Styrene-acrylic emulsion keeps stablizing in cement mortar；It is applied in preferred embodiment three with the component proportion in preferred embodiment two, equally
The styrene-acrylic emulsion of preferred embodiment three can be made to keep stablizing in cement mortar.But just not all right in turn, i.e. preferred embodiment three
The selection of middle functional monomer and stabilizer and proportioning cannot make preferred embodiment one with styrene-acrylic emulsion in preferred embodiment two in cement
It keeps stablizing in mortar, the selection of functional monomer and stabilizer and proportioning cannot make benzene in preferred embodiment one in preferred embodiment two
Acrylic emulsion keeps stablizing in cement mortar.
Technical solution two：The preparation method of modified cement mortar styrene-acrylic emulsion is provided：
The preparation method of the modified cement mortar styrene-acrylic emulsion, technique used are semicontinuous pre-emulsification seed emulsion
Polymerization is as follows：
(1) initiator solution is prepared, prepares pH buffer；
(2) water prepared in initiator solution and pH buffer is deducted from total Water, with the 25wt% in remaining water
Prepare the blended emulsifier being made of anion emulsifier and nonionic emulsifier；
(3) styrene, butyl acrylate and functional monomer used in synthesis are uniformly mixed, obtain mix monomer；
(4) pre-emulsification is carried out to mix monomer；Pre-emulsification step is as follows：95wt% in blended emulsifier is added in into reaction
Device adds in pH buffer, and under conditions of 40 DEG C of water-baths and speed of agitator is 1000r/min, all mix is added dropwise in 30mins
Monomer is closed, after mix monomer is added dropwise, continues to stir up to pre-emulsion；
(5) seed emulsion is prepared：Remaining all water and the blended emulsifier of remaining 5wt% are added in into reactor,
Solution in reaction vessel is warming up to 80~82 DEG C, 5 are added dropwise into reaction vessel under the conditions of speed of agitator is 160r/min
The pre-emulsion of~10wt% and the initiator of 20wt%, wherein initiator are same prior in pre-emulsion dropwise addition 5mins, 30mins
When be added dropwise up to blue seed emulsion；
(6) main reaction：Under 80~82 DEG C of water-baths and speed of agitator is newborn for the seed prepared under the conditions of 120r/min to (5)
Continue that remaining pre-emulsion and initiator is added dropwise in liquid, dripped off in 2.5~3h, wherein initiator is later than pre-emulsion half an hour
It drips off, stops heating, cooling after keeping the temperature 1~2 hour at 90 DEG C；
(7) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with pH adjusting agent；
(8) it is discharged and filtered with the strainer of 120 mesh, lotion after being filtered；
(9) stabilizer is added into lotion after filtering as needed to get to modified cement mortar styrene-acrylic emulsion.
When the present invention proposes the lotion of synthesis different glass temperature Styrene-acrylic copolymer, rational functionality how is selected
Monomer component proportioning, emulsifier and stabilizer structure and the scheme of polymerization technique, it can be ensured that obtained polymer emulsion energy
It is enough to keep stablizing, and make modified mortar that there is better performance in cement mortar, reduced TG temperature in being studied before solving
The problem that degree polymer emulsion is easily demulsified in cement mortar.Different glass made from method and technique provided by the present invention
The lotion of temperature copolymer can increase substantially the fluidity of cement mortar under the conditions of the same ratio of mud, and gradual loss
It is small；Flexural strength, adhesion strength, deformability, flexibility and the water resistance of hardening cement mortar are improved significantly, Ke Yiguang
It is general to be applied in various mortar products.
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) the present invention provides the lotions of different glass temperature Styrene-acrylic copolymer can keep stable in cement mortar
Functional monomer component, volume and emulsifier, stabilizer structure selection method, the present invention polymerization process condition under, close
Lotion into different glass temperature copolymer out all has good compatibility with cement mortar, is studied before solving
The problem that the lotion of middle low Tg copolymer is easily demulsified in cement mortar.
(2) styrene-acrylic emulsion made from method provided by the invention and technique is when composite modified to mortar, can be
Improve the mobility of mortar under the conditions of normal aggregate-to-cement ratio and the ratio of mud well, and amount of air entrainment is smaller, it can be largely
Flexural strength, adhesion strength, deformability, flexibility and the water resistance of hardened mortar are improved, reduces the brittleness of mortar.
(3) polymerization technique used in the present invention is simple, and raw material are cheap and easy to get, is suitble to large-scale industrial production.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
The source of raw material and specification are shown in Table 1 in embodiment.The performance test of prepared lotion or computational methods are shown in Table 2.
1 embodiment raw material sources of table and specification
| Material name | Specification | Source |
| Butyl acrylate | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| Styrene | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| Acrylic acid | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| Methacrylic acid | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| Acrylamide | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| N hydroxymethyl acrylamide | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| Hydroxyethyl methacrylate | Technical grade | Degussa |
| Sodium peroxydisulfate | It analyzes pure | Traditional Chinese medicines chemical reagent |
| Ammonium persulfate | It analyzes pure | Traditional Chinese medicines chemical reagent |
| Lauryl sodium sulfate | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| Neopelex | Chemistry is pure | Traditional Chinese medicines chemical reagent |
| P alkylphenylaceticacid DOWFAX-2A1 | Technical grade | DOW Chemical |
| Fatty alcohol polyoxyethylene ether AEO9 | Technical grade | Hai'an petrochemical industry |
| Fatty alcohol polyoxyethylene ether Lutensol AT50 | Technical grade | BASF |
| Alkyl phenol polyoxyethylene ether OP10 | Technical grade | Hai'an petrochemical industry |
| Sodium bicarbonate | It analyzes pure | Traditional Chinese medicines chemical reagent |
| Ammonium hydroxide | It analyzes pure | Traditional Chinese medicines chemical reagent |
| Sodium hydroxide | It analyzes pure | Traditional Chinese medicines chemical reagent |
2 emulsion property of table is tested or computational methods
If not having specified otherwise in following embodiment, % refers both to mass percent.
Embodiment 1：
It prepares and calculates Styrene-acrylic copolymer lotion of the glass transition temperature between -30~-20 DEG C according to FOX formula.
(1) preparation of blended emulsifier：1 part of lauryl sodium sulfate and 1.5 parts of alkyl phenol polyoxyethylene ether OP10 is molten
To get blended emulsifier solution for standby in 16 parts of water.
(2) 0.6 part of ammonium persulfate is dissolved in 30 parts of water and obtains initiator solution.
(3) 0.3 part of sodium bicarbonate is dissolved in 3 parts of water and obtains pH buffer solutions.
(4) by 28.5 parts of styrene, 66.5 parts of n-butyl acrylates, 2 parts of acrylic acid, 2 parts of N hydroxymethyl acrylamides, 1
Part hydroxyethyl methacrylate is uniformly mixed to obtain mix monomer.
(5) preparation of pre-emulsion.PH buffer solutions all in 95% blended emulsifier in (1) and (3) are added in
In four-hole boiling flask, under conditions of 40 DEG C of water-baths and blender rotating speed is 1000r/min, it is added dropwise in all (4) and makes in 30mins
Standby mix monomer.After mix monomer is added dropwise, continue to stir 5mins up to pre-emulsion.
(6) seed emulsion is prepared.Water-bath pot temperature is adjusted to 80~84 DEG C.48 parts of water and residue are added in into four-hole boiling flask
5% blended emulsifier, first dripped into four-hole boiling flask under the conditions of 80~84 DEG C of water-baths and blender rotating speed is 160r/min
After adding a part of initiator, then 10% pre-emulsion and 20% initiator are added dropwise simultaneously, 30mins is added dropwise up to blue
Color seed emulsion.
(7) main reaction.The seed prepared under the conditions of 80~82 DEG C of water-baths and blender rotating speed is 120r/min in (6)
Continue that remaining pre-emulsion and initiator is added dropwise in lotion, 3h is dripped off, and wherein initiator is later than pre-emulsion half an hour and drips off.
Stop heating, cooling after keeping the temperature one hour at 90 DEG C.
(8) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with 26% ammonium hydroxide.
(9) it is filtered with 120 mesh filter screens.
Embodiment 2：
Styrene-acrylic copolymer lotion of the glass transition temperature between -20~-10 DEG C is calculated according to FOX formula.
(1) preparation of blended emulsifier：0.5 part of lauryl sodium sulfate and 1 part of alkyl phenol polyoxyethylene ether OP10 is molten
To get blended emulsifier solution for standby in 16 parts of water.
(2) 0.6 part of ammonium persulfate is dissolved in 30 parts of water and obtains initiator solution.
(3) 0.4 part of sodium bicarbonate is dissolved in 4 parts of water and obtains pH buffer solutions.
(4) by 33.4 parts of styrene, 62.1 parts of n-butyl acrylates, 1.5 parts of acrylic acid, 2 parts of N hydroxymethyl acrylamides,
1 part of hydroxyethyl methacrylate is uniformly mixed to obtain mix monomer.
(5) preparation of pre-emulsion is the same as embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.The difference is that the water added in reaction vessel is 94 parts.
(7) main reaction.With embodiment 1.
(8) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with 5% sodium hydroxide.
(9) polymer emulsion available for mortar is obtained with the filtering of 120 mesh filter screens.
Embodiment 3：
Styrene-acrylic copolymer lotion of the glass transition temperature between -20~-10 DEG C is calculated according to FOX formula.
(1) preparation of blended emulsifier：By 0.5 part of lauryl sodium sulfate and 1.5 parts of fatty alcohol polyoxyethylene ether AEO9
It is dissolved in 16 parts of water to get blended emulsifier solution for standby.
(2) 0.6 part of ammonium persulfate is dissolved in 30 parts of water and obtains initiator solution.
(3) 0.3 part of sodium bicarbonate is dissolved in 3 parts of water and obtains pH buffer solutions.
(4) by 34 parts of styrene, 63 parts of n-butyl acrylates, 1 part of methacrylic acid, 1 part of N hydroxymethyl acrylamide, 1
Part hydroxyethyl methacrylate conjunction is uniform to obtain mix monomer.
(5) preparation of pre-emulsion is the same as embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Unlike, the amount of water into reaction vessel is 60 parts.
(7) main reaction.With embodiment 1.
(8) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with 5% sodium hydroxide.
(9) it is filtered with 120 mesh filter screens.
(10) the stabilizer OP10 that rear addition accounts for latex solids content 1.5% into lotion obtains can be used for modifying mortar
Polymer emulsion.
Embodiment 4：
Styrene-acrylic copolymer lotion of the glass transition temperature between -10~0 DEG C is calculated according to FOX formula.
(1) preparation of blended emulsifier:1 part of p alkylphenylaceticacid DOWFAX-2A1 and 1.5 parts of alkyl phenols are gathered
Ethylene oxide ether OP40 is dissolved in 16 parts of water to get blended emulsifier solution for standby.
(2) 0.5 part of potassium peroxydisulfate is dissolved in 25 parts of water and obtains initiator solution.
(3) 0.3 part of sodium bicarbonate is dissolved in 3 parts of water and obtains pH buffer solutions.
(4) 39 parts of styrene, 59 parts of n-butyl acrylates, 1 part of acrylic acid, 1 part of N hydroxymethyl acrylamide are mixed equal
It is even to obtain mix monomer.
(5) preparation of pre-emulsion is the same as embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Unlike, the amount of water into reaction vessel is 60 parts.
(7) main reaction.With embodiment 1.
(8) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with 5% sodium hydroxide.
(9) with 120 mesh strainer filtering.
Embodiment 5：
Styrene-acrylic copolymer lotion of the glass transition temperature between -10~0 DEG C is calculated according to FOX formula.
(1) preparation of blended emulsifier:By 0.5 part of p alkylphenylaceticacid DOWFAX-2A1 and 1.5 parts of alkyl phenols
Polyoxyethylene ether OP40 is dissolved in 13 parts of water to get blended emulsifier solution for standby.
(2) 0.75 part of potassium peroxydisulfate is dissolved in 37.5 parts of water and obtains initiator solution.
(3) 0.4 part of sodium bicarbonate is dissolved in 4 parts of water and obtains pH buffer solutions.
(4) 44 parts of styrene, 54 parts of n-butyl acrylates, 1 part of methacrylic acid, 1 part of acrylamide are uniformly mixed
Mix monomer.
(5) preparation of pre-emulsion is the same as embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Unlike, the water added in into reaction vessel is 43 parts, dropwise addition
Pre-emulsion is 5% in (5).
(7) main reaction.With embodiment 1.
(8) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with 5% sodium hydroxide.
(9) it is filtered with 120 mesh filter screens.
Embodiment 6：
(1) preparation of blended emulsifier:1 part of lauryl sodium sulfate and 1.5 parts of fatty alcohol polyoxyethylene ether AEO9 is molten
To get blended emulsifier solution for standby in 13 parts of water.
(2) 0.5 part of potassium peroxydisulfate is dissolved in 25 parts of water and obtains initiator solution.
(3) 0.4 part of sodium bicarbonate is dissolved in 4 parts of water and obtains pH buffer solutions.
(4) 49 parts of styrene, 49 parts of n-butyl acrylates, 2 parts of acrylic acid are uniformly mixed to obtain mix monomer.
(5) preparation of pre-emulsion is the same as embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.The difference is that it is 56 parts that water is added in into reaction vessel.
(7) main reaction.With embodiment 1.
(8) lotion that will be cooled to room temperature is adjusted to pH between 7~8 with 26% ammonium hydroxide.
(9) it is filtered with 120 mesh filter screens.
3 are shown in Table as the polymer emulsion performance parameter obtained by above example.
3 polymer emulsion basic performance of table
By the styrene-acrylic emulsion of embodiment 1- embodiments 6 for modified cement mortar, cement used is PI425 cement, used
Sand is the common river sand of fineness modulus 2.52, and particle diameter distribution is：1.7% is accounted for less than 0.15mm, is less than 0.3mm more than 0.15mm
14.2% is accounted for, 41.7% is accounted for less than 0.63mm more than 0.3mm, 23.8% is accounted for less than 1.25mm more than 0.63mm, more than 1.25mm
10.3% is accounted for less than 2.36mm, 8.3% is accounted for less than 5mm more than 2.36.It is 0.1 in polymer solids/cement quality ratio, water/water
Mud mass ratio is 0.5, and sand/cement quality ratio is 3, under conditions of antifoaming agent volume is the 0.5% of quality of the emulsion, forming polymer
Emulsion modified mortar.Maintenance method is dry curing after wet curing 7 days 21 days.The physical property of Polymer-Modified Mortar such as table 4.It is right
It is with the pure water cement mortar under experiment condition than sample.
The physical property of 4 Polymer-Modified Mortar of table
| Comparative sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Jumping table fluidity/mm | 120 | 190 | 255 | 245 | 227 | 255 | 240 |
| 1h fluidities/mm | 100 | 173 | 240 | 232 | 203 | 240 | 226 |
| 2h fluidities/mm | 100 | 165 | 220 | 218 | 185 | 224 | 210 |
| Flexural strength/MPa | 7.5 | 8.3 | 11.2 | 8.8 | 10 | 11.1 | 9.6 |
| Compression strength/MPa | 30.8 | 23.6 | 28.9 | 25.3 | 36.5 | 38.4 | 45.2 |
| Elasticity modulus/GPa | 14.4 | 8.8 | 13.3 | 8.6 | 12.9 | 12.4 | 13.5 |
| It just splits and absorbs energy/J/m2 | 19.8 | 52.4 | 58.9 | 80.7 | 54.7 | 38.9 | 33.1 |
| Strain | 4.5*10-4 | 9.5*10-4 | 1.0*10-3 | 1.4*10-3 | 7.9*10-4 | 6.7*10-4 | 6.0*10-4 |
| Adhesion strength/MPa | 0.8 | 2.1 | 2.8 | 2.5 | 2.8 | 2.5 | 2.4 |
| Water absorption rate/% | 7.0 | 2.8 | 2.3 | 3.1 | 2.6 | 3.7 | 4.5 |
The polymer emulsion prepared according to polymer emulsion component choosing method provided by the present invention and preparation process exists
The fluidity of cement mortar can be increased substantially under conditions of the identical ratio of mud, and with the extension of time, fluidity damages
Mistake is smaller, illustrates there is good compatibility with mortar under the conditions of high aggregate-to-cement ratio according to polymer emulsion produced by the present invention.
Compared to comparative sample mortar, the anti-folding that lotion incorporation prepared by the method according to the invention and technique can improve mortar is strong
Degree just splits absorption energy, strain, adhesion strength, reduces the elasticity modulus and water absorption rate of mortar.When the glass transition temperature of styrene-acrylic emulsion
The compression strength of modified mortar is to reduce compared to comparative sample when less than -10 DEG C, but the vitrifying temperature of styrene-acrylic emulsion
When degree is higher than -10 DEG C, under the conditions of ratio of muds are waited, polymer emulsion can also improve the compression strength of mortar.Polymer
Monomer component difference influences the performance of mortar very big in lotion, and when soft monomer comparision contents are high, modified mortar has
Higher strain and smaller water absorption rate, but corresponding mechanical property is relatively weak；When duroelasts comparision contents are high
It waits, the strain of modified mortar is smaller, but its anti-folding, resistance to compression, elasticity modulus are higher.Therefore it can be provided according to the present invention
Method and technique by adjusting the component in polymer emulsion come obtain the polymer emulsion of different performance be applied to it is different
In mortar product.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-described embodiment, abilities
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (5)
1. a kind of modified cement mortar styrene-acrylic emulsion, which is characterized in that be prepared by the component of following parts by weight：
Ingredients weight parts
Styrene 25 ~ 38
Butyl acrylate 59 ~ 72
Functional monomer 3 ~ 6
Anion emulsifier 0.5 ~ 1
Nonionic emulsifier 0.5 ~ 1.5
Initiator 0.4 ~ 0.75
PH buffer 0.3 ~ 0.5
Appropriate pH adjusting agent
Water 100 ~ 150；
Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7 ~ 8；
Functional monomer is selected from 1-2 parts by weight of acrylic acid, 1-2 parts by weight N hydroxymethyl acrylamide, 1-2 parts by weight metering systems
The compounding of sour hydroxyl ethyl ester；
The one kind of the nonionic emulsifier in alkyl phenol polyoxyethylene ether or fatty alcohol polyoxyethylene ether；
The anion emulsifier is in lauryl sodium sulfate, neopelex or alkyl phenylate disulfonate
One kind, the one kind of the initiator in ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
A kind of 2. modified cement mortar styrene-acrylic emulsion according to claim 1, which is characterized in that the non-ionic emulsifier
Agent is structure of the water-wet side EO chain elements below 20.
3. a kind of modified cement mortar styrene-acrylic emulsion, which is characterized in that be prepared by the component of following parts by weight：
Ingredients weight parts
Styrene 38 ~ 46
Butyl acrylate 52 ~ 60
Functional monomer 2
Anion emulsifier 0.5 ~ 1
Nonionic emulsifier 0.5 ~ 1.5
Initiator 0.4 ~ 0.75
PH buffer 0.3 ~ 0.5
Appropriate pH adjusting agent
Water 100 ~ 150；
Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7 ~ 8；
Functional monomer is selected from 1 parts by weight of acrylic acid and the compounding of 1 parts by weight N hydroxymethyl acrylamide；
The one kind of the nonionic emulsifier in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween；
The anion emulsifier is in lauryl sodium sulfate, neopelex or alkyl phenylate disulfonate
One kind, the one kind of the initiator in ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
A kind of 4. modified cement mortar styrene-acrylic emulsion according to claim 3, which is characterized in that the non-ionic emulsifier
Agent is structure of the water-wet side EO chain elements more than 40.
5. a kind of modified cement mortar styrene-acrylic emulsion, which is characterized in that be prepared by the component of following parts by weight：
Ingredients weight parts
Styrene 47 ~ 49
Butyl acrylate 49 ~ 51
Functional monomer 2 ~ 6
Anion emulsifier 0.5 ~ 1
Nonionic emulsifier 0.5 ~ 1.5
Initiator 0.4 ~ 0.75
PH buffer 0.3 ~ 0.5
Appropriate pH adjusting agent
Water 100 ~ 150；
Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7 ~ 8；
The functional monomer is selected from acrylic acid, methacrylic acid, acrylamide, N hydroxymethyl acrylamide, metering system
One or more compoundings in sour hydroxyl ethyl ester, hydroxy propyl methacrylate, hydroxy-ethyl acrylate or hydroxypropyl acrylate；
The one kind of the nonionic emulsifier in alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or tween；
The anion emulsifier is in lauryl sodium sulfate, neopelex or alkyl phenylate disulfonate
One kind, the one kind of the initiator in ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
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| CN112020538B (en) * | 2018-04-28 | 2022-04-29 | 陶氏环球技术有限责任公司 | Polymer modified cementitious compositions |
| CN109734837A (en) * | 2018-12-19 | 2019-05-10 | 常熟巴德富科技有限公司 | A kind of water-resistant type K11 lotion and preparation method thereof |
| CN111138600B (en) * | 2019-12-27 | 2023-01-06 | 广东银洋环保新材料有限公司 | Butylbenzene-modified zero-ammonia acrylic waterproof mortar emulsion, preparation method thereof and waterproof mortar |
| CN112551989A (en) * | 2020-12-28 | 2021-03-26 | 成都鹿杭磊建筑科技有限公司 | Preparation method of modified cement-based composite material |
| CN114181344A (en) * | 2021-11-26 | 2022-03-15 | 甘肃中研同创材料科技有限责任公司 | Anti-corrosion and anti-freezing polymer emulsion of acrylic modified cement-based material and preparation method thereof |
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| CN101735541A (en) * | 2009-11-10 | 2010-06-16 | 上海漠王复合材料科技有限公司 | Environmental-friendly type emulsion for heat insulating material and preparation method thereof |
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| CN101735541A (en) * | 2009-11-10 | 2010-06-16 | 上海漠王复合材料科技有限公司 | Environmental-friendly type emulsion for heat insulating material and preparation method thereof |
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