CN103183795B - 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, 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, little loss of slump, the consumption that can increase substantially the blended material such as flyash, breeze strong with cement adaptability, significantly can save cement, configure the advantages such as high-strength, super high strength concrete, be widely used in the concrete works of the 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, have impact on concrete intensity, and reducing concrete 's air-containing is problem in urgent need to solve in water reducer exploitation.Traditional method generally in water reducer after Compounded Antifoamer control its air content.Defoamer is wide in variety, and difference on effect is comparatively large, also exists and water reducer compatibility problem simultaneously.Polycarboxylate water-reducer Molecular Structure Design has larger degree of freedom, and its performance also has larger development space, also emerges in an endless stream both at home and abroad to the research of polycarboxylate water-reducer.
Disclose a kind of high performance water-reducer method in CN101293946A, wherein by the molecular weight of adjustment Methylacrylic acid polyethylene glycol single armor ether ester, change carboxylic side-chain and polyoxyethylene base side chain ratio, thus adjustment water reducer air content.
A kind of alkyloxy side chain of introducing when polycarboxylate water-reducer synthesizes is disclosed to improve the method for consistency in US5661206, adopt methoxy poly (ethylene glycol) unsaturated ester and unsaturated acid copolymerization, and add a small amount of PEP-101, suitably improve concrete air content.
Disclose in US6187841 by improving the ratio of alkoxyl group polyoxyethylene glycol unsaturated ester and unsaturated acid and then suitably improving the method for air content and intensity.
Disclose a kind of preparation method of polycarboxylic acid series water reducing agents for efficient aerocrote in CN1316398A, it is in copolymerization process, and employing butanone is solvent, after completion of the reaction, need steam desolventize through underpressure distillation.
But method disclosed in these documents and product or complex manufacturing, be unfavorable for scale operation; Or product air content is lower, but slump retaining is poor, cement adaptability is narrow; Or employing organic solvent, not only environment is unfriendly, and production cost is high.
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 by A, B, C tri-kinds of monomers polymkeric substance obtained by random copolymerization, its weight-average molecular weight is 10000 ~ 30000, and the mol ratio wherein between each monomer is A: B: C equal 0.2 ~ 1: 3 ~ 10: 30 ~ 50; And monomer A is perfluoro alkyl phosphoester acrylic ester, and there is following structural formula (I):
In formula (I), n is the integer of 1 ~ 5; R
ffor 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 the integer of 2 ~ 10, and x is the integer of 2 ~ 20, and y is the integer of 3 ~ 20; R
1, R
2for C
1~ C
6alkylidene group;
Monomers B has following structural formula (II):
In formula (II), a, b are the integers of 2 ~ 4, and a ≠ b; H is the integer of 0 ~ 100; K is the integer of 0 ~ 100, and 10≤h+k≤100, R
3for C
1~ C
8alkenyl; And
Monomer C has following structural formula (III):
In formula (III), R
1, R
2, R
3for H ,-CH
3or-(CH
2)
scOOM
2, M
1, M
2for 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 equal 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.
Again on the one hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer, the molecular weight of wherein said monomers B is 900 ~ 4000, and accounts for 10% ~ 90% of each monomer total mass.
Again on the one hand, the invention provides a kind of low gas content amount concrete polycarboxylate water-reducer, wherein said monomers B for being selected from allyl polyether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, 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 the one in MALEIC ANHYDRIDE, maleic acid, vinylformic acid and methacrylic acid.
In addition, the present invention also provides a kind of method preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, and the method comprises the steps:
1) add monomer A, monomers B in the reactor, 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 DEG C;
2) to deriving from step 1) reaction system in drip initiator, initiator amount be monomer A, B, C total mass 0.5% ~ 5%, time for adding is 1 ~ 4 hour;
3) keep as above temperature 6 ~ 8 hours, be then cooled to normal temperature, and adjust ph is to neutral, obtains described polymkeric substance.
On the one hand, the invention provides a kind of method 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 preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, the consumption of wherein said radical initiator be monomer A, B, C total mass 0.5% ~ 5%.
Again on the one hand, the invention provides a kind of method preparing above-mentioned low gas content amount concrete polycarboxylate water-reducer, wherein step 3) described in conciliation pH to neutrality be utilize mass percent be 30% ~ 50% the NaOH aqueous solution complete.
Compared with prior art, owing to introducing perfluoro alkyl phosphoester acrylic ester monomer in water reducer of the present invention, make it have good their defoaming function, thus, when it is used as water reducer, concrete can be made to 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, one or more in alkylene thiazolinyl polyoxyethylene, polyethenoxy ether, and the molecular weight of these monomers is alternative strong, therefore by selecting monomer A and the B of suitable molecular weight, make synthesized water reducer can 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 also has that volume is few, slump retaining good, and the advantage such as production technique is simple, environmental friendliness, production cost are low.
In order to understand the present invention better, hereinafter, with reference to embodiment below, the present invention is further illustrated.Unless made separate stipulations herein, the same meaning that scientific and technical terminology used herein is all understood usually with general technical staff of the technical field of the invention.Wherein mentioned material, method and embodiment are below only for illustration of, instead of the restriction to scope of the present invention.
Embodiment
In this manual, water reducer refers under concrete workability and cement consumption permanence condition, can reduce 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, ordinary water-reducing agent (as sulfonated lignin) can be divided into, 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 being used as low gas content amount concrete polycarboxylate water-reducer, this polymkeric substance is obtained by random copolymerization by A, B, C tri-kinds of monomers, weight-average molecular weight is 10000 ~ 30000, and the mol ratio between each monomer is 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 formula (I), n is the integer of 1 ~ 5; R
ffor 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 the integer of 2 ~ 10, and x is the integer of 2 ~ 20, and y is the integer of 3 ~ 20; R
1, R
2for C
1~ C
6alkylidene group;
Monomers B has following structural formula (II):
In formula (II), a, b are the integers of 2 ~ 4, and a ≠ b; H is the integer of 0 ~ 100; K is the integer of 0 ~ 100, and 10≤h+k≤100, R
3for C
1~ C
8alkenyl; And
Monomer C has following structural formula (III):
In formula (III), R
1, R
2, R
3for H ,-CH
3or-(CH
2)
scOOM
2, M
1, M
2for 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, mol ratio A: B: the C of preferred each monomer is 0.3 ~ 1: 3 ~ 9: 30 ~ 45, exceed this scope, be difficult to realize multipolymer and there is suitable side chain density and pectination, and such polymkeric substance is not having space steric effect with during the differing materials effect such as cement.
In one embodiment, described monomer A is reacted by fluorine alcohol compound and Phosphorus Oxychloride, again with diol reaction, the perfluoralkyl phosphate of synthesis containing hydroxyl, then by its acrylated, or the dibasic alcohol directly added containing acrylic double bond, can obtain perfluoro alkyl phosphoester acrylic ester monomer, and concrete synthetic method refers to CN101302232A.Whole disclosures of the document are all incorporated herein by reference.In order to ensure the froth breaking effect of 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%, to guarantee that final water reducer gives full play to froth breaking effect, balance the various performances of this water reducer, and reduce the intensity of concrete 's air-containing and Concrete Structure.
In one embodiment, described monomers B is polyoxyethylene, polyethenoxy ether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, polyethenoxy ether, be preferably methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, polyethenoxy ether.If the molecular weight of monomers B is too small, then polymerization rate is too fast, and system conversion value is lower; If the molecular weight of monomers B is excessive, polymerization rate is excessively slow, does not reach polymerization effect.Consider the over-all properties of final water reducer, the molecular weight of preferred monomers B is 900 ~ 4000 simultaneously, and the consumption of monomers B is 10% ~ 90% of each monomer total mass.Above-mentioned monomers B can be buied from the market, such as, molecular weight be 950 ~ 1100 alkylene thiazolinyl polyoxyethylene, polyethenoxy ether can buy from Liaoning AoKe Chemical Co., Ltd with the trade name of OXAC-605; Molecular weight be 2250 ~ 2550 alkylene thiazolinyl polyoxyethylene, polyethenoxy ether can buy from Liaoning AoKe Chemical Co., Ltd with the trade name of OXAC-608; Molecular weight be 1000 ~ 1200 methyl thiazolinyl polyoxyethylene, polyethenoxy ether can buy from Liaoning AoKe Chemical Co., Ltd with the trade name of OXAB-501A; Molecular weight be 2700 ~ 3330 allyl polyether can buy from Liaoning AoKe Chemical Co., Ltd with the trade name of OXAA-660.
In one embodiment, described monomer C is the one in MALEIC ANHYDRIDE, maleic acid, vinylformic acid, methacrylic acid, preferred MALEIC ANHYDRIDE.Above-mentioned monomer C is commercially available, and such as, MALEIC ANHYDRIDE can be buied from Jin Tenglong trade Co., Ltd of Shenzhen.
It is to be noted, the term " alkenyl " mentioned in this specification sheets refers to side chain containing at least one carbon-to-carbon double bond or linear aliphatic hydrocarbon monoradical, such as vinyl, propenyl, n-butene base, isobutenyl, 3-methyl but-2-ene base, n-pentenyl etc.; Term " alkylidene group " refers to the side chain or straight chain saturated aliphatic hydrocarbon divalent group, such as methylene radical, ethylidene, propylidene, sub-normal-butyl etc. that have and specify carbonatoms.
In another embodiment, the invention provides a kind of method preparing polymkeric substance as low gas content amount concrete polycarboxylate water-reducer, the method comprises the steps:
1) add monomer A, monomers B in the reactor, 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 DEG C;
2) to deriving from step 1) reaction system in drip initiator, initiator amount be monomer A, B, C total mass 0.5% ~ 5%, time for adding is 1 ~ 4 hour;
3) keep as above temperature 6 ~ 8 hours, be then cooled to normal temperature, and adjust ph is to neutral, obtains the polymkeric substance making low gas content amount concrete polycarboxylate water-reducer thus.
In one embodiment, be radical initiator for initiator of the present invention, 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 conventional initiator well known in the art, can buy by market.
In one embodiment, the consumption of described radical initiator be monomer A, B, C total mass 0.5% ~ 5%, this those skilled in the art will readily understand.
In one embodiment, described adjust ph to neutrality utilizes highly basic such as the aqueous solution of potassium hydroxide, sodium hydroxide to carry out; In the present invention, preferably employing mass percent is the NaOH aqueous solution of 30% ~ 50%.
Those skilled in the art will readily understand, temperature of reaction is important to Raolical polymerizable, and temperature is too low, and polyreaction is difficult to carry out, and temperature is too high, then easily side reaction occurs.Therefore, in embodiments of the invention, preferable reaction temperature is 70 ~ 90 DEG C.
Consider the impact on polyreaction and polymerisate of order of addition(of ingredients) and feed rate, combine the performance of required carboxylic acid water reducer simultaneously, in embodiments of the invention, preferably monomer A, B, C are added in water, and then drip radical initiator, and preferably in 1 ~ 4 hour, complete dropping.Easy understand rate of addition is too fast, and material reaction is insufficient, and rate of addition is excessively slow, then affect production efficiency.Therefore, in embodiments of the invention, after being preferably added dropwise to complete, reactant is incubated 6 ~ 8 hours at the temperature of 70 ~ 90 DEG C, to carry out with reacting fully, so both can improve the utilization ratio of raw material, also can obtain the satisfactory polymerisate of performance simultaneously.
In order to understand characteristic of the present invention and advantage better, water reducer of the present invention is also applied in actual concrete by contriver.
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 material and envrionment temperature all should remain on (20 ± 3) DEG C.Adopt that to meet the nominal capacity that JG3036 requires be the single horizontal shaft type forced stirrer of 60 liters, low gas content polycarboxylic acids water reducing agent, cement, sand, stone are once dropped into stirrer, stir 2 minutes together adding the mixing water being mixed with admixture, after discharging, with manually turning to evenly on iron plate, test.A sample got by each concrete, and the slump, divergence and the slump 1 hour rheological parameters' change with time amount all represents with the mean value of three test-results.Concrete slump measures according to GB/T50080, but the slump is the concrete of (210 ± 10) millimeter, divide two-layer charging, every layer of loading is highly the half that cylinder is high, every layer plugs and pounds 15 times with plugging and pounding rod, cylinder is vertically mentioned, makes concrete be natural flow state, measure the slump and divergence.After the slump refers to that fresh concrete flows out from slump bucket, the top of slump bucket and the distance of concrete vertex.After divergence refers to Concrete in Natural flowing, the expanded area on iron plate, is measured by diameter, measures and represents with the mean value of three test-results.After measuring in the test specimen tube that nuzzles up of loading gauze, container is added a cover, and leaving standstill to 1 hour (calculating when stirring from adding water), then pouring out, and iron plate turns to after evenly with spade, again measures the slump and divergence.
In application test, the performance with following conventional parameter characterization polycarboxylate water-reducer of the present invention:
1) water-reducing rate measures
Water-reducing rate be the slump substantially identical time, reference cement and by the difference of inspection concrete unit consumption of water and the ratio of normal concrete unit consumption of water.
2) content measurement
By GB/T50080 gas-water mixed type gas content, and illustrate by instrument and operate, but concrete mix once should be filled and a little higher than container, with shaking table jolt ramming 15 seconds ~ 20 seconds.During test, air content represents with the arithmetical av of three Specimen Determination values.
3) compressive strength rate measures
Compressive strength rate with mix Fresh Concrete with Admixtures and normal concrete with the length of time ultimate compression strength ratio represent.Ultimate compression strength by inspection concrete and normal concrete is undertaken testing and calculating by GB/T50081, when test specimen makes, vibrate 15 seconds ~ 20 seconds with shaking table, test specimen precuring temperature is (20 ± 3) DEG C, and compressive strength rate represents with the arithmetical av of three Specimen Determination values.
Other parameter or detailed description please refer to GB/8076-2008.
Its space steric effect can better be played by during the effect of the sand material such as low gas content polycarboxylic acids water reducing agent and cement according to above preparation method, concrete workability is good, occur without bleeding, segregation phenomenon, reach object of the present invention, namely a kind of stable performance, low gas content, high diminishing are provided, strong to cement adaptability, slump retaining good and the polycarboxylate water-reducer of environmentally safe.
Example one
In the reactor, add 94 grams of water and 4.3 grams of monomer A (molecular weight is the perfluoralkyl phosphate mono acrylic ester of 1700), (molecular weight is the alkylene thiazolinyl polyoxyethylene of 2600 to 78 grams of monomers B, polyethenoxy ether), 35.5 grams of monomer C (MALEIC ANHYDRIDE), be heated with stirring to 80 DEG C, then initiator (0.71 gram of ammonium persulphate and 40 grams of water mixture) is dripped, time for adding is 3 hours, digestion time is 4 hours, normal temperature is cooled to after reaction terminates, extremely neutral by the NaOH aqueous solution adjust ph of mass concentration 30%, discharging, both high-performance polycarboxylic acids water reducing agent product was obtained, products obtained therefrom solid content is 40%, resulting polymers weight-average molecular weight is 25830.
Monomer A is
Example two
In the reactor, add 105 grams of water and 12 grams of monomer A (molecular weight is the perfluoralkyl phosphate mono acrylic ester of 6000), (molecular weight is the methyl thiazolinyl polyoxyethylene of 2000 to 70 grams of monomers B, polyethenoxy ether), 54 grams of monomer C (MALEIC ANHYDRIDE), be heated with stirring to 80 DEG C, then initiator (2.85 grams of ammonium persulphates and 40 grams of water mixture) is dripped, time for adding is 3.5 hours, digestion time is 4 hours, normal temperature is cooled to after reaction terminates, extremely neutral by the NaOH aqueous solution adjust ph of mass concentration 30%, discharging, both high-performance polycarboxylic acids water reducing agent product was obtained, products obtained therefrom solid content is 36%, resulting polymers weight-average molecular weight is 27900.
Monomer A is
Example three
In the reactor, add 82.5 grams of water and 18 grams of monomer A (molecular weight is the perfluoro alkyl phosphoester acrylic ester of 1000), (molecular weight is the alkylene thiazolinyl polyoxyethylene of 1500 to 27.5 grams of monomers B, polyethenoxy ether), 40.8 grams of monomer C (vinylformic acid), be heated with stirring to 70 DEG C, then initiator (2.24 grams of ammonium persulphates and 20 grams of water mixture) is dripped, time for adding is 2.5 hours, digestion time is 3.5 hours, normal temperature is cooled to after reaction terminates, extremely neutral by the NaOH aqueous solution adjust ph of mass concentration 30%, discharging, both high-performance polycarboxylic acids water reducing agent product was obtained, products obtained therefrom solid content is 43%, resulting polymers weight-average molecular weight is 21500.
Monomer A is
Example four
In the reactor, add 128 grams of water and 2.55 grams of monomer A (molecular weight is the perfluoro alkyl phosphoester acrylic ester of 1700), (molecular weight is the alkylene thiazolinyl polyoxyethylene of 1100 to 49.5 grams of monomers B, polyethenoxy ether), 46.9 grams of monomer C (methacrylic acid), be heated with stirring to 70 DEG C, then initiator (0.89 gram of hydrogen peroxide and 40 grams of water mixture) is dripped, time for adding is 3.5 hours, digestion time is 4.5 hours, normal temperature is cooled to after reaction terminates, extremely neutral by the NaOH aqueous solution adjust ph of mass concentration 30%, discharging, both high-performance polycarboxylic acids water reducing agent product was obtained, products obtained therefrom solid content is 40%, resulting polymers weight-average molecular weight is 29900.
Monomer A is
Example five
In the reactor, add 80 grams of water and 6.4 grams of monomer A (molecular weight is the perfluoro alkyl phosphoester acrylic ester of 1600), (molecular weight is the methyl thiazolinyl polyoxyethylene of 3000 to 50 grams of monomers B, polyethenoxy ether and alkylene thiazolinyl polyoxyethylene, polyethenoxy ether is 1: 1 mixing according to mol ratio), 32 grams of monomer C (vinylformic acid), be heated with stirring to 90 DEG C, then initiator (1.06 grams of Potassium Persulphates and 20 grams of water mixture) is dripped, time for adding is 2.5 hours, digestion time is 3.5 hours, normal temperature is cooled to after reaction terminates, extremely neutral by the NaOH aqueous solution adjust ph of mass concentration 30%, discharging, both high-performance polycarboxylic acids water reducing agent product was obtained, products obtained therefrom solid content is 40%, resulting polymers weight-average molecular weight is 17900.
Monomer A is
Application examples one
Under room temperature is 23 DEG C of conditions, little wild water in field mud P.O.42.5 is used to carry out concrete test.Take the water reducer 14.25 grams (volume is 0.15%) that example one synthesizes, the ratio that cement, sand, stone, water and flyash are 1: 2.02: 2.95: 0.4: 0.21 according to proportioning weighs.Low gas content polycarboxylic acids water reducing agent, cement, sand, stone once being dropped into stirrer, stirring 2 minutes, after discharging together, with manually turning to evenly testing on iron plate adding the mixing water being mixed with admixture.Divide two-layer charging by concrete, every layer of loading is highly the half that cylinder is high, and every layer plugging and pounding 15 times with plugging and pounding rod, vertically being mentioned by cylinder, makes concrete be natural flow state, measures the slump and divergence, measures and represent with the mean value of three test-results.Add a cover in the test specimen tube that nuzzles up of loading gauze after measuring, leaving standstill to 1 hour (calculating when stirring from adding water), then pouring out, iron plate turns to after evenly with spade, measure the slump and divergence according to slump measuring method again, measuring result is in table 1.
Water-reducing rate be the slump substantially identical time, reference cement and the little wild difference of water in field cement concrete unit consumption of water and the ratio of normal concrete unit consumption of water, water-reducing rate measuring result is in table 1.
By GB/T50080 gas-water mixed type gas content, and illustrate by instrument and operate, 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 with the arithmetical av of three Specimen Determination values, and measuring result is in 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.Undertaken testing and calculating by GB/T50081, when test specimen makes, vibrate 15 seconds ~ 20 seconds with shaking table, compressive strength rate represents with the arithmetical av of three Specimen Determination values, and measuring result is in table 1.
Application examples two
Under room temperature is 23 DEG C of conditions, little wild water in field mud P.O.42.5 is used to carry out concrete test.Take the water reducer 15.83 grams (volume is 0.15%) that example two synthesizes, the ratio that cement, sand, stone, water and flyash are 1: 2.02: 2.95: 0.4: 0.21 according to proportioning weighs.
Concrete operations are measured by the method being similar to application examples one, and measuring result is in table 1.
Application examples three
Under room temperature is 23 DEG C of conditions, little wild water in field mud P.O.42.5 is used to carry out concrete test.Take the water reducer 13.25 grams (volume is 0.15%) that example three synthesizes, the ratio that cement, sand, stone, water and flyash are 1: 2.02: 2.95: 0.4: 0.21 according to proportioning weighs.
Concrete operations are measured by the method being similar to application examples one, and measuring result is in table 1.
Application examples four
Under room temperature is 23 DEG C of conditions, little wild water in field mud P.O.42.5 is used to carry out concrete test.Take the water reducer 14.25 grams (volume is 0.15%) that example four synthesizes, the ratio that cement, sand, stone, water and flyash are 1: 2.02: 2.95: 0.4: 0.21 according to proportioning weighs.
Concrete operations are measured by the method being similar to application examples one, and measuring result is in table 1.
Application examples five
Under room temperature is 23 DEG C of conditions, little wild water in field mud P.O.42.5 is used to carry out concrete test.Take the water reducer 14.25 grams (volume is 0.15%) that example pentahapto becomes, the ratio that cement, sand, stone, water and flyash are 1: 2.02: 2.95: 0.4: 0.21 according to proportioning weighs.
Concrete operations are measured by the method being similar to application examples one, and measuring result is in table 1.
Table 1 low gas content polycarboxylic acids water reducing agent concrete evaluating data
Note: " h " representative " hour " in table, " d " representative " my god ".
From the concrete evaluating data of table 1 low gas content polycarboxylic acids water reducing agent, under low-dosage condition, in example, to have water-reducing rate high for each water reducer, air content is low, and divergence after 1 hour is comparatively large, concrete workability is good, without bleeding, segregation phenomenon appearance, and ultimate compression strength is higher, solve the problem that the air content that often runs in polycarboxylate water-reducer use procedure is higher.
Although in order to the present invention is described, disclose the preferred embodiments of the invention, but it will be understood by those of skill in the art that when not departing from the design of the present invention and scope that claims limit, various amendment, interpolation and replacement can be made to the present invention.
Claims (10)
1. a polymkeric substance, is characterized in that, this polymkeric substance is obtained by random copolymerization by A, B, C tri-kinds of monomers, and weight-average molecular weight is 10000 ~ 30000, and the mol ratio wherein between each monomer is A: B: C equal 0.2 ~ 1: 3 ~ 10: 30 ~ 50; And monomer A is perfluoro alkyl phosphoester acrylic ester, and there is following structural formula (I):
In formula (I), n is the integer of 1 ~ 5; R
ffor 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 the integer of 2 ~ 10, and x is the integer of 2 ~ 20, and y is the integer of 3 ~ 20; R
1, R
2for C
1~ C
6alkylidene group;
Monomers B has following structural formula (II):
In formula (II), a, b are the integers of 2 ~ 4, and a ≠ b; H is the integer of 0 ~ 100; K is the integer of 0 ~ 100, and 10≤h+k≤100, R
3for C
1~ C
8alkenyl; And
Monomer C has following structural formula (III):
In formula (III), R
4, R
5, R
6for H ,-CH
3or-(CH
2)
scOOM
2, M
1, M
2for 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 equal 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 for being selected from allyl polyether, methyl thiazolinyl polyoxyethylene, polyethenoxy ether, one or more in alkylene thiazolinyl polyoxyethylene, polyethenoxy ether.
6. polymkeric substance according to claim 1 and 2, is characterized in that, described monomer C is selected from the one in MALEIC ANHYDRIDE, maleic acid, vinylformic acid and methacrylic acid.
7. prepare a method for the polymkeric substance according to any one of claim 1 ~ 6, the method comprises the steps:
1) add monomer A, monomers B, monomer C and water in the reactor, wherein the mass ratio of water and monomers B is 1.0 ~ 3.5, and is heated with stirring to 70 ~ 90 DEG C;
2) to deriving from step 1) reaction system in drip initiator, initiator amount be monomer A, B, C total mass 0.5% ~ 5%, time for adding is 1 ~ 4 hour;
3) keep as above temperature 6 ~ 8 hours, be then cooled to normal temperature, and adjust ph is to neutral, obtains 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. the method according to claim 7 or 8, the consumption of wherein said radical initiator be monomer A, B, C total mass 0.5% ~ 5%.
10. method according to claim 7, wherein step 3) described in conciliation pH to neutrality be utilize mass percent be 30% ~ 50% the NaOH aqueous solution complete.
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| CN104231182B (en) * | 2014-09-22 | 2017-06-09 | 科之杰新材料集团有限公司 | A kind of esters collapse protective poly-carboxylic acid water reducing agent and preparation method thereof |
| JP6171038B2 (en) * | 2015-03-31 | 2017-07-26 | 花王株式会社 | Dispersant composition for hydraulic composition |
| CN105061640B (en) * | 2015-07-22 | 2017-01-11 | 陕西科技大学 | Fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on emulsifier and method |
| CN105236806B (en) * | 2015-10-22 | 2017-03-22 | 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 |
| CN108250343B (en) * | 2016-12-28 | 2020-06-26 | 江苏苏博特新材料股份有限公司 | Compound, air-entraining copolymer, preparation method thereof and application of air-entraining copolymer as concrete rheology modifier |
| CN107337790B (en) * | 2016-12-30 | 2020-08-07 | 江苏苏博特新材料股份有限公司 | Synthesis and application of polyether phosphate water reducing agent with hyperbranched tail end |
| 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 |
| WO2019229888A1 (en) * | 2018-05-30 | 2019-12-05 | 竹本油脂株式会社 | Antifoaming agent for hydraulic composition, additive for hydraulic composition, and hydraulic composition |
| CN110903056B (en) * | 2018-09-18 | 2022-04-01 | 武汉源锦商品混凝土有限公司 | High-strength self-compacting fair-faced concrete and preparation method thereof |
| CN112724414B (en) * | 2021-01-21 | 2022-06-14 | 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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| US5371159A (en) * | 1990-05-23 | 1994-12-06 | Asahi Denka Kogyo K.K. | Solution polymerization with reactive modifier |
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