CN101386490A - Allyl polyglycol ether type polycarboxylic acid series dehydragent and preparation method thereof - Google Patents
Allyl polyglycol ether type polycarboxylic acid series dehydragent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an allyloxypolyethyleneglycol type polycarboxylate water reducing agent and a method for preparing the same, wherein the water reducing agent is a polymer obtained through polymerization; the polymer comprises the following components in weight percentage: 30 to 50 percent of unsaturated polyoxyalkylene group ether monomer(a), 5 to 20 percent of unsaturated monocarboxylic acid and derivative monomer(b) of unsaturated monocarboxylic acid, 1 to 20 percent of unsaturated dicarboxylic acid(c) and 40 to 60 percent of water; the components undergo polymerization in a water solution at a temperature of between 45 and 70 DEG C in the presence of a redox initiator to form the water reducing agent. The polycarboxylate water reducing agent has the advantages of high conversion rate of reaction product, good cohesiveness and super high dispersibility and excellent performance when applied to high strength concrete.
Description
Technical field
The present invention relates to a kind of industrial chemicals preparation field, relate in particular to a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent and preparation method thereof with superpower dissemination.
Background technology
In current concrete industry, the weather resistance and the intensity that improve concrete structure have become common recognition, and adopting the poly carboxylic acid series water reducer of high diminishing to reduce the unit water yield is conventional means.
For many years, for reducing the unit water yield, poly carboxylic acid series water reducer updates, and all is difficult to satisfy day by day complicated concrete raw material and workability requirement now.In patent CN128887OA, announced and contained the polyoxyethylene glycol monoallyl ether of specific ratios and the method that toxilic acid is monomeric poly carboxylic acid series water reducer a kind of in oxidation-reduction system, the preparation, its temperature of reaction is 70～110 ℃, oxygenant is hydrogen peroxide or persulphate, and reductive agent is Hypophosporous Acid, 50 or its salt.The water-reducing property that facts have proved this water reducer is insufficient, need could obtain good dispersive ability under the higher solids volume, and major cause is that polyoxyethylene glycol mono allyl ether and toxilic acid are that monomeric copolymerization is very low.In addition, patent CN1167739A discloses a kind of method for preparing poly-carboxylic-acid cement dispersant, earlier alkoxyl group multi alkylidene diol and (methyl) acrylate are carried out transesterification reaction under the effect of basic catalyst and prepare alkoxyl group multi alkylidene diol list (methyl) acrylate, mix with (methyl) vinylformic acid again, persulfuric acid by effect under copolymerization make polycarboxylate water-reducer.The polycarboxylate water-reducer unstable product quality that this type of uses alkoxyl group multi alkylidene diol list (methyl) acrylate monomer to produce, bad adaptability with different sandstone materials and concrete mineral Additive, the water-reducing rate big rise and big fall often appear, the capricious phenomenon of concrete slump loss, in addition, liquid state stores with transportation etc. all may cause the quality product fluctuation, has exposed some insoluble technical problems.Patent CN1343642A discloses a kind of cement dispersants and has used its cement composition, by making necessary component with allyl polyglycol monomer (a), unsaturated unit carboxylic acid (b), add other polymerisable monomer and prepare water reducer, the multipolymer water-reducing rate height that this method obtains, but cement composition adhesive aggregation performance also has deficiency.CN10118646OA has announced that a kind of is the poly carboxylic acid series water reducer and the synthetic method thereof of raw material with the allyl polyglycol; with allyl polyglycol, maleic anhydride, methyl acrylate, ammonium persulphate, stannous sulfate and water etc. by nitrogen protection; the process reacting by heating is synthesized and is obtained; though this method has solved the polyoxyethylene glycol monoallyl ether and toxilic acid is the low problem of monomeric copolymerization; but its water-reducing rate is still not high enough; selective to component materials of concrete; bad adaptability; in the high water reducing rate field, still can not satisfy the requirement of dispersing property.Patent CN1412175 discloses a kind of preparation method of allyl ester ether monomer and the method for preparing water reducer with this monomer, to make weight-average molecular weight under the initiator be 13500 multipolymer making of Diisopropyl azodicarboxylate under 80 ℃ with this refined allyl ester ether monomer and maleic anhydride, again this multipolymer and alkyl polyalkylene glycol are obtained a kind of micro-cross-linked cement dispersants 100 ℃ of following esterifications, make it and different cement have relatively better adaptability, this technology is complicated, makes that the cost of the finished product is very high.
Summary of the invention
Embodiment of the present invention provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent and preparation method thereof, this water reducer conversion rate of reaction product height, cohesiveness is good, can present very polymolecularity with addition seldom, particularly in the high water reducing rate field, application has excellent performance in concrete.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent, and this water reducer is the polymkeric substance that obtains after the polymerization, by the per-cent that accounts for total polymer weight, comprises following each component in the polymkeric substance:
Unsaturated polyalkylene oxide base ether monomer (a) 30～50%
Unsaturated monocarboxylic acid and derivatives monomer thereof (b) 5～20%
Unsaturated dicarboxylic acid (c) 1～20%
Water 40～60%
Wherein, described unsaturated polyalkylene oxide base ether monomer (a) is represented by general formula (1):
General formula (1) XO (R
1O) nH
X represents to comprise the thiazolinyl of 2～4 carbon atoms, R in the general formula (1)
1O represents to have the oxyethylene group of 2～4 carbon atoms, and n is the average addition mole number of the group of oxyethylene group, and it represents arbitrary number of 20～150, and in multipolymer, monomer (a) is wherein one or both or multiple mixture;
Described unsaturated monocarboxylic acid and derivatives monomer thereof (b) are represented by general formula (2):
General formula (2)
R in the general formula (2)
2Represent hydrogen, methyl, R
3Represent OM
1, M wherein
1Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, in multipolymer, monomer (b) is wherein one or both or multiple mixture;
Described unsaturated dicarboxylic acid (c) is represented by general formula (3):
General formula (3)
M in the general formula (3)
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, R
4Represent OM
3Perhaps O (R
5O) mR
6, M wherein
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, wherein, R
5O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
6Represent hydrogen or alkyl group, phenyl group or the organic amine of 1～12 carbonatoms are arranged, m is the average addition mole number of oxyalkylene group, it represents arbitrary number of 1～35, and in multipolymer, unsaturated dicarboxylic acid (c) is wherein one or both or multiple mixture.
Also comprise in the described water reducer: other the gathered monomer (d) that accounts for water reducer gross weight 1～24%; Described other can gather monomer (d) and comprise: any one or two kinds of or multiple mixture in unsaturated sulfonic acid or its salt, unsaturated amides, the vinyl ester.
Described unsaturated sulfonic acid or its salt comprise: any one or two kinds of mixture in (methyl) allyl sulphonic acid or its salt, styrene sulfonic acid or its salt.
Described unsaturated amides comprises: any one or two kinds of mixture in 2-Methacrylamide, 3-propene sulfonic acid or its salt.
Described vinyl ester comprises: any one or two kinds of mixture in vinyl-acetic ester, the propionate.
Embodiment of the present invention also provides a kind of preparation method of allyl polyglycol ether type polycarboxylic acid series dehydragent, and this method comprises:
The gross weight that makes product in preparation is 100%, and getting each component by following amount ranges is raw material, comprising:
Unsaturated polyalkylene oxide base ether monomer (a) 30～50%
Unsaturated monocarboxylic acid and derivatives monomer thereof (b) 5～20%
Unsaturated dicarboxylic acid (c) 1～20%
Water 40～60%
Adopt redox initiation system to make above-mentioned each component carry out polymerization in the aqueous solution under 45～70 ℃ of temperature, the polymkeric substance that obtains after the polymerization is allyl polyglycol ether type polycarboxylic acid series dehydragent.
Described method specifically comprises:
After unsaturated polyalkylene oxide base ether monomer (a), unsaturated dicarboxylic acid (c), oxygenant and water mixing, be warming up to 45～70 ℃ by institute's water gross weight 50～80%;
In above-mentioned reacted mixing solutions, drip remainder water and unsaturated monocarboxylic acid and the mixed aqueous solution of derivatives monomer (b) and reductive agent simultaneously, dripped 2.5～3.5 hours, after finishing, be to continue insulation 25～35 minutes under 45～70 ℃ the condition in temperature of reaction, polyreaction is finished, and insulation finishes postcooling, adds the NaOH neutralization, adjust concentration to 40%～60% of polymkeric substance, promptly obtain allyl polyglycol ether type polycarboxylic acid series dehydragent.
Described method also comprises: in unsaturated polyalkylene oxide base ether monomer (a), unsaturated dicarboxylic acid (c), water and oxygenant mixing step, add other simultaneously and can gather monomer (d), other can gather monomer (d) and comprise: unsaturated sulfonic acid or its salt, unsaturated amides, vinyl ester, in multipolymer, other can gather monomer (d) and be wherein a kind of independent use or two or more mixtures; This other can gather monomer (d) consumption be as the criterion prepare the product gross weight 1～24%.
Oxygenant in the described redox initiation system is a kind of in hydroperoxide, the persulphate or their mixture; The consumption of described oxygenant is 0.2%～10% of a used total monomer weight.
Reductive agent in the described redox initiation system is a kind of in the sub-compound, L-xitix of sulphur or their mixture; The consumption of described reductive agent is 0.1～5% of a used total monomer weight.
The technical scheme that is provided by the invention described above embodiment as can be seen, embodiment of the present invention is by forming allyl polyglycol ether type polycarboxylic acid series dehydragent with unsaturated polyalkylene oxide base ether monomer (a), unsaturated monocarboxylic acid and derivatives monomer (b) thereof and unsaturated dicarboxylic acid (c) polymerization under redox initiator system, a most important feature of this water reducer is that molecular structure is changeable, and its excellent performance has superpower dissemination.In concrete, mix under a spot of situation (be generally cement gross weight 0.5%～1.5%), promptly have high water reducing rate and the good slump keeps, can satisfy higher construction requirement, improve concrete strength and weather resistance largely.
Embodiment
Embodiment of the present invention provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent and preparation method thereof, this water reducer has superpower dissemination, this water reducer is to adopt redox initiation system by following each component, the polymkeric substance that copolymerization forms in the aqueous solution, by account for total polymer weight hundred change than, comprise each component and content in the polymkeric substance and be: unsaturated polyalkylene oxide base ether monomer (a) 30～50%, unsaturated monocarboxylic acid and derivatives monomer (b) 5～20% thereof, unsaturated dicarboxylic acid (c) 1～20%, water 40～60%.
During actual fabrication, also get each component by above-mentioned part by weight, each component is adopted redox initiation system under 45～70 ℃ of temperature, carry out polymerization in the aqueous solution, the polymkeric substance that obtains after the polymerization is water reducer.This water reducer has the conversion rate of reaction product height, can present very polymolecularity with addition seldom, particularly in the high water reducing rate field, and its excellent performance when it is used in concrete.
For ease of understanding, the invention will be further described below by specific embodiment.
Embodiment one
Present embodiment provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent with superpower dissemination, with existing be that raw-material poly carboxylic acid series water reducer is compared with allyl polyglycol ether, the conversion rate of reaction product height of this water reducer, can present very polymolecularity with addition seldom, particularly in the high water reducing rate field, excellent performance when it is used in concrete, this water reducer is to adopt redox initiation system by following each component, the polymkeric substance that copolymerization forms in the aqueous solution, to account for the per-cent of total polymer weight, contain in this polyalcohol water reducing agent:
Unsaturated polyalkylene oxide base ether monomer (a) 30～50% (accounting for the per-cent of total polymer weight)
Unsaturated monocarboxylic acid and derivatives monomer thereof (b) 5～20% (accounting for the per-cent of total polymer weight)
Unsaturated dicarboxylic acid (c) 1～20% (accounting for the per-cent of total polymer weight)
Water 40～60% (accounting for the per-cent of total polymer weight)
Wherein, described unsaturated polyalkylene oxide base ether monomer (a) is represented by general formula (1):
General formula (1) XO (R
1O) nH
X represents to comprise the thiazolinyl of 2～4 carbon atoms, R in the general formula (1)
1O represents to have the oxyethylene group of 2～4 carbon atoms, and n is the average addition mole number of the group of oxyethylene group, and it represents arbitrary number of 20～150, and in multipolymer, monomer (a) is wherein one or both or multiple mixture;
Described unsaturated monocarboxylic acid and derivatives monomer thereof (b) are represented by general formula (2):
General formula (2)
R in the general formula (2)
2Represent hydrogen, methyl, R
3Represent OM
1, M wherein
1Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, in multipolymer, monomer (b) is wherein one or both or multiple mixture;
Described unsaturated dicarboxylic acid (c) is represented by general formula (3):
General formula (3)
M in the general formula (3)
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, R
4Represent OM
3Perhaps O (R
5O) mR
6, M wherein
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, R
5O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
6Represent hydrogen or alkyl group, phenyl group or the organic amine of 1～12 carbonatoms are arranged, m is the average addition mole number of oxyalkylene group, it represents arbitrary number of 1～35, and in multipolymer, unsaturated dicarboxylic acid (c) is wherein one or both or multiple mixture.
In above-mentioned polyalcohol water reducing agent, can also comprise other the gathered monomer (d) that accounts for unsaturated polyalkylene oxide base ether monomer (a), unsaturated monocarboxylic acid and derivatives monomer (b) thereof and unsaturated dicarboxylic acid (c) gross weight 1～25%, this other can gather monomer (d) and specifically comprise: unsaturated sulfonic acid or its salt, unsaturated amides, vinyl ester, in multipolymer, other can gather monomer (d) and be wherein one or both or multiple mixture.
In other above-mentioned gathered monomer (d), described unsaturated sulfonic acid or its salt comprise: any one or two kinds of mixture in (methyl) allyl sulphonic acid or its salt, styrene sulfonic acid or its salt; Described unsaturated amides comprises: any one or two kinds of mixture in 2-Methacrylamide, 3-propene sulfonic acid or its salt; Described vinyl ester comprises: any one or two kinds of mixture in vinyl-acetic ester, the propionate.
During the above-mentioned water reducer of actual fabrication, each feed composition that is adopted is specially: unsaturated polyalkylene oxide base ether monomer (a) is: the allyl polyglycol ether of molecular weight 600～5000; Monomer (b) is: (methyl) vinylformic acid and carboxylic acid derivative monomer thereof, as: (methyl) vinylformic acid, (methyl) acrylamide, (methyl) methyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc.; Monomer (c) is: dicarboxylic acid and carboxylate monomers thereof such as maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid; Monomer (d) is: other thiazolinyl and carboxylic acid derivative monomer etc. comprise: unsaturated sulfonic acid or its salt, as: (first generation) allyl sulphonic acid or its salt, styrene sulfonic acid or its salt, methylpropene sodium sulfonate etc.; Vinyl ester is as vinyl-acetic ester, propionate etc.Initiator in the redox initiation system that adopts comprises: ammonium persulphate, hydrogen peroxide etc., and reductive agent comprises: Sulfothiorine, sodium bisulfite, stannous sulfate, L-xitix etc.; Neutralization sodium hydroxide and water etc.In preparation process, monomer (a) can all or part ofly add when the reaction beginning, monomer (b), (c), (d) can add when the reaction beginning, also can add after the reaction beginning in batches or continuously, perhaps these adding methods are combined use.
The preparation polycarboxylate water-reducer is to be necessary component with following each component, and the gross weight that makes polymkeric substance with last preparation is 100%, and the consumption of each component all provides with the percentage that accounts for final polymeric articles gross weight:
The consumption of the allyl polyglycol monomer (a) of molecular weight 1000～6000 accounts for 30～50% of product gross weight, the consumption of (methyl) vinylformic acid unsaturated carboxylic acid and derivatives monomer (b) thereof accounts for 5～20% of product gross weight, the consumption of unsaturated dicarboxylic acid and derivatives monomer thereof (c) accounts for 1～20% of product gross weight, the consumption of water is to account for 40～60% of product gross weight, adopt redox initiation system to make each monomer component carry out polymerization in the aqueous solution as initiator under 45～70 ℃ temperature, the multipolymer that obtains after the copolymerization is the water reducer of the embodiment of the invention.
Concrete preparation method is: after unsaturated polyalkylene oxide base ether monomer (a), unsaturated dicarboxylic acid (c), oxygenant and the above-mentioned water mixing that makes water gross weight 50～80%, be warming up to 45～70 ℃, reacted 2.5～3.5 hours;
In above-mentioned reacted mixing solutions, drip remainder water and unsaturated monocarboxylic acid and the mixed aqueous solution of derivatives monomer (b) and reductive agent simultaneously, temperature of reaction is 45～70 ℃, after dropwising, under temperature of reaction, continue insulation 25～35 minutes, polyreaction is finished, and insulation finishes postcooling, adds the NaOH neutralization, adjust concentration to 40%～60% of polymkeric substance, promptly obtain allyl polyglycol ether type polycarboxylic acid series dehydragent.
In with unsaturated polyalkylene oxide base ether monomer (a), unsaturated dicarboxylic acid (c), water and oxygenant mixing step, add other simultaneously and can gather monomer (d), other can gather monomer (d) and comprise: unsaturated sulfonic acid or its salt, unsaturated amides, vinyl ester, in multipolymer, other can gather monomer (d) and be wherein a kind of independent use or two or more mixtures; This other can gather monomer (d) consumption finally make 1～24% of product gross weight for it.
Among the above-mentioned preparation method, the oxygenant in the redox initiation system can adopt hydroperoxide, as hydrogen peroxide, tertbutyl peroxide etc.; Reductive agent in the redox initiation system can adopt the sub-compound or the L-xitix of sulphur, as sodium bisulfite, Sulfothiorine, hydroxyl methyl sodium bisulfite, V-Brite B etc.In the preparation, the oxygenant consumption is 0.2%～10% of a used total monomer weight, and the reductive agent consumption is 0.1～5% of a used total monomer weight.Adding neutralization is adjusted to 40%～60% with the consumption of NaOH with the concentration with polymkeric substance and is as the criterion.
The synthetic product of preparation is shallow colourless or light yellow transparent liquid, concentration is 40%～60%, in concrete, mix a small amount of (be generally cement gross weight 0.5%～1.5%), have high water reducing rate and good slump maintenance, higher construction requirement be can satisfy, concrete strength and weather resistance improved largely.
Embodiment two
Present embodiment provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent, be used to prepare this water reducer following each component consumption all by weight, comprising:
1200g allyl polyglycol ether 1200
The acrylic acid monomer of 105g
The 49g maleic anhydride
The 25g methylpropene sodium sulfonate
1095g deionized water (add at twice, add 700g for the first time, the second time adds 395g and the acrylic acid monomer of 105g is mixed into the Acrylic Acid Monomer aqueous solution)
The hydrogen peroxide of 30g 27.5%
250g concentration is 5% methylol sodium sulfite solution
360g?30％NaOH；
Disposing agitator, thermometer, Dropping feeder, add 1200g allyl polyglycol ether 1200 in the glass flask of reflux cooler, the 700g deionized water, the 49g maleic anhydride, the 25g methylpropene sodium sulfonate, 30g concentration is 27.5% hydrogen peroxide mixing, after being warmed up to 65 ℃, dripping simultaneously in above-mentioned glass flask in 3 hours by 395g deionized water and 105g vinylformic acid blended monomer solution and 250g concentration is 5% methylol sodium sulfite solution, temperature of reaction is controlled at 65 ℃, after dropwising, continue insulation 30 minutes down at 65 ℃, polyreaction is finished, insulation finishes postcooling, adding 360g concentration is the 30%NaOH neutralization, the concentration of adjusting polymkeric substance is 45%, obtain the poly carboxylic acid series water reducer of the embodiment of the invention, convenient for describing in follow-up contrast experiment's use, with this water reducer called after PC-1.
Embodiment three
Present embodiment provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent, be used to prepare this water reducer following each component add-on all by weight, comprising:
2100g allyl polyglycol ether 2400
The 129g methacrylic acid
249g toxilic acid poly(oxyethylene glycol) 400 monoesters (98:400)
1771g deionized water (use at twice for the first time to add 1300g, remaining 471g deionized water is used for being mixed into methacrylic acid solution with the 129g methacrylic acid)
30g concentration is 27.5% hydrogen peroxide
250g concentration is 5% L-ascorbic acid solution
360g concentration is 30% NaOH
Disposing agitator, thermometer, Dropping feeder, add 2100g allyl polyglycol ether 2400 in the glass flask of reflux cooler, the 1300g deionized water, 249g toxilic acid poly(oxyethylene glycol) 400 monoesters (98:400), 30g concentration is 27.5% hydrogen peroxide, after being warmed up to 65 ℃, in 3 hours, in above-mentioned glass flask, drip simultaneously and mixed the 129g methacrylic acid, the monomer solution of 471g deionized water and 250g concentration are 5% L-ascorbic acid solution, temperature of reaction is controlled at 65 ℃, after dropwising, insulation made polyreaction complete in about 30 minutes under 65 ℃, insulation finishes postcooling, add 36 parts of concentration and be 30% NaOH neutralization, adjust concentration to 45%, obtain the poly carboxylic acid series water reducer of present embodiment, convenient for describing in follow-up contrast experiment's use, with this water reducer called after PC-2.
Embodiment four
Present embodiment provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent, be used to prepare this water reducer following each component add-on all by weight, comprising:
2000g allyl polyglycol ether 3600
The 95g sodium acrylate
100g vinylformic acid
The 45g methylene-succinic acid
The 41g methylpropene sodium sulfonate
1745g deionized water (add at twice, add 1350g for the first time, remaining 395g deionized water and 95g sodium acrylate and 100g vinylformic acid are mixed into monomer solution)
The 13g ammonium persulphate
250g concentration is 5% methylol sodium sulfite solution
360g concentration is 30% NaOH
Disposing agitator, thermometer, Dropping feeder, add 2000g allyl polyglycol ether 3600 in the glass flask of reflux cooler, the 1350g deionized water, the 45g methylene-succinic acid, the 41g methylpropene sodium sulfonate, the ammonium persulphate of 13g, after being warmed up to 65 ℃, in 3 hours, in above-mentioned glass flask, drip sodium acrylate simultaneously respectively by 95g, monomer solution that 100g vinylformic acid and the mixing of 395g deionized water form and 250g concentration are 5% methylol sodium sulfite solution, temperature of reaction is controlled at 65 ℃, after dropwising, insulation made polyreaction complete in about 30 minutes under 65 ℃, insulation finishes postcooling, adding 36g concentration is 30% NaOH neutralization, is adjusted to concentration 45%, obtains the poly carboxylic acid series water reducer of present embodiment, convenient in follow-up contrast experiment uses, describing, with this water reducer called after PC-3.
Embodiment five
Present embodiment provides a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent, be used to prepare this water reducer following each component add-on all by weight, comprising:
1800g allyl polyglycol ether 4800
105g vinylformic acid
The 43g methacrylic acid
The 40g maleic anhydride
1662g deionized water (add at twice, add 1300g for the first time, remaining 362g deionized water and 105g vinylformic acid and 43g methacrylic acid are mixed into monomer solution)
The 13g ammonium persulphate
250g concentration is 5% methylol sodium sulfite solution
360g concentration is 30% NaOH
Disposing agitator, thermometer, Dropping feeder, add 1800g allyl polyglycol ether 4800 in the glass flask of reflux cooler, the 1300g deionized water, the 250g maleic anhydride, the ammonium persulphate of 130g, after being warmed up to 65 ℃, in 3 hours, in reaction vessel, drip vinylformic acid simultaneously by 105g, 43g methacrylic acid and the composite monomer solution of remaining 362g deionized water and 250g concentration are 5% methylol sodium sulfite solution, temperature of reaction is controlled at 65 ℃, after dropwising, insulation made polyreaction complete in about 30 minutes under 65 ℃, insulation finishes postcooling, adding 360g concentration is 30% NaOH neutralization, being adjusted to concentration is 45%, obtain the poly carboxylic acid series water reducer of present embodiment, convenient in follow-up contrast experiment uses, describing, with this water reducer called after PC-4.
Comparing embodiment one
Present embodiment provides a kind of water reducer that contrasts usefulness, be used to prepare this water reducer following each component add-on all by weight, following raw materials used add-on all by weight, disposing agitator, thermometer, Dropping feeder, add 120 parts of allyl polyglycol ethers 1200 in the glass flask of reflux cooler, 7.5 part vinylformic acid, 70 parts of deionized waters, 3.0 the hydrogen peroxide of part 27.5%, after being warmed up to 65 ℃, dripped respectively simultaneously in reaction vessel in 3 hours and mixed the monomer solution of 39.5 parts of deionized waters of 10.5 parts of vinylformic acid and 25 part 5% methylol sodium sulfite solution, temperature of reaction is controlled at 65 ℃.After dropwising, continue insulation 30 minutes down at 65 ℃, insulation finishes postcooling, adds 15 parts of 30%NaOH neutralizations, is adjusted to concentration 45%, obtains the relatively poly carboxylic acid series water reducer of usefulness, for follow-up contrast experiment uses, with this water reducer called after C-1.
Comparing embodiment two
Present embodiment provides a kind of water reducer that contrasts usefulness, be used to prepare this water reducer following each component add-on all by weight, disposing agitator, thermometer, Dropping feeder, add 240 parts of allyl polyglycol ethers 2400 in the glass flask of reflux cooler, 130 parts of deionized waters, 49.8 part toxilic acid poly(oxyethylene glycol) 400 monoesters (9.8:40), 3.0 the hydrogen peroxide of part 27.5%, after being warmed up to 65 ℃, dripped simultaneously in reaction vessel in 3 hours and mixed the monomer solution of 30.5 parts of deionized waters of 19.5 parts of Propylene glycol monoacrylates and 25 part 5% L-ascorbic acid solution, temperature of reaction is controlled at 65 ℃.After dropwising, insulation made polyreaction complete in about 30 minutes under 65 ℃, and insulation finishes postcooling, add 36 parts of 30%NaOH neutralizations, be adjusted to concentration 45%, obtain the relatively poly carboxylic acid series water reducer of usefulness, for follow-up contrast experiment uses, with this water reducer called after C-2.
Comparing embodiment three
Present embodiment provides a kind of water reducer that contrasts usefulness, be used to prepare this water reducer following each component add-on all by weight, disposing agitator, thermometer, Dropping feeder, add 240 parts of allyl polyglycol ethers 3600 in the glass flask of reflux cooler, 130 parts of deionized waters, 9.1 part sodium acrylate, 4.5 the methylpropene sodium sulfonate of part, 1.3 the ammonium persulphate of part, after being warmed up to 65 ℃, in 3 hours, in reaction vessel, drip respectively simultaneously and mixed 12.9 parts of methacrylic acids, 37.1 the monomer solution of part deionized water and 25 part 5% methylol sodium sulfite solution, temperature of reaction is controlled at 65 ℃.After dropwising, insulation made polyreaction complete in about 30 minutes under 65 ℃, and insulation finishes postcooling, add 36 parts of 30%NaOH neutralizations, be adjusted to concentration 45%, obtain the relatively poly carboxylic acid series water reducer of usefulness, for follow-up contrast experiment uses, with this water reducer called after C-3.
Comparing embodiment four
Present embodiment provides a kind of water reducer that contrasts usefulness, be used to prepare this water reducer following each component add-on all by weight, disposing agitator, thermometer, Dropping feeder, add 240 parts of allyl polyglycol ethers 4800 in the glass flask of reflux cooler, 130 parts of deionized waters, 14.7 part maleic anhydride, 6.5 the vinyl acetate of part, 5.0 the hydrogen peroxide of part 27.5%, after being warmed up to 65 ℃, in 3 hours, in reaction vessel, drip simultaneously and mixed 7.2 parts of vinylformic acid, 4.3 part methacrylic acid, 38.5 the monomer solution of part deionized water and 25 part 5% methylol sodium sulfite solution, temperature of reaction is controlled at 65 ℃.After dropwising, insulation made polyreaction complete in about 30 minutes under 65 ℃, and insulation finishes postcooling, added 36 parts of 30%NaOH neutralizations, was adjusted to concentration 45%, obtained the relatively poly carboxylic acid series water reducer of usefulness, for using called after C-4 in the subsequent experimental.
Below by corresponding experiment, to compare among the water reducer C-1 to C-4 that obtain in the water reducer PC-1 to PC-4 that obtain in the foregoing description two to five and the comparing embodiment one to four, the performance of the water reducer for preparing in the embodiment of the invention is further elaborated.
(1) clean slurry test
Clean slurry degree of mobilization test (GB/T8077-2000): adopt reference cement, the clean slurry degree of mobilization according to GB8077-87 test cement the results are shown in Table 1.
The clean slurry of table 1 slump test
As known from Table 1, the preparation water reducer is owing to can not satisfy (a) and (b), (c), (d) each component condition simultaneously among the comparative example one to four, cause dispersing property and keep the performance deficiency, and the polycarboxylate water-reducer volume of preparation is lower in the embodiment of the invention two to five, and the stability that has better dispersiveness and disperse to keep.
(2) C45 concrete test:
Adopt ordinary Portland cement P.O 42.5, medium sand (fineness modulus 2.65, silt content 2%), rubble (particle diameter 5～25mm, grade continuously) etc., concrete mix sees Table 2.Mix concrete under above-mentioned condition, and measure the concrete slump, air content, slump retention value etc., it the results are shown in Table 3.
Table 2 concrete test proportioning
| Water cement ratio | Sand coarse aggregate ratio | (the kg/m of unit 3) |
| Water | Cement | Sand | Stone | ||
| 0.41 | 0.41 | 165 | 400 | 735 | 1054 |
Table 3 concrete test
Annotate: slump retention value: leave standstill the slump/initial slump * 100% behind the 60min
Test shows, with respect to the water reducer among the comparative example one to four, adopts the poly-carboxylic-acid cement dispersant of preparation in the embodiment of the invention two to five, just can obtain the higher slump under lower volume, and have good slump hold facility.
(3) C100 concrete test:
Adopt ordinary Portland cement P.O 42.5, medium sand (river sand, fineness modulus 2.65, silt content 0%), design of scattered small flowers and plants hilllock rock (particle diameter 5～15mm, continuously grade) etc., concrete mix sees Table 4, mix concrete under above-mentioned condition, and measure the concrete initial slump and 1 hour slump, it the results are shown in Table 5.
Table 4 concrete test proportioning
| Water-cement ratio | Sand coarse aggregate ratio | (the kg/m of unit 3) |
| Water | Cement | Sand | Stone | The silicon ash | Slag powders | ||
| 0.20 | 0.485 | 150 | 510 | 795 | 845 | 65 | 170 |
Table 5 concrete test result
| Poly carboxylic acid series water reducer | Solid volume (%) | The initial slump (mm) | 1 hour slump (mm) |
| PC-1 | 0.6 | 225 | 225 |
| PC-2 | 0.6 | 235 | 240 |
| PC-3 | 0.6 | 236 | 220 |
| PC-4 | 0.6 | 228 | 225 |
| C-1 | 0.9 | 195 | / |
| C2 | 1.05 | 180 | / |
| C-3 | 0.95 | 205 | / |
| C-4 | 0.95 | 190 | / |
Test shows, in superelevation diminishing field, adopts the poly-carboxylic-acid cement dispersant of preparation in the embodiment of the invention two to five, can obtain the higher slump, and have good slump hold facility, and the water reducer among the comparative example then is difficult to meet the demands.
In sum, the water reducer for preparing in the embodiment of the invention, during use in concrete incorporation few (be generally cement gross weight 0.5%～1.5%), have high water reducing rate and good slump maintenance, higher construction requirement be can satisfy, concrete strength and weather resistance improved largely.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; the present invention is not caused any restriction because of the succession of each embodiment relation yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1, a kind of allyl polyglycol ether type polycarboxylic acid series dehydragent is characterized in that, this water reducer is the polymkeric substance that obtains after the polymerization, by the per-cent that accounts for total polymer weight, comprises following each component in the polymkeric substance:
Unsaturated polyalkylene oxide base ether monomer (a) 30～50%
Unsaturated monocarboxylic acid and derivatives monomer thereof (b) 5～20%
Unsaturated dicarboxylic acid (c) 1～20%
Water 40～60%
Wherein, described unsaturated polyalkylene oxide base ether monomer (a) is represented by general formula (1):
General formula (1) XO (R
1O) nH
X represents to comprise the thiazolinyl of 2～4 carbon atoms, R in the general formula (1)
1O represents to have the oxyethylene group of 2～4 carbon atoms, and n is the average addition mole number of the group of oxyethylene group, and it represents arbitrary number of 20～150, and in multipolymer, monomer (a) is wherein one or both or multiple mixture;
Described unsaturated monocarboxylic acid and derivatives monomer thereof (b) are represented by general formula (2):
General formula (2)
R in the general formula (2)
2Represent hydrogen, methyl, R
3Represent OM
1, M wherein
1Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, in multipolymer, monomer (b) is wherein one or both or multiple mixture;
Described unsaturated dicarboxylic acid (c) is represented by general formula (3):
General formula (3)
M in the general formula (3)
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, R
4Represent OM
3Perhaps O (R
5O) mR
6, M wherein
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine, wherein, R
5O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
6Represent hydrogen or alkyl group, phenyl group or the organic amine of 1～12 carbonatoms are arranged, m is the average addition mole number of oxyalkylene group, it represents arbitrary number of 1～35, and in multipolymer, unsaturated dicarboxylic acid (c) is wherein one or both or multiple mixture.
2, water reducer according to claim 1 is characterized in that, also comprises in the described water reducer: other the gathered monomer (d) that accounts for water reducer gross weight 1～24%; Described other can gather monomer (d) and comprise: any one or two kinds of or multiple mixture in unsaturated sulfonic acid or its salt, unsaturated amides, the vinyl ester.
3, water reducer according to claim 2 is characterized in that, described unsaturated sulfonic acid or its salt comprise: any one or two kinds of mixture in (methyl) allyl sulphonic acid or its salt, styrene sulfonic acid or its salt.
4, water reducer according to claim 2 is characterized in that, described unsaturated amides comprises: any one or two kinds of mixture in 2-Methacrylamide, 3-propene sulfonic acid or its salt.
5, water reducer according to claim 2 is characterized in that, described vinyl ester comprises: any one or two kinds of mixture in vinyl-acetic ester, the propionate.
6, a kind of preparation method of allyl polyglycol ether type polycarboxylic acid series dehydragent is characterized in that, this method comprises:
The gross weight that makes product in preparation is 100%, and getting each component by following amount ranges is raw material, comprising:
Unsaturated polyalkylene oxide base ether monomer (a) 30～50%
Unsaturated monocarboxylic acid and derivatives monomer thereof (b) 5～20%
Unsaturated dicarboxylic acid (c) 1～20%
Water 40～60%
Adopt redox initiation system to make above-mentioned each component carry out polymerization in the aqueous solution under 45～70 ℃ of temperature, the polymkeric substance that obtains after the polymerization is allyl polyglycol ether type polycarboxylic acid series dehydragent.
7, method according to claim 6 is characterized in that, described method specifically comprises:
After unsaturated polyalkylene oxide base ether monomer (a), unsaturated dicarboxylic acid (c), oxygenant and water mixing, be warming up to 45～70 ℃ by institute's water gross weight 50～80%;
In above-mentioned reacted mixing solutions, drip remainder water and unsaturated monocarboxylic acid and the mixed aqueous solution of derivatives monomer (b) and reductive agent simultaneously, dripped 2.5～3.5 hours, after finishing, be to continue insulation 25～35 minutes under 45～70 ℃ the condition in temperature of reaction, polyreaction is finished, and insulation finishes postcooling, adds the NaOH neutralization, adjust concentration to 40%～60% of polymkeric substance, promptly obtain allyl polyglycol ether type polycarboxylic acid series dehydragent.
8, method according to claim 6, it is characterized in that, described method also comprises: in unsaturated polyalkylene oxide base ether monomer (a), unsaturated dicarboxylic acid (c), water and oxygenant mixing step, add other simultaneously and can gather monomer (d), other can gather monomer (d) and comprise: unsaturated sulfonic acid or its salt, unsaturated amides, vinyl ester, in multipolymer, other can gather monomer (d) and be wherein a kind of independent use or two or more mixtures; This other can gather monomer (d) consumption be as the criterion prepare the product gross weight 1～24%.
According to claim 6 or 7 described methods, it is characterized in that 9, the oxygenant in the described redox initiation system is a kind of in hydroperoxide, the persulphate or their mixture; The consumption of described oxygenant is 0.2%～10% of a used total monomer weight.
According to claim 6 or 7 described methods, it is characterized in that 10, the reductive agent in the described redox initiation system is a kind of in the sub-compound, L-xitix of sulphur or their mixture; The consumption of described reductive agent is 0.1～5% of a used total monomer weight.
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