CN1314614C - Concrete water reducing agent of polycarboxylic acid and its prepn process - Google Patents
Concrete water reducing agent of polycarboxylic acid and its prepn process Download PDFInfo
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- CN1314614C CN1314614C CNB2004100613134A CN200410061313A CN1314614C CN 1314614 C CN1314614 C CN 1314614C CN B2004100613134 A CNB2004100613134 A CN B2004100613134A CN 200410061313 A CN200410061313 A CN 200410061313A CN 1314614 C CN1314614 C CN 1314614C
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Abstract
The present invention relates to a polyocarboxy acid water-reducing agent for concrete and a preparation method thereof. The water-reducing agent has the technical scheme that polyethylene glycol and acrylic acid react under the catalysis of a catalyst to be synthesized into an esterification matter PEA which is copolymerized with sodium methyl allyl sulfonate and the acrylic acid to form the water-reducing agent containing a carboxyl group, a sulfonic group and a polyoxyethylene chain side chain. The produced polyocarboxy acid water-reducing agent for concrete has the advantages of low alkali content and high water-reducing rate; furthermore, when the water-reducing agent is added by the weight ratio of 0.6 to 1.2% to a gelation material, the operation is the concrete is labor-saving, a cement mixing matter has the advantages of high fluidity and favorable workability, the slump constant loss can be effectively restrained, and the water-reducing agent has sufficient early strength in a hardening initial stage. The water-reducing agent has the advantage of simple production technology, easy reaction condition control, no environment pollution and low cost. The polyocarboxy acid water-reducing agent for concrete can be used as an important component of high-performance concrete and is widely used for the fields of industrial and civil architecture, hydrotechnics and road traffic engineering, and the water-reducing agent has obvious economical and social benefits.
Description
Technical field
The invention belongs to a kind of polycarboxylic acid series water reducing agent and preparation method.
Technical background
As everyone knows, effective for making rapid operation when the cement mixture operation, and the early stage demoulding requires cement mixture to have high workability with the reduction of erection time, and the effectively loss of inhibition of slump, and sclerosis initial stage has sufficient early strength.The cement water reducing agent of China is that product is a main flow with naphthalene system and melamine at present, and the cement mixture workability of this series products is bad, has the problem that water-reducing rate is not high, slump-loss is big.Though use water-soluble ethylene copolymer cement dispersant slump-loss little, prolong time of coagulation greatly, causes early strength low, can not well satisfy the needs of engineering, and complex manufacturing.Domestic also do not have polyacrylic high performance concrete water reducer at present.And maleic anhydride series, the vinylformic acid system high-performance water reducing agent of states such as Japan, the U.S., Italy have obtained widely using, and technology is very ripe, but preparation technology is very complicated, and to the requirement height of conversion unit.
The synthetic method of Japan report maleic anhydride high performance concrete water reducer was divided into for two steps and finishes.The first step: behind the nitrogen purge autoclave; under the nitrogen protection condition; make catalyzer with sodium methylate; slowly feed oxyethane in the methyl alcohol in reaction vessel, keep 140 ℃, the reaction down of 0.05-0.5MPa pressure, then; reaction mixture is cooled to room temperature; in reaction vessel, add NaOH, be warming up to 110 ℃, keep the dehydration of 20mmHg pressure.Subsequently, nitrogen pressure is increased to 0.1MPa, slowly in mixture, add a certain amount of chlorallylene and stirring.After 4 hours, when mixture basicity is reduced to a stationary value, use the HCl neutralise mixt from the reaction beginning, the separating by-products salt can obtain allyl ethers, as the raw material of next step reaction.Second the step: with toluene as solvent; under nitrogen protection; in having the reaction vessel of condensation; the allyl ethers and the maleic anhydride that are generated with the first step reaction carry out polyreaction; polymerization temperature is 80 ℃, stir make it to react 4 hours after, under 110 ℃, 10mmHg pressure; steam and remove toluene solvant, obtaining transparent viscous liquid is final product.This shows that maleic anhydride series high-performance cement water reducing agent production preparation is very complicated, and reaction process is very high to the requirement of equipment.
Introduce among the Te Kaiping 9-286648, taking by weighing polyoxyethylene (oxyethane) 33mol, monomethyl monoallyl ether 1mol, allyl sodium sulfonate 1mol and Maleic Acid, Anhydrous 3mol in the four-hole boiling flask that agitator, thermometer, prolong, nitrogen ingress pipe are housed is dissolved in the 1480g water, add ammonium persulphate 0.75mol as polymerization starter, 50 ± 2 ℃ were reacted 12 hours under nitrogen atmosphere, obtained interpolymer X.
Report among the CN1316398A, methyl Soxylat A 25-7, Resorcinol and tosic acid are put into reaction vessel, under 85 ± 3 ℃ temperature, after stirring is dissolved Resorcinol and tosic acid fully, drip methyl methacrylate in container, speed is dripped in control, drips off in 15 ± 5 minutes, maintain the temperature at then in 85 ± 2 ℃ of scopes, reacted 8 ± 0.5 hours.Reaction generates methacrylic acid methyl polyoxyethylene ether-ester, contains polymerizable double bond in its molecular structure.Add the 20-30% of butanone total amount again in the first step product, temperature is controlled at 83 ± 3 ℃, stirs.Drip in methacrylic acid methyl polyoxyethylene ether-ester with remaining butanone dissolving methacrylic acid and dibenzoyl peroxide (BPO) back then, with polymerization reaction take place.Speed is dripped in control, makes it to drip off in 1.5 ± 0.5 hours, and control reaction temperature is in 83 ± 3 ℃ of scopes, reacts 3 ± 0.3 hours.After reaction finishes substantially, underpressure distillation under 80 ± 5 ℃ of conditions, steaming desolventizes, and obtains the polycarboxylic acid series high-performance cement water reducing agent.
This shows that above cement water reducing agent process for producing is very complicated, severe reaction conditions is wayward, and reaction process is very high to the requirement of equipment, is unfavorable for industrial production.
Summary of the invention:
The objective of the invention is to overcome water reducer complex manufacturing in the past, water-reducing rate is not high, the shortcoming that slump-loss is too fast, a kind of polycarboxylic acid series water reducing agent and preparation method are provided, this water reducer performance is high and stable, synthesis technique is simple, easy control of reaction conditions, is easy to suitability for industrialized production.
The present invention adopts following technical proposals to realize:
A kind of polycarboxylic acid series water reducing agent, its molecular weight are 10000～50000, and expression formula is:
In the formula: R represents CH
3A=4～23
m＝20～80 n＝5～20
K=10～40 M represent Na
+Or NH
4 +
The preparation method of the cement water reducing agent that above-mentioned expression formula is represented, its synthesis technique was divided into for two steps, the first step: as solvent, the vitriol oil is made catalyzer with toluene, carries out esterification with the polyoxyethylene glycol and the vinylformic acid of molecular weight 1000 under 90 ± 5 ℃ of conditions of temperature, used vinylformic acid added in 100 ± 10 minutes, in 5 ± 0.5 hours reaction times, after reaction is finished, extract water and toluene out, make polyethylene glycol acrylate, its reaction formula is:
In the formula: a=4～23
Second step: in the polyethylene glycol acrylate that makes, add methylpropene sodium sulfonate and vinylformic acid, with ammonium persulphate or Sodium Persulfate as initiator, mercaptoethanol is as chain-transfer agent, carry out polyreaction in 85 ± 5 ℃ in the aqueous solution, described vinylformic acid and initiator and chain-transfer agent added at 100 ± 10 minutes, 6 ± 0.5 hours reaction times, after reaction is finished, with sodium hydroxide pH=6.5 ± 0.5 that neutralizes, obtain 30wt% poly carboxylic acid series water reducer solution, its reaction formula is:
In the formula: a=4～23 m=20～80
R represents CH
3N=5～20
M represents Na
+Or NH
4 +K=10～40
The mol ratio of described polyoxyethylene glycol and acrylic acid reactive material is 1: 1; Catalyzer vitriol oil consumption is 0.5～3% of polyoxyethylene glycol and a vinylformic acid total mass; Vinylformic acid: methylpropene sodium sulfonate: the polyethylene glycol acrylate mol ratio is 6: 2: 2; Ammonium persulphate or Sodium Persulfate initiator amount are 1～8% of vinylformic acid consumption mole number; Chain-transfer agent mercaptoethanol consumption is 2～10% of a vinylformic acid consumption mole number.
Described catalyzer vitriol oil consumption is 2% of polyoxyethylene glycol and a vinylformic acid total mass.
Described initiator ammonium persulfate or Sodium Persulfate consumption are 3% of vinylformic acid consumption mole number.
The described consumption of crossing the chain-transfer agent mercaptoethanol is 8% of a vinylformic acid consumption mole number.
The synthetic of polyacrylic acid series concrete water-reducing agent of the present invention is to utilize polyoxyethylene glycol, adopts esterification to introduce two keys, again with vinylformic acid, methylpropene sodium sulfonate copolymerization; need not nitrogen protection; temperature of reaction is constant, and reinforced program is simple, and reaction conditions is easy to control.Adopt the concrete of polyacrylic acid series concrete water-reducing agent of the present invention preparation, when this water reducer volume of 30wt% concentration be cement weight 0.65% the time, the concrete mix slump can reach 19cm; When volume was 1.2%, water-reducing rate can reach 30%, and concrete 3d ultimate compression strength improves 70～120%, and 28d ultimate compression strength improves 50～80%, and 90d ultimate compression strength improves 30～40%; High guarantor collapsed, and 2 hours slumps of concrete are not lost substantially, and are acted upon by temperature changes hardly; The good anti-bleeding of workability, education resistance can be good, and concrete pumping resistance is little, are convenient to carry; Concrete surface does not have bleeding line, no air pocket, aberration is little, Surface Quality of Concrete good; Alkali content is low; Chloride ion-containing not is to the reinforcing bar non-corrosiveness; Freeze-thaw-ability and anti-carbonization ability significantly improve than normal concrete; Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 20% than naphthalene; The adaptation of product is strong, is adapted to the cement of plurality of specifications, model, and especially suitable and high-quality fly ash, the compatible preparation of slag isoreactivity adulterant are high-strength, high-durability, the contour performance concrete of self-compacting; Product performance are stable, and long storage is not stratified, the nothing precipitation, does not have crystallization winter; Advantages such as the product nontoxic pollution-free does not contain formaldehyde, and is environmentally safe.
Embodiment
The proportioning of each reactant is as follows among the following embodiment:
The proportioning of each reactant is as follows among the following embodiment:
Polyoxyethylene glycol: vinylformic acid=1: 1 (mol ratio); Catalyzer vitriol oil consumption is 0.5～3wt% of polyoxyethylene glycol+vinylformic acid total amount, and the best is 2wt%; Vinylformic acid: methylpropene sodium sulfonate: polyethyleneglycol acroleic acid esterification thing (PEA)=6: 2: 2 (mol ratio); The initiator ammonium persulfate consumption is 1～8% of a vinylformic acid consumption mole number, and the best is 3%; Chain-transfer agent mercaptoethanol consumption is 2～10% of a vinylformic acid consumption mole number, and the best is 8%;
Embodiment 1:
Get best proportioning
With molecular weight is 1000 polyoxyethylene glycol 100.00g, vitriol oil 2.14g, and toluene 100.00g puts into reaction vessel, under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, and dropwise addition of acrylic acid 7.20g in container controls rate of addition again, dripped off at 100 ± 10 minutes, maintain the temperature at 90 ± 5 ℃, reacted again 5 hours, vacuumized 1 hour, extraction is anhydrated and toluene, and reaction generates polyoxyethylene glycol mono acrylic ester (PEA).With PEA52.70g and methylpropene sodium sulfonate 7.91g, put into reaction vessel, add the water of 136.74g, stir, heat up, one side dropwise addition of acrylic acid 10.80g under 80 ± 5 ℃ of temperature, drip on one side mass percent and be 5% solution ammonium persulphate 20.52g and mass percent and be 10% solution mercaptoethanol 9.36g, the control rate of addition dripped off at 100 ± 10 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6 hours.Add sodium hydroxide after the cooling again and regulate PH=6.5 ± 0.5, obtain polycarboxylic acid series water reducing agent of the present invention.
Embodiment 2:
With molecular weight 1000 polyoxyethylene glycol 100g, vitriol oil 1.07g and toluene 100g put into reaction vessel, and under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, again to container kind dropwise addition of acrylic acid 7.2g, the control rate of addition dripped off at 100 ± 10 minutes, maintained the temperature at 90 ± 5 ℃, reacted again 5 hours, vacuumized 1 hour, and extracted out and anhydrate and toluene, reaction generates polyoxyethylene glycol mono acrylic ester (PEA).52.70g PEA and 7.91g methylpropene sodium sulfonate are put into reaction vessel, add 136.74g water, stir, heat up, dropwise addition of acrylic acid 10.80g on one side under 80 ± 5 ℃ of temperature is that 5% solution ammonium persulphate 20.52g and mass percent are 10% solution mercaptoethanol 9.36g Yi Bian drip mass percent, the control rate of addition, dripped off at 100 ± 10 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6 hours.Add sodium hydroxide after the cooling again and regulate PH=6.5 ± 0.5, obtain polycarboxylic acid series water reducing agent of the present invention.
Embodiment 3:
With molecular weight 1000 polyoxyethylene glycol 100.00g, vitriol oil 2.14g and toluene 100.00g put into reaction vessel, and under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, again to container kind dropwise addition of acrylic acid 7.20g, the control rate of addition dripped off at 100 ± 10 minutes, maintained the temperature in 90 ± 5 ℃ of scopes, reacted again 5 hours, vacuumized 1 hour, and extracted out and anhydrate and toluene, reaction generates polyoxyethylene glycol mono acrylic ester (PEA).With PEA52.70g, methylpropene sodium sulfonate 7.91g puts into reaction vessel, add 143.58g water, stir, heat up, one side dropwise addition of acrylic acid 10.80g under 80 ± 5 ℃ of temperature, drip on one side mass percent and be 5% solution ammonium persulphate 13.68g and mass percent and be 10% solution mercaptoethanol 9.36g, the control rate of addition dripped off at 100 ± 10 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6 hours.Add sodium hydroxide after the cooling again and regulate PH=6.5 ± 0.5, obtain polycarboxylic acid series water reducing agent of the present invention.
Embodiment 4:
With molecular weight is 1000 polyoxyethylene glycol 100.00g, vitriol oil 2.14g, and toluene 100.00g puts into reaction vessel, under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, again to container kind dropwise addition of acrylic acid 7.20g, and the control rate of addition, dripped off at 100 ± 10 minutes, maintain the temperature in 90 ± 5 ℃ of scopes, reacted again 5 hours, vacuumized 1 hour, extraction is anhydrated and toluene, and reaction generates polyoxyethylene glycol mono acrylic ester (PEA).With PEA52.70g, methylpropene sodium sulfonate 7.91g puts into reaction vessel, add 128.91g water, stir, heat up, one side dropwise addition of acrylic acid 10.80g under 80 ± 5 ℃ of temperature, drip on one side mass percent and be 5% solution ammonium persulphate 34.20g and mass percent and be 10% solution mercaptoethanol 9.36g, the control rate of addition dripped off at 100 ± 10 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6 hours.Add sodium hydroxide after the cooling again and regulate PH=6.5 ± 0.5, obtain polycarboxylic acid series water reducing agent of the present invention.
Embodiment 5:
With molecular weight 1000 polyoxyethylene glycol 100.00g, vitriol oil 2.14g, toluene 100.00g puts into reaction vessel, under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, to container kind dropwise addition of acrylic acid 7.20g control rate of addition, dripped off again, maintain the temperature at 90 ± 5 ℃ at 100 ± 10 minutes, reacted again 5 hours, vacuumized 1 hour, and went out to anhydrate and toluene, reaction generates polyoxyethylene glycol mono acrylic ester (PEA).With PEA52.70g, methylpropene sodium sulfonate 7.91g puts into reaction vessel, add 134.40g water, stir, heat up, one side dropwise addition of acrylic acid 10.80g under 80 ± 5 ℃ of temperature, drip on one side mass percent and be 5% solution ammonium persulphate 20.52g and mass percent and be 10% solution mercaptoethanol 11.70g, the control rate of addition dripped off at 100 ± 10 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6 hours.Add sodium hydroxide after the cooling again and regulate PH=6.5 ± 0.5, obtain polycarboxylic acid series water reducing agent of the present invention.
Embodiment 6:
With molecular weight is 1000 polyoxyethylene glycol 100.00g, vitriol oil 2.14g, and toluene 100.00g puts into reaction vessel, under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, again to container kind dropwise addition of acrylic acid 7.20g, and the control rate of addition, dripped off at 100 ± 10 minutes, maintain the temperature at 90 ± 5 ℃, reacted again 5 hours, vacuumized 1 hour, go out to anhydrate and toluene, reaction generates polyoxyethylene glycol mono acrylic ester (PEA).With PEA52.70g, methylpropene sodium sulfonate 7.91g puts into reaction vessel, add 142.59g water, stir, heat up, one side dropwise addition of acrylic acid 10.80g under 80 ± 5 ℃ of temperature, drip on one side mass percent and be 5% solution ammonium persulphate 20.52g and mass percent and be 10% solution mercaptoethanol 3.51g, the control rate of addition dripped off at 100 ± 10 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6 hours.Add sodium hydroxide after the cooling again and regulate PH=6.5 ± 0.5, obtain polycarboxylic acid series water reducing agent of the present invention.
Claims (7)
1. a polycarboxylic acid series water reducing agent is characterized in that molecular weight is 10000～50000, and expression formula is:
In the formula: R represents CH
3A=4～23
m＝20～80 n＝5～20
K=10～40 M represent Na
+Or NH
4 +
2. the preparation method of the described polycarboxylic acid series water reducing agent of claim 1, it is characterized in that: synthesis technique was divided into for two steps, the first step: with toluene as solvent, the vitriol oil is made catalyzer, carries out esterification with the polyoxyethylene glycol and the vinylformic acid of molecular weight 1000 under 90 ± 5 ℃ of conditions of temperature, and used vinylformic acid added in 100 ± 10 minutes, after reaction is finished, extract water and toluene out, make polyethylene glycol acrylate, its reaction formula is:
In the formula: a=4～23
Second step: in the polyethylene glycol acrylate that the first step makes, add methylpropene sodium sulfonate and vinylformic acid, with ammonium persulphate or Sodium Persulfate as initiator, mercaptoethanol is as chain-transfer agent, in the aqueous solution, carry out polyreaction in 85 ± 5 ℃, described vinylformic acid and initiator and chain-transfer agent added at 100 ± 10 minutes, after reaction is finished, with sodium hydroxide pH=6.5 ± 0.5 that neutralizes, obtain 30wt% poly carboxylic acid series water reducer solution, its reaction formula is:
In the formula: a=4～23 m=20～80
R represents CH
3N=5～20
M represents Na
+Or NH
4 +K=10～40
In the described the first step, polyoxyethylene glycol and acrylic acid mol ratio are 1: 1; Catalyzer vitriol oil consumption is 0.5～3% of polyoxyethylene glycol and acrylic acid total mass; In described second step, vinylformic acid: methylpropene sodium sulfonate: the mol ratio of polyethylene glycol acrylate is 6: 2: 2, ammonium persulphate or Sodium Persulfate initiator amount are 1～8% of vinylformic acid consumption mole number, and chain-transfer agent mercaptoethanol consumption is 2～10% of a vinylformic acid consumption mole number.
3. the preparation method of polycarboxylic acid series water reducing agent as claimed in claim 2 is characterized in that catalyzer vitriol oil consumption is 2% of polyoxyethylene glycol and a vinylformic acid total mass.
4. the preparation method of polycarboxylic acid series water reducing agent as claimed in claim 2 is characterized in that initiator ammonium persulfate or Sodium Persulfate consumption are 3% of vinylformic acid consumption mole number.
5. the preparation method of polycarboxylic acid series water reducing agent as claimed in claim 2, the consumption that it is characterized in that the chain-transfer agent mercaptoethanol is 8% of a vinylformic acid consumption mole number.
6. the preparation method of polycarboxylic acid series water reducing agent as claimed in claim 2 is characterized in that the first step reaction time of esterification is 5 ± 0.5 hours.
7. the preparation method of polycarboxylic acid series water reducing agent as claimed in claim 2 is characterized in that the second step polyreaction is 6 ± 0.5 hours.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457796C (en) * | 2006-10-11 | 2009-02-04 | 重庆大学 | Poly carboxylic acid series super plasticizer and its preparing method |
| CN101205128B (en) * | 2007-11-21 | 2010-06-09 | 厦门市建筑科学研究院集团股份有限公司 | Early strength type polycarboxylic acid series high-performance water reducing agent and method for manufacturing same |
| CN101255113B (en) * | 2007-11-28 | 2011-07-20 | 武汉华轩高新技术有限公司 | Methylacrylic acid polyethylene glycol single armor ether ester and preparation method thereof |
| CN101376576B (en) * | 2008-10-10 | 2011-05-04 | 上海建研建材科技有限公司 | High-early strength type polycarboxylic acids dehydragent and preparation technique thereof |
| CN101624270B (en) * | 2009-08-03 | 2012-01-04 | 常州汇迪建材有限公司 | High-efficiency polycarboxylic acid series water reducing agent and preparation method thereof |
| CN102746471A (en) * | 2011-04-27 | 2012-10-24 | 江苏尼高科技有限公司 | Preparation method of polycarboxylate water reducer for CA mortar |
| CN103145928A (en) * | 2012-08-29 | 2013-06-12 | 成都理工大学 | Low-cost polyester polycarboxylic acid water reducer |
| CN104761176B (en) * | 2015-03-31 | 2017-11-10 | 陕西友邦新材料科技有限公司 | Compound polycarboxylate water-reducer and preparation method thereof |
| CN105837765A (en) * | 2016-06-04 | 2016-08-10 | 石家庄市长安育才建材有限公司 | Ester-type high-early-strength water reducing agent and preparation method thereof |
| CN109232827A (en) * | 2018-08-25 | 2019-01-18 | 太和县鑫泰高科新型建筑材料有限公司 | It is a kind of to have fluidized high-performance polycarboxylic acids water reducing agent |
| CN108976363A (en) * | 2018-08-25 | 2018-12-11 | 太和县鑫泰高科新型建筑材料有限公司 | A kind of high water reducing rate high-performance water reducing agent |
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| JP2000159555A (en) * | 1998-11-27 | 2000-06-13 | Nippon Shokubai Co Ltd | Production of cement additive |
| CN1316398A (en) * | 2000-04-04 | 2001-10-10 | 北京市建筑材料科学研究院 | Polycarboxylic acid series water reducing agents for efficient aerocrote |
| US6437027B1 (en) * | 1998-11-30 | 2002-08-20 | Taiheiyo Cement Corporation | Process for producing dispersant for powdery hydraulic composition |
| US6762220B1 (en) * | 1999-02-15 | 2004-07-13 | Mbt Holding Ag | Cement additive |
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Patent Citations (4)
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|---|---|---|---|---|
| JP2000159555A (en) * | 1998-11-27 | 2000-06-13 | Nippon Shokubai Co Ltd | Production of cement additive |
| US6437027B1 (en) * | 1998-11-30 | 2002-08-20 | Taiheiyo Cement Corporation | Process for producing dispersant for powdery hydraulic composition |
| US6762220B1 (en) * | 1999-02-15 | 2004-07-13 | Mbt Holding Ag | Cement additive |
| CN1316398A (en) * | 2000-04-04 | 2001-10-10 | 北京市建筑材料科学研究院 | Polycarboxylic acid series water reducing agents for efficient aerocrote |
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