CN106117420A - 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 PDF

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CN106117420A
CN106117420A CN201610595738.6A CN201610595738A CN106117420A CN 106117420 A CN106117420 A CN 106117420A CN 201610595738 A CN201610595738 A CN 201610595738A CN 106117420 A CN106117420 A CN 106117420A
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emulsion
styrene
cement mortar
modified cement
acrylic emulsion
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CN106117420B (en
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韩冬冬
陈维灯
钟世云
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Tongji University
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Tongji University
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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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to a kind of modified cement mortar styrene-acrylic emulsion and preparation method thereof, modified cement mortar styrene-acrylic emulsion is made up of the component of following components and weight portion: 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 agent 0.3～0.5, stabilizer 0～2, pH adjusting agent are appropriate, 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 stable in cement mortar, and makes modified mortar have better performance, solves low Tg polymer emulsion difficult problem of easy breakdown of emulsion in cement mortar in research before.

Description

A kind of modified cement mortar styrene-acrylic emulsion and preparation method thereof
Technical field
The invention belongs to building material technical field, especially relate to a kind of modified cement mortar styrene-acrylic emulsion and system thereof Preparation Method.
Background technology
Ordinary cement sill bond strength is low, and fragility is big, and impermeability, crack resistance, frost resistance are poor.For common cement-base These shortcomings that material exists, people start to explore use polymer and blend with the property improving ordinary cement sill with cement Energy.After adding polymeric material, many performances of cement-based material such as intensity, deformability, adhesive property, water resistance, Endurance qualities etc. all can have improvement, degree and the polymer cement ratio ratio of cement weight (weight of solid polymer with) of improvement, be polymerized The kind of thing and performance etc. have much relations.
The research of the polymer emulsion used by terms of polymer cement waterproof paint is the most, the product of exploitation also phase Relatively enrich for, the most fewer about polymer emulsion kind used in modified cement mortar, and be concentrated mainly on The product of the international major company such as BASF, Tao Shi.Owing to, in polymer cement waterproof paint, the amount ratio of cement and sand is relatively Few, therefore emulsion stability contradiction in polymer cement waterproof paint does not highlight.And in Polymer-Modified Mortar, water Mud and sand are key components, and polymer emulsion volume is mostly between the 1%-20% of cement quality, and it is anti-that hydrated cementitious discharges The stability of polymer emulsion all can be caused the biggest impact by the shear agitation in number ion and mixed process, especially exists The vitrification point ratio of polymer is the when of relatively low, and this is particularly problematic, and many emulsions are gone back when modified cement mortar There is the phenomenon such as emulsion extravasation, slurry instability, have a strong impact on the quality of polymer-modified cement mortar.On market almost There is no the domestic emulsion kind of stay in grade, cement mortar in good standing and concrete modifying.
In recent years, modified mortar polymer emulsion has been done some researchs by some research worker.
Chinese patent CN101062850A discloses a kind of flexible acrylic ester emulsion for sand pulp, mainly highlights and can carry The adhesion strength of high cement products, but be not directed to the compatibility of polymer emulsion and mortar and polymer emulsion to mortar other The impact of aspect of performance.
Chinese patent CN101386663A discloses a kind of multi-functional acrylic acid emulsion, and its prepared emulsion is claimed permissible Improve the performance of mortar, but within it holding, do not have the data that emulsion can successfully use in mortar, only prepare waterproof The performance data of coating.
Chinese patent CN1587178A discloses a kind of polymer emulsion for cement-based material diminishing and preparation side thereof Method, its polymer emulsion prepared has good diminishing efficiency, can be by reducing water consumption under conditions of waiting fluidity Improve rupture strength and the adhesion strength of mortar, and reduce the water absorption rate of mortar.But, its polymerization monomer has used substantial amounts of subtracting Water preparation polymerization macromer methoxyl polyethylene glycol methacrylate, methoxylation polypropylene glycol Polyethylene Glycol metering system Acid esters, polyethylene glycol methacrylate-styrene polymer etc., these raw materials are not only easy to get not as traditional emulsion polymerization monomer, and valency Lattice are relatively expensive, substantially increase the cost of polymer emulsion.And emulsifying agent used by it is reactive emulsifier, current domestic right Limited in the exploitation of reactive emulsifier, price is high, and kind is few, and the kind that application performance is good is the most less, and its molecular structure is complicated, Influence factor is many, and regularity is strong, if in emulsifying agent, polyreaction radical reaction speed is too fast or excessively all can affect polymerization slowly Thing emulsion intercalation method.Further, it is mainly a kind of water reducer rather than the emulsion of cement mortar modification.
Chinese patent CN102718922A discloses the preparation method of a kind of modified road concrete polyacrylate emulsion, The polyacrylate dispersion obtained can preferably improve the performance of mortar.But there is no to hand over the workability with mortar (i.e. not have Illustrate how to ensure emulsion stability in mortar), caking property, the performance such as resistance to water, the mortar formula that it is prepared is not handed over In generation, have no idea the most comprehensively to compare the performance of prepared emulsion.And technique used is core-shell emulsion polymerization technique, although nucleocapsid Emulsion polymerization can need to design the latex particle of different structure according to performance, but the configuration to its emulsion particle Can not control accurately.And owing to factor to be designed and influence factor are a lot, the most accurate in large-scale production Control various factors impact be a challenge the biggest.
Chinese patent CN101687952A discloses a kind of cement mortar admixture aqueous synthetic-resin emulsion, cement sand Starch additive reemulsification aqueous synthetic-resin emulsion powder and use its cement mortar admixture, being 3 at aggregate-to-cement ratio, water Gray scale is 0.7, under conditions of polymer cement ratio is 0.1, and the highest only 170mm of initial fluidity of its mortar, illustrate in this patent The polymer emulsion announced and latex powder and are not bery stablized in mortar (so just using the highest ratio of mud), the most so The high ratio of mud can cause the degradation of other performances of mortar, although does not the most provide the pressure-proof and snap-resistent of mortar Etc. mechanical property.
It can be seen that China is at present for research the imperfection of modified mortar polymer emulsion, the polymerization developed Thing emulsion there is also many problems.And, it is most important that all it is not specifically mentioned in above publication and how to select Monomer component proportioning and technique can allow its synthesized emulsion stably use in mortar.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of modified cement mortar is provided With styrene-acrylic emulsion and preparation method thereof.
For problem present in background technology, the present inventor has carried out substantial amounts of experimentation.Find impact Styrene-acrylic emulsion principal element of stability in cement mortar has four: first, and the impact of vitrification point, in identical polymerization When technique is with identical functional monomer, the different stability to polymer emulsion in cement slurry of vitrification point and Good stabilizer structure choice has the biggest impact；Secondly, vitrification point is identical when, what impact was maximum is function The selection of property monomer and proportioning thereof；Again, select the stabilizer of suitable construction, make emulsion can be used for cement mortar；Finally, polymerization Emulsion stability in cement mortar is also had a significant impact by the controlling of technique.By the above influence factor of Reasonable adjustment, poly- Compound emulsion just can be good at using in mortar without there is consistency problem.
When the present invention proposes the emulsion of synthesis different glass temperature Styrene-acrylic copolymer, how to select the most functional Monomer component proportioning, emulsifying agent and stabilizer structure and the scheme of polymerization technique, it can be ensured that the polymer emulsion energy obtained Enough holding in cement mortar, stablizes, and makes modified mortar have better performance.
The purpose of the present invention can be achieved through the following technical solutions:
Technical scheme one: offer modified cement mortar styrene-acrylic emulsion:
A kind of modified cement mortar styrene-acrylic emulsion, is made up of the component of following components and weight portion:
Preferably, described functional monomer is selected from acrylic acid, methacrylic acid, acrylamide, N-methylol acryloyl One or more in amine, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, 2-(Acryloyloxy)ethanol or Hydroxypropyl acrylate Compounding.
Preferably, described anion emulsifier is selected from sodium lauryl sulphate, dodecylbenzene sodium sulfonate or alkylbenzene One in ether disulfonate.
Preferably, described nonionic emulsifier is selected from alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween In one；Described stabilizer one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween.
Preferably, described initiator one in Ammonium persulfate., sodium peroxydisulfate or potassium peroxydisulfate.
Preferably, described pH buffer agent be concentration be the sodium bicarbonate of 10wt%, pH adjusting agent is ammonia, 5wt% Sodium hydroxide or potassium hydroxide.
Preferred version one: modified cement mortar styrene-acrylic emulsion, is made up of the component of following components and weight portion:
In this preferred version, functional monomer is selected from 1-2 parts by weight of acrylic acid, 1-2 weight portion N-methylol acryloyl Amine, 1-2 weight parts of methacrylic acid hydroxyl ethyl ester compounding；Described nonionic emulsifier is selected from alkylphenol polyoxyethylene or fat One in fat polyoxyethylenated alcohol；Described stabilizer is in alkylphenol polyoxyethylene or fatty alcohol-polyoxyethylene ether A kind of；Described nonionic emulsifier and stabilizer preferred water-wet side EO chain element structure below 20.
In this preferred implementation, according to FOX formula calculated copolymer vitrification point at-30 DEG C～-10 DEG C Between.
Preferred version two: modified cement mortar styrene-acrylic emulsion, is made up of the component of following components and weight portion:
In this preferred version, functional monomer is selected from 1 parts by weight of acrylic acid and 1 weight portion N hydroxymethyl acrylamide Compounding；Described nonionic emulsifier one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween；Institute The stabilizer stated one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween；Described nonionic Emulsion Agent and stabilizer preferred water-wet side EO chain element structure more than 40.
In this preferred implementation, according to FOX formula calculated copolymer vitrification point-10 DEG C～0 DEG C it Between.
Preferred version three: modified cement mortar styrene-acrylic emulsion, is made up of the component of following components and weight portion:
In this preferred version, described functional monomer is selected from acrylic acid, methacrylic acid, acrylamide, N-methylol One in acrylamide, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, 2-(Acryloyloxy)ethanol or Hydroxypropyl acrylate Or it is multiple compounding；Described nonionic emulsifier is in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween A kind of；Described stabilizer one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween.This is the most real Execute in mode, according to FOX formula calculated copolymer vitrification point more than 0 DEG C.
From preferred version one to preferred version three, in component formula to the requirement of functional monomer and stabilizer increasingly Low.I.e. by the proportioning of the functional monomer in preferred version one and stabilizer so that preferred version two and preferred version three Styrene-acrylic emulsion keeps stable in cement mortar；It is applied in preferred version three with the component proportion in preferred version two, equally The styrene-acrylic emulsion that can make preferred version three keeps stable in cement mortar.But, the most not all right in turn, i.e. preferred version three Middle functional monomer and the selection of stabilizer and proportioning can not make preferred version one and styrene-acrylic emulsion in preferred version two at cement Keeping stable in mortar, in preferred version two, functional monomer and the selection of stabilizer and proportioning can not make benzene in preferred version one Acrylic emulsion keeps stable in cement mortar.
Technical scheme two: the preparation method of offer modified cement mortar styrene-acrylic emulsion:
The preparation method of described modified cement mortar styrene-acrylic emulsion, technique used is semicontinuous pre-emulsification seed emulsion Polymerization, specifically comprises the following steps that
(1) preparation initiator solution, prepares pH buffer agent；
(2) water during deduction prepares initiator solution and pH buffer agent from total Water, with the 25wt% in remaining water The blended emulsifier that preparation is made up of anion emulsifier and nonionic emulsifier；
(3) by styrene used for synthesis, butyl acrylate and functional monomer mix homogeneously, mix monomer is obtained；
(4) mix monomer is carried out pre-emulsification；Pre-emulsification step is as follows: the 95wt% in blended emulsifier is added reaction Device, adds pH buffer agent, and under conditions of 40 DEG C of water-baths and speed of agitator are 1000r/min, in 30mins, dropping is all of mixed Close monomer, after mix monomer dropping, continue to stir i.e. to obtain pre-emulsion；
(5) seed emulsion is prepared: in reactor, add remaining all water and the blended emulsifier of remaining 5wt%, Solution in reaction vessel is warming up to 80～82 DEG C, under the conditions of speed of agitator is 160r/min, in reaction vessel, drips 5 ～the pre-emulsion of 10wt% and the initiator of 20wt%, wherein initiator drips 5mins prior to pre-emulsion, in 30mins with Time drip and complete obtain blue seed emulsion；
(6) primary response: under 80～82 DEG C of water-baths and speed of agitator is the seed breast prepared to (5) under the conditions of 120r/min Continuing in liquid to drip remaining pre-emulsion and initiator, drip off in 2.5～3h, wherein initiator is later than pre-emulsion half an hour Drip off, after being incubated 1～2 hour at 90 DEG C, stop heating, cooling；
(7) the emulsion pH adjusting agent that will be cooled to room temperature is adjusted to pH between 7～8；
(8) filter with the filter screen discharging of 120 mesh, emulsion after being filtered；
(9) after filtering, emulsion adds stabilizer as required, i.e. obtain modified cement mortar styrene-acrylic emulsion.
When the present invention proposes the emulsion of synthesis different glass temperature Styrene-acrylic copolymer, how to select the most functional Monomer component proportioning, emulsifying agent and stabilizer structure and the scheme of polymerization technique, it can be ensured that the polymer emulsion energy obtained Enough holding in cement mortar, stablizes, and makes modified mortar have better performance, solves reduced TG temperature in research before Degree polymer emulsion difficult problem of easy breakdown of emulsion in cement mortar.The different glass that method provided by the present invention and technique prepare The emulsion of temperature copolymer all can make the fluidity of cement mortar increase substantially under the conditions of the same ratio of mud, and gradual loss Little；The rupture strength of hardened cement mortar, adhesion strength, deformability, pliability and resistance to water are improved significantly, Ke Yiguang General it is applied in various mortar product.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) emulsion that the invention provides different glass temperature Styrene-acrylic copolymer can keep stable in cement mortar Functional monomer component, volume and emulsifying agent, stabilizer structure choice method, under the polymerization process condition of the present invention, close The emulsion becoming different glass temperature copolymer out all has the good compatibility with cement mortar, solves and studies before The emulsion of middle low Tg copolymer is a difficult problem for easy breakdown of emulsion in cement mortar.
(2) styrene-acrylic emulsion that the method provided by the present invention and technique prepare to mortar composite modified time, all 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 less, it is possible to largely Improve the rupture strength of hardened mortar, adhesion strength, deformability, pliability and resistance to water, reduce the fragility of mortar.
(3) polymerization technique used by the present invention is simple, and raw material is cheap and easy to get, is suitable for large-scale commercial production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
In embodiment, source and the specification of raw material are shown in Table 1.Performance test or the computational methods of prepared emulsion are shown in Table 2.
Table 1 embodiment raw material sources and specification
Material name Specification Source
Butyl acrylate Chemical pure Traditional Chinese medicines chemical reagent
Styrene Chemical pure Traditional Chinese medicines chemical reagent
Acrylic acid Chemical pure Traditional Chinese medicines chemical reagent
Methacrylic acid Chemical pure Traditional Chinese medicines chemical reagent
Acrylamide Chemical pure Traditional Chinese medicines chemical reagent
N hydroxymethyl acrylamide Chemical pure Traditional Chinese medicines chemical reagent
Hydroxyethyl methylacrylate Technical grade Degussa
Sodium peroxydisulfate Analytical pure Traditional Chinese medicines chemical reagent
Ammonium persulfate. Analytical pure Traditional Chinese medicines chemical reagent
Sodium lauryl sulphate Chemical pure Traditional Chinese medicines chemical reagent
Dodecylbenzene sodium sulfonate Chemical 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
Alkylphenol polyoxyethylene OP10 Technical grade Hai'an petrochemical industry
Sodium bicarbonate Analytical pure Traditional Chinese medicines chemical reagent
Ammonia Analytical pure Traditional Chinese medicines chemical reagent
Sodium hydroxide Analytical pure Traditional Chinese medicines chemical reagent
The test of table 2 emulsion property or computational methods
If not having specified otherwise in following example, % refers both to mass percent.
Embodiment 1:
Prepare and calculate vitrification point Styrene-acrylic copolymer emulsion between-30～-20 DEG C according to FOX formula.
(1) preparation of blended emulsifier: by molten to 1 part of sodium lauryl sulphate and 1.5 parts of alkylphenol polyoxyethylene OP10 In 16 parts of water, obtain blended emulsifier solution for standby.
(2) 0.6 part of Ammonium persulfate. is dissolved in 30 parts of water to obtain initiator solution.
(3) 0.3 part of sodium bicarbonate is dissolved in 3 parts of water to obtain pH buffer solution.
(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 methylacrylate mix homogeneously obtains mix monomer.
(5) preparation of pre-emulsion.All of pH buffer solution in the blended emulsifier of 95% in (1) and (3) is added In four-hole boiling flask, under conditions of 40 DEG C of water-baths and blender rotating speed are 1000r/min, system in dropping all (4) in 30mins Standby mix monomer.After mix monomer dropping, continue stirring 5mins and i.e. obtain pre-emulsion.
(6) seed emulsion is prepared.Water-bath temperature is adjusted to 80～84 DEG C.48 parts of water and residue is added in four-hole boiling flask 5% blended emulsifier, first drip in four-hole boiling flask under the conditions of 80～84 DEG C of water-baths and blender rotating speed are 160r/min After adding a part of initiator, then be simultaneously added dropwise the pre-emulsion of 10% and the initiator of 20%, 30mins dropping complete i.e. obtain blue Color seed emulsion.
(7) primary response.The seed prepared in (6) under the conditions of 80～82 DEG C of water-baths and blender rotating speed are 120r/min Continuing in emulsion to drip remaining pre-emulsion and initiator, 3h drips off, and wherein initiator is later than pre-emulsion and drips off half an hour. Heating, cooling is stopped after being incubated one hour at 90 DEG C.
(8) the emulsion ammonia of 26% that will be cooled to room temperature is adjusted to pH between 7～8.
(9) filter with 120 mesh filter screens.
Embodiment 2:
Vitrification point Styrene-acrylic copolymer emulsion between-20～-10 DEG C is calculated according to FOX formula.
(1) preparation of blended emulsifier: by molten to 0.5 part of sodium lauryl sulphate and 1 part of alkylphenol polyoxyethylene OP10 In 16 parts of water, obtain blended emulsifier solution for standby.
(2) 0.6 part of Ammonium persulfate. is dissolved in 30 parts of water to obtain initiator solution.
(3) 0.4 part of sodium bicarbonate is dissolved in 4 parts of water to obtain pH buffer solution.
(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 methylacrylate mix homogeneously obtains mix monomer.
(5) preparation of pre-emulsion is with embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Except for the difference that the water added in reaction vessel is 94 parts.
(7) primary response.With embodiment 1.
(8) the emulsion sodium hydroxide of 5% that will be cooled to room temperature is adjusted to pH between 7～8.
(9) i.e. obtain can be used for the polymer emulsion of mortar with 120 mesh filter screens filtrations.
Embodiment 3:
Vitrification point Styrene-acrylic copolymer emulsion between-20～-10 DEG C is calculated according to FOX formula.
(1) preparation of blended emulsifier: by 0.5 part of sodium lauryl sulphate and 1.5 parts of fatty alcohol-polyoxyethylene ether AEO9 It is dissolved in 16 parts of water, obtains blended emulsifier solution for standby.
(2) 0.6 part of Ammonium persulfate. is dissolved in 30 parts of water to obtain initiator solution.
(3) 0.3 part of sodium bicarbonate is dissolved in 3 parts of water to obtain pH buffer solution.
(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 methylacrylate conjunction is uniform obtains mix monomer.
(5) preparation of pre-emulsion is with embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Except for the difference that, the amount of water in reaction vessel is 60 parts.
(7) primary response.With embodiment 1.
(8) the emulsion sodium hydroxide of 5% that will be cooled to room temperature is adjusted to pH between 7～8.
(9) filter with 120 mesh filter screens.
(10) the stabilizer OP10 that rear interpolation accounts for latex solids content 1.5% in emulsion i.e. obtains can be used for modifying mortar Polymer emulsion.
Embodiment 4:
Vitrification point Styrene-acrylic copolymer emulsion 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 Oxygen vinyl Ether OP40 is dissolved in 16 parts of water, obtains blended emulsifier solution for standby.
(2) 0.5 part of potassium peroxydisulfate is dissolved in 25 parts of water to obtain initiator solution.
(3) 0.3 part of sodium bicarbonate is dissolved in 3 parts of water to obtain pH buffer solution.
(4) by 39 parts of styrene, 59 parts of n-butyl acrylates, 1 part of acrylic acid, 1 part of N hydroxymethyl acrylamide mixing all Even mix monomer.
(5) preparation of pre-emulsion is with embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Except for the difference that, the amount of water in reaction vessel is 60 parts.
(7) primary response.With embodiment 1.
(8) the emulsion sodium hydroxide of 5% that will be cooled to room temperature is adjusted to pH between 7～8.
(9) with 120 mesh ground strainer filterings.
Embodiment 5:
Vitrification point Styrene-acrylic copolymer emulsion 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, obtains blended emulsifier solution for standby.
(2) 0.75 part of potassium peroxydisulfate is dissolved in 37.5 parts of water to obtain initiator solution.
(3) 0.4 part of sodium bicarbonate is dissolved in 4 parts of water to obtain pH buffer solution.
(4) 44 parts of styrene, 54 parts of n-butyl acrylates, 1 part of methacrylic acid, 1 part of acrylamide mix homogeneously are obtained Mix monomer.
(5) preparation of pre-emulsion is with embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Except for the difference that, the water added in reaction vessel is 43 parts, dropping Pre-emulsion is 5% in (5).
(7) primary response.With embodiment 1.
(8) emulsion 5% sodium hydroxide that will be cooled to room temperature is adjusted to pH between 7～8.
(9) filter with 120 mesh filter screens.
Embodiment 6:
(1) preparation of blended emulsifier: by molten to 1 part of sodium lauryl sulphate and 1.5 parts of fatty alcohol-polyoxyethylene ether AEO9 In 13 parts of water, obtain blended emulsifier solution for standby.
(2) 0.5 part of potassium peroxydisulfate is dissolved in 25 parts of water to obtain initiator solution.
(3) 0.4 part of sodium bicarbonate is dissolved in 4 parts of water to obtain pH buffer solution.
(4) 49 parts of styrene, 49 parts of n-butyl acrylates, 2 parts of acrylic acid mix homogeneously are obtained mix monomer.
(5) preparation of pre-emulsion is with embodiment 1.
(6) seed emulsion is prepared.With embodiment 1.Except for the difference that adding water in reaction vessel is 56 parts.
(7) primary response.With embodiment 1.
(8) the emulsion ammonia of 26% that will be cooled to room temperature is adjusted to pH between 7～8.
(9) filter with 120 mesh filter screens.
It is shown in Table 3 by the polymer emulsion performance parameter of above example gained.
Table 3 polymer emulsion key property
The styrene-acrylic emulsion of embodiment 1-embodiment 6 is used for modified cement mortar, and cement used is PI425 cement, used Sand is the common river sand of modulus of fineness 2.52, and its particle diameter is distributed as: account for 1.7% less than 0.15mm, more than 0.15mm less than 0.3mm Account for 14.2%, account for 41.7% more than 0.3mm less than 0.63mm, account for 23.8%, more than 1.25mm more than 0.63mm less than 1.25mm Account for 10.3% less than 2.36mm, account for 8.3% more than 2.36 less than 5mm.It is 0.1 at polymer solids/cement quality ratio, water/water Mud mass ratio is 0.5, and sand/cement quality ratio is 3, under conditions of defoamer volume is the 0.5% of quality of the emulsion, and forming polymer Emulsion modified mortar.Maintenance method is dry curing 21 days after wet curing 7 days.The physical property of Polymer-Modified Mortar such as table 4.Right It is the striaght cement mortar under same experiment condition than sample.
The physical property of table 4 Polymer-Modified Mortar
Control 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 fluidity/mm 100 173 240 232 203 240 226
2h fluidity/mm 100 165 220 218 185 224 210
Rupture strength/MPa 7.5 8.3 11.2 8.8 10 11.1 9.6
Comprcssive strength/MPa 30.8 23.6 28.9 25.3 36.5 38.4 45.2
Elastic modelling quantity/GPa 14.4 8.8 13.3 8.6 12.9 12.4 13.5
Just split absorption 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 technology exists All can increase substantially the fluidity of cement mortar, and prolongation over time under conditions of the identical ratio of mud, fluidity damages Lose less, illustrate that the polymer emulsion prepared according to the present invention has the good compatibility under the conditions of high aggregate-to-cement ratio with mortar. Compared to control sample mortar, the anti-folding that the emulsion incorporation prepared according to method and the technique of the present invention all can improve mortar is strong Spend, just split absorption energy, strain, adhesion strength, reduce elastic modelling quantity and the water absorption rate of mortar.Vitrification point when styrene-acrylic emulsion The when of less than-10 DEG C, the comprcssive strength of modified mortar is to reduce compared to control sample, but the vitrification temperature of styrene-acrylic emulsion The when that degree being higher than-10 DEG C, under the conditions of waiting ratio of mud, polymer emulsion also is able to improve the comprcssive strength of mortar.Polymer In emulsion, the different performance impact to mortar of monomer component is very big, and the when of soft monomer comparision contents height, its modified mortar has Higher strain and less water absorption rate, but corresponding mechanical property is the most weak；When duroelasts comparision contents is high Waiting, the strain of modified mortar is smaller, but its anti-folding, resistance to compression, elastic modelling quantity are higher.Therefore can provide according to the present invention Method and technique obtain the polymer emulsion of different performance by adjusting the component in polymer emulsion and be applied to different In mortar product.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use invention. These embodiments obviously easily can be made various amendment by person skilled in the art, and described herein typically Principle is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability Field technique personnel should be the present invention's according to the announcement of the present invention, the improvement made without departing from scope and amendment Within protection domain.

Claims (10)

1. a modified cement mortar styrene-acrylic emulsion, it is characterised in that be made up of the component of following components and weight portion:
Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7～8.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that described functional list Body is selected from acrylic acid, methacrylic acid, acrylamide, N hydroxymethyl acrylamide, hydroxyethyl methylacrylate, methacrylic acid One or more in hydroxypropyl acrylate, 2-(Acryloyloxy)ethanol or Hydroxypropyl acrylate compound.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that described anion breast Agent one in sodium lauryl sulphate, dodecylbenzene sodium sulfonate or alkyl phenylate disulfonate.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that described nonionic Emulsion Agent one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween；Described stabilizer is selected from alkyl One in phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether or tween.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that described initiator choosing One in Ammonium persulfate., sodium peroxydisulfate or potassium peroxydisulfate.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that described pH buffer agent Being the sodium bicarbonate of 10wt% for concentration, pH adjusting agent is ammonia, the sodium hydroxide of 5wt% or potassium hydroxide.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that by following components and weight The component composition of amount part:
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 weight portion N hydroxymethyl acrylamide, 1-2 weight portion metering system Compounding of acid hydroxyl ethyl ester；
Described nonionic emulsifier one in alkylphenol polyoxyethylene or fatty alcohol-polyoxyethylene ether；Described is steady Determine agent one in alkylphenol polyoxyethylene or fatty alcohol-polyoxyethylene ether；Described nonionic emulsifier and stabilizer Preferably water-wet side EO chain element structure below 20.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that by following components and weight The component composition of amount part:
Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7～8；
Compounding selected from 1 parts by weight of acrylic acid and 1 weight portion N hydroxymethyl acrylamide of functional monomer；
Described nonionic emulsifier one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween；Institute The stabilizer stated one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween；Described nonionic Emulsion Agent and stabilizer are selected from water-wet side EO chain element structure more than 40.
A kind of modified cement mortar styrene-acrylic emulsion the most according to claim 1, it is characterised in that by following components and weight The component composition of amount part:
Wherein, pH adjusting agent addition meets modified cement mortar styrene-acrylic emulsion pH between 7～8；
Described functional monomer is selected from acrylic acid, methacrylic acid, acrylamide, N hydroxymethyl acrylamide, metering system One or more in acid hydroxyl ethyl ester, Hydroxypropyl methacrylate, 2-(Acryloyloxy)ethanol or Hydroxypropyl acrylate compound；
Described nonionic emulsifier one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween；Institute The stabilizer stated one in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or tween.
10. a preparation method for modified cement mortar styrene-acrylic emulsion as claimed in any one of claims 1-9 wherein, its feature It is, specifically comprises the following steps that
(1) preparation initiator solution, prepares pH buffer agent；
(2) water during deduction prepares initiator solution and pH buffer agent from total Water, prepares with the 25wt% in remaining water The blended emulsifier being made up of anion emulsifier and nonionic emulsifier；
(3) by styrene used for synthesis, butyl acrylate and functional monomer mix homogeneously, mix monomer is obtained；
(4) mix monomer is carried out pre-emulsification；Pre-emulsification step is as follows: the 95wt% in blended emulsifier is added reactor, Adding pH buffer agent, under conditions of 40 DEG C of water-baths and speed of agitator are 1000r/min, in 30mins, all of mixing of dropping is single Body, after mix monomer dropping, continues to stir i.e. to obtain pre-emulsion；
(5) seed emulsion is prepared: in reactor, add remaining all water and the blended emulsifier of remaining 5wt%, will be anti- Answer the solution in container to be warming up to 80～82 DEG C, under the conditions of speed of agitator is 160r/min in reaction vessel drip 5～ The pre-emulsion of 10wt% and the initiator of 20wt%, wherein initiator drips in 5mins, 30mins simultaneously prior to pre-emulsion Drip and complete i.e. obtain blue seed emulsion；
(6) primary response: under 80～82 DEG C of water-baths and speed of agitator be under the conditions of 120r/min in seed emulsion prepared by (5) Continuing to drip remaining pre-emulsion and initiator, drip off in 2.5～3h, wherein initiator is later than pre-emulsion and drips half an hour Complete, stop heating, cooling after being incubated 1～2 hour at 90 DEG C；
(7) the emulsion pH adjusting agent that will be cooled to room temperature is adjusted to pH between 7～8；
(8) filter with the filter screen discharging of 120 mesh, emulsion after being filtered；
(9) after filtering, emulsion adds stabilizer as required, i.e. obtain modified cement mortar styrene-acrylic emulsion.
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CN107459249A (en) * 2017-08-28 2017-12-12 西安理工大学 A kind of curing of river silt
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
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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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CN107141393A (en) * 2017-05-17 2017-09-08 云南中烟工业有限责任公司 A kind of styrene-acrylic emulsion used for water color ink and preparation method thereof
CN107459249A (en) * 2017-08-28 2017-12-12 西安理工大学 A kind of curing of river silt
CN107459249B (en) * 2017-08-28 2021-02-12 西安理工大学 Method for solidifying river sludge
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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
CN111138600A (en) * 2019-12-27 2020-05-12 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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