CN1724447A - Water reducing agent of poly carboxylic acid series concrete and its preparation process - Google Patents
Water reducing agent of poly carboxylic acid series concrete and its preparation process Download PDFInfo
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- CN1724447A CN1724447A CN 200510018890 CN200510018890A CN1724447A CN 1724447 A CN1724447 A CN 1724447A CN 200510018890 CN200510018890 CN 200510018890 CN 200510018890 A CN200510018890 A CN 200510018890A CN 1724447 A CN1724447 A CN 1724447A
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- water reducing
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- polyoxyethylene glycol
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Abstract
A poly-carboxylic acid-series water reducing agent for high-performance concrete is prepared through reaction between sodium methylacrylsulfonate and acrylic acid under the action of trigger to obtain a high-molecular polymer, and esterifying reaction on polyethanediol. Its advantages are low content of alkali, high water reducing effect, and high effect to improve performance of concrete.
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 reduction of erection time, require cement mixture to have high workability, 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.And maleic anhydride series, the vinylformic acid system high-performance water reducing agent of the development of states such as Japan, the U.S., Italy have high water reducing rate, and numerous premium propertiess such as low slump loss have obtained using widely.
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 ℃, and stirring reaction is after 4 hours, under 110 ℃ of temperature and 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 ℃ of 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) 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 was reacted 3 ± 0.3 hours in 83 ± 3 ℃ of scopes; 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.
The most frequently used method of domestic synthetic polyacrylic acid based water reducer: the first step is a synthesizing polyethylene glycol mono acrylic ester macromonomer, and then form high molecular polymer with some material copolymerization that contain active group, the process more complicated, reaction conditions is wayward.
As seen from the above, previous methods synthesizing polycarboxylic acid dehydragent technology more complicated, severe reaction conditions is wayward, and is very high to equipment requirements, is unfavorable for industrial production.
Summary of the invention:
The objective of the invention is to overcome water reducer complex manufacturing in the past, to the equipment requirements height, problems such as water-reducing rate is not high, a kind of polycarboxylic acid series water reducing agent and preparation method are provided, with this method synthetic water reducer have high water reducing rate, synthesis technique is simple, reaction conditions is simple and easy to control, be easy to advantages such as suitability for industrialized production.
The characteristics of method of the present invention are that first polymerization forms the high molecular polymer main chain that has active group, and then grafting polyoxyethylene glycol side chain.
The technical scheme that realizes the object of the invention is:
A kind of polycarboxylic acid series water reducing agent, its molecular weight are 5000～100000, and its molecular formula is:
In the formula: R represents CH
3Perhaps H;
m＝10～100；
n＝10～45；
k＝10～100；
M represents Na
+Or NH
4 +
The synthesis technique of polyacrylic acid series concrete water-reducing agent of the present invention was divided into for two steps,
The first step: make initiator with ammonium persulphate or Sodium Persulfate, it is in 80 ± 5 ℃ the methylpropene sodium sulfonate solution that vinylformic acid and initiator slowly are added drop-wise to temperature, drips off stirring reaction 〉=6.5 hour in 1～1.5 hour, generation has the high molecular polymer of active group, and its reaction formula is:
In the formula: R represents CH
3Perhaps H;
m＝10～150；
k＝10～100；
M represents Na
+Or NH
4 +
Second step: in the high molecular polymer that has active group that the first step makes, add polyoxyethylene glycol, with tosic acid as catalyzer, stirring reaction 〉=10 hour under 100 ± 5 ℃ of conditions of temperature, after reaction is finished, add water dissolution, with the sodium hydroxide pH=7 that neutralizes, obtain poly carboxylic acid series water reducer solution, its reaction formula is:
In the formula: R represents CH
3Perhaps H;
m＝10～150；
n＝10～45；
k＝10～100；
a＝4～23；
M represents Na
+Or NH
4 +
The mol ratio of wherein said vinylformic acid and methylpropene sodium sulfonate reactive material is 0.05～0.5, preferred 0.1～0.2; The consumption of initiator ammonium persulfate is 0.5～10%, preferred 4.5～6.0% of methylpropene sodium sulfonate and a vinylformic acid total mass; It is 0.1～0.6 that the second step used polyoxyethylene glycol of esterification and the first step are reacted used acrylic acid mol ratio, preferred 0.3～0.4; Esterifying catalyst tosic acid consumption is 1～10%, preferred 2～4% of polyoxyethylene glycol and the high molecular polymer total mass that has active group.
The synthetic of polyacrylic acid series concrete water-reducing agent of the present invention is to utilize vinylformic acid, methylpropene sodium sulfonate copolymerization to generate the high molecular polymer main chain that has active group; pass through esterification grafting polyoxyethylene glycol side chain with polyoxyethylene glycol again; need not nitrogen protection; temperature of reaction is constant; reinforced program is simple; reaction conditions is easy to control, and pollution-free.Adopt the concrete of polyacrylic acid series concrete water-reducing agent of the present invention preparation, when this water reducer volume with 30wt% concentration be cement weight 0.8% the time, the concrete mix slump can reach 19cm; When volume was 1.1%, water-reducing rate can reach 30%, and 3 days ultimate compression strength of concrete improves more than 60%, and ultimate compression strength improved more than 50% in 28 days, and ultimate compression strength improved more than 30% in 90 days; 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; 28 days shrinking percentages of concrete are that analog high efficiency water reducing agent is low 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, the high performance concrete of high-durability, 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
Embodiment 1:
With methylpropene sodium sulfonate 7.91g, put into reaction vessel, the water that adds 15.82g, stir, heat up, one side dropwise addition of acrylic acid 72g under 80 ± 5 ℃ of temperature, drip ammonium persulfate solution (0.39g ammonium persulphate and 0.79g water) on one side, reactive material methylpropene sodium sulfonate and acrylic acid mol ratio are 0.05: 1, the initiator ammonium persulfate consumption is 0.5% of methylpropene sodium sulfonate and a vinylformic acid total mass, and the control rate of addition dripped off in 90 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6.5 hours.The polyoxyethylene glycol 100g that adds molecular weight 1000 again, tosic acid 1.79g, wherein polyoxyethylene glycol and used acrylic acid mol ratio are 0.1: 1, and the tosic acid consumption is 1% of polyoxyethylene glycol and the high molecular polymer total mass that has active group, stir and continue heating, react 11h again, stop heating, when treating that temperature is reduced to 50～60 ℃, add 419.78g water stirring and dissolving, regulate PH=7 with sodium hydroxide again, obtain the polycarboxylic acid series water reducing agent of concentration 30wt%.
Take by weighing little wild field 525 silicate cement 300g, measure water 87g, adopt truncated cone circle mould (Φ
On=36mm, Φ
Down=64mm h=60mm) measures the clean slurry degree of mobilization of mixing this water reducer.When volume was solid content 0.10%, quiet slurry degree of mobilization can reach 160mm.
Embodiment 2:
With methylpropene sodium sulfonate 7.91g, put into reaction vessel, the water that adds 15.82g, stir, heat up, one side dropwise addition of acrylic acid 7.2g under 80 ± 5 ℃ of temperature, drip ammonium persulfate solution (1.51g ammonium persulphate and 3.02g water) on one side, reactive material methylpropene sodium sulfonate and acrylic acid mol ratio are 0.5: 1, the initiator ammonium persulfate consumption is 10% of methylpropene sodium sulfonate and a vinylformic acid total mass, and the control rate of addition dripped off in 90 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6.5 hours.The polyoxyethylene glycol 60g that adds molecular weight 1000 again, tosic acid 7.5g, wherein polyoxyethylene glycol and used acrylic acid mol ratio are 0.6: 1, the tosic acid consumption is 10% of polyoxyethylene glycol and the high molecular polymer total mass that has active group, stir and continue heating, react 11h again, stop heating, when treating that temperature is reduced to 50～60 ℃, add 175.25g water stirring and dissolving, regulate PH=7 with sodium hydroxide again, obtain the polycarboxylic acid series water reducing agent of concentration 30wt%.
Take by weighing little wild field 525 silicate cement 300g, measure water 87g, adopt truncated cone circle mould (Φ
On=36mm, Φ
Down=64mm h=60mm) measures the clean slurry degree of mobilization of mixing this water reducer.When volume was solid content 0.10%, quiet slurry degree of mobilization can reach 160mm.
Embodiment 3:
With methylpropene sodium sulfonate 7.91g, put into reaction vessel, the water that adds 15.82g, stir, heat up, one side dropwise addition of acrylic acid 36g under 80 ± 5 ℃ of temperature, drip ammonium persulfate solution (1.98g ammonium persulphate and 3.96g water) on one side, reactive material methylpropene sodium sulfonate and acrylic acid mol ratio are 0.1: 1, the initiator ammonium persulfate consumption is 4.5% of methylpropene sodium sulfonate and a vinylformic acid total mass, and the control rate of addition dripped off in 90 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6.5 hours.The polyoxyethylene glycol 150g that adds molecular weight 1000 again, tosic acid 3.87g, wherein polyoxyethylene glycol and used acrylic acid mol ratio are 0.3: 1, and the tosic acid consumption is 2% of polyoxyethylene glycol and the high molecular polymer total mass that has active group, stir and continue heating, react 11h again, stop heating, when treating that temperature is reduced to 50～60 ℃, add 452.44g water stirring and dissolving, regulate PH=7 with sodium hydroxide again, obtain the polycarboxylic acid series water reducing agent of concentration 30wt%.
Take by weighing little wild field 525 silicate cement 300g, measure water 87g, adopt truncated cone circle mould (Φ
On=36mm, Φ
Down=64mm h=60mm) measures the clean slurry degree of mobilization of mixing this water reducer.When volume was solid content 0.10%, quiet slurry degree of mobilization can reach 220mm.
Embodiment 4:
With methylpropene sodium sulfonate 7.91g, put into reaction vessel, the water that adds 15.82g, stir, heat up, one side dropwise addition of acrylic acid 18g under 80 ± 5 ℃ of temperature, drip ammonium persulfate solution (1.55g ammonium persulphate and 3.1g water) on one side, reactive material methylpropene sodium sulfonate and acrylic acid mol ratio are 0.2: 1, the initiator ammonium persulfate consumption is 6.0% of methylpropene sodium sulfonate and a vinylformic acid total mass, and the control rate of addition dripped off in 90 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6.5 hours.The polyoxyethylene glycol 100g that adds molecular weight 1000 again, tosic acid 5.03g, wherein polyoxyethylene glycol and used acrylic acid mol ratio are 0.4: 1, and the tosic acid consumption is 4% of polyoxyethylene glycol and the high molecular polymer total mass that has active group, stir and continue heating, react 11h again, stop heating, when treating that temperature is reduced to 50～60 ℃, add 293.77g water stirring and dissolving, regulate PH=7 with sodium hydroxide again, obtain the polycarboxylic acid series water reducing agent of concentration 30wt%.
Take by weighing little wild field 525 silicate cement 300g, measure water 87g, adopt truncated cone circle mould (Φ
On=36mm, Φ
Down=64mm h=60mm) measures the clean slurry degree of mobilization of mixing this water reducer.When volume was solid content 0.10%, quiet slurry degree of mobilization can reach 220mm.
Embodiment 5:
With methylpropene sodium sulfonate 7.91g, put into reaction vessel, the water that adds 15.82g, stir, heat up, one side dropwise addition of acrylic acid 21.6g under 80 ± 5 ℃ of temperature, drip ammonium persulfate solution (1.48g ammonium persulphate and 2.96g water) on one side, reactive material methylpropene sodium sulfonate and acrylic acid mol ratio are 1/6, the initiator ammonium persulfate consumption is 5% of a methylpropene sodium sulfonate reconciliation vinylformic acid total mass, and the control rate of addition dripped off in 90 minutes, keep 85 ± 5 ℃ of temperature, reacted again 6.5 hours.The polyoxyethylene glycol 105g that adds molecular weight 1000 again, tosic acid 4.04g, wherein polyoxyethylene glycol and used acrylic acid mol ratio are 0.35: 1, and catalyzer tosic acid consumption is 3% of polyoxyethylene glycol and the high molecular polymer total mass that has active group; Stir and continue heating, react 11h again, stop heating, when treating that temperature is reduced to 50～60 ℃, add 313.85g water stirring and dissolving, regulate PH=7 with sodium hydroxide again, obtain the polycarboxylic acid series water reducing agent of concentration 30wt%.
Take by weighing little wild field 525 silicate cement 300g, measure water 87g, adopt truncated cone circle mould (Φ
On=36mm, Φ
Down=64mm h=60mm) measures the clean slurry degree of mobilization of mixing this water reducer.When volume was solid content 0.10%, quiet slurry degree of mobilization can reach 250mm.
From the result of embodiment as can be seen, the processing condition of synthetic this polyacrylic acid series concrete water-reducing agent are: the mol ratio of methylpropene sodium sulfonate and vinylformic acid reactive material is 0.05～0.5: 1, is preferably 0.1～0.2, and the best is 1/6; The used quality of initiator ammonium persulfate or Sodium Persulfate is 0.5～10% of methylpropene sodium sulfonate and a vinylformic acid total mass, is preferably 4.5～6.0%, and the best is 5%; It is 0.1～0.6 that the second step used polyoxyethylene glycol of esterification and the first step are reacted used acrylic acid mol ratio, is preferably 0.3～0.4, and the best is 0.35; Esterifying catalyst tosic acid consumption is polyoxyethylene glycol and 1～10% of the high molecular polymer total mass that has active group, is preferably 2～4%, and the best is 3%.
Claims (6)
1. a polycarboxylic acid series water reducing agent is characterized in that its molecular weight is 5000～100000, and molecular formula is:
In the formula: R represents CH
3Perhaps H;
m＝10～100；
n＝10～45；
k＝10～100；
M represents Na
+Or NH
4 +
2. the preparation method of the described cement water reducing agent of claim 1, it is characterized in that: synthesis technique was divided into for two steps,
The first step: make initiator with ammonium persulphate or Sodium Persulfate, under 80 ± 5 ℃ of conditions of temperature, vinylformic acid and initiator slowly be added drop-wise to temperature and be in 80 ± 5 ℃ the methylpropene sodium sulfonate solution, dripped off in 1～1.5 hour, stirring reaction 〉=6.5 hour, generation has the high molecular polymer of active group
In the formula: R represents CH
3Perhaps H;
m＝10～150；
k＝10～100；
M represents Na
+Or NH
4 +
Second step: make esterifying catalyst with tosic acid, the high molecular polymer that has active group that the polyoxyethylene glycol and the first step are obtained mixes, stirring reaction 〉=10 hour under 100 ± 5 ℃ of conditions of temperature, after reaction is finished, add water dissolution, and, obtain polycarboxylic acid series water reducing agent with the sodium hydroxide PH=7 that neutralizes
In the formula: R represents CH
3Perhaps H;
m＝10～100；
n＝10～45；
k＝10～100；
M represents Na
+Or NH
4 +
The mol ratio of wherein said vinylformic acid and methylpropene sodium sulfonate reactive material is 0.05～0.5; The consumption of initiator ammonium persulfate is 0.5～10% of methylpropene sodium sulfonate and a vinylformic acid total mass; It is 0.1～0.6 that the second step used polyoxyethylene glycol of esterification and the first step are reacted used acrylic acid mol ratio; Esterifying catalyst tosic acid consumption is 1～10% of polyoxyethylene glycol and the high molecular polymer total mass that has active group.
3. the preparation method of cement water reducing agent as claimed in claim 2, the mol ratio that it is characterized in that methylpropene sodium sulfonate and vinylformic acid reactive material is 0.1～0.2.
4. the preparation method of cement water reducing agent as claimed in claim 2 is characterized in that initiator ammonium persulfate or Sodium Persulfate consumption are 4.5～6.0% of methylpropene sodium sulfonate and vinylformic acid total mass.
5. the preparation method of cement water reducing agent as claimed in claim 2 is characterized in that it is 0.3～0.4 that the second step used polyoxyethylene glycol of esterification and the first step are reacted used acrylic acid mol ratio.
6. the preparation method of cement water reducing agent as claimed in claim 2 is characterized in that esterifying catalyst tosic acid consumption is 2～4% of polyoxyethylene glycol and the high molecular polymer total mass that has active group.
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| CN100457796C (en) * | 2006-10-11 | 2009-02-04 | 重庆大学 | Poly carboxylic acid series super plasticizer and its preparing method |
| CN100463872C (en) * | 2006-11-23 | 2009-02-25 | 苏州夏诺高分子技术有限公司 | Preparation method of polycarboxylate water reducing agent |
| CN100509683C (en) * | 2006-09-30 | 2009-07-08 | 江苏博特新材料有限公司 | Low molecular weight copolymer dispersant and preparing method thereof |
| CN101293946B (en) * | 2008-06-20 | 2010-06-02 | 武汉理工大学 | Method for preparing bleed air controllable polycarboxylic acids water reducing agents |
| 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 |
| 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 |
| 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 |
| CN102875047A (en) * | 2012-10-17 | 2013-01-16 | 兰州大学 | Polycarboxylic high-efficiency water reducing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY114306A (en) * | 1995-07-13 | 2002-09-30 | Mbt Holding Ag | Cement dispersant method for production thereof and cement composition using dispersant |
| TW200426124A (en) * | 2003-04-10 | 2004-12-01 | Nippon Catalytic Chem Ind | Polycarboxylic acid cement dispersant and method for producing concrete secondary product |
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2005
- 2005-06-09 CN CNB200510018890XA patent/CN1308257C/en not_active Expired - Fee Related
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| CN100463872C (en) * | 2006-11-23 | 2009-02-25 | 苏州夏诺高分子技术有限公司 | Preparation method of polycarboxylate water reducing agent |
| 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 |
| CN101293946B (en) * | 2008-06-20 | 2010-06-02 | 武汉理工大学 | Method for preparing bleed air controllable polycarboxylic acids water reducing agents |
| 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 |
| CN102875047A (en) * | 2012-10-17 | 2013-01-16 | 兰州大学 | Polycarboxylic high-efficiency water reducing agent and preparation method thereof |
| CN102875047B (en) * | 2012-10-17 | 2015-05-27 | 兰州大学 | Polycarboxylic high-efficiency water reducing agent and preparation method thereof |
| CN105906769A (en) * | 2016-04-29 | 2016-08-31 | 华侨大学 | Ester polycarboxylic acid water reducing agent with chitosan for concrete and method for preparing ester polycarboxylic acid water reducing agent |
| CN110255960A (en) * | 2019-04-11 | 2019-09-20 | 武汉理工大学 | A kind of antisettling agent and its preparation method and application |
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