CN1844022A - Reduction-reducing crack-resisting concrete superplasticizer of graft copolymer and method for preparing the same - Google Patents
Reduction-reducing crack-resisting concrete superplasticizer of graft copolymer and method for preparing the same Download PDFInfo
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Abstract
Disclosed is a shrinkage-reduction anti-cracking type grafted copolymer concrete superplasticiser, which is prepared from monomer a of acroleic acid or salts, monomer b of alkoxy polyether monoacrylate, monomer c of maleic anhydride hemiester or its salts, monomer d of alpha-propenol omega-methyl polyether and monomer e of phenylethene through free radical copolymerization reaction, wherein the molar ratio of the monomer a, b, c, d and e being 1 : 0.2-0.5 : 0.10-0.25 : 0.10-0.20 : 0-0.10.
Description
Technical field
The invention belongs to concrete structure and concrete works technical field, specially refer to technical field of concrete additives, be specifically related to a kind ofly to reduce, preparation method, the application of anti-cracking poly carboxylic acid series concrete superplasticizer.
Background technology
Concrete has developed into contemporary topmost Structural Engineering material, China's cement annual production in 2005 has broken through 1,000,000,000 tons, cement that its fundamental construction consumed and concrete amount all are in rank first, and Cement Production not only expends a large amount of Mineral resources and the energy, and produce a large amount of CO
2, discharge a large amount of dust.The Sustainable development of building material industry is to reduce resource and energy consumption in the production process of employing, material at raw material on the one hand as far as possible, on the other hand green energy conservation in use.Therefore the outlet of concrete industry Sustainable development is used modern science and technology exactly and is improved concrete work-ing life, reduces as far as possible and causes waste and the building waste of repairing or removing.And volume stability influences the main factor of concrete durability often, is the important prerequisite that concrete reaches life requirement, and the bad direct result of volume stability causes the crack exactly.Therefore how to improve concrete volume stability and consequent cracking and be the big technical barrier that concrete academia and engineering technical personnel for many years face.
Concrete admixture especially superplasticizer is the key that realizes concrete high-performanceization, and naphthalene water reducer application at present is the most general, but it exists fatal weakness to increase concrete contraction exactly.Concrete shrinkage and the crack that produces can reduce concrete penetrating quality finally influences concrete performance performance, reduces its work-ing life.Generally adopt both at home and abroad at present and add the drying shrinkage that cement expansive material comes compensating concrete, but volume big (10-15% of cement amount), contaminate environment during production; And the concrete that adds swelling agent must carry out wet curing, increased difficulty to Construction control; Mix swelling agent and can compensate the early stage drying shrinkage of soil in the concrete of high water-cement ratio, but early expansion is big more, the concrete later stage shrinks bigger, and expansion performance is relatively poor in the low water binder ratio concrete, basically can not compensate for shrinkage.Novel organic antishrinking agent (shrinkage reducing agent) can effectively reduce concrete contraction, but volume higher (2-3% of cement amount), the cost increase is very big, and itself does not also have the diminishing function, be difficult in the middle low-strength concrete that has a large capacity and a wide range, widely popularize, even in high-strength concrete, also, promote and get up also to have very big difficulty because it has adverse influence to intensity.
" multifunctional carboxylic-acid comb-shape graft copolymer concrete superplasticizer " of applicant's development (CN200510037872.6) has good dispersion, the guarantor is collapsed and enhancement function, also can reduce concrete dry shrinkage to a certain extent, but the amplitude that reduces also is nowhere near, and is difficult to compare with the effect of reducing of economization agent under so low volume.
CN200510057130.X has reported a kind of polyacrylic acid salts shrinkage-reducing-agent and preparation method thereof, this admixture has the good effect of reducing, but volume is still higher, account for 2% of cement consumption, though the report water-reducing rate can reach 15-18%, but the 28d compressive strength rate is 108% only, and reinforced effects is relatively poor.
US2005/0096413 discloses a kind of multifunctional type admixture, and its major ingredient is the multipolymer of α-vinyl carbinol ω-methyl polyethers-maleic anhydride.When adopting ordinary portland cement when water/cement is W/C=0.30,24h self-desiccation shrinking percentage is compared and has been reduced 15%-25% with common high-efficiency water-reducing agent of poly-carboxylic acid Chupol HP-11 (Takemoto Yushi Kabushhiki Kaisha production).When adopting the silicon ash concrete at W/C=0.17, the 24h self-desiccation shrinks to be compared and has reduced 18.4%-24.5% with common high-efficiency water-reducing agent of poly-carboxylic acid Chupol SSP-104 (Takemoto Yushi KabushhikiKaisha production).From report, volume is compared a certain distance in addition at the 0.27%-0.57% of cement amount with the effect of reducing of economization agent.
US20050124737 discloses a kind of multifunctional type admixture, and its major ingredient is the multipolymer of α-vinyl carbinol ω-methyl polyethers-maleic anhydride.Investigated under the condition of W/C=0.47, volume is at the 0.35%-0.92% of cement amount, and 26 all concrete drying shrinkages are 4.9 * 10 among the embodiment
-4-5.6 * 10
-4, the dry shrinking percentage of 26 all concrete is 5.4 * 10 in the comparative example
-4-7.7 * 10
-4
JP8268741 has also reported a kind of multifunctional type admixture, its major ingredient also is the multipolymer of α-vinyl carbinol ω-methyl polyethers-maleic anhydride, it has diminishing and reducing function simultaneously, mixed 0.2% o'clock, water-reducing rate can reach 18%, and the dry contraction of 28d concrete is compared with benchmark and reduced about 35% (320kgC/m3, benchmark concrete W/C=0.638, examined concrete W/C=0.522, water is surveyed length just after supporting 7d).
In sum, still there is tangible not enough problem at present relevant multifunctional type admixture, these products all are to be main raw material(s) with α-vinyl carbinol ω-methyl polyethers basically, price is higher, the multipolymer of α-vinyl carbinol ω-methyl polyethers-maleic anhydride is relatively poor to the dispersing property of cement simultaneously, and water-reducing rate is not enough.
Summary of the invention
What the present invention will solve is exactly the weak point of above-mentioned existing multifunctional type admixture, provide a kind of production technology simple relatively and have the water-reducing rate height, reinforced effects is good, drying shrinkage is low, resistance to cleavage is good, cheap reduces, anti-cracking grafted copolymer as concrete super-plasticizing agent and preparation technology thereof.
The applicant finds that the main chain chemical structure of graft copolymer is very big to concrete effect of contraction, is the graft copolymer drying shrinkage minimum of main chain with vinylformic acid or α-vinyl carbinol ω-methyl polyethers.
The applicant also finds, organic antishrinking agent is generally low-molecular-weight alkyl, polyether, and side chain (AO) also is an alkyl, polyether in the graft copolymer, its side chain chemical structure and character are close with organic antishrinking agent character, in graft copolymer, introduce certain low-molecular-weight alkyl, polyether and not only can reduce concrete dry shrinkage greatly, but also can improve dispersiveness cement.
Based on above-mentioned research, the present invention adopts following technical scheme:
The present invention is by monomer a: vinylformic acid or its salt, monomer b: alkoxy polyether mono acrylic ester, monomer c: maleic anhydride half-ester or its salt, monomer d: α-vinyl carbinol ω-methyl polyethers and monomer c: vinylbenzene is prepared from by free radicals copolymerization reaction, wherein monomer a: monomer b: monomer c: monomer d: the mol ratio of monomer e is 1: 0.2～0.5: 0.10～0.25: 0.10～0.20: 0～0.10.
Be known substance beyond the above-mentioned monomer a-monomer e demonomerization c, wherein:
Monomer a represents with general formula 1:
M in the formula
1Expression hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group.
Monomer b represents with general formula 2:
R is the alkyl of 1～4 carbon atom in the formula, AO is the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more this oxyalkylene groups, if AO is the mixture of two or more this oxyalkylene groups, can add these groups with block or random form so, n is the average addition mole number of oxyalkylene group, is 5～40.
Esterification takes place by monoalkoxy polyethers shown in the general formula (5) and vinylformic acid to generate in the represented monomer b of general formula (2) under the condition of a small amount of solvent medium, acid catalyst and a little stopper.
N is the average addition mole number of oxyalkylene group in the formula, is 5～40, and the oxyalkylene that is fit to comprises oxyethane, propylene oxide, butylene oxide ring etc., and composition thereof.They can be linearity or branched polymers, homopolymer or multipolymer, random or segmented copolymer, diblock or segmented copolymer.This alkoxy polyether mono acrylic ester is copolymerized to certain dispersive ability and reducing function mainly is provided in the main chain.
Monomer c represents with general formula 3:
M in the formula
2Expression hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group, p and q are 0～8 integers, and 2≤p+q≤8.
The represented monomer c of general formula (3) is taken place directly under the solvent-free condition that catalyzer arranged by the monoalkoxy polyethers with reducing function shown in the general formula (6) and maleic anhydride that esterification generates.It is copolymerized in the main polymer chain not only can reduce concrete contraction, and can also provide certain sterically hindered, thereby improves the dispersive ability of multipolymer.
P and q are 0～8 integers in the formula, and 2≤p+q≤8.
The preparation method of above-mentioned monomer c belongs to traditional esterification, this process is relatively easily with simple, in reaction vessel, add the represented component that reduces of general formula (6), add then and the maleic anhydride that reduces molar ratio such as component, 100～160 ℃ of reactions 3 hours, obtaining the red-brown transparent liquid was monomer c.
Monomer d represents with general formula 4:
M is 4～25 integer in the formula
Monomer e is a vinylbenzene.
According to the present invention, the preparation technology of carboxyl acid graft copolymer has three steps at least, in the first step reaction, general formula (2) and the described alkoxy polyether mono acrylic ester of general formula (3) carry out graft reaction by monoalkoxy polyethers and the vinylformic acid shown in the general formula (5), and it can esterification take place according to common esterifying reaction method and generate under the condition of a small amount of solvent medium, acid catalyst and a little stopper; In the reaction of second step, maleic anhydride is to be relatively easy to the polyethers esterification with reducing function; The 3rd step free radicals copolymerization reaction, it can not carry out under the situation of difficult with known radical initiator according to usual method.To describe this process and technology in detail below.
Though because monomer b is known substance, do not have commercially availablely, monomer c is non-known substance, therefore preparation method of the present invention comprises the steps:
1, preparation monomer b
Traditional esterification is adopted in the preparation of monomer b, and this method belongs to known technology, vinylformic acid and monoalkoxy polyethers in the reaction process (mol ratio be 1: 1 to 5: 1, excessive vinylformic acid can be retained in the mixture, participates in next step copolymerization.
In above-mentioned esterification, it may be favourable adopting catalyzer, and adoptable catalyzer comprises the vitriol oil, tosic acid, solid super-strong acid, phosphoric acid and phosphorous acid, and they can mix use separately or with arbitrary proportion.Catalyst consumption is being 0.5～5% of reaction mass (the monoalkoxy polyethers shown in the general formula (5) and acrylic acid gross weight).
In above-mentioned esterification, adopt organic solvent to make azeotropic agent and can improve esterification efficient, azeotropic agent forms azeotropic mixture with the water that reaction generates.The organic solvent that is fit to do azeotropic agent comprises aliphatic hydrocarbon, naphthenic hydrocarbon or aromatic hydrocarbon, and aliphatic hydrocarbon is selected from hexane, decane, undecane, dodecane; Naphthenic hydrocarbon is selected from hexanaphthene, methylcyclohexane; Aromatic hydrocarbon is selected from benzene, toluene, adjacent,, right-dimethylbenzene.The content of azeotropic agent in reaction mixture should be and is 10～40% of reaction mass (the monoalkoxy polyethers shown in the general formula (5) and acrylic acid gross weight).
For the too early polymerization of the unsaturated ester that prevents vinylformic acid and generation, must use some traditional stoppers, Resorcinol for example, thiodiphenylamine, Resorcinol-methyl ether or two-tertiary butyl-p-cresol, they can mix use separately or with arbitrary proportion, and the consumption of stopper is 0.005～0.8% of vinylformic acid weight.
Esterification reaction temperature is at 80～160 ℃, and is relevant with the azeotropic agent boiling point that is adopted, and temperature is controlled at the azeotropic agent backflow and is advisable.The time of esterification can be monitored by the quantity that determine to generate water, when actual reception to moisture and theoretical aquifer yield when being close, stopped reaction.
When for example preparing the methoxy poly (ethylene glycol) mono acrylic ester, earlier specified molecular weight size methoxy poly (ethylene glycol) and excessive vinylformic acid input are had in the reaction vessel of oven dry of water trap, drop into the stopper that measures again, the carrying out that an amount of acid catalyst of the back input that stirs quickens esterification, the organic solvent that the back adding measures is as the viscosity adjustment composition of azeotropic agent and material, slowly be warming up to solvent refluxing, under this temperature and return velocity, kept 6～15 hours, when actual reception to moisture and theoretical aquifer yield when being close, stopped reaction, and under this temperature, reclaim solvent from water trap, the band solvent recuperation is closed on when finishing, and slightly applies some negative pressure, further with receiving solvent.After esterification finished, the excessive vinylformic acid and the methoxy poly (ethylene glycol) mono acrylic ester solution of preparation can be participated in next step polyreaction directly in the esterification process, do not need extra separating step.
2, preparation monomer c
The big monomer c of the described reducing function of general formula (3) is taken place under the condition of a little catalyzer by monoalkoxy polyethers shown in the general formula (6) and maleic anhydride that esterification generates, the mol ratio of monoalkoxy polyethers and maleic anhydride remained on 1: 1, or maleic anhydride is more excessive a little.Choosing of catalyzer also is crucial, comprises the vitriol oil, tosic acid and solid super-strong acid, and they can be used alone or as a mixture.The consumption of acid catalyst is being 0.5～5% of a reaction mass (the monoalkoxy polyethers shown in the general formula (6) and the gross weight of maleic anhydride), and when consumption was lower than 0.5%, esterification efficient can descend significantly, has prolonged reaction time of esterification.If consumption is higher than 5%, product colour deepens, and not only side reaction increases simultaneously, and has caused unnecessary waste.
The temperature of esterification is preferably at 100～160 ℃, and temperature can effectively be controlled the viscosity of reaction mass in suitable scope, help the carrying out that reacts.If temperature is low excessively, the viscosity of reaction mass is very high, has increased the resistance that stirs, the speed of reaction can reduce significantly, and the reaction times prolongs, and temperature is above 160 ℃, increased the probability that side reaction takes place, the monoalkoxy polyethers may be degraded simultaneously, influences the performance of the finished product.The time of esterification does not have strict restriction, generally at 2～6 hours, gets brown transparent liquid.
3, copolymerization
Monomer a, monomer b, monomer c, monomer d and monomer e are carried out free radicals copolymerization reaction by 1: 0.2～0.5: 0.10～0.25: 0.10～0.20: 0～0.10 mol ratio, and add the alkali neutralization reaction, the pH value is adjusted to 7.0～8.5 and promptly makes finished product.
In the step 3, monomer a is necessary, and vinylformic acid excessive after step 2 esterification can be monomer a as the reaction mass in the step 3 directly, and its hydroxy-acid group provides adsorption site and electric repulsion in multipolymer.
Monomer b is that the alkoxy polyether mono acrylic ester shown in the general formula (2) is copolymerized in the main chain, and it is sterically hindered that its side chain mainly provides, and certain reducing function is provided simultaneously.The mol ratio of b/a is controlled at 0.2～0.5, if monomer b ratio is low excessively, it is relatively poor that then the multipolymer of being produced reduces effect.If ratio is too high, then synthetic multipolymer dissemination a little less than.
Functional monomer c is that this maleic anhydride half-ester and the salt with reducing function shown in the general formula (3) is copolymerized in the main chain, and its side chain mainly provides reducing function, provides sterically hindered simultaneously, thereby improves the dispersive ability of graft copolymer to cement.Monomer c accounts for 0.10～0.25 (mol than) of monomer a component, and monomer c ratio is low excessively, and then the synthetic multipolymer reduces, effect of prestressed is relatively poor, if ratio is too high, then the multipolymer of being produced is relatively poor to the dispersive ability of cement.
Monomer d be general formula (4) expression α-vinyl carbinol ω-methyl polyethers as comonomer be copolymerized to mainly provide in the main chain reduce, anti-cracking function and sterically hindered.Monomer d accounts for 0.10～0.20 (mol ratio) of monomer a component, if the ratio of monomer d is too low, then the effect of synthetic multipolymer reduction concrete shrinkage is relatively poor, if ratio is too high, then the multipolymer of being produced is relatively poor to the dispersing property of cement.
Monomer e can select, and ratio general and monomer a is 0～0.10 (mol ratio).
Raolical polymerizable itself is unimportant comparatively speaking, and it can carry out under not difficult evil situation with known radical initiator according to usual method.The initiator that is suitable for the inventive method that the skilled professional and technical personnel in present technique field knows is conventional oil soluble radical initiator and composition thereof; comprise Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide or different third hydrogen peroxide or peroxy dicarbonate diisopropyl fat etc.; join whole initiators in the reaction mixture should account for to add the monomer integral molar quantity about 1.0～4.0%, its actual add-on and the initiator type that is adopted are relative.
The molecular weight of multipolymer can utilize the polymeric chain transfer agent to select control, as thiohydracrylic acid, and Thiovanic acid, mercaptoethanol and Dodecyl Mercaptan.The consumption of polymeric chain transfer agent in polymerization process is 1.0～5.0% of monomer a+b+c+d+e gross weight.
Monomer b mixture with the first step preparation, the monomer c of second step preparation, and monomer a is (if excessive monomer a is not enough during preparation monomer b, then need to add in addition), monomer d, even small amounts of monomer e component and initiator and chain-transfer agent mix according to a certain percentage, stir and be made into monomer mixed solution, monomer mixed solution was slowly added temperature while stirring in 2～6 hours be in 60～100 ℃ of quantitative organic solvents, the amount of organic solvent is to control copolymerization monomer weight concentration in 15～40% scopes, after slowly adding, insulation reaction is 2～5 hours under stirring condition, prepares the thick solution of lurid homogeneous transparent.The reaction medium that copolymerization adopts is ethyl acetate, tetrahydrofuran (THF), methyl iso-butyl ketone (MIBK) isopolarity solvent.
After polyreaction finished, underpressure distillation removed and desolvates, and adds water cooling, adds alkali reaction carboxylic acid or acid anhydrides are transformed salifiable form, and the pH value of its finished product preferably is adjusted to 7.0～8.5, and the pH value is crossed low and too high, and then the package stability of multipolymer is all bad.
Weight-average molecular weight among the present invention is not particularly limited, generally 10, and 000-80,000, if molecular weight is too little or too big, its dispersing property to cement is all bad.
The present invention's conventional volume in use is 0.15～0.3% of total glue material weight, and water-reducing rate can reach 15%-30%, and the 28d drying shrinkage is compared with the concrete of mixing naphthalene water reducer and reduced 40-50%, compares with normal concrete and has reduced 30-50%.If addition is less than 0.10%, dispersion effect is unsafty with reducing effect so.If opposite addition surpasses 0.3%, then not only produce waste economically, and do not bring the corresponding growth on the effect.Therefore product of the present invention be a kind of have simultaneously reduce, the multifunctional concrete admixture of functions such as cracking resistance, diminishing, enhancing, can be widely used in portland-type cement concrete and the mortar, product mainly substitutes naphthalene system, economization agent and swelling agent mainly are applicable to high cracking resistance, the contour performance concrete works of low contraction.
Certainly, product of the present invention also can mix use with at least a thionamic acid based water reducer known in the state of the art, Lignins ordinary water-reducing agent and the existing polycarboxylic acid series additive of being selected from.
In addition, except that known cement water reducing agent above-mentioned, the present invention also can add air entrapment agent, retardant, hardening accelerator, tackifier, economization agent and defoamer etc. in use.
Of the present inventionly reduce, anti-cracking carboxyl acid graft copolymer concrete superplasticizer has following characteristics:
1. prepared graft copolymer also shows outstanding dispersing property among the present invention under very low volume, in conventional concrete, adds the 0.10-0.3% (effectively solid part) of cement consumption, thisly adds affiliation and brings a lot of gratifying effects.Volume is 0.2% o'clock for the cement amount volume, and water-reducing rate can reach more than 25%, and the 28d compressive strength rate is compared with normal concrete and reached more than 170%.The 28d drying shrinkage is compared with the concrete of mixing naphthalene water reducer and has been reduced 40-50%, compares with normal concrete and has reduced 30-50%.
2. prepared graft copolymer has significantly improved concrete resistance to cleavage among the present invention, and the crack on concrete time is compared and prolonged 2 days with mixing naphthalene water reducer, and only for mixing 13% of FDN, cracking time also postpones area of cracks greatly.
3. compare with microdilatancy type admixture, not only volume is low, and the maintenance of concrete (mortar) be need not special requirement, can prepare C20～C60 cracking resistance, antiseepage concrete under-5 ℃～38 ℃ temperature conditions.
4. compare with organic antishrinking agent, this multipolymer volume is less than 10% of organic antishrinking agent.Has the diminishing reinforced effects simultaneously; Solved present novel organic antishrinking agent cost height, to the intensity unfavourable defect.
Embodiment
Following examples more detailed description the process and the performance of copolymer of prepared according to the methods of the invention graft copolymer, and these embodiment provide in the mode of explanation, but these embodiment never limit the scope of the invention, wherein used monomer code name and structure sees Table 1 among the embodiment, and said admixture dosage all is meant the percentage ratio of by mass of cement in the application examples.
A) adopt firm Sigma730 numerical value surface tension apparatus (ring method) test, polymer concentration is 0.5%
B) in the embodiment of the invention, the weight-average molecular weight of polymkeric substance adopts Wyatt technology corporation gel permeation chromatograph to measure (miniDAWN Tristar laser light scattering detector).
C) in the Application Example of the present invention, the cement that is adopted is the new 425R.P.O of Nantong China, and sand is fineness modulus
Medium sand, stone is that particle diameter is the rubble of 5～20mm continuous grading.
D) water-reducing rate and air content test method are carried out with reference to the relevant regulations of GB8076-1997 " concrete admixture ", and concrete crushing strength and compressive strength rate are carried out with reference to the relevant regulations of GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ".
E) the dry shrinkage proportioning of concrete adopts the proportioning of GB8076-1997 regulation, and its test method is carried out with reference to the relevant regulations of GBJ82-85 " Standard for test methods of longterm performance and durability of ordinary concrete ".
F) early-age plastic split test method is with reference to " concrete structure durability design and construction guide ", sample dimensions 600mm * 600mm * 63mm.
Table 1
| Monomer a | General formula (1) | a-1 | Vinylformic acid |
| Monomer b | General formula (2) | b-1 | Methoxy poly (ethylene glycol) mono acrylic ester (n=9) |
| b-2 | Methoxy poly (ethylene glycol) mono acrylic ester (n=17) | ||
| b-3 | Methoxy poly (ethylene glycol) mono acrylic ester (n=5) | ||
| b-4 | Methoxy poly (ethylene glycol) mono acrylic ester (n=33) | ||
| b-5 | Methoxyl group five ethylene glycol four propylene glycol mono acrylic esters (n=9) | ||
| Monomer c | General formula (3) | c-1 | Butoxy polypropylene glycol polyoxyethylene glycol maleic anhydride list half ester (p=2, q=2, M 2＝H) |
| c-2 | Butoxy polypropylene glycol maleic anhydride list half ester (p=0, q=2, M 2＝H) | ||
| c-3 | Butoxy polyoxyethylene glycol maleic anhydride list half ester (p=4, q=0, M 2＝H) | ||
| c-4 | Butoxy polypropylene glycol polyoxyethylene glycol maleic anhydride list half ester p=4, q=4, M 2＝H) | ||
| Monomer d | General formula (4) | d-1 | Allyl group methoxyl group polyethers (m=12) |
| d-2 | Allyl group methoxyl group polyethers (m=6) | ||
| d-3 | Allyl group methoxyl group polyethers (m=23) | ||
| Monomer e | e-1 | Vinylbenzene | |
Remarks: monomer b adopts the described method of step 1 to be prepared from;
Monomer c adopts the described method of step 2 to be prepared from.
Embodiment 1
In the 2000ml glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is housed, add the 600ml ethyl acetate, use the nitrogen purging reaction vessel while stir, and be warming up to 75 ℃.Then with 1.0mol monomer a-1,0.35mol monomer b-1 (n=9) and 0.2mol monomer c-1 (p=2, q=2, M
2=H), 0.15mol monomer d-1 (m=12) and 0.05mol vinylbenzene, 0.027mol Diisopropyl azodicarboxylate (AIBN), 8.5g thiohydracrylic acid, also add the 200ml ethyl acetate simultaneously, and stir and make uniform monomer solution, it is added dropwise to reactor, the dropping time is 3h, dropwises back insulation reaction 4h, heats up and reclaims ethyl acetate organic solution, can repeatedly use, thin up cooling, and add the alkali pH value 7.5 that neutralizes, must solid content be 30.7% brown transparent liquid, molecular weight is 42,000.
Embodiment 2
In the 2000ml glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is housed, add the 600ml ethyl acetate, use the nitrogen purging reaction vessel while stir, and be warming up to 75 ℃.Then with 1.0mol monomer a-1,0.20mol monomer b-2 (n=17) and 0.15mol monomer c-3 (p=4, q=0, M
2=H) and 0.15mol monomer d-1 (m=12), 0.040mol Diisopropyl azodicarboxylate (AIBN), 10.2g thiohydracrylic acid, also add the 200ml ethyl acetate simultaneously, and stir and make uniform monomer solution, it is added dropwise to reactor, the dropping time is 5h, dropwises back insulation reaction 3h, heats up and reclaims ethyl acetate organic solution, can repeatedly use, thin up cooling, and add the alkali pH value 7.5 that neutralizes, solid content is 30.2% brown transparent liquid, molecular weight is 29,000.
Embodiment 3
In the 2000ml glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is housed, add the 800ml ethyl acetate, use the nitrogen purging reaction vessel while stir, and be warming up to 75 ℃.Then with 1.0mol monomer a-1,0.45mol monomer b-3 (n=5) and 0.25mol monomer c-2 (p=0, q=2, M
2=H) and 0.20mol monomer d-2 (m=6), and 0.05mol vinylbenzene, 0.05mol Diisopropyl azodicarboxylate (AIBN), 3.0g thiohydracrylic acid also adds the 400ml ethyl acetate simultaneously, and stirs and make uniform monomer solution, it is added dropwise to reactor, and the dropping time is 4h, dropwises back insulation reaction 4h, heat up again and reclaim ethyl acetate organic solution, can repeatedly use, add water cooling, and add the alkali pH value 7.5 that neutralizes, solid content is 30.2% brown transparent liquid, and molecular weight is 35,000.
Embodiment 4
In the 2000ml glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is housed, add the 600ml ethyl acetate, use the nitrogen purging reaction vessel while stir, and be warming up to 75 ℃.Then with 1.0mol monomer a-1,0.20mol monomer b-4 (n=33) and 0.10mol monomer c-4 (p=4, q=4, M
2=H) and 0.12mol monomer d-3 (m=23), and 0.08mol vinylbenzene, 0.030mol Diisopropyl azodicarboxylate (AIBN), 8.0g thiohydracrylic acid, also add the 200ml ethyl acetate simultaneously, and stir and make uniform monomer solution, it is added dropwise to reactor, the dropping time is 6h, dropwise back insulation reaction 2h, heat up again and reclaim ethyl acetate organic solution, can repeatedly use, add water cooling, and add the alkali pH value 7.5 that neutralizes, solid content is 30.2% brown transparent liquid, and molecular weight is 37,000.
Embodiment 5
In the 2000ml glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is housed, add the 600ml ethyl acetate, use the nitrogen purging reaction vessel while stir, and be warming up to 75 ℃.Then with 1.0mol monomer a-1,0.35mol monomer b-5 (n=9) and 0.15mol monomer c-1 (p=2, q=2, M
2=H) and 0.15mol monomer d-3 (m=23), 0.020mol Diisopropyl azodicarboxylate (AIBN), 15.5g thiohydracrylic acid, also add the 200ml ethyl acetate simultaneously, and stir and make uniform monomer solution, it is added dropwise to reactor, the dropping time is 4h, dropwises back insulation reaction 3h, heats up and reclaims ethyl acetate organic solution, can repeatedly use, add water cooling, and add the alkali pH value 7.5 that neutralizes, solid content is 30.2% brown transparent liquid, molecular weight is 40,000.
Table 2
| Multipolymer | Polymer monomers structure and mol ratio | Molecular weight | Surface tension | |||||||||
| (a) | Mole | (b) | Mole | (c) | Mole | (d) | Mole | (e) | Mole | M w | mN.m -1 | |
| Embodiment 1 | a-1 | 1.0 | b-1 | 0.35 | c-1 | 0.20 | d-1 | 0.15 | e-1 | 0.05 | 42000 | 43.5 |
| Embodiment 2 | a-1 | 1.0 | b-2 | 0.20 | c-3 | 0.15 | d-1 | 0.15 | - | - | 29000 | 39.8 |
| Embodiment 3 | a-1 | 1.0 | b-3 | 0.45 | c-2 | 0.25 | d-2 | 0.20 | e-1 | 0.05 | 35000 | 40.2 |
| Embodiment 4 | a-1 | 1.0 | b-4 | 0.20 | c-4 | 0.10 | d-3 | 0.12 | c-1 | 0.08 | 37000 | 44.5 |
| Embodiment 5 | a-1 | 1.0 | b-5 | 0.35 | c-1 | 0.10 | d-3 | 0.10 | - | - | 40000 | 41.3 |
Application Example 1
Estimate the dispersing property of synthetic embodiment 1-5 institute synthetic carboxyl acid graft copolymer, the effect that reinforced effects and reduction are shunk, with reference to GB8076-1997 " concrete admixture " proportioning, fixedly water cement ratio is 0.42, by adjusting multipolymer volume control concrete slump at 8 ± 1cm, Comparative Examples 1 is naphthalenesulfonate formaldehyde condensation compound water reducer (brief note FDN), volume is 0.47% of a cement weight, Comparative Examples 2 is for mixing 0.45% naphthalenesulfonate formaldehyde condensation compound water reducer and 0.20% Diethylene Glycol dipropylene glycol single-butyl ether economization agent (brief note SRA) again, and test-results sees Table 3:
| Volume (%) | Air content (%) | Ultimate compression strength (Mpa) drying shrinkage (* 10 -6) | ||||||
| 3d | 7d | 28d | 28d | 60d | ||||
| Embodiment | Embodiment 1 | 0.20 | 2.7 | 47.2 | 59.8 | 66.3 | -153.167 | -216.383 |
| Embodiment 2 | 0.16 | 2.3 | 48.6 | 63.7 | 68.9 | -168.091 | -256.122 | |
| Embodiment 3 | 0.29 | 2.9 | 45.3 | 61.5 | 65.1 | -142.356 | -203.421 | |
| Embodiment 4 | 0.15 | 2.5 | 49.1 | 63.2 | 67.5 | -173.375 | -248.678 | |
| Embodiment 5 | 0.20 | 2.5 | 48.7 | 62.9 | 68.5 | -165.323 | -208.337 | |
| Comparative Examples | Comparative Examples 1 | 0.47 | 3.0 | 45.3 | 54.3 | 60.9 | -278.812 | -412.433 |
| Comparative Examples 2 | 0.45+2.0 | 4.7 | 40.3 | 48.5 | 54.1 | -162.337 | -232.785 | |
Find out that from table 3 test-results embodiment of the invention institute synthetic graft copolymer all not only has good dispersing property to cement, and reinforced effects is obvious.Under the condition with water cement ratio, mixing embodiment of the invention ratio, to mix naphthalenesulfonate formaldehyde condensation compound water reducer reinforced effects remarkable, and by contrast, mixing naphthalenesulfonate formaldehyde condensation compound water reducer and economization agent again has adverse influence to intensity.From the dry shrinkage performance, embodiment of the invention institute synthetic multipolymer can effectively reduce concrete dry shrinkage, under water cement ratio, compare and reduced by 30～50% with mixing the naphthalenesulfonate formaldehyde condensation compound water reducer, it is suitable with mixing 0.20% economization agent to reduce effect, even better effects if, and volume descends significantly.
Application Example 2
With 1 synthetic carboxyl acid graft copolymer of embodiment is that example is investigated different copolymer thing volume to the influence to diminishing, reinforced effects, with reference to GB8076-1997 " concrete admixture " proportioning, change the multipolymer volume, by adjusting water consumption control concrete slump at 8 ± 1cm, test-results sees Table 4.
Table 4
| Volume (%) | Water cement ratio | Water-reducing rate (%) | Air content (%) | Ultimate compression strength (MPa)/compressive strength rate (%) | |||
| R3 | R7 | R28 | |||||
| Embodiment 1 | 0 0.16 0.20 0.24 0.30 0.36 | 0.538 0.438 0.420 0.41 0.402 0.398 | / 18.6 22.3 23.8 25.2 25.5 | 2.3 3.1 2.5 2.3 2.5 2.5 | 25.8/100 45.4/176 45.6/177 48.2/187 51.2/198 50.3/195 | 36.5/100 60.3/165 61.2/167 62.7/172 65.9/180 64.2/176 | 41.7/100 64.8/155 66.2/159 67.3/161 69.2/166 67.8/163 |
| FDN FDN+SRA | 0.45 0.45+2.0 | 0.422 0.413 | 21.6 23.2 | 3.1 4.9 | 47.2/183 40.6/157 | 55.6/152 50.5/138 | 57.3/137 53.7/129 |
When embodiment of the invention volume be cement 0.16% the time, just has 18.6% water-reducing rate, volume is 0.20% o'clock, just has 22.3% water-reducing rate, its water-reducing rate surpasses the level of general high efficiency water reducing agent in the market, volume was greater than 0.30% o'clock of cement consumption, and water-reducing rate can reach 25%.Increase with admixture dosage, the water-reducing rate increasing degree is very little, and volume is 0.30% to reach saturation point basically.And do not delay concrete time of coagulation.Institute of the present invention synthetic graft copolymer has good reinforced effects, and the ultimate compression strength of 3d improves 70～120%, and the ultimate compression strength of 7d brings up to 70～100%, and the ultimate compression strength of 28d can increase by 60～80%, and the ultimate compression strength of 60d can increase by 50～70%.When volume be increased to cement consumption 0.30% the time, intensity increases slowly, even slightly descends on the contrary.Therefore strengthen and economic angle from diminishing, the optimum mix amount is proper between 0.20～0.30%.
Comparative test result shows simultaneously: mix economization agent again ultimate compression strength has been produced adverse influence, guaranteeing that though the adding of economization agent has reduced water consumption, intensity decreases on the contrary under the constant situation of water reducer volume.
Application Example 3
With 1 synthetic carboxyl acid graft copolymer of present embodiment is that example is investigated the multipolymer volume to the concrete shrinkage Effect on Performance, and making fresh concrete just make the slump by the adjustment water consumption is 8 ± 1cm, and test the results are shown in Table 5.
When adding 0.16% graft copolymer of the present invention, the 28d drying shrinkage is compared with benchmark and has been reduced by 24%, and 60d has reduced by 25.1%; Added 0.20% o'clock, the 28d drying shrinkage is compared with benchmark and has been reduced by 44%, and 60d has reduced by 45%, has reached the effect of reducing of mixing 2% economization agent again basically.Continue to increase volume, increase to and mix 0.30%, the 28d drying shrinkage has reduced by 41.5%, and 60d has reduced by 35.3%, reduces the effect of shrinking and compares to some extent and weaken with mixing 0.20%.
Under each volume of table 5 to the influence of concrete shrinkage
| Admixture | Volume % | Difference shrinking percentage in the length of time (* 10 -6) | |||||
| 1d | 3d | 7d | 14d | 28d | 60d | ||
| Blank FDN FDN+SRA | / 0.45 0.45+2.0 | -5.22088 -18.0723 -1.80723 | -41.7671 -56.3253 -24.2972 | -95.9839 -108.635 -58.2329 | -165.863 -179.016 -96.5863 | -270.08 -283.584 -155.823 | -381.2 -401.4 -223.0 |
| Embodiment 1 | 0.16 0.20 0.24 0.30 | -10.4418 8.032129 3.212851 3.212851 | -46.2851 3.313254 -17.8554 -14.0562 | -83.5341 -31.0241 -51.6867 -41.1647 | -131.827 -72.6908 -88.8554 -84.739 | -206.627 -145.783 -149.839 -158.233 | -285.8 -209.4 -213.8 -246.6 |
Application Example 4
Adopt dull and stereotyped split test to estimate of the influence of 1 synthetic graft copolymer of present embodiment, adopt the new 42.5P.O cement of China, and adopt naphthalene series high-efficiency water-reducing agent (FDN) and organic antishrinking agent SRA as a comparison cracking performance.Fixedly water-cement ratio 0.32, sand coarse aggregate ratio 0.40, gel material content 470kg/m
3, control the concrete slump at 18-20cm.
Table 6 admixture kind influences concrete early-age plastic rimose
| The admixture kind | Cracking time | Maximum is split wide/mm | Area of cracks/mm 3 |
| Embodiment 1 Comparative Examples 1 is mixed FDN Comparative Examples 2 and is mixed FDN+2%SRA again | 6h20min 3h10min 4h40min | 0.27 1.O 0.6 | 100.15 763.32 293.05 |
Mix the early stage area of cracks maximum of concrete of FDN, fracture width is the wideest, reaches 1mm, add graft copolymer area of cracks of the present invention and only be 13% of FDN, fracture width has only 0.27mm, and cracking time also postpones greatly, and is better when effect of prestressed is mixed again than FDN and economization agent.
Claims (13)
1, a kind ofly reduce, the anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that by monomer a: vinylformic acid or its salt, monomer b: alkoxy polyether mono acrylic ester, monomer c: maleic anhydride half-ester or its salt, monomer d: α-vinyl carbinol ω-methyl polyethers and monomer c: vinylbenzene is prepared from by free radicals copolymerization reaction, aforementioned monomer a: monomer b: monomer c: monomer d: the mol ratio of monomer c is 1: 0.2～0.5: 0.10～0.25: 0.10～0.20: 0～0.10.
2, as claimed in claim 1ly reduce, the anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that described monomer a represents with general formula 1:
M in the formula
1Expression hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group.
3, as claimed in claim 1ly reduce, the anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that described monomer b represents with general formula 2:
R is the alkyl of 1～4 carbon atom in the formula, and AO is the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more this oxyalkylene groups, and n is the average addition mole number of oxyalkylene group, is 5～40.
4, as claimed in claim 1ly reduce, the anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that described monomer c represents with general formula 3:
M in the formula
2Expression hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group, p and q are 0～8 integers, and 2≤p+q≤8.
5, as claimed in claim 1ly reduce, the anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that described monomer d represents with general formula 4:
M is 4～25 integer in the formula.
6, claim 1 to 5 describedly reduce, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that comprising the steps:
1) preparation monomer b: under the condition that azeotropic agent, acid catalyst and stopper exist, carry out esterification by 1: 1 to 5: 1 mol ratio by monoalkoxy polyethers shown in the general formula (5) and vinylformic acid;
2) preparation monomer c: by 1: 1 mol ratio esterification takes place directly under the condition of catalyzer by the monoalkoxy polyethers shown in the general formula (6) and maleic anhydride with reducing function;
3) monomer a, monomer b, monomer c, monomer d and monomer e are carried out free radicals copolymerization reaction by 1: 0.2～0.5: 0.10～0.25: 0.10～0.20: 0～0.10 mol ratio under the condition that radical initiator exists, and adding the alkali neutralization reaction, the pH value is adjusted to 7.0～8.5 and promptly makes finished product.
7, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that adoptable catalyzer comprises the vitriol oil, tosic acid, solid super-strong acid, phosphoric acid and phosphorous acid in the step 1), they can mix use separately or with arbitrary proportion; Catalyst consumption is being 0.5～5% of the monoalkoxy polyethers shown in the general formula (5) and acrylic acid gross weight.
8, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that adopting in the step 1) organic solvent to make azeotropic agent, the organic solvent that is fit to do azeotropic agent comprises aliphatic hydrocarbon, naphthenic hydrocarbon or aromatic hydrocarbon, wherein aliphatic hydrocarbon is selected from hexane, decane, undecane, dodecane; Naphthenic hydrocarbon is selected from hexanaphthene, methylcyclohexane; Aromatic hydrocarbon is selected from benzene, toluene, adjacent,, right-dimethylbenzene; The content of azeotropic agent in reaction mixture should be 10～40% of the monoalkoxy polyethers shown in the general formula (5) and acrylic acid gross weight.
9, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that stopper is selected from Resorcinol in the step 1), thiodiphenylamine, Resorcinol-methyl ether or two-tertiary butyl-p-cresol, its consumption are 0.005～0.8% of vinylformic acid weight.
10, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that step 2) in adoptable catalyzer comprise the vitriol oil, tosic acid and solid super-strong acid, they can be used alone or as a mixture; The consumption of acid catalyst is being 0.5～5% of the gross weight of monoalkoxy polyethers with reducing function shown in the general formula (6) and maleic anhydride.
11, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that step 1) and 2) temperature of reaction be 100～160 ℃.
12, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, it is characterized in that the initiator in the step 3) is conventional oil soluble radical initiator and composition thereof, comprise Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide or different third hydrogen peroxide or peroxy dicarbonate diisopropyl fat; The consumption of initiator is each monomer integral molar quantity about 1.0～4.0% in the step 3.
13, as reduce as described in the claim 6, the preparation method of anti-cracking grafted copolymer as concrete super-plasticizing agent, the molecular weight that it is characterized in that the multipolymer that step 3) generates can utilize the polymeric chain transfer agent to select control, aforementioned polymeric chain transfer agent selected from mercapto propionic acid, Thiovanic acid, mercaptoethanol and Dodecyl Mercaptan, its consumption be in the step 3) each total monomer weight 1.0～5.0%.
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