CN102557513A - Crotonic acid system polycarboxylic acid high-performance water reducer - Google Patents
Crotonic acid system polycarboxylic acid high-performance water reducer Download PDFInfo
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Abstract
The invention relates to the field of chemical industry, in particular to a crotonic acid system polycarboxylic acid high-performance water reducer. The water reducer is prepared by copolymerizing 60 to 80 mass percent of first monomers, 20 to 40 mass percent of second monomers and 0 to 20 mass percent of third monomers, wherein the first monomers comprise methoxy polyethylene glycol crotonate, methoxy polyethylene glycol mono-crotonate, allylpolyethyleneglycol (APEG) and the like; the second monomers comprise crotonic acid, ethyl crotonate or ethyl crotonate and the like; and the third monomers comprise acrylic acid, methacrylic acid, maleic anhydride, methylmaleic acid, itaconic acid, methyl acrylate, hydroxyethyl acrylate, hydroxy-propyl acrylate, sodium allylsulfonate or acrylamide and the like. a preparation process for the water reducer is simple and low in cost, and the polycarboxylic acid high-performance water reducer with excellent performance can be prepared under the condition of not using high-cost monomers such as methacrylic acid, acrylic acid or 2-acrylamide-2-methylpropanesulfonic acid, sodium methallylsulphonate, sodium allylsulfonate and the like.
Description
Technical field
The present invention relates to chemical field, particularly a kind of Ba Dousuan is a high performance water reducing agent of polyocarboxy acid.
Background technology
Cement concrete has become the maximum material of construction of world consumption now, in its production process, and the concrete admixture component that is absolutely necessary, and water reducer is a topmost integral part in the concrete admixture.At present in the home market, the admixture of application is to be first, second and third product of representative with xylogen phosphate-gallate series, naphthalene system, poly carboxylic acid in generation.First-generation product sulfonated lignin system has the function of bleed and slow setting concurrently because water-reducing rate is low, so many and the composite use of other water reducers; Naphthalene water reducer is because molecular structure restriction, has defectives such as, concrete slump retaining poor performance not good to cement adaptability in the use; Polycarboxylate water-reducer has, plurality of advantages such as dispersing property good, function of slump protection excellence good with cement adaptability, thereby becomes the focus of research.
The high performance water reducing agent of polyocarboxy acid of thin type structure mainly contains two kinds to the dissemination mechanism of cement: the one, contain carboxylic acid group, sulfonic polar group dependence electrostatic repulsion dispersion cement granules, and discharge the free water of cement granules parcel; The 2nd, the long side chain and the water that contain the EO group form hydrogen bond, produce sterically hindered effect, prevent cement granules each other near.The high performance water reducing agent of polyocarboxy acid preparation method is at present: adopt big monomer of function that has the long side chain of EO and the minor comonomer that has functional groups such as carboxyl or sulfonic group to carry out copolyreaction; The radical aqueous solution copolymerizations that adopt legal more, and the big monomer of function has products such as TPEG, MPEG unsaturated acid ester, APEG, and minor comonomer adopts vinylformic acid, methylacrylic acid or its ester derivative more.
Chinese patent CN101104686A adopts polyethenoxy ether metacrylic acid ester, methylacrylic acid, sodium allyl sulfonate to prepare high performance water reducing agent of polyocarboxy acid; Chinese patent CN200910011175.1 adopts allyl polyethenoxy ether, maleic anhydride, toxilic acid, vinylformic acid, methylacrylic acid, itaconic anhydride, 2-acrylic amide-copolymerization high performance water reducing agent of polyocarboxy acid such as 2-methyl propane sulfonic acid; One or more mixture causes the allyl polyether-type high efficiency water reducing agent that one-step polymerization obtains through inorganic peroxide in Chinese patent CN101225148 employing allyl polyethenoxy ether monomer, maleic anhydride monomer and (methyl) sodium allyl sulfonate, 2-acrylic amide-2-methyl propane sulfonic acid, methylene-succinic acid, vinylformic acid and the acrylic amide in water solution system.The above preparation method has all adopted (methyl) vinylformic acid or (methyl) monomer of sodium allylsulfonate; This type monomer unit price is higher at present; Production cost is high; Carboxylic acid reaction such as maleic anhydride, methylene-succinic acid is active bigger with (methyl) acrylic acid reactive behavior gap in addition, and there is dispersed bad or function of slump protection defect of bad in the product of preparation.
Summary of the invention
To above-mentioned defective; It is high performance water reducing agent of polyocarboxy acid that the present invention provides a kind of Ba Dousuan, can not use the high performance water reducing agent of polyocarboxy acid of preparing excellent performance under the expensive monomeric conditions such as methylacrylic acid, vinylformic acid or 2-acrylic amide-2-methyl propane sulfonic acid, methallylsulfonic acid sodium, sodium allyl sulfonate fully.
In order to realize the foregoing invention purpose, the present invention provides following technical scheme:
The invention provides a kind of Ba Dousuan is high performance water reducing agent of polyocarboxy acid, and its weight-average molecular weight is 15000～35000 scopes, and structure is suc as formula shown in the I:
Formula I
Wherein, X is selected from carbonyl or methylene radical;
R
1, R
2, R
3, R
4, R
6, R
7Independently be selected from hydrogen or methyl;
R
5Be selected from hydrogen, carboxyl or-CH
2COOH;
R
8Be selected from-SO
3Na, amido ,-COOCH
2CHOHCH
3,-COOCH
2CH
2OH;
M
1, M
2Independently be selected from hydrogen, methyl, ethyl or-Na;
N is the integer in 14～40 scopes;
A is the integer in 1～2 scope, and b is the integer in 1～7 scope, and c is the integer in 0～5 scope, and d is the integer in 0～6 scope.
In the water reducer provided by the invention, said first monomer mainly provides EO (oxyethane) long side chain, shown in formula III.
Formula III
Contain two keys and carboxyl in the unsaturated fatty acids Ba Dousuan molecule; Has very strong reactivity; Esterification can take place in its carboxyl; With methoxy poly (ethylene glycol) ether-ether generation methoxy poly (ethylene glycol) crotonate, the big monomer of function that the methoxy poly (ethylene glycol) crotonate can be used as polycarboxylate water-reducer uses, and all can prepare polycarboxylate water-reducer with copolymerization such as Ba Dousuan, vinylformic acid, methylacrylic acid, maleic anhydrides under certain conditions; Ba Dousuan is as unsaturated carboxylic acid, and its polymerization activity is higher than monomers such as maleic anhydride, can instead of propylene acid be used for the production of polycarboxylate water-reducer.
The present invention also provides the preparation technology of above-mentioned water reducer, and raw material comprises the monomer of following massfraction:
Structure accounts for 60～80% of monomer total mass suc as formula first monomer shown in the II, and the said first monomeric molecular-weight average is 800～2400;
Formula II
Wherein, R
1, R
2, R
3, R
4Be selected from hydrogen or methyl;
Second monomer accounts for 20～40% of monomer total mass, and said second monomer is a kind of or both the above mixtures in Ba Dousuan or the Ba Dousuan verivate;
The 3rd monomer accounts for 0～20% of monomer total mass, and said the 3rd monomer is a kind of or both the above mixtures in carboxylic acid, sulfonic acid, carboxylic acid derivative or the sulfonic acid;
Under the condition of secluding air; Is (50～80) with water according to mass ratio with first monomer: 100 mix, and are warming up to 50～90 ℃ and add initiator, in 2～3h, add second monomer and/or the 3rd monomer; After in 3～4h, adding the chain-transfer agent reaction then; Be cooled to 20～45 ℃, adding alkali adjusting pH value is 6～8, promptly gets.
Preferably, among the preparation technology of water reducer provided by the invention, said first monomer comprises a kind of or both the above mixtures among methoxy poly (ethylene glycol) crotonate, polyoxyethylene glycol Ba Dousuan monoesters, APEG, TPEG or the SPEG.
Preferably, among the preparation technology of water reducer provided by the invention, said second monomer comprises a kind of or both the above mixtures in Ba Dousuan, methyl crotonate or the ethyl crotonate.
As preferably, said second monomer accounts for 30～35% of monomer total mass.
Preferably; Among the preparation technology of water reducer provided by the invention, said the 3rd monomer comprises a kind of or both the above mixtures in vinylformic acid, methylacrylic acid, maleic anhydride, toxilic acid, fumaric acid, citraconic acid, methylene-succinic acid, methyl acrylate, TEB 3K, Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, sodium allyl sulfonate, methallylsulfonic acid sodium, 2-acrylic amide-2-methyl propane sulfonic acid or the acrylic amide.
Preferably, among the preparation technology of water reducer provided by the invention, said initiator comprises a kind of or both the above mixtures in organic peroxide initiator, inorganic peroxy class initiator or the oxidation-reduction trigger system.
As preferentially, said initiator comprises ydrogen peroxide 50, ammonium persulphate, Potassium Persulphate, ydrogen peroxide 50-vitamins C, ammonium persulphate-anhydrous sodium sodium pyrosulfate, ammonium persulphate-sodium hypophosphite.
Preferably, among the preparation technology of water reducer provided by the invention, said chain-transfer agent is Thiovanic acid and/or mercaptoethanol.
The present invention also provides the preparation technology of above-mentioned water reducer, and raw material comprises the monomer of following massfraction:
Structure accounts for 60～80% of monomer total mass suc as formula first monomer shown in the II, and the said first monomeric molecular-weight average is 800～2400;
Formula II
Wherein, R
1, R
2, R
3, R
4Be selected from hydrogen or methyl;
Second monomer accounts for 20～40% of monomer total mass, and said second monomer is one or more the mixture in Ba Dousuan or the Ba Dousuan verivate;
The 3rd monomer accounts for 0～20% of monomer total mass, and said the 3rd monomer is one or more a mixture of maleic anhydride, toxilic acid, fumaric acid, citraconic acid, methylene-succinic acid;
Under the condition of secluding air, first monomer, the 3rd monomer are mixed with water, the mass ratio of said first monomer and water is (50～80): 100; Be warming up to 50～90 ℃ and add initiator; In 2～3h, add second monomer, in 3～4h, after the reaction of adding chain-transfer agent, be cooled to 20～45 ℃ then; Adding alkali adjusting pH value is 6～8, promptly gets.
Preferably, among the preparation technology of water reducer provided by the invention, said first monomer comprises a kind of or both the above mixtures among methoxy poly (ethylene glycol) crotonate, polyoxyethylene glycol Ba Dousuan monoesters, APEG, TPEG or the SPEG.
Preferably, among the preparation technology of water reducer provided by the invention, said second monomer comprises a kind of or both the above mixtures in Ba Dousuan, methyl crotonate or the ethyl crotonate.
As preferably, said second monomer accounts for 30～35% of monomer total mass.
Preferably, among the preparation technology of water reducer provided by the invention, said initiator comprises a kind of or both the above mixtures in organic peroxide initiator, inorganic peroxy class initiator or the oxidation-reduction trigger system.
As preferably, said initiator comprises ydrogen peroxide 50, ammonium persulphate, Potassium Persulphate, ydrogen peroxide 50-vitamins C, ammonium persulphate-anhydrous sodium sodium pyrosulfate, ammonium persulphate-sodium hypophosphite.
In some embodiments of the invention, among the preparation technology provided by the invention, the consumption of initiator is 1～4% of a monomer heavy amount.
Preferably, among the preparation technology of water reducer provided by the invention, said chain-transfer agent is Thiovanic acid and/or mercaptoethanol.
The invention provides a kind of water reducer and preparation method thereof; It is that monomer prepares polycarboxylate water-reducer that the present invention uses Ba Dousuan; Contain two keys and carboxyl in the unsaturated fatty acids Ba Dousuan molecule, have very strong reactivity, monomeric range of choice when greatly having expanded the preparation water reducer; Improve the handiness of polycarboxylate water-reducer molecular designing, can design novel high performance water reducing agent of polyocarboxy acid; Ba Dousuan of the present invention is that the preparation technology of polycarboxylate water-reducer is simple, with low cost; Can not use fully under the expensive monomeric conditions such as methylacrylic acid, vinylformic acid or 2-acrylic amide-2-methyl propane sulfonic acid, methallylsulfonic acid sodium, sodium allyl sulfonate; Prepare the high performance water reducing agent of polyocarboxy acid of excellent performance, and the water reducer that makes is dispersed, function of slump protection is better.
Embodiment
The invention provides a kind of Ba Dousuan is high performance water reducing agent of polyocarboxy acid, and its weight-average molecular weight is 15000～35000, and structure is suc as formula shown in the I:
Formula I
Wherein, X is selected from carbonyl or methylene radical;
R
1, R
2, R
3, R
4, R
6, R
7Independently be selected from hydrogen or methyl;
R
5Be selected from hydrogen, carboxyl or-CH
2COOH;
R
8Be selected from-SO
3Na, amido ,-COOCH
2CHOHCH
3,-COOCH
2CH
2OH;
M
1, M
2Independently be selected from hydrogen, methyl, ethyl or-Na;
N is the integer in 14～40 scopes;
A is the integer in 1～2 scope, and b is the integer in 1～7 scope, and c is the integer in 0～5 scope, and d is the integer in 0～6 scope.
The present invention also provides the preparation technology of above-mentioned water reducer, and raw material comprises the monomer of following weight fraction:
Structure accounts for 60～80% of monomer total mass suc as formula first monomer shown in the II, and the said first monomeric molecular-weight average is 800～2400;
Formula II
Wherein, R
1, R
2, R
3, R
4Be selected from hydrogen or methyl;
Second monomer accounts for 20～40% of monomer total mass, and said second monomer is a kind of or both the above mixtures in Ba Dousuan or the Ba Dousuan verivate;
The 3rd monomer accounts for 0～20% of monomer total mass, and said the 3rd monomer is a kind of or both the above mixtures in carboxylic acid, sulfonic acid, carboxylic acid derivative or the sulfonic acid;
Under the condition of secluding air; Is (50～80) with water according to mass ratio with first monomer: 100 mix, and are warming up to 50～90 ℃ and add initiator, in 2～3h, add second monomer and/or the 3rd monomer; After in 3～4h, adding the chain-transfer agent reaction then; Be cooled to 20～45 ℃, adding alkali adjusting pH value is 6～8, promptly gets.
Preferably, among the preparation technology of water reducer provided by the invention, said first monomer comprises a kind of or both the above mixtures among methoxy poly (ethylene glycol) crotonate, polyoxyethylene glycol Ba Dousuan monoesters, APEG, TPEG or the SPEG.
Preferably, among the preparation technology of water reducer provided by the invention, said second monomer comprises a kind of or both the above mixtures in Ba Dousuan, methyl crotonate or the ethyl crotonate.
As preferably, said second monomer accounts for 30～35% of monomer total mass.
Preferably; Among the preparation technology of water reducer provided by the invention, said the 3rd monomer comprises a kind of or both the above mixtures in vinylformic acid, methylacrylic acid, maleic anhydride, toxilic acid, fumaric acid, citraconic acid, methylene-succinic acid, methyl acrylate, TEB 3K, Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, sodium allyl sulfonate, methallylsulfonic acid sodium, 2-acrylic amide-2-methyl propane sulfonic acid or the acrylic amide.
Preferably, among the preparation technology of water reducer provided by the invention, said initiator comprises a kind of or both the above mixtures in organic peroxide initiator, inorganic peroxy class initiator or the oxidation-reduction trigger system.
As preferably, said initiator comprises ydrogen peroxide 50, ammonium persulphate, Potassium Persulphate, ydrogen peroxide 50-vitamins C, ammonium persulphate-anhydrous sodium sodium pyrosulfate, ammonium persulphate-sodium hypophosphite.
Preferably, among the preparation technology of water reducer provided by the invention, said chain-transfer agent is Thiovanic acid and/or mercaptoethanol.
The present invention also provides the preparation technology of above-mentioned water reducer, and raw material comprises the monomer of following weight fraction:
Structure accounts for 60～80% of monomer total mass suc as formula first monomer shown in the II, and the said first monomeric molecular-weight average is 800～2400;
Formula II
Wherein, R
1, R
2, R
3, R
4Be selected from hydrogen or methyl;
Second monomer accounts for 20～40% of monomer total mass, and said second monomer is a kind of or both the above mixtures in Ba Dousuan or the Ba Dousuan verivate;
The 3rd monomer accounts for 0～20% of monomer total mass, and said the 3rd monomer is a kind of or both the above mixtures in maleic anhydride, toxilic acid, fumaric acid, citraconic acid, the methylene-succinic acid;
Under the condition of secluding air, first monomer, the 3rd monomer are mixed with water, the mass ratio of said first monomer and water is (50～80): 100; Be warming up to 50～90 ℃ and add initiator; In 2～3h, add second monomer, in 3～4h, after the reaction of adding chain-transfer agent, be cooled to 20～45 ℃ then; Adding alkali adjusting pH value is 6～8, promptly gets.
Preferably, among the preparation technology of water reducer provided by the invention, said first monomer comprises a kind of or both the above mixtures among methoxy poly (ethylene glycol) crotonate, polyoxyethylene glycol Ba Dousuan monoesters, APEG, TPEG or the SPEG.
Preferably, among the preparation technology of water reducer provided by the invention, said second monomer comprises a kind of or both the above mixtures in Ba Dousuan, methyl crotonate or the ethyl crotonate.
As preferably, said second monomer accounts for 30～35% of monomer total mass.
Preferably, among the preparation technology of water reducer provided by the invention, said initiator comprises a kind of or both the above mixtures in organic peroxide initiator, inorganic peroxy class initiator or the oxidation-reduction trigger system.
As preferably, said initiator comprises ydrogen peroxide 50, ammonium persulphate, Potassium Persulphate, ydrogen peroxide 50-vitamins C, ammonium persulphate-anhydrous sodium sodium pyrosulfate, ammonium persulphate-sodium hypophosphite.
In some embodiments of the invention, among the preparation technology provided by the invention, the consumption of initiator is 1～4% of a monomer heavy amount.
Preferably, among the preparation technology of water reducer provided by the invention, said chain-transfer agent is Thiovanic acid and/or mercaptoethanol.
Preferably, among the preparation technology of water reducer provided by the invention, also be included in the step of 65～85 ℃ of insulations.
As preferably, among the preparation technology of water reducer provided by the invention, also be included in the step of 65～85 ℃ of insulations, soaking time is 1h.
It is that monomer prepares polycarboxylate water-reducer that the present invention uses Ba Dousuan; Contain two keys and carboxyl in the unsaturated fatty acids Ba Dousuan molecule; Has very strong reactivity; Monomeric range of choice when greatly having expanded the preparation water reducer has improved the handiness of polycarboxylate water-reducer molecular designing, can design the high performance water reducing agent of polyocarboxy acid of new capability; Ba Dousuan of the present invention is that the preparation technology of polycarboxylate water-reducer is simple, with low cost; Can not use fully under the expensive monomeric conditions such as methylacrylic acid, vinylformic acid or 2-acrylic amide-2-methyl propane sulfonic acid, methallylsulfonic acid sodium, sodium allyl sulfonate; Prepare the high performance water reducing agent of polyocarboxy acid of excellent performance, and the water reducer that makes is dispersed, function of slump protection is better.
Ba Dousuan provided by the invention is that agents useful for same all can be buied by market in high performance water reducing agent of polyocarboxy acid and preparation method thereof.
For those skilled in the art can understand technical scheme provided by the present invention better,, further set forth the present invention below in conjunction with embodiment.
Embodiment 1
In the four-hole boiling flask of the logical nitrogen protection of 250ml, add methoxy poly (ethylene glycol) 160g and Ba Dousuan 21g, system temperature is increased to 130 ℃, reaction 2h makes the methoxy poly (ethylene glycol) crotonate.
In the four-hole boiling flask of being furnished with TM, reinforcement whisking appliance, tap funnel, condensing surface, add methoxy poly (ethylene glycol) crotonate 100g, maleic anhydride 24.5g, deionized water 100g; Logical nitrogen protection is elevated to 65 ℃ with system temperature, adds ammonium persulphate 3.1g simultaneously; Ba Dousuan 30g wiring solution-forming 2.5h dropwises, and Thiovanic acid 1.2g wiring solution-forming 3h dropwises, and is warming up to 80 ℃ of insulation 1h; Be cooled to 45 ℃, add a certain amount of caustic soda neutralization, obtain yellow solution; Solid content is more than 20%, and weight-average molecular weight is about 15000, and structure is suc as formula shown in the I.
Formula I
Wherein, X is a carbonyl;
R
1Be methyl;
R
2, R
3, R
4, R
6Be hydrogen;
R
5Be carboxyl;
M
1, M
2For-Na;
N=10, a are the integer in 1～2 scope, and b is the integer in 3～7 scopes, and c is the integer in 2～5 scopes, d=0.
Embodiment 2
In the four-hole boiling flask of being furnished with TM, reinforcement whisking appliance, tap funnel, condensing surface, add TPEG360.0g, deionized water 155.0g, logical nitrogen protection is elevated to 50 ℃ with system temperature; Add ammonium persulphate 2.5g simultaneously, Ba Dousuan 45.2g wiring solution-forming 2.5h dropwises, and Thiovanic acid 0.98g wiring solution-forming 3h dropwises; In 65 ℃ of insulation 1h, be cooled to 45 ℃, add a certain amount of caustic soda neutralization; Obtain yellow solution, solid content is more than 40%, and weight-average molecular weight is 28500; Structure is suc as formula shown in the I, and wherein, X is a methylene radical; R
1, R
2Be methyl; R
3, R
4Be hydrogen; M
1, M
2For-Na; N=40, a are the integer in 1～2 scope, and b is the integer in 3～7 scopes, c=0, d=0.
Embodiment 3
In the four-hole boiling flask of being furnished with TM, reinforcement whisking appliance, tap funnel, condensing surface, add TPEG360.0g, deionized water 155.0g, logical nitrogen protection is elevated to 65 ℃ with system temperature; Add ammonium persulphate 2.8g simultaneously, Ba Dousuan 30.0g and Propylene glycol monoacrylate 26.0g wiring solution-forming 2.5h dropwise, and Thiovanic acid 1.0g wiring solution-forming 3h dropwises; In 65 ℃ of insulation 1h, be cooled to 45 ℃, add a certain amount of caustic soda neutralization; Obtain yellow solution, solid content is more than 40%, and weight-average molecular weight is 15000; Structure is suc as formula shown in the I, and wherein, X is a methylene radical; R
1, R
2Be methyl; R
3, R
4, R
7Be hydrogen; R
8For-COOCH
2CHOHCH
3M
1, M
2For-Na; N=40, a are the integer in 1～2 scope, and b is the integer in 2～6 scopes, and c=0, d are the integer in 1～3 scope.
Embodiment 4
In the four-hole boiling flask of being furnished with TM, reinforcement whisking appliance, tap funnel, condensing surface, add SPEG360.0g, deionized water 155.0g, logical nitrogen protection; System temperature is elevated to 65 ℃, adds ammonium persulphate 2.5g simultaneously, Ba Dousuan 30g and acrylic amide 14.2g wiring solution-forming 2.5h dropwise; Thiovanic acid 0.98g wiring solution-forming 3h dropwises, and is warming up to 65 ℃ of insulation 1h, is cooled to 45 ℃; Add a certain amount of caustic soda neutralization, obtain yellow solution, solid content is more than 40%; Weight-average molecular weight is 22500, and structure is suc as formula shown in the I, and X is a methylene radical; R
1, R
2Be methyl; R
3, R
4, R
7Be hydrogen; R
8Be carboxamido-group; M
1, M
2For-Na; N=40, a are the integer in 1～2 scope, and b is the integer in 2～6 scopes, and c=0, d are the integer in 1～3 scope.
Embodiment 5
In the four-hole boiling flask of being furnished with TM, reinforcement whisking appliance, tap funnel, condensing surface, add APEG240.0g, maleic anhydride 24.5g, deionized water 200.0g, logical nitrogen protection; System temperature is elevated to 85 ℃, adds sodium hypophosphite 1.5g simultaneously, Ba Dousuan 25.8g wiring solution-forming 2.5h dropwises, and ammonium persulphate 4.5g wiring solution-forming 3h dropwises; Be warming up to 90 ℃ of insulation 1h, be cooled to 45 ℃, add a certain amount of caustic soda neutralization; Obtain yellow solution, solid content is more than 40%, and weight-average molecular weight is 30500; Structure is suc as formula shown in the I, and wherein, X is a methylene radical; R
1, R
2, R
3, R
4, R
6Be hydrogen; R
5Be carboxyl; M
1, M
2For-Na; N=40, a are the integer in 1～2 scope, and b is the integer in 2～6 scopes, and c is the integer in 1～5 scope, d=0.
Embodiment 6
Use:
The effect of the embodiment of the invention 1 to embodiment 5 is as shown in table 1; This experiment concrete design strength grade is C30; Used cement is the PO42.5R class g cement, and flyash is I level ash, grain fineness number modulus 2.8; Coarse aggregate is the rubble of 5～31.5mm; Carry out the workability test of mix according to GB/T50080-2002 " normal concrete mix method for testing performance standard ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete " carries out the mensuration of ultimate compression strength, and the ultimate compression strength sample dimensions is the standard specimen of 150mm * 150mm * 150mm.
Table 1 application performance test-results
Can find out from table 1 result:
Polycarboxylate water-reducer of the present invention can be designed the product of different performance according to the market requirement, has greatly expanded the accommodation of polycarboxylate water-reducer molecular designing.Good with the product function of slump protection of embodiment 4 preparations like embodiment 3, the product dispersing property of embodiment 1 preparation is relatively good.
The preparation technology of polycarboxylate water-reducer of the present invention is simple, with low cost; Compare with associated sample both domestic and external; Can use or not use fully under the expensive monomeric conditions such as vinylformic acid, methylacrylic acid, 2-acrylic amide-2-methyl propane sulfonic acid, sodium allyl sulfonate, methyl-propyl sodium sulfonate a small amount of, prepare the high performance water reducing agent of polyocarboxy acid of excellent performance.
The invention discloses a kind of Ba Dousuan is high performance water reducing agent of polyocarboxy acid, and those skilled in the art can use for reference this paper content, suitably improves processing parameter and realizes.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they all are regarded as and are included in the present invention.Method of the present invention and application are described through preferred embodiment; Described protection scope of the present invention is not limited to the above embodiments; The related personnel obviously can change or suitably change and combination methods and applications of the present invention in not breaking away from content of the present invention, spirit and scope, realizes and use technology of the present invention.
Claims (10)
1. a Ba Dousuan is a high performance water reducing agent of polyocarboxy acid, it is characterized in that, its weight-average molecular weight is 15000～35000, and structure is suc as formula shown in the I:
Formula I
Wherein, X is selected from carbonyl or methylene radical;
R
1, R
2, R
3, R
4, R
6, R
7Independently be selected from hydrogen or methyl;
R
5Be selected from hydrogen, carboxyl or-CH
2COOH;
R
8Be selected from-SO
3Na, amido ,-COOCH
2CHOHCH
3,-COOCH
2CH
2OH;
M
1, M
2Independently be selected from hydrogen, methyl, ethyl or-Na;
N is the integer in 14～40 scope;
A is the integer in 1～2 scope, and b is the integer in 1～7 scope, and c is the integer in 0～5 scope, and d is the integer in 0～6 scope.
2. preparation technology of water reducer according to claim 1 is characterized in that raw material comprises the monomer of following massfraction:
Structure accounts for 60～80% of monomer total mass suc as formula first monomer shown in the II, and the said first monomeric molecular-weight average is 800～2400;
Formula II
Wherein, R
1, R
2, R
3, R
4Be selected from hydrogen or methyl;
Second monomer accounts for 20～40% of monomer total mass, and said second monomer is a kind of or both the above mixtures in Ba Dousuan or the Ba Dousuan verivate;
The 3rd monomer accounts for 0～20% of monomer total mass, and said the 3rd monomer is a kind of or both the above mixtures in carboxylic acid, sulfonic acid, carboxylic acid derivative or the sulfonic acid;
Under the condition of secluding air; Is (50～80) with water according to mass ratio with first monomer: 100 mix, and are warming up to 50～90 ℃ and add initiator, in 2～3h, add second monomer and/or the 3rd monomer; After in 3～4h, adding the chain-transfer agent reaction then; Be cooled to 20～45 ℃, adding alkali adjusting pH value is 6～8, promptly gets.
3. preparation technology according to claim 2 is characterized in that, said first monomer comprises a kind of or both the above mixtures among methoxy poly (ethylene glycol) crotonate, polyoxyethylene glycol Ba Dousuan monoesters, APEG, TPEG or the SPEG.
4. preparation technology according to claim 2 is characterized in that, said second monomer comprises a kind of or both the above mixtures in Ba Dousuan, methyl crotonate or the ethyl crotonate.
5. preparation technology according to claim 2; It is characterized in that said the 3rd monomer comprises a kind of or both the above mixtures in vinylformic acid, methylacrylic acid, maleic anhydride, toxilic acid, fumaric acid, citraconic acid, methylene-succinic acid, methyl acrylate, TEB 3K, Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, sodium allyl sulfonate, methallylsulfonic acid sodium, 2-acrylic amide-2-methyl propane sulfonic acid or the acrylic amide.
6. preparation technology according to claim 2 is characterized in that, said second monomer accounts for 30～35% of monomer total mass.
7. preparation technology of water reducer according to claim 1 is characterized in that raw material comprises the monomer of following weight fraction:
Structure accounts for 60～80% of monomer total mass suc as formula first monomer shown in the II, and the said first monomeric molecular-weight average is 800～2400;
Formula II
Wherein, R
1, R
2, R
3, R
4Be selected from hydrogen or methyl;
Second monomer accounts for 20～40% of monomer total mass, and said second monomer is a kind of or both the above mixtures in Ba Dousuan or the Ba Dousuan verivate;
The 3rd monomer accounts for 0～20% of monomer total mass, and said the 3rd monomer is one or more the mixture in maleic anhydride, toxilic acid, fumaric acid, citraconic acid, the methylene-succinic acid;
Under the condition of secluding air, first monomer, the 3rd monomer are mixed with water, the mass ratio of said first monomer and water is (50～80): 100; Be warming up to 50～90 ℃ and add initiator; In 2～3h, add second monomer, in 3～4h, after the reaction of adding chain-transfer agent, be cooled to 20～45 ℃ then; Adding alkali adjusting pH value is 6～8, promptly gets.
8. preparation technology according to claim 7 is characterized in that, said first monomer comprises a kind of or both the above mixtures among methoxy poly (ethylene glycol) crotonate, polyoxyethylene glycol Ba Dousuan monoesters, APEG, TPEG or the SPEG.
9. preparation technology according to claim 7 is characterized in that, said second monomer comprises a kind of or both the above mixtures in Ba Dousuan, methyl crotonate or the ethyl crotonate.
10. preparation technology according to claim 7 is characterized in that, said second monomer accounts for 30～35% of monomer total mass.
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