CN103183795A - Low air content polycarboxylic acid water reducer and preparation method thereof - Google Patents
Low air content polycarboxylic acid water reducer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low air content concrete polycarboxylic acid water reducer and a preparation method thereof. The water reducer is a polymer formed by random copolymerization of A, B and C monomers and has an average molecular weight of 10000-30000, wherein structures of the monomer A, B and C are respectively shown as the following formula (I), (II) and (III), and the meaning of each symbol involved in the formulas can be seen in the specification. The preparation method provided in the invention takes polyoxyethylene and polyoxypropylene ether with a molecular weight of 900-4000 as polymerization monomers to perform random free radical copolymerization in an aqueous solution system. Due to the introduction of perfluoroalkyl phosphate acrylate to a side chain, the air-entraining defoaming function of the water reducer can be improved, and at the same time, the distribution density of main and side chains tends to be more reasonable, so that the water-reducing rate, cement adaptability and slump retention of the water reducer can be improved. In addition, the preparation method involved in the invention has a simple process and less pollution, and can significantly improve the production efficiency and production benefits.
Description
Technical field
The present invention relates to a kind of polymkeric substance and preparation method thereof, more specifically, the present invention is specifically related to a kind of low gas content amount concrete polycarboxylate water-reducer and preparation method thereof.
Background technology
Along with the concrete development of China in recent years, concrete various aspects of performance improves constantly, and is also more and more higher to the requirement of cement water reducing agent.Polycarboxylate water-reducer is third generation high-performance water reducing agent, have that volume is low, water-reducing rate is high, slump-loss is little,, the consumption that can increase substantially blended materials such as flyash, breeze strong with cement adaptability, can save cement significantly, dispose advantages such as high-strength, super high strength concrete, be widely used in the concrete works of high strength such as high-speed railway, bridge, hydro project, high-durability, high cement adaptability.
At present, the common problem that polycarboxylate water-reducer runs in using is that air content is higher, has influenced concrete intensity, and reducing concrete 's air-containing is the problem that urgent need will solve in the water reducer exploitation.Traditional method generally in water reducer the back Compounded Antifoamer control its air content.Defoamer is wide in variety, and difference on effect is bigger, also exists and the water reducer compatibility problem simultaneously.The polycarboxylate water-reducer Molecular Structure Design has bigger degree of freedom, and its performance also has bigger development space, and the research to polycarboxylate water-reducer both at home and abroad also emerges in an endless stream.
Disclose a kind of water reducer synthetic method among the CN101293946A, wherein by adjusting the molecular weight of Methylacrylic acid polyethylene glycol single armor ether ester, changed carboxylic side-chain and polyoxyethylene base side chain ratio, thereby adjusted the water reducer air content.
A kind of method that the alkoxyl group side chain improves consistency of introducing when polycarboxylate water-reducer is synthetic is disclosed among the US5661206, adopt methoxy poly (ethylene glycol) unsaturated ester and unsaturated acid copolymerization, and add a spot of PEP-101, suitably improved concrete air content.
Disclose among the US6187841 by the ratio of improving alkoxyl group polyoxyethylene glycol unsaturated ester and unsaturated acid and then the method for suitably improving air content and intensity.
Disclose a kind of preparation method of polycarboxylic acid series water reducing agents for efficient aerocrote among the CN1316398A, it is in copolymerization process, and the employing butanone is solvent, after reaction finishes, needs to desolventize through the underpressure distillation steaming.
Yet disclosed method and product or complex manufacturing are unfavorable for scale operation in these documents; Perhaps the product air content is lower, but slump retaining is relatively poor, cement adaptability is narrow; Perhaps adopt organic solvent, not only environment is unfriendly, and the production cost height.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides the concrete polycarboxylate water-reducer of a kind of low gas content amount, this water reducer is the polymkeric substance that is made by random copolymerization by A, B, three kinds of monomers of C, its weight-average molecular weight is 10000～30000, and wherein the mol ratio between each monomer is A: B: C equals 0.2～1: 3～10: 30～50; And monomer A is perfluoro alkyl phosphoester acrylic ester, and has following structural formula (I):
In the formula (I), n is 1～5 integer; R
fBe fluorine alcohol compound group: R
f'-CH
2CH (OCOCH
3) CH
2OH or R
f'-(CH
2)
m-OH, wherein R
f' be-[CF (CF)
3CF
2O]
xCF
2CF
2-,-CF
2O[CF (CF
3) CF
2O]
x(CF
2O)
yCF
2-or-CF
2O (CF
2CF
2O)
x(CF
2O)
yCF
2-, wherein m is 2～10 integer, and x is 2～20 integer, and y is 3～20 integer; R
1, R
2Be C
1～C
6Alkylidene group;
Monomers B has following structural formula (II):
In the formula (II), a, b are 2～4 integers, and a ≠ b; H is 0～100 integer; K is 0～100 integer, and 10≤h+k≤100, R
3Be C
1～C
8Alkenyl; And
Monomer C has following structural formula (III):
In the formula (III), R
1, R
2, R
3For H ,-CH
3Or-(CH
2)
sCOOM
2, M
1, M
2Be H or basic metal, s is the integer of satisfied 0≤s≤3, when-(CH
2)
sCOOM
2When existing, its can with COOM
1Or other-(CH
2)
sCOOM
2Form acid anhydrides.
On the one hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer, the mol ratio between wherein said each monomer is A: B: C equals 0.3～1: 3～9: 30～45.
On the other hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer, the molecular weight of wherein said monomer A is 400～8000, and accounts for 2%～10% of each monomer total mass.
On the one hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer again, the molecular weight of wherein said monomers B is 900～4000, and accounts for 10%～90% of each monomer total mass.
On the one hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer again, wherein said monomers B is for being selected from allyl polyether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, the polyethenoxy ether.
Again on the one hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer, wherein said monomer C is selected from a kind of in MALEIC ANHYDRIDE, maleic acid, vinylformic acid and the methacrylic acid.
In addition, the present invention also provides a kind of method for preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, and this method comprises the steps:
1) in reactor, add monomer A, monomers B, monomer C and water, wherein the mass ratio of water and monomers B is 1.0～3.5, and is heated with stirring to 70～90 ℃;
2) drip initiator in the reaction system that derives from step 1), initiator amount is 0.5%～5% of monomer A, B, C total mass,, the dropping time is 1～4 hour;
3) keep as above temperature 6～8 hours, be cooled to normal temperature then, and regulate pH value to neutrality, obtain described polymkeric substance.
On the one hand, the invention provides a kind of method for preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, wherein said radical initiator is ammonium persulphate, Potassium Persulphate, azo-bis-isobutyrate hydrochloride or hydrogen peroxide.
On the other hand, the invention provides a kind of method for preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, the consumption of wherein said radical initiator is 0.5%～5% of monomer A, B, C total mass.
Again on the one hand, the invention provides a kind of method for preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, wherein the conciliation pH described in the step 3) is that to utilize mass percent be that 30%～50% the NaOH aqueous solution is finished to neutrality.
Compared with prior art, owing to introduced the perfluoro alkyl phosphoester acrylic ester monomer in the water reducer of the present invention, make it have good their defoaming function, thereby, when it is used as water reducer, can make concrete have lower air content and the intensity of Geng Gao.
Secondly, because monomer A is perfluoro alkyl phosphoester acrylic ester, monomers B is for being selected from allyl polyether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, in alkylene thiazolinyl polyoxyethylene, the polyethenoxy ether one or more, and the molecular weight of these monomers is alternative strong, so can be by selecting monomer A and the B of suitable molecular weight, make the water reducer that is synthesized to adapt to the cement of different size, that is water reducer of the present invention have better cement consistency.
In addition, water reducer of the present invention has also that volume is few, slump retaining good, and advantage such as production technique is simple, environmental friendliness, production cost are low.
In order to understand the present invention better, hereinafter, the embodiment with reference to the back is described more specifically the present invention.Unless this paper makes separate stipulations, the employed scientific and technical terminology of this paper all with the same meaning of general technical staff of the technical field of the invention institute common sense.Wherein the embodiment of mentioned material, method and back only is used for explanation, rather than to the restriction of scope of the present invention.
Embodiment
In this manual, water reducer refers under concrete workability and cement consumption permanence condition, can reduce the mixing water amount, improve concrete strength; Or under workability and intensity permanence condition, save the concrete admixture of cement consumption.By its water-reducing rate size, can be divided into ordinary water-reducing agent (as sulfonated lignin), high efficiency water reducing agent (comprising naphthalene system, melamine system, sulfamate system, aliphatics based water reducer etc.) and high-performance water reducing agent (as polycarboxylic acids high efficiency energy water reducer).
In one embodiment, the invention provides a kind of polymkeric substance as low gas content amount concrete polycarboxylate water-reducer, this polymkeric substance is made by random copolymerization by A, B, three kinds of monomers of C, weight-average molecular weight is 10000～30000, and the mol ratio between each monomer is that A: B: C is 0.2～1: 3～10: 30～50; Wherein monomer A is perfluoro alkyl phosphoester acrylic ester, and has following structural formula (I):
In the formula (I), n is 1～5 integer; R
fBe fluorine alcohol compound group: R
f'-CH
2CH (OCOCH
3) CH
2OH or R
f'-(CH
2)
m-OH, wherein R
f' be-[CF (CF)
3CF
2O]
xCF
2CF
2-,-CF
2O[CF (CF
3) CF
2O]
x(CF
2O)
yCF
2-or-CF
2O (CF
2CF
2O)
x(CF
2O)
yCF
2-, wherein m is 2～10 integer, and x is 2～20 integer, and y is 3～20 integer; R
1, R
2Be C
1～C
6Alkylidene group;
Monomers B has following structural formula (II):
In the formula (II), a, b are 2～4 integers, and a ≠ b; H is 0～100 integer; K is 0～100 integer, and 10≤h+k≤100, R
3Be C
1～C
8Alkenyl; And
Monomer C has following structural formula (III):
In the formula (III), R
1, R
2, R
3For H ,-CH
3Or-(CH
2)
sCOOM
2, M
1, M
2Be H or basic metal, s is the integer of satisfied 0≤s≤3, when-(CH
2)
sCOOM
2When existing, its can with COOM
1Or other-(CH
2)
sCOOM
2Form acid anhydrides.
In one embodiment, the mol ratio A of preferred each monomer: B: C is 0.3～1: 3～9: 30～45, exceed this scope, be difficult to realize that multipolymer has suitable side chain density and pectination, and such polymkeric substance is not having space steric effect with differing materials such as cement as the time spent.
In one embodiment, described monomer A is by fluorine alcohol compound and Phosphorus Oxychloride reaction, again with diol reaction, the synthetic perfluoralkyl phosphate that contains hydroxyl, then with its acrylated, perhaps directly add the dibasic alcohol that contains acrylic double bond, can obtain the perfluoro alkyl phosphoester acrylic ester monomer, concrete synthetic method sees CN101302232A for details.Whole disclosures of the document all are incorporated herein by reference.Froth breaking effect in order to ensure water reducer of the present invention, the molecular weight of monomer A is generally 400～8000, be preferably 500～6000, and the consumption of monomer A is 2%～10% of each monomer total mass, be preferably 3%～8%, give full play to the froth breaking effect, the various performances of this water reducer of balance, and reduction concrete 's air-containing and the concrete intensity of enhancing to guarantee final water reducer.
In one embodiment, described monomers B is polyoxyethylene, polyethenoxy ether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, in alkylene thiazolinyl polyoxyethylene, the polyethenoxy ether one or more, be preferably methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, the polyethenoxy ether.If the molecular weight of monomers B is too small, then polymerization rate is too fast, and the system conversion value is lower; If the molecular weight of monomers B is excessive, polymerization rate is slow excessively, does not reach polymerization effect.Consider the over-all properties of final water reducer simultaneously, the molecular weight of preferred monomers B is 900～4000, and the consumption of monomers B is 10%～90% of each monomer total mass.Above-mentioned monomers B can be buied from the market, and for example, molecular weight is that 950～1100 alkylene thiazolinyl polyoxyethylene, polyethenoxy ether can be buied with the trade name of OXAC-605 from Liaoning AoKe Chemical Co., Ltd; Molecular weight is that 2250～2550 alkylene thiazolinyl polyoxyethylene, polyethenoxy ether can be buied with the trade name of OXAC-608 from Liaoning AoKe Chemical Co., Ltd; Molecular weight is that 1000～1200 methyl thiazolinyl polyoxyethylene, polyethenoxy ether can be buied with the trade name of OXAB-501A from Liaoning AoKe Chemical Co., Ltd; Molecular weight is that 2700～3330 allyl polyether can be buied with the trade name of OXAA-660 from Liaoning AoKe Chemical Co., Ltd.
In one embodiment, described monomer C is a kind of in MALEIC ANHYDRIDE, maleic acid, vinylformic acid, the methacrylic acid, preferred MALEIC ANHYDRIDE.Above-mentioned monomer C is commercially available, and for example, MALEIC ANHYDRIDE can be risen imperial trade Co., Ltd from Shenzhen's gold and be buied.
It is to be noted, the term of mentioning in this specification sheets " alkenyl " refers to contain side chain or the linear aliphatic hydrocarbon monoradical of at least one carbon-to-carbon double bond, for example vinyl, propenyl, n-butene base, isobutenyl, 3-methyl but-2-ene base, just-pentenyl etc.; Term " alkylidene group " refers to have side chain or straight chain saturated aliphatic hydrocarbon divalent group, for example methylene radical, ethylidene, propylidene, the inferior normal-butyl etc. of specifying carbonatoms.
In another embodiment, the invention provides a kind of preparation as the method for the polymkeric substance of low gas content amount concrete polycarboxylate water-reducer, this method comprises the steps:
1) in reactor, add monomer A, monomers B, monomer C and water, wherein the mass ratio of water and monomers B is 1.0～3.5, and is heated with stirring to 70～90 ℃;
2) drip initiator in the reaction system that derives from step 1), initiator amount is 0.5%～5% of monomer A, B, C total mass,, the dropping time is 1～4 hour;
3) keep as above temperature 6～8 hours, be cooled to normal temperature then, and regulate pH value to neutrality, obtain doing the polymkeric substance of low gas content amount concrete polycarboxylate water-reducer thus.
In one embodiment, being used for initiator of the present invention is radical initiator, and this radical initiator is selected from ammonium persulphate, Potassium Persulphate, azo-bis-isobutyrate hydrochloride or hydrogen peroxide, initiator system of ammonium persulfate.Above-mentioned radical initiator is initiator commonly used well known in the art, can be by buying on the market.
In one embodiment, the consumption of described radical initiator is 0.5%～5% of monomer A, B, C total mass, and this those skilled in the art will readily understand.
In one embodiment, described adjusting pH value extremely neutrality be to utilize the aqueous solution of highly basic such as potassium hydroxide, sodium hydroxide to carry out; In the present invention, preferably adopting mass percent is 30%～50% the NaOH aqueous solution.
Those skilled in the art will readily understand that temperature of reaction is important to Raolical polymerizable, temperature is low excessively, and polyreaction is difficult to carry out, and temperature is too high, and side reaction then takes place easily.Therefore, in embodiments of the invention, preferable reaction temperature is 70～90 ℃.
Consider that order of addition(of ingredients) and feed rate are to the influence of polyreaction and polymerisate, while is in conjunction with the performance of required carboxylic acid water reducer, in embodiments of the invention, preferably monomer A, B, C are added in the water, and then the dropping radical initiator, and preferably in 1～4 hour, finish dropping.It is too fast to understand rate of addition easily, and material reaction is insufficient, and rate of addition is slow excessively, then influences production efficiency.Therefore, in embodiments of the invention, after preferably being added dropwise to complete, reactant is incubated 6～8 hours under 70～90 ℃ temperature, to carry out with reacting fully, so both can improve utilization ratio of raw materials, also can obtain the satisfactory polymerisate of performance simultaneously.
In order to understand characteristic of the present invention and advantage better, the contriver also is applied to water reducer of the present invention in the actual concrete.
At first, water reducer of the present invention and cement, sand, stone, water and other admixture are carried out blending with certain proportioning by JGJ55.Various concrete test materials and envrionment temperature all should remain on (20 ± 3) ℃.It is 60 liters single horizontal shaft type forced stirrer that employing meets nominal capacity that JG3036 requires, low gas content polycarboxylic acids water reducing agent, cement, sand, stone are once dropped into stirrer, the mixing water that is mixed with admixture in adding stirred 2 minutes together, after the discharging,, test with manually turning to evenly on iron plate.Each concrete is got a sample, the slump, divergence and the slump 1 hour through the time variable quantity all represent with the mean value of three test-results.Concrete slump is measured according to GB/T50080, but the slump is the concrete of (210 ± 10) millimeter, divides two-layer charging, packing into highly for every layer is high half of tube, and every layer of usefulness is inserted tamper and inserted and smash 15 times, and tube is vertically mentioned, make concrete be the nature flow state, measure the slump and divergence.After the slump refers to that fresh concrete flows out from slump bucket, the distance of the top of slump bucket and concrete vertex.After divergence referred to that concrete flows naturally, the expanded area on iron plate was measured by diameter, measures and represents with the mean value of three test-results.Pack into after the measurement in the test specimen tube that nuzzles up with gauze, container is added a cover, and leaves standstill to 1 hour (beginning to calculate when water stirs from adding), pours out then, turning with spade on the iron plate after evenly, measures the slump and divergence again.
In application test, with the performance of following parameter characterization polycarboxylate water-reducer of the present invention commonly used:
1) water-reducing rate is measured
Water-reducing rate is slump when basic identical, reference cement and examined the difference of concrete unit consumption of water and the ratio of normal concrete unit consumption of water.
2) air content is measured
Press GB/T50080 gas-water mixed type air content determinator, and operate by the instrument explanation, but concrete mix should once be filled and a little higher than container, with shaking table jolt ramming 15 seconds～20 seconds.During test, air content is represented with the arithmetical av of three sample measured values.
3) compressive strength rate is measured
Compressive strength rate with mix admixture concrete and normal concrete with the length of time ultimate compression strength ratio represent.Being examined the ultimate compression strength of concrete and normal concrete tests and calculates by GB/T50081, when test specimen is made, with shaking table vibration 15 seconds～20 seconds, test specimen precuring temperature was (20 ± 3) ℃, and compressive strength rate is represented with the arithmetical av of three sample measured values.
Other parameter or detailed description please refer to GB/8076-2008.
According to above preparation method sandstone material such as low gas content polycarboxylic acids water reducing agent and cement are done the time spent and can better bring into play its space steric effect, concrete workability is good, no bleeding, segregation phenomenon occur, reach purpose of the present invention, namely provide a kind of stable performance, low gas content, high diminishing, strong to cement adaptability, slump retaining good and the polycarboxylate water-reducer of environmentally safe.
Example one
In reactor, add 94 gram water and 4.3 gram monomer A (molecular weight is 1700 perfluoralkyl phosphate mono acrylic ester), (molecular weight is 2600 alkylene thiazolinyl polyoxyethylene to 78 gram monomers B, polyethenoxy ether), 35.5 gram monomer C (MALEIC ANHYDRIDE), be heated with stirring to 80 ℃, drip initiator (0.71 gram ammonium persulphate and 40 gram water mixture) then, the dropping time is 3 hours, digestion time is 4 hours, and reaction is cooled to normal temperature after finishing, and regulates the pH value to neutral with the NaOH aqueous solution of mass concentration 30%, discharging, both got the high-performance polycarboxylic acids water reducing agent product, the products obtained therefrom solid content is 40%, and the resulting polymers weight-average molecular weight is 25830.
Monomer A is
Example two
In reactor, add 105 gram water and 12 gram monomer A (molecular weight is 6000 perfluoralkyl phosphate mono acrylic ester), (molecular weight is 2000 methyl thiazolinyl polyoxyethylene to 70 gram monomers B, polyethenoxy ether), 54 gram monomer C (MALEIC ANHYDRIDE), be heated with stirring to 80 ℃, drip initiator (2.85 gram ammonium persulphates and 40 gram water mixture) then, the dropping time is 3.5 hours, digestion time is 4 hours, and reaction is cooled to normal temperature after finishing, and regulates the pH value to neutral with the NaOH aqueous solution of mass concentration 30%, discharging, both got the high-performance polycarboxylic acids water reducing agent product, the products obtained therefrom solid content is 36%, and the resulting polymers weight-average molecular weight is 27900.
Monomer A is
Example three
In reactor, add 82.5 gram water and 18 gram monomer A (molecular weight is 1000 perfluoro alkyl phosphoester acrylic ester), 27.5 (molecular weight is 1500 alkylene thiazolinyl polyoxyethylene to the gram monomers B, polyethenoxy ether), 40.8 gram monomer C (vinylformic acid), be heated with stirring to 70 ℃, drip initiator (2.24 gram ammonium persulphates and 20 gram water mixture) then, the dropping time is 2.5 hours, digestion time is 3.5 hours, and reaction is cooled to normal temperature after finishing, and regulates the pH value to neutral with the NaOH aqueous solution of mass concentration 30%, discharging, both got the high-performance polycarboxylic acids water reducing agent product, the products obtained therefrom solid content is 43%, and the resulting polymers weight-average molecular weight is 21500.
Monomer A is
Example four
In reactor, add 128 gram water and 2.55 gram monomer A (molecular weight is 1700 perfluoro alkyl phosphoester acrylic ester), 49.5 (molecular weight is 1100 alkylene thiazolinyl polyoxyethylene to the gram monomers B, polyethenoxy ether), 46.9 gram monomer C (methacrylic acid), be heated with stirring to 70 ℃, drip initiator (0.89 gram hydrogen peroxide and 40 gram water mixture) then, the dropping time is 3.5 hours, digestion time is 4.5 hours, and reaction is cooled to normal temperature after finishing, and regulates the pH value to neutral with the NaOH aqueous solution of mass concentration 30%, discharging, both got the high-performance polycarboxylic acids water reducing agent product, the products obtained therefrom solid content is 40%, and the resulting polymers weight-average molecular weight is 29900.
Monomer A is
Example five
In reactor, add 80 gram water and 6.4 gram monomer A (molecular weight is 1600 perfluoro alkyl phosphoester acrylic ester), (molecular weight is 3000 methyl thiazolinyl polyoxyethylene to 50 gram monomers B, polyethenoxy ether and alkylene thiazolinyl polyoxyethylene, polyethenoxy ether is mixing in 1: 1 according to mol ratio), 32 gram monomer C (vinylformic acid), be heated with stirring to 90 ℃, drip initiator (1.06 gram Potassium Persulphates and 20 gram water mixture) then, the dropping time is 2.5 hours, digestion time is 3.5 hours, reaction is cooled to normal temperature after finishing, regulate the pH value to neutral with the NaOH aqueous solution of mass concentration 30%, discharging, both got the high-performance polycarboxylic acids water reducing agent product, the products obtained therefrom solid content is 40%, and the resulting polymers weight-average molecular weight is 17900.
Monomer A is
Application examples one
Be under 23 ℃ of conditions in room temperature, use little wild water in field mud P.O.42.5 to carry out concrete test.Take by weighing example one synthetic water reducer 14.25 and restrain (volume is 0.15%), cement, sand, stone, water and flyash are 1: 2.02: 2.95 according to proportioning: 0.4: 0.21 ratio is carried out weighing.Low gas content polycarboxylic acids water reducing agent, cement, sand, stone are once dropped into stirrer, and the mixing water that is mixed with admixture in adding stirred 2 minutes together, after the discharging, on iron plate with manually turning to evenly testing.Divide two-layer charging with concrete, packing into highly for every layer is high half of tube, and every layer of usefulness is inserted tamper and inserted and smash 15 times, and tube is vertically mentioned, and makes concrete be the nature flow state, measures the slump and divergence, measures and represents with the mean value of three test-results.Pack in the test specimen tube that nuzzles up with gauze after the measurement and add a cover, leave standstill to 1 hour (beginning when water stirs to calculate from adding), pour out then, turning with spade on the iron plate after evenly, measure the slump and divergence according to slump measuring method again, measuring result sees Table 1.
Water-reducing rate is slump when basic identical, the difference of reference cement and little wild water in field cement concrete unit consumption of water and the ratio of normal concrete unit consumption of water, and the water-reducing rate measuring result sees Table 1.
Press GB/T50080 gas-water mixed type air content determinator, and operate by the instrument explanation, concrete mix is once filled and a little higher than container, with shaking table jolt ramming 15 seconds～20 seconds, during test, air content represents that with the arithmetical av of three sample measured values measuring result sees Table 1.
The water reducer that compressive strength rate synthesizes with example one, little wild water in field cement concrete and the ratio of normal concrete with ultimate compression strength in the length of time.Test and calculate by GB/T50081, when test specimen was made, with shaking table vibration 15 seconds～20 seconds, compressive strength rate represented that with the arithmetical av of three sample measured values measuring result sees Table 1.
Application examples two
Be under 23 ℃ of conditions in room temperature, use little wild water in field mud P.O.42.5 to carry out concrete test.Take by weighing example two synthetic water reducers 15.83 and restrain (volume is 0.15%), cement, sand, stone, water and flyash are 1: 2.02: 2.95 according to proportioning: 0.4: 0.21 ratio is carried out weighing.
Concrete operations are measured by the method that is similar to application examples one, and measuring result sees Table 1.
Application examples three
Be under 23 ℃ of conditions in room temperature, use little wild water in field mud P.O.42.5 to carry out concrete test.Take by weighing example three synthetic water reducers 13.25 and restrain (volume is 0.15%), cement, sand, stone, water and flyash are 1: 2.02: 2.95 according to proportioning: 0.4: 0.21 ratio is carried out weighing.
Concrete operations are measured by the method that is similar to application examples one, and measuring result sees Table 1.
Application examples four
Be under 23 ℃ of conditions in room temperature, use little wild water in field mud P.O.42.5 to carry out concrete test.Take by weighing example four synthetic water reducers 14.25 and restrain (volume is 0.15%), cement, sand, stone, water and flyash are 1: 2.02: 2.95 according to proportioning: 0.4: 0.21 ratio is carried out weighing.
Concrete operations are measured by the method that is similar to application examples one, and measuring result sees Table 1.
Application examples five
Be under 23 ℃ of conditions in room temperature, use little wild water in field mud P.O.42.5 to carry out concrete test.Take by weighing water reducer 14.25 grams (volume is 0.15%) that the example pentahapto becomes, cement, sand, stone, water and flyash are 1: 2.02: 2.95 according to proportioning: 0.4: 0.21 ratio is carried out weighing.
Concrete operations are measured by the method that is similar to application examples one, and measuring result sees Table 1.
Table 1 low gas content polycarboxylic acids water reducing agent concrete evaluating data
Annotate: " h " representative in the table " hour ", " d " representative " my god ".
From the concrete evaluating data of table 1 low gas content polycarboxylic acids water reducing agent as can be known, under the low-dosage condition, each water reducer has the water-reducing rate height in the example, air content is low, and the divergence after 1 hour is bigger, and concrete workability is good, and no bleeding, segregation phenomenon occur, and ultimate compression strength is higher, has solved the air content problem of higher that often runs in the polycarboxylate water-reducer use.
Though for the present invention is described, the preferred embodiments of the invention are disclosed, but it will be understood by those of skill in the art that under the situation that does not break away from design of the present invention that claims limit and scope, can make various modifications, interpolation and replacement to the present invention.
Claims (10)
1. a polymkeric substance is characterized in that, this polymkeric substance is to be made by random copolymerization by A, B, three kinds of monomers of C, and weight-average molecular weight is 10000～30000, and wherein the mol ratio between each monomer is A: B: C equals 0.2～1: 3～10: 30～50; And monomer A is perfluoro alkyl phosphoester acrylic ester, and has following structural formula (I):
In the formula (I), n is 1～5 integer; R
fBe fluorine alcohol compound group: R
f'-CH
2CH (OCOCH
3) CH
2OH or R
f'-(CH
2)
m-OH, wherein R
f' be-[CF (CF)
3CF
2O]
xCF
2CF
2-,-CF
2O[CF (CF
3) CF
2O]
x(CF
2O)
yCF
2-or-CF
2O (CF
2CF
2O)
x(CF
2O)
yCF
2-, wherein m is 2～10 integer, and x is 2～20 integer, and y is 3～20 integer; R
1, R
2Be C
1～C
6Alkylidene group;
Monomers B has following structural formula (II):
In the formula (II), a, b are 2～4 integers, and a ≠ b; H is 0～100 integer; K is 0～100 integer, and 10≤h+k≤100, R
3Be C
1～C
8Alkenyl; And
Monomer C has following structural formula (III):
In the formula (III), R
4, R
5, R
6For H ,-CH
3Or-(CH
2)
sCOOM
2, M
1, M
2Be H or basic metal, s is the integer of satisfied 0≤s≤3, when-(CH
2)
sCOOM
2When existing, its can with COOM
1Or other-(CH
2)
sCOOM
2Form acid anhydrides.
2. polymkeric substance according to claim 1 is characterized in that, the mol ratio between described each monomer is A: B: C equals 0.3～1: 3～9: 30～45.
3. polymkeric substance according to claim 1 and 2 is characterized in that, the molecular weight of described monomer A is 400～8000, and accounts for 2%～10% of each monomer total mass.
4. polymkeric substance according to claim 1 and 2 is characterized in that, the molecular weight of described monomers B is 900～4000, and accounts for 10%～90% of each monomer total mass.
5. polymkeric substance according to claim 1 and 2 is characterized in that, described monomers B is for being selected from allyl polyether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, the polyethenoxy ether.
6. polymkeric substance according to claim 1 and 2 is characterized in that, described monomer C is selected from a kind of in MALEIC ANHYDRIDE, maleic acid, vinylformic acid and the methacrylic acid.
7. method for preparing each described polymkeric substance in the claim 1～6, this method comprises the steps:
1) add monomer A, monomers B, monomer C and water in reactor, wherein the mass ratio of water and monomers B is 1.0～3.5, and is heated with stirring to 70～90 ℃;
2) drip initiator in the reaction system that derives from step 1), initiator amount is 0.5%～5% of monomer A, B, C total mass, and the dropping time is 1～4 hour;
3) keep as above temperature 6～8 hours, be cooled to normal temperature then, and regulate pH value to neutrality, obtain described polymkeric substance.
8. method according to claim 7, wherein said radical initiator is ammonium persulphate, Potassium Persulphate, azo-bis-isobutyrate hydrochloride or hydrogen peroxide.
9. according to claim 7 or 8 described methods, the consumption of wherein said radical initiator is 0.5%～5% of monomer A, B, C total mass.
10. according to the method for claim 7, wherein the conciliation pH described in the step 3) is that to utilize mass percent be that 30%～50% the NaOH aqueous solution is finished to neutrality.
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| CN104231182A (en) * | 2014-09-22 | 2014-12-24 | 科之杰新材料集团有限公司 | Ester slump retaining type polycarboxylate water reducer and preparation method thereof |
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| CN105236806A (en) * | 2015-10-22 | 2016-01-13 | 石家庄市长安育才建材有限公司 | Phosphoric-acid-base modified polycarboxylic-acid water reducer with high adaptability and preparation method thereof |
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| CN108250343A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | Compound, research work of air entrained type copolymer and preparation method thereof and the application as concrete rheological modifying agent |
| CN108503255A (en) * | 2018-03-30 | 2018-09-07 | 湖北工业大学 | A kind of preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization |
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| CN112203997A (en) * | 2018-05-30 | 2021-01-08 | 竹本油脂株式会社 | Defoaming agent for hydraulic composition, additive for hydraulic composition, and hydraulic composition |
| CN112724414A (en) * | 2021-01-21 | 2021-04-30 | 江苏奥莱特新材料股份有限公司 | Polycarboxylate superplasticizer with polyphosphonate side chains and preparation method thereof |
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| CN112203997A (en) * | 2018-05-30 | 2021-01-08 | 竹本油脂株式会社 | Defoaming agent for hydraulic composition, additive for hydraulic composition, and hydraulic composition |
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