CN105367698B - A kind of elastic water-proof emulsion - Google Patents
A kind of elastic water-proof emulsion Download PDFInfo
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- CN105367698B CN105367698B CN201510833053.6A CN201510833053A CN105367698B CN 105367698 B CN105367698 B CN 105367698B CN 201510833053 A CN201510833053 A CN 201510833053A CN 105367698 B CN105367698 B CN 105367698B
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Abstract
The invention discloses a kind of elastic water-proof emulsion, it is characterised in that the emulsion is the olefinic compounds at least having an intramolecular one unsaturated group（a）, a molecule at least there are the olefinic compounds of two unsaturated groups（b）, intramolecular carries can crosslink the unsaturated compound of reactive group at room temperature（c）With the unsaturated compound with carboxyl or anhydride group（d）, in emulsifying agent（e）In the presence of be dissolved in water by adding one kind after emulsion polymerization and can be with（c）The compound of chemical crosslink reaction occurs at room temperature（f）And obtain.Elastic emulsion produced by the invention has excellent Calcium ion stability, it is good with the compatibility of cement, water resistance is excellent, crack resistence performance is good, prepare the features such as simple and cost is cheap, suitable for concrete water-proof, cement waterproofing mortar, building external paint, adhesive and the fields such as biomaterial are waited, particularly suitable for the waterproof of foam concrete, cement waterproofing mortar and building external paint etc..
Description
Technical field
The present invention relates to a kind of preparation method of elastic water-proof emulsion, belong to Polymer Synthesizing field.The present invention is used as one
Kind elastic water-proof emulsion is mainly used in concrete water-proof, cement waterproofing mortar, building external paint and adhesive and biomaterial
Deng field, the special standby waterproof for being suitable for foam concrete, cement waterproofing mortar, building external paint etc..
Background technology
External wall heat insulating material for external in China's mainly has expanded polystyrene (EPS) (EPS) plate and extruded polystyrene at present
(XPS) plate etc. more than 10 is planted, and these organic heat-insulating plates have the advantages that light and high insulating effect, but exists inflammable, is easily led
Cause the disadvantages such as fire.Foamed concrete has the defects of preventing fires, be fire-retardant, nontoxic, safe, compensate for organic insulation material,
Therefore inorganic heat insulation material is the developing direction of future architecture insulation material, it will progressively substitute existing organic insulation material,
One of leading products as future architecture insulation.The thermal conductivity factor of inorganic material is greater than dry state, heat insulation effect meeting during hygrometric state
Substantially reduce, because foamed concrete has a microporosity structure, the hydrated product and powder of cement to the wetability of water compared with
It is good so as to cause water absorption rate higher, can make in addition after inorganic material water suction under low-temperature cold weather because of freeze thawing intensity decreases from
And cause structure to be destroyed, influence the service life of foamed concrete, it is therefore desirable to add waterproofing agent to reduce foamed concrete
Water absorption rate, improve the heat insulation effect and service life of foamed concrete.At present most of foam concrete be using plus aliphatic acid/
Soap adds the hydrophober such as organic silicon emulsion, due to the hydrophober such as aliphatic acid/soap or organic silicon emulsion, tool
There is surface tension low, the adhesion between foam concrete is poor, reduces the mechanical strength of foam concrete, simultaneously because foam
Concrete surface tension force is low, and cement and foam concrete surface adhesion are influenceed in subsequent technique, causes cement easily to come off
Etc. disadvantage.
Chinese patent discloses CN104609891A and discloses a kind of preparation method of new Thief zone concrete waterproofer, presses
Parts by weight meter, successively by polyoxyethylene groups ethers nonionic fluorocarbon surfactant, sorbitan ester, para hydroxybenzene first
Sour methyl esters, boric acid fat, retarder, modifying agent are added in deionized water, are configured to help penetrating fluid, then by sodium metasilicate, calcium silicates
It is added to after sodium methyl silicate mixed in equal amounts in acidic buffer, then helps sepage to mix with above-mentioned, stir, produce height
Permeate concrete waterproofer.It the method use fluorocarbon surfactant, sorbitan ester, methyl p-hydroxybenzoate, boron
Sour fat etc., cause product cost height.Chinese patent discloses CN104446122A and discloses a kind of modified concrete waterproofing agent, by with
The raw material of lower parts by weight is made：- 10 parts of polyamide 6, aluminium hydroxide 3-10 parts, epoxy resin 6-8 parts, kaolin 7-11 parts,
Dibutyl phthalate 5-10 parts, calcium carbonate 1-5 parts, defoamer 3-5 parts, tetraethyl orthosilicate 6-8 parts, silica 1-4
Part, polyvinyl alcohol 7-10 parts, phenyl salicylate 6-8 parts, oleic acid 2-4 parts, oil emulsion 1-5 parts.It the method use polyamide, ring
The raw materials such as oxygen tree fat, dibutyl phthalate, polyvinyl alcohol, have that emulsification is difficult, and storage is unstable, at the same polyvinyl alcohol into
Water is met after film the disadvantage such as can also dissolve again.Chinese invention patent discloses CN103819127A and discloses a kind of cement mortar coagulation
Soil strengthens the preparation method of efficient organic silicon emulsion waterproofing agent, and its step is：Octene, isopropyl are added in three-necked flask first
Alcohol, nitrogen is filled with, heating water bath, is reacted under reflux, decompression steams octyltri-ethoxysilane；Then in three-necked flask,
MTES is added, dimethyl siloxane ring body is reacted to obtain methyl silicon with being hydrolyzed after catalyst balance
The partial hydrolysis prepolymer of resin；Octyltri-ethoxysilane and methyl silicon resin prepolymer are finally weighed, adds nonionic table
Face activating agent alkyl alcohol ethoxylates, stir, add water emulsification, add buffer solution, obtain water-proof emulsion；Or
Water is added in emulsifying kettle and then adds nonionic surfactant, buffer solution in kettle, high-speed shearing machine is opened, is slowly added into
Octyltri-ethoxysilane and silicone prepolymer, then emulsified, it can also obtain identical water-proof emulsion.This method complex procedures,
It is with high costs, the problems such as organic volatile (VOC) also be present.Above method is both for the concrete that is poured in is poured, to its surface
It is coated and it is penetrated into inside concrete, so as to have certain waterproof effect, but is not suitable for mixing with cement mortar
Poured into a mould after conjunction.
Chinese invention patent discloses CN103304727A and discloses a kind of hud typed elastic emulsion, and it is with poly- (acrylic acid
Butyl ester-styrene) it is core, poly- (butyl acrylate-styrene)/poly-methyl methacrylate using polymethyl methacrylate as shell
Ester core shell structure aqueous polymer emulsion, by butyl acrylate, styrene, lauryl sodium sulfate, OP-10, glycol dinitrate
Base acrylate, propyl methacrylate and deionized water add initiator emulsion polymerization that poly- (butyl acrylate-styrene) is made
Emulsion, then methyl methacrylate is added drop-wise in the emulsion and polymerize to obtain core-shell emulsion.This method is not to high molecular polymerization
Thing is crosslinked, and is not enough to obtain elasticity and the emulsion of good mechanical properties.Chinese invention patent discloses CN102321326A public affairs
A kind of preparation method of room temperature self-crosslinking acrylic ester elastic emulsion is opened, using hud polymerization technique, in shell introducing crosslinked
Monomer, stratum nucleare glass transition temperature (Tg) is designed to -40 DEG C~-15 DEG C, shell Tg is designed to 5 DEG C~40 DEG C, and gathers in emulsion
Conjunction finishes, and after adjusting pH to 8~9, adds a certain amount of crosslinking agent, and the room-temperature self crosslinking elastic emulsion of core shell structure is made.Should
For method only in shell introducing crosslinked monomer, the polymer molecule of stratum nucleare is still linear structure, is not enough to obtain elasticity and water proofing property
The good emulsion of energy.Chinese invention patent discloses CN103709316A and discloses a kind of preparation side of double self cross-linking elastic emulsion
Method, two kinds of post-crosslinking modes are combined by it：First, produce crosslinking by adding polyvalent metal ion compound；Second, by breast
DAAM is added when liquid polymerize and participates in emulsion copolymerization, makes to carry ketone carbonyl on gained copolymer chain, it is then newborn herein
The binary hydrazides such as AH are added in liquid, double self cross-linking elastic emulsion is made.This method by by add polyvalent metal from
Sub- compound and carboxyl reaction generate the complex compound of metal ion and carboxyl, and the complex compound can be dissolved again in the basic conditions,
Therefore the waterproof of the concrete of strong basicity is not suitable for, it is steady that emulsion prepared by above several method does not possess enough calcium ions
It is qualitative, be not suitable for mixing with the cement mortar of strong basicity, otherwise will cause to be demulsified, so as to lose water-proof function.
The content of the invention
The purpose of the present invention is exactly to obtain a kind of high molecular polymer elasticity that can be used for foamed concrete waterproof
Emulsion, it is poor to solve current calcium ion stability of emulsion, it is impossible to cement mortar compatible use, be adapted to foam concrete and produced
The characteristic of volume contraction in journey, prevent foam concrete from ftractureing, improve the water proofing property and heat-insulating property of foam concrete.The present invention
The elastic emulsion of production has and the compatibility of cement is good, water resistance is excellent, it is elastic it is high, prepare that simple, cost is cheap, is easy to
The features such as popularization, it is adapted to the fields such as concrete water-proof, cement waterproofing mortar, building external paint and adhesive.
The latex particle obtained by emulsion polymerization is the ball particulate of about tens to hundreds of nanosizeds, in film forming
During, with the volatilization of moisture, latex particle is mutually gathered, and under capillary force, ball particle deforms, and becomes
Regular hexagon, the diffusion melting for the concurrent subchain estranged that contacts with each other between latex particle, latex particle border disappears, so as to be formed
One complete film, it is to lean on model ylid bloom action power and part hydrogen bond action between in general linear structure emulsion molecule, belongs to
Physical force, it is that the strand curled is stretched first during film stretching is applied, film is elongated, and works as external influence
When power is more than the interaction force between strand, the sliding between strand occurs, macroscopical phenomenon is exactly the tension force of film
Low and poor flexibility, and deformed after stretching and be not easy to recover, or recover very slow.
The design philosophy of the present invention is in emulsion polymerization process, and being added in mix monomer at least has two in a kind of molecule
The olefinic compounds (b) and intramolecular of individual unsaturated group carry the unsaturationization that can crosslink reactive group at room temperature
Compound (c), during emulsion polymerization, using two or more insatiable hungers in olefinic compounds (b) and double bond with
Olefinic compounds (a) are copolymerized, and are internally formed a small cross-linked structure in latex particle by being chemically crosslinked, so
During the diffusion for the concurrent subchain estranged that contacted with each other afterwards during emulsion film forming, between latex particle, unsaturated chemical combination is utilized
Carrying at room temperature on thing (c) strand can crosslink reactive group and crosslinking agent (f) reaction, by latex particle and latex
Strand between particle is connected by chemical covalent bonds, it is such the advantages of be to effectively improve the phase interaction between strand
With raising applies film dynamic performance, elongation at break and water resistance, while can return to original state quickly after film deformation.If
Only with a molecule at least there are the olefinic compounds (b) of two unsaturated groups and olefinic compounds (a) to be copolymerized, obtain
Emulsion can only latex particle be internally formed one crosslinking small network structure, during emulsion film forming, latex
During the diffusion for the concurrent subchain estranged that contacted with each other between particle, the molecule of network structure will hinder the diffusion between strand,
Mechanical property raising to film is limited；If only using the insatiable hunger at room temperature with the group that can crosslink reaction
It is copolymerized with compound (c) and olefinic compounds (a), water-soluble cross-linker molecules (f) are difficult to enter during film forming
To inside hydrophobic latex particle, cross-linking reaction may occur only at the part point of latex particle and latex particle engagement edge
In subchain, and the strand inside latex particle cannot be crosslinked.
Embodiment of the present invention provides：
1st, a kind of elastic water-proof emulsion, it is characterised in that the emulsion is that an intramolecular is had into a unsaturated group
At least there are the olefinic compounds (b) of two unsaturated groups, intramolecular to carry in room for olefinic compounds (a), an intramolecular
Temperature is lower can to crosslink the unsaturated compound (c) of reactive group and the unsaturated compound with carboxyl or anhydride group
(d) one kind is added after, in the presence of emulsifying agent (e) by emulsion polymerization to be dissolved in water and chemistry can occur at room temperature with (c)
The compound (f) of cross-linking reaction and obtain；The ratio that above-mentioned (b)~(f) accounts for whole polymer monomer amount is respectively：
2nd, elastic water-proof emulsion according to claim 1, wherein one intramolecular has a unsaturated group
Olefinic compounds (a) it is characterized in that selected from (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid second
Ester, (methyl) hydroxy-ethyl acrylate, (methyl) glycidyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acryloyl
Amine, (methyl) isobornyl acrylate, ethene, styrene, vinylacetate, acrylonitrile, vinyl chloride, vinylidene chloride, ethene
Yl pyridines, vinylbenzenesulfonic acid sodium, butadiene, chlorobutadiene and pentadiene one or more kinds of composition therein.By
There is good water resistance and alkaline resistance properties in the elastic demand of synthesis, therefore the intramolecular selected has an insatiable hunger
It is preferably the olefinic compounds that Polarity comparision is low and alkaline resistance properties is good with the olefinic compounds (a) of group.
3rd, elastic water-proof emulsion according to claim 1, wherein one molecule at least has two unsaturated groups
The olefinic compounds (b) of group are it is characterized in that selected from (alkoxide) cyclohexane dimethanol diacrylate, (alkoxide) hexylene glycol two
Acrylate, (alkoxide) bisphenol a diacrylate, diethylene glycol acrylate, butanediol diacrylate, (alkoxide) are new
Diacrylate, Tetraethylene glycol diacrylate, triethylene-glycol diacrylate, (alkoxide) three hydroxyl first
Base propane triacrylate, (alkoxide) pentaerythritol triacrylate, (alkoxide) glycerol triacrylate and divinyl
Base benzene one or more kinds of composition therein.
The said one molecule at least olefinic compounds (b) with two unsaturated groups preferably account for whole polymer monomer
The 0.05%~8% of amount, more preferably 0.1%~6%.Because when olefinic compounds (b) addition is less than 0.05%, gather
Polymer network structure crosslink density is low, does not have effective cross-linking effect, water-resistance property of coating and poor mechanical property；When olefinic chemical combination
Thing (b) addition be higher than when 8%, derivatized polymers crosslink density is big, during emulsion film forming, latex particle it
Between contact with each other concurrent subchain estranged diffusion when, the molecule of network structure hinders the diffusion of strand, cause strand it
Between mutual winding lack, can also hinder at room temperature with the unsaturated compound (c) of reactive group and crosslinking can be crosslinked
The cross-linking reaction of agent (f), so as to cause water-resistance property of coating and poor mechanical property, simultaneously because crosslink density is high, become film
It is stiff without elasticity.
4th, elastic water-proof emulsion according to claim 1, wherein the intramolecular with can hand at room temperature
Join the unsaturated compound (c) of reactive group it is characterized in that selected from (methyl) methacrylaldehyde, methyl vinyl ketone, (methyl) propylene
Sour acetoacetoxyethyl, (methyl) acrylic acid acetoacetyl amido ethyl ester and DAAM one kind therein or two
The composition of the kind above.
Above-mentioned unsaturated compound (c) addition at room temperature with the group that can crosslink reaction preferably accounts for entirely
The 0.1%~10% of amount of monomer, more preferably 0.5%~8%.Because when olefinic compounds (c) addition is less than 0.1%
When, derivatized polymers crosslink density is low, does not have effective cross-linking effect, water-resistance property of coating and poor mechanical property；Work as alkene
Belong to compound (b) addition to be higher than when 10%, derivatized polymers crosslink density is big, makes film become very crisp without bullet
Property.Compound (c) containing ketone carbonyl and containing the reaction between hydrazide group or the compound (f) of amido when there is water to deposit not
It can occur, at room temperature and during emulsion film forming, with the volatilization of moisture and the volatilization of nertralizer ammonia, in the catalysis of carboxyl
Under effect, cross-linking reaction gradually occurs, and forms thermoset cross-linked film.
5th, elastic water-proof emulsion according to claim 1, wherein the unsaturationization with carboxyl or anhydride group
Compound (d) is it is characterized in that selected from (methyl) acrylic acid, maleic anhydride, (methyl) THPA one or two therein
Composition above.
Above-mentioned unsaturated compound (d) addition with carboxyl or anhydride group preferably accounts for the 0.1% of whole amount of monomer
~10%, more preferably 0.5%~8%.Carboxyl can play the catalytic action of cross-linking reaction during emulsion film forming.It is less than
When 0.1%.Catalytic action unobvious or cross-linking reaction are slow；During higher than 10%, cause emulsion polymerization unstable, emulsion viscosity
Height, simultaneously because the introducing of excessive carboxyl will cause the hydrophily of film strong, water resistance declines.
6th, elastic water-proof emulsion according to claim 1, wherein the emulsifying agent (e) is it is characterized in that be selected from response type
The composition of emulsifying agent, non-reactive anion emulsifier and non-reactive nonionic emulsifier three, reactive emulsifier its
It is characterized in being selected from pi-allyl epoxide polyethylene glycol oxide, pi-allyl hydroxyalkylated sulfonic acid sodium, maleic anhydride derivative sodium sulfonate, 2- third
Acrylamide base -2- methyl-propane sulfonic acids, methoxy polyethylene glycol methacrylate-styrene polymer, sodium vinyl sulfonate, 2- methyl -2- third
Alkene -1- sodium sulfonates, SSS, or 2- acrylamido -2- methybutane sodium sulfonates；Non-reactive anion emulsifier
It is characterized in that lauryl sodium sulfate is selected from, and neopelex, dodecyl sodium sulfate, alcohol sulfosuccinates,
Alkyl alcohol ether sodium sulphate, sulfosuccinate；Alkyl phenol ether sulfate；Non-reactive nonionic emulsifier is it is characterized in that be selected from alkane
Base alcohol polyethers, alkyl phenol polyether.
The composition of mentioned emulsifier (e) preferably reactive emulsifier, anion emulsifier and nonionic emulsifier.It is above-mentioned
Emulsifying agent (e) addition preferably accounts for the 0.1%~5% of whole amount of monomer.Water-proof emulsion for concrete, must be requested that emulsion
It is good with the compatibility of cement, that is to say, that emulsion must have sufficiently strong Calcium ion stability, i.e. water-proof emulsion and cement bonded sand
When slurry mixes cast, emulsion must have good stability, it is impossible to be demulsified, otherwise polymer molecule is analysed from aqueous phase
Out, the effect of waterproof is not had.Due to generating strong alkaline substance after cement and water reaction, while there is substantial amounts of electricity in cement
Xie Zhi, this can all have influence on emulsion intercalation method.When individually using reactive emulsifier or nonionic emulsifier, emulsion polymerization
Difficulty, gel is more, and reactive emulsifier price is higher；When individually using anion emulsifier, the calcium ion of emulsion is stable
Property is poor.Using reactive emulsifier, anion emulsifier and nonionic emulsifier composition when there is polymerization-stable, calcium ion
Stability is good and the features such as water resistance is good.Because reactive emulsifier can be aggregated on latex particle strand, and water
When mud mixes, emulsifier molecules will not migrate, and can be good at keeping emulsion intercalation method, add nonionic emulsifier,
Thick hydrated sheath is formed around latex particle by nonionic emulsifier, resists the effect of electrolyte charge, can be very big
Raising emulsion Calcium ion stability.When emulsifying agent (e) addition is less than 0.1%, it is steady not possess enough calcium ions for emulsion
Qualitative, when emulsifying agent (e) addition is higher than 5%, the water resistance of emulsion is deteriorated.
7th, elastic water-proof emulsion according to claim 1, wherein described be dissolved in water and can change at room temperature with (c)
Learn the compound (f) of cross-linking reaction it is characterized in that hydrazides and binary selected from water-soluble binary and polybasic carboxylic acid with it is more
Composition more than one or both of first amine, it is characterized in that the hydrazides of the binary of solvable water and polybasic carboxylic acid is selected from carbonic acid two
Hydrazides, careless acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, the hydrazides of pimelic acid two or glutaric and polymerization
Polynary two hydrazides of thing；Water-soluble binary and polyamine are it is characterized in that selected from ethylenediamine, butanediamine, hexamethylene diamine, divinyl three
Amine, triethylene tetramine, TEPA and polymeric polyamine.
The above-mentioned compound (f) for being dissolved in water and chemical crosslink reaction occurring at room temperature with (c), with working as (c) monomer
Amount ratio preferably 0.5~1.5, more preferably 0.6~1.2.When equivalent proportion is less than 0.5, substantial amounts of (c) cannot be crosslinked, and equivalent proportion is high
When 1.5, substantial amounts of hydroaropic substance is introduced, water resistance declines.
8th, elastic water-proof emulsion according to claim 1, it is characterised in that the vitrifying of elastic water-proof emulsion polymer
Transition temperature TgFor -50 DEG C~30 DEG C.The film poor mechanical property when temperature is less than -50 DEG C, dirt-resistant poor performance；When temperature height
Film poor flexibility when 30 DEG C.
It is well known in the art for preparing the polymerization technique of aqueous emulsion polymer.Conventional free radical can be used to draw
Agent, such as peroxide are sent out, such as hydrogen peroxide, sodium peroxide, potassium peroxide, tert-butyl peroxide, ammonium persulfate, persulfuric acid
Potassium, sodium peroxydisulfate, emulsion polymerization temperature can be between 40 DEG C~90 DEG C；Oxidation-reduction trigger system can also be used,
It can such as use outside above-mentioned oxidant, the reducing agent is such as：Sodium sulfoxylate formaldehyde, ascorbic acid, arabo-ascorbic acid, sulfurous acid
Sodium, sodium hydrogensulfite, sodium thiosulfate or sodium dithionate, can also use the metal salts such as iron, copper, manganese, silver, nickel or palladium as
The catalyst of oxidation-reduction reaction, addition 0.01%~1%, emulsion polymerization temperature can be between 0 DEG C~80 DEG C.
Conventional buffer can be used when emulsion polymerization is carried out in the present invention, such as sodium carbonate, sodium acid carbonate, sodium phosphate, phosphoric acid hydrogen two
Sodium, sodium dihydrogen phosphate or their compositions.
It is well known in the art for preparing the technique of foam concrete, physical foaming method can be used also to use and changed
Learn foaming method.Illustrate the method that waterproof foam concrete is prepared using elastic water-proof emulsion of the present invention, including following step
Suddenly：
(1) preparation of slurry：
By 100 parts of cement, 20 parts of lightweight active powder material flyash, 0.5 part of foam stabilizer, 0.5 part of polycarboxylate dehydragent, promote
70 parts of solidifying 1.5 parts of agent, 20 parts of elastic water-proof emulsion, 1.2 parts of polypropylene fibre and water, are added in agitator tank, are stirred
It is even to obtain the slurry of good fluidity；
(2) foaming：
10 parts of the agent hydrogen peroxide that will foam under agitation is added in the above-mentioned slurry made or is 0.4m by volume3Bubble
Foam is added in above-mentioned slurry, is uniformly mixed, and obtains the pasty slurry of good fluidity, and the slurry is injected in mould,
Foaming；
(3) conserve：
After shaping, according to different maintenance methods, maintenance is stripped after 2 hours~7 days, continues to conserve after the demoulding, can adopt
With standard curing (20 DEG C of temperature, relative humidity be more than 90%), natural curing 28 days, steam curing (40 DEG C~100 DEG C of temperature,
12 hours~48 hours), steam press maintenance (0.5MPa~1.5MPa, 5~24 hours) produces foam concrete.
Also it can add in above process or be not added with elastic water-proof emulsion, above-mentioned foam concrete is cut as needed
After being cut into the foam concrete of certain specification, by elastic water-proof Emulsion Spraying on six faces of foam concrete, treat that emulsion is done
Waterproof foam concrete is produced after dry film forming.
Advantages of the present invention or advantageous effects
Compared with prior art, the present invention has following advantages and advantageous effects：
(1) present invention combines the crosslinking in latex particle between crosslinking and latex particle, and obtained emulsion has
The features such as mechanical property is good, and elasticity is high and water resistance is strong；
(2) it is steady using the composition of reactive emulsifier, anion emulsifier and nonionic emulsifier, emulsion polymerization process
Fixed, emulsion has excellent Calcium ion stability, good with the compatibility of cement, the advantages that not interfering with following process；
(3) with after the emulsion and cement mortar mixing, in the drying process of concrete, polymer passes through in cement and bone
The film with high cohesive force is formed between material, and blocks the micropore in mortar.The aquation of cement is synchronous with the film forming of polymer
Carry out, eventually form cement by the inierpeneirating network structure together with being interweaved with polymer film, there is concrete excellent
Water resistance；The group such as carboxyl on polymer molecular chain can also react with the silicate in cement etc. simultaneously, so as to change
It is apt to mechanical property, crack resistence performance of concrete etc..
(4) preparation is simple, cost is cheap, is easy to promote；
(5) it is adapted to the fields such as concrete water-proof, cement waterproofing mortar, building external paint, adhesive and biomaterial.
Embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, person skilled in art according to foregoing invention content to some nonessential modifications and adaptations for making of the present invention,
Still fall within protection scope of the present invention.
Method of testing：
The elongation at break of elastic water-proof emulsion film：Emulsion is dried at room temperature for the thick glued membranes of 1mm are made after film forming,
Dumbbell shaped is cut into, according to national standard《Plastic tensile performance lab scale quadrat method》GB/T 16421-1996 are tested；
Foam concrete volume water absorption rate：Elastic water-proof emulsion is added in foamed concrete slurry, elastic water-proof breast
Liquid addition is the 20% of foam concrete amount of solid, using chemical blowing process, after natural curing 28 days, is entered according to GB/T5486
Row test；
The compatibility of elastic water-proof emulsion and cement：By water, elastic water-proof emulsion and cement and by weight be 1:2:2.5
Ratio be mixed evenly after, place 1h, seen whether that emulsion breaking, the lump that precipitation and appearance can not disperse etc. is bad
Phenomenon, do not pass through if any then expression elastic water-proof emulsion and the compatibility of cement.
Embodiment 1：
In tri- mouthfuls of reactors of 2000ml equipped with mechanical agitator, condenser pipe and constant pressure funnel, buffer carbonic acid is added
Hydrogen sodium 1g and water 250ml, stirring and dissolving are simultaneously heated to 80 DEG C；By styrene 196g, butyl acrylate 140g, Isooctyl acrylate monomer
145g, hydroxy-ethyl acrylate 7.5g, acrylic acid 7.5g, the group of hexanediyl ester and trimethylolpropane trimethacrylate
Compound 4g, DAAM 4g stirring and dissolvings obtain mix monomer completely, are poured under high velocity agitation dissolved with response type
Emulsifying agent 1.8g, anion emulsifier 1.8g, nonionic emulsifier 3.6g 250ml water in, emulsification 15min obtain pre-emulsification list
Body, 10% pre-emulsification monomer is added in reactor, adds ammonium persulfate 1.5g initiator initiated polymerizations, treat system
Become blue, after monomers flow back disappears, remaining pre-emulsification monomer is added dropwise, about 3h is added, and it is anti-that pre-emulsification monomer adds follow-up continuation of insurance temperature
1h is answered, is cooled to 70 DEG C, adds TBHP 0.5g and sodium sulfoxylate formaldehyde 0.5g to be eliminated after carrying out monomer, is cooled to 40
DEG C or so, pH=7.5~8.0 are neutralized to ammoniacal liquor, crosslinking agent adipic dihydrazide 2g is added, filters and packages to obtain elastic water-proof
Emulsion.Wherein reactive emulsifier is the combination of pi-allyl epoxide polyethylene glycol oxide (12) and propyl group hydroxyalkylated sulfonic acid sodium (SAHS)
Thing, anion emulsifier are the composition of lauryl sodium sulfate and neopelex, and nonionic emulsifier is alkyl
Phenol polyethers (DP-4000).Emulsion particle diameter is 220 nanometers, Gu it is 50% to contain, glass transition temperature TgFor -15 DEG C.
Embodiment 2：
In tri- mouthfuls of reactors of 2000ml equipped with mechanical agitator, condenser pipe and constant pressure funnel, buffer carbonic acid is added
Hydrogen sodium 1g and water 250ml, stirring and dissolving are simultaneously heated to 75 DEG C；By vinyl acetate 290g, butyl acrylate 198g, methacrylic acid
5g, zinn glutaric alcohol diacrylate and pentaerythritol triacrylate composition 7.5g, acrylic acid acetoacetoxyethyl
7.5g stirring and dissolvings obtain mix monomer completely, are poured under high velocity agitation dissolved with reactive emulsifier 2g, anionic emulsifying
Agent 2g, nonionic emulsifier 4g 250ml water in, emulsification 15min obtain pre-emulsification monomer, by 10% pre-emulsification monomer add
Into reactor, ammonium persulfate 1.5g initiator initiated polymerizations are added, system for the treatment of becomes blue, after monomers flow back disappears, is added dropwise
Remaining pre-emulsification monomer, about 3h are added, and pre-emulsification monomer adds follow-up continuous insulation reaction 1h, adds TBHP 0.5g
Eliminated after carrying out monomer with sodium sulfoxylate formaldehyde 0.5g, be cooled to 40 DEG C or so, pH=7.5~8.0 are neutralized to ammoniacal liquor, added
Crosslinking agent hexamethylene diamine 2.5g, filter and package to obtain elastic water-proof emulsion.Wherein reactive emulsifier is that allyloxy nonyl phenol gathers
The composition of oxygen ethene (10) ether ammonium sulfate (DNS-86) and sodium vinyl sulfonate (SVS), anion emulsifier is dodecyl
The composition of sodium sulfonate and alcohol sulfosuccinates (A-6828), nonionic emulsifier are alkyl phenol polyether (trade name CO-
858).Emulsion particle diameter is 250 nanometers, Gu it is 50% to contain, glass transition temperature TgFor -10 DEG C.
Embodiment 3：
In tri- mouthfuls of reactors of 2000ml equipped with mechanical agitator, condenser pipe and constant pressure funnel, buffer carbonic acid is added
Hydrogen sodium 1g and water 250ml, stirring and dissolving are simultaneously heated to 50 DEG C；By GMA 25g, vinyl chloride 100g, third
Olefin(e) acid butyl ester 70g, vinylidene chloride 300g, THPA 5g, the group of diethylene glycol acrylate and butanediol diacrylate
Compound 7.5g, methacrylic acid acetoacetyl amido ethyl ester 5g stirring and dissolvings obtain mix monomer completely, incline under high velocity agitation
Enter to dissolved with reactive emulsifier 2g, anion emulsifier 2g, nonionic emulsifier 4g 250ml water in, emulsification 15min obtain
Pre-emulsification monomer, 10% pre-emulsification monomer is added in reactor, while the Some redox initiator tert-butyl group is added dropwise
Hydrogen peroxide 1.5g and sodium sulfoxylate formaldehyde 1.5g, initiator initiated polymerization, system for the treatment of becomes blue, after monomers flow back disappears,
Remaining pre-emulsification monomer and redox initiator is added dropwise, about 3h is added, and pre-emulsification monomer adds follow-up continuous insulation reaction 1h,
40 DEG C or so are cooled to, pH=7.5~8.0 is neutralized to ammoniacal liquor, adds crosslinking agent ethylenediamine 2.5g, filter and package to obtain elasticity
Water-proof emulsion.Wherein reactive emulsifier is 2- acrylates amide groups -2- methyl-propane sulfonic acids salt (abbreviation AMPS), and-alkene
The composition of propyl group epoxide -2- hydroxypropanesulfonic acid salt (trade name COPS-1), anion emulsifier are dodecyl sodium sulfate
With the composition of sulfosuccinate (trade name UCAN-32), nonionic emulsifier is alkylol polyethers (trade name A-780).
Emulsion particle diameter is 220 nanometers, Gu it is 50% to contain, glass transition temperature TgFor -5 DEG C.
Embodiment 4：
In tri- mouthfuls of reactors of 2000ml equipped with mechanical agitator, condenser pipe and constant pressure funnel, buffer carbonic acid is added
Hydrogen sodium 1g and water 250ml, stirring and dissolving, and temperature is controlled at 5 DEG C -8 DEG C；By styrene 150g, butadiene 350g, acrylic acid
5g, (alkoxide) cyclohexane dimethanol diacrylate and Tetraethylene glycol diacrylate composition 2.5g, methyl-prop
Olefin(e) acid acetoacetoxyethyl 2.5g stirring and dissolvings obtain mix monomer completely, are poured under high velocity agitation dissolved with response type
Emulsifying agent 2g, anion emulsifier 2g, nonionic emulsifier 4g 250ml water in, emulsification 15min obtain pre-emulsification monomer, will
10% pre-emulsification monomer is added in reactor, adds TBHP 1.5g and sodium sulfoxylate formaldehyde 1.5g initiators to draw
Polymerisation is sent out, remaining pre-emulsification monomer is added dropwise, about 3h is added, and pre-emulsification monomer adds follow-up continuous insulation reaction 1h, is taken out true
Sky removes unreacted monomer, is neutralized to pH=7.5~8.0 with ammoniacal liquor, adds crosslinking agent diethylenetriamine 0.75g, filter and package
Obtain elastic water-proof emulsion.Wherein reactive emulsifier is 2- methyl -2- propylene -1- sodium sulfonates (abbreviation SM)) and 2- acryloyls
The composition of amine -2- methyl isophthalic acids-propane sulfonic acid sodium (AMPSA), anion emulsifier are lauryl sodium sulfate and dodecyl
The composition of sodium sulfonate, nonionic emulsifier are alkyl phenol polyether (trade name DP-400).Emulsion particle diameter is 250 nanometers, admittedly contain
For 48%, glass transition temperature TgFor -25 DEG C.
Embodiment 5：
In tri- mouthfuls of reactors of 2000ml equipped with mechanical agitator, condenser pipe and constant pressure funnel, buffer carbonic acid is added
Hydrogen sodium 1g and water 250ml, stirring and dissolving are simultaneously heated to 40 DEG C；By chlorobutadiene 495g, acrylic acid 5g, triethylene-glycol dipropyl
The composition 7.5g of olefin(e) acid ester and (alkoxide) trimethylolpropane trimethacrylate, acetoacetoxyethyl methacrylate
5g stirring and dissolvings obtain mix monomer completely, are poured under high velocity agitation dissolved with reactive emulsifier 2g, anion emulsifier
2g, nonionic emulsifier 4g 250ml water in, emulsification 15min obtain pre-emulsification monomer, 10% pre-emulsification monomer is added to
In reactor, ammonium persulfate 1.5g initiator initiated polymerizations are added, system for the treatment of becomes blue, after monomers flow back disappears, is added dropwise surplus
Under pre-emulsification monomer, about 3h adds, and pre-emulsification monomer adds follow-up continuous insulation reaction 1h, add TBHP 0.5g and
Sodium sulfoxylate formaldehyde 0.5g is eliminated after carrying out monomer, is neutralized to pH=7.5~8.0 with ammoniacal liquor, is added crosslinking agent diethylenetriamine
2.5g, filter and package to obtain elastic water-proof emulsion.Wherein reactive emulsifier is the (abbreviation of 2- methyl -2- propylene -1- sodium sulfonates
SM)) and 2- acrylamides -2- methyl isophthalic acids-propane sulfonic acid sodium (AMPSA) composition, anion emulsifier is dodecyl sulphur
The composition of sour sodium and dodecyl sodium sulfate, nonionic emulsifier are alkyl phenol polyether (trade name DP-400).Emulsion particle diameter
For 300 nanometers, Gu it is 48% to contain, glass transition temperature TgFor -40 DEG C.
Embodiment 6：
In tri- mouthfuls of reactors of 2000ml equipped with mechanical agitator, condenser pipe and constant pressure funnel, buffer carbonic acid is added
Hydrogen sodium 1g and water 250ml, stirring and dissolving are simultaneously heated to 80 DEG C；By methyl methacrylate 196g, butyl acrylate 145g, propylene
Acid different monooctyl ester 140g, hydroxy-ethyl acrylate 7.5g, acrylic acid 7.5g, hexanediyl ester and trimethylolpropane tris propylene
The composition 5g of acid esters, DAAM 5g stirring and dissolvings obtain mix monomer completely, are poured under high velocity agitation molten
Reactive pattern emulsifying agent 1.8g, anion emulsifier 1.8g, nonionic emulsifier 3.6g 250ml water in, emulsification 15min obtain
Pre-emulsification monomer, 10% pre-emulsification monomer is added in reactor, adds ammonium persulfate 1.5g initiators and trigger polymerization anti-
Should, system for the treatment of becomes blue, after monomers flow back disappears, remaining pre-emulsification monomer is added dropwise, about 3h is added, and pre-emulsification monomer adds follow-up
Continuous insulation reaction 1h, add TBHP 0.5g and sodium sulfoxylate formaldehyde 0.5g to be eliminated after carrying out monomer, be cooled to 40 DEG C
Left and right, pH=7.5~8.0 are neutralized to ammoniacal liquor, crosslinking agent adipic dihydrazide 2.5g is added, filters and packages to obtain elastic water-proof
Emulsion.Wherein reactive emulsifier is the combination of pi-allyl epoxide polyethylene glycol oxide (12) and propyl group hydroxyalkylated sulfonic acid sodium (SAHS)
Thing, anion emulsifier are the composition of lauryl sodium sulfate and neopelex, and nonionic emulsifier is alkyl
Alcohol polyethers (A-3060).Emulsion particle diameter is 180 nanometers, Gu it is 50% to contain, glass transition temperature TgFor -15 DEG C.
Comparative example 1：
The composition of hexanediyl ester and trimethylolpropane trimethacrylate and double is not added with polymerized monomer
Acetone acrylamide, remaining is the same as embodiment 1.
Comparative example 2：
DAAM is not added with polymerized monomer, remaining is the same as embodiment 1.
Comparative example 3：
The composition of hexanediyl ester and trimethylolpropane trimethacrylate is not added with polymerized monomer, remaining is same
Embodiment 1.
Comparative example 4：
Add nonionic emulsifier in emulsifying agent, be not added with reactive emulsifier and anion emulsifier, remaining is the same as embodiment 6.
Comparative example 5：
Add reactive emulsifier and anion emulsifier in emulsifying agent, be not added with nonionic emulsifier, remaining is the same as embodiment 6.
Comparative example 6：
Add anion emulsifier and nonionic emulsifier in emulsifying agent, be not added with reactive emulsifier, remaining is the same as embodiment 6.
1~embodiment of embodiment 6, the test result of 1~comparative example of comparative example 6 are listed in Table 1 below.
Claims (7)
1. a kind of elastic water-proof emulsion, it is characterised in that the emulsion is the olefinic that an intramolecular is had into a unsaturated group
Compound (a), a molecule at least have the olefinic compounds (b) of two unsaturated groups, intramolecular with room temperature may be used
To crosslink the unsaturated compound (c) of reactive group and unsaturated compound (d) with carboxyl or anhydride group, in breast
Water is dissolved in by addition one kind after emulsion polymerization in the presence of agent (e) and chemical crosslink reaction can occur at room temperature with (c)
Compound (f) and obtain；Wherein described emulsifying agent (e) is it is characterized in that reactive emulsifier, non-reactive anion emulsifier
With the composition of non-reactive nonionic emulsifier three, reactive emulsifier is it is characterized in that be selected from pi-allyl epoxide polyoxyethylene
Alkene, pi-allyl hydroxyalkylated sulfonic acid sodium, maleic anhydride derivative sodium sulfonate, 2- acrylamido -2- methyl-propane sulfonic acids, methoxyl group
Polyethylene glycol methacrylate-styrene polymer, sodium vinyl sulfonate, 2- methyl -2- propylene -1- sodium sulfonates, SSS, or 2- third
Acrylamide base -2- methybutane sodium sulfonates；Non-reactive anion emulsifier is it is characterized in that be selected from lauryl sodium sulfate, and 12
Sodium alkyl benzene sulfonate, dodecyl sodium sulfate, alcohol sulfosuccinates, alkyl alcohol ether sodium sulphate, sulfosuccinate；Alkyl
Phenolic ether sulphate；Non-reactive nonionic emulsifier is it is characterized in that be selected from alkylol polyethers, alkyl phenol polyether；
The ratio that above-mentioned (b)~(f) accounts for whole polymer monomer amount is respectively：
2. elastic water-proof emulsion according to claim 1, wherein one intramolecular has the alkene of a unsaturated group
Belong to compound (a), it is characterized in that selected from (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) ethyl acrylate,
(methyl) hydroxy-ethyl acrylate, (methyl) glycidyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylamide,
(methyl) isobornyl acrylate, ethene, styrene, vinylacetate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine
Pyridine, vinylbenzenesulfonic acid sodium, butadiene, chlorobutadiene and pentadiene one or more kinds of composition therein.
3. elastic water-proof emulsion according to claim 1, wherein one molecule at least has two unsaturated groups
Olefinic compounds (b), it is characterized in that selected from (alkoxide) cyclohexane dimethanol diacrylate, the propylene of (alkoxide) hexylene glycol two
Acid esters, (alkoxide) bisphenol a diacrylate, diethylene glycol acrylate, butanediol diacrylate, (alkoxide) new penta 2
Alcohol diacrylate, Tetraethylene glycol diacrylate, triethylene-glycol diacrylate, (alkoxide) trihydroxy methyl third
Alkane triacrylate, (alkoxide) pentaerythritol triacrylate, (alkoxide) glycerol triacrylate and divinylbenzene
One or more kinds of composition therein.
4. elastic water-proof emulsion according to claim 1, wherein described carried in intramolecular can crosslink at room temperature
The unsaturated compound (c) of reactive group, it is characterized in that selected from (methyl) methacrylaldehyde, methyl vinyl ketone, (methyl) propylene
Sour acetoacetoxyethyl, (methyl) acrylic acid acetoacetyl amido ethyl ester and DAAM one kind therein or two
The composition of the kind above.
5. elastic water-proof emulsion according to claim 1, wherein the unsaturated compound with carboxyl or anhydride group
(d), it is characterized in that selected from (methyl) acrylic acid, maleic anhydride, (methyl) THPA it is therein it is one or two kinds of with
On composition.
6. elastic water-proof emulsion according to claim 1, wherein described be dissolved in water and chemistry friendship can occur at room temperature with (c)
Join the compound (f) of reaction it is characterized in that hydrazides and binary and polyamine selected from water-soluble binary and polybasic carboxylic acid
One or both of more than composition, it is characterized in that the hydrazides of the binary of solvable water and polybasic carboxylic acid is selected from the acyl of carbonic acid two
Hydrazine, careless acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, the hydrazides of pimelic acid two or glutaric and polymer
Polynary two hydrazides；Water-soluble binary and polyamine it is characterized in that selected from ethylenediamine, butanediamine, hexamethylene diamine, diethylenetriamine,
Triethylene tetramine, TEPA and polymeric polyamine.
7. elastic water-proof emulsion according to claim 1, it is characterised in that the glass transition of elastic water-proof emulsion polymer
Temperature TgBetween -50 DEG C~30 DEG C.
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| CN105645838A (en) * | 2016-03-09 | 2016-06-08 | 文登蓝岛建筑工程有限公司 | Composite silicon concrete waterproofer and preparation method thereof |
| EP3472250B1 (en) * | 2016-06-17 | 2022-03-23 | Dow Global Technologies, LLC | Coating composition with improved liquid stain repellency |
| CN110892026B (en) * | 2017-07-17 | 2022-12-02 | 科思创(荷兰)有限公司 | Crosslinkable aqueous coating composition |
| CN107603301B (en) * | 2017-10-27 | 2020-05-12 | 青岛科技大学 | Preparation method of special resin for water metal paint |
| CN111574657A (en) * | 2020-05-28 | 2020-08-25 | 东联北方科技(北京)有限公司 | Styrene-acrylic emulsion |
| MX2023002658A (en) * | 2020-09-08 | 2023-03-28 | Dow Global Technologies Llc | Aqueous curable adhesive composition and laminated article thereof. |
| CN112220158B (en) * | 2020-09-24 | 2021-09-10 | 温州程泓鞋业有限公司 | Cold-bonding waterproof shoe and processing technology thereof |
| CN112321765B (en) * | 2020-11-23 | 2022-08-12 | 临沂大学 | Waterproof coating based on self-crosslinking modified styrene-acrylic emulsion and preparation method and application thereof |
| CN116543970B (en) * | 2023-07-05 | 2023-09-29 | 特变电工(德阳)电缆股份有限公司 | Compact metal shielding structure medium voltage cable |
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| CN1624009A (en) * | 2004-09-21 | 2005-06-08 | 华南理工大学 | Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof |
| CN102898578A (en) * | 2012-07-16 | 2013-01-30 | 杭州师范大学 | Self-crosslinking silicone-acrylate copolymer emulsion and preparation method |
| CN102992689A (en) * | 2012-11-01 | 2013-03-27 | 江苏博特新材料有限公司 | High-performance concrete protection material and preparation method thereof |
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| CN1624009A (en) * | 2004-09-21 | 2005-06-08 | 华南理工大学 | Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof |
| CN102898578A (en) * | 2012-07-16 | 2013-01-30 | 杭州师范大学 | Self-crosslinking silicone-acrylate copolymer emulsion and preparation method |
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