CN102443115A - Method for producing slow-release cement dispersing agents - Google Patents
Method for producing slow-release cement dispersing agents Download PDFInfo
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- CN102443115A CN102443115A CN2011103123673A CN201110312367A CN102443115A CN 102443115 A CN102443115 A CN 102443115A CN 2011103123673 A CN2011103123673 A CN 2011103123673A CN 201110312367 A CN201110312367 A CN 201110312367A CN 102443115 A CN102443115 A CN 102443115A
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- slow release
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Abstract
The invention discloses a method for preparing cement additives, in particular to a method for producing slow-release cement dispersing agents, which belongs to the field of chemical building materials for buildings. The method has the advantages that the cement flowability retainability and the dispersing performance can be obviously improved, the gas content is low, the adaptability to the cement is improved, the concrete collapsbillity retainability is improved, and the stirring viscosity of the concrete is reduced.
Description
Technical field
The invention discloses a kind of preparation method of cement additire, specifically relate to a kind of working method of slow release type cement dispersants, belong to chemical building material for building field.
Background technology
In the concrete Application Areas, the use of admixture is to improve directly the most effective way such as concrete strength, serviceability, endurance quality.The carboxylic acid type cement dispersants is widelyd popularize by country on highway, railway, bridge in recent years, and then is able to fast development, manufacturer's emerge in multitude, and carboxylic acid type cement dispersants technology is also known gradually.Though existing conventional poly carboxylic acid additive has workability preferably to new sand cutting slurry or concrete; But the slump is still bigger through time loss; Through composite traditional slow setting component such as glucose sodium etc. improvement can be arranged slightly; But this method also can be restricted, and causes early age strength of concrete too low sometimes, also exists coagulation component and cement consistency to go wrong and the too fast and undesired gelatin phenomenon of slump-loss takes place.
Summary of the invention
In order to solve the technical problem that exists in the prior art; The object of the present invention is to provide a kind of degree of mobilization retentivity and dispersing property that can significantly improve cement; Air content is less; Raising improves the concrete slump retentivity to the flexibility of cement, has reduced the slow release type cement dispersants of concrete mix viscosity.
The technical scheme that the present invention adopts is:
A kind of working method of slow release type cement dispersants; It is characterized in that; Carry out the first step condensation reaction with MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups earlier; Carry out the second step condensation reaction with the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block again, obtain macromole reactive monomer X; Macromole reactive monomer X with contain unsaturated allylic long-chain polyoxy ethene polyethers (c), function monomer (z), under the initiation of initiator, carry out Raolical polymerizable, obtain the finished product Y.
Further,
The said structural formula that contains the polyoxy ethene polyethers (a) of two hydroxy functional groups is:
HO-(CH2-CH2-O) n-H (n is 12～25);
The structural formula of the allyl polyether (b) of the oxygen ethene of said monohydroxy and oxypropylene block is:
CH2-CH-O-(CH2-CH2-O) m-(CH (CH3)-CH2-O-) o-H (m, o are 3～15);
The said structural formula that contains unsaturated allylic long-chain polyoxy ethene polyethers (c) is:
CH2=CH-O-(CH2-CH2-O) n-H (n is 12～25);
The structural formula of said macromole reactive monomer X is:
The structural formula of said the finished product Y is:
(wherein, z is a function monomer).
The preparation method of a kind of slow release type cement dispersants of the present invention; This slow release type cement dispersants is used the oxygen ethene polyethers of two hydroxyls, the oxygen ethene of monohydroxy and the polyethers of oxypropylene block and is condensed into important high reactivity macromonomer with MALEIC ANHYDRIDE respectively not to be listed as on year-on-year basis; Again with the Raolical polymerizable that carries out that contains unsaturated allylic long-chain polyoxy ethene polyethers and other function monomers; And in specific pH reaction system, carry out; Special surface-active macromonomer structure guarantees that it can provide enough crosslinked slowly-releasing molecular structures to guarantee the maintenance of cement flows degree and concrete slump; This method not only can avoid polymerization system to cause a large amount of gels generations, polymerization failure because of too high reactive behavior simultaneously, and can guarantee that the MWD of final product is balanced.
In the slow release type cement dispersants structure of the present invention owing to have oxygen ethene, the oxypropylene group of very a high proportion of ester group slowly-releasing cross-linking set, carboxyl and different ratios; These reactive groups are because different affine water is dredged mechanism, and polarity chemical bond and cement molecule and water mutual effect, can significantly improve the degree of mobilization retentivity and the dispersing property of cement; Air content is less; Raising improves the concrete slump retentivity to the flexibility of cement, has reduced concrete mix viscosity.
The concrete operations step of slow release type cement dispersants of the present invention is following:
1., with 18.5～34.8% (quality percentage compositions; MALEIC ANHYDRIDE down together) and 5～8% the polyoxy ethene polyethers (a) that contains two hydroxy functional groups are put into reaction vessel, heat up, mix the stopper of back adding 0.3～1.1% and 1.4～3.8% catalyzer, feed nitrogen protection; And reflux with nitrogen atmosphere; Water that produces in the separating reaction process and lower boiling small-molecule substance, controlled temperature reacted 3～5 hours at 100～115 ℃;
2., in reaction vessel, add the oxygen ethene of 10～13% monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 120～135 ℃, continue reaction 1～3 hour, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add solvent, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 80～95 ℃;
4., macromole reactive monomer X is placed in the reaction vessel adding pH buffered soln, conditioned reaction system pH;
5., 41～55% the unsaturated allylic long-chain polyoxy ethene polyethers (c) that contains is become solution with 2～21.2% function monomer (z) with dissolution with solvents;
6., 1～4% initiator is become solution with dissolution with solvents;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 2～4 hours, the control dropping temperature is 80～95 ℃;
8., drip end back insulation 1～3 hour;
9., cooling, add solution by 4.5～7% sodium hydroxide preparation, promptly get the finished product Y.
Preferably, said catalyzer is the tosic acid or the vitriol oil.
Preferably, said stopper is Resorcinol, thiodiphenylamine or MEHQ.
Preferably, the function monomer (z) that uses of said Raolical polymerizable is in methyl acrylate, methylacrylic acid hydroxyl ethyl ester and the sodium allyl sulfonate one or more.
Preferably, the initiator of said Raolical polymerizable is Potassium Persulphate and hydrogen peroxide composite initiation system.
Preferably, the pH value of said Raolical polymerizable system remains 3～5.
Preferably, said Raolical polymerizable uses solvent to be water.
Preferably, said Raolical polymerizable uses solvent to be deionized water.
Embodiment
Embodiment 1
Charging capacity is in parts by weight, and is as shown in the table,
Production craft step is following:
1., MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups are put into reaction vessel; Heat up, mix the back and add stopper and catalyzer; Feed nitrogen protection, and reflux water that produces in the separating reaction process and lower boiling small-molecule substance with nitrogen atmosphere; Controlled temperature reacted 5 hours at 107 ℃;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 135 ℃, continue reaction 1 hour, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add deionized water, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 90 ℃;
4., macromole reactive monomer X is placed in the reaction vessel, add pH buffered soln, the conditioned reaction system pH is 4.5;
5., will contain unsaturated allylic long-chain polyoxy ethene polyethers (c) and become solution with 10 parts of deionized water dissolvings with function monomer (z);
6., initiator is become solution with 9 parts of deionized water dissolvings;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 2 hours, the control dropping temperature is 88 ℃;
8., drip end back insulation 1 hour;
9., cooling, add sodium hydroxide solution, promptly get the finished product Y (note is made PC-B1).
Embodiment 2
Charging capacity is in parts by weight, and is as shown in the table,
Production craft step is following:
1., MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups are put into reaction vessel; Heat up, mix the back and add stopper and catalyzer; Feed nitrogen protection, and reflux water that produces in the separating reaction process and lower boiling small-molecule substance with nitrogen atmosphere; Controlled temperature reacted 3.5 hours at 100 ℃;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 120 ℃, continue reaction 2.5 hours, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add deionized water, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 87 ℃;
4., macromole reactive monomer X is placed in the reaction vessel, add pH buffered soln, the conditioned reaction system pH is 3;
5., will contain unsaturated allylic long-chain polyoxy ethene polyethers (c) and become solution with 7.5 parts of deionized water dissolvings with function monomer (z);
6., initiator is become solution with 9 parts of deionized water dissolvings;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 3.5 hours, the control dropping temperature is 80 ℃;
8., drip end back insulation 1.5 hours;
9., cooling, add sodium hydroxide solution, promptly get the finished product Y (note is made PC-B2).
Embodiment 3
Charging capacity is in parts by weight, and is as shown in the table,
Production craft step is following:
1., MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups are put into reaction vessel; Heat up, mix the back and add stopper and catalyzer; Feed nitrogen protection, and reflux water that produces in the separating reaction process and lower boiling small-molecule substance with nitrogen atmosphere; Controlled temperature reacted 3 hours at 103 ℃;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 123 ℃, continue reaction 1.5 hours, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add deionized water, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 80 ℃;
4., macromole reactive monomer X is placed in the reaction vessel, add pH buffered soln, the conditioned reaction system pH is 5;
5., will contain unsaturated allylic long-chain polyoxy ethene polyethers (c) and become solution with 19 parts of deionized water dissolvings with function monomer (z);
6., initiator is become solution with 27 parts of deionized water dissolvings;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 3 hours, the control dropping temperature is 93 ℃;
3., drip end back insulation 3 hours;
9., cooling, add sodium hydroxide solution, promptly get the finished product Y (note is made PC-B3).
Embodiment 4
Charging capacity is in parts by weight, and is as shown in the table,
Production craft step is following:
1., MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups are put into reaction vessel; Heat up, mix the back and add stopper and catalyzer; Feed nitrogen protection, and reflux water that produces in the separating reaction process and lower boiling small-molecule substance with nitrogen atmosphere; Controlled temperature reacted 4.5 hours at 115 ℃;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 132 ℃, continue reaction 3 hours, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add deionized water, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 85 ℃;
4., macromole reactive monomer X is placed in the reaction vessel, add pH buffered soln, the conditioned reaction system pH is 3.5;
5., will contain unsaturated allylic long-chain polyoxy ethene polyethers (c) and become solution with 2.6 parts of deionized water dissolvings with function monomer (z);
6., initiator is become solution with 9 parts of deionized water dissolvings;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 2.5 hours, the control dropping temperature is 95 ℃;
3., drip end back insulation 2.5 hours;
9., cooling, add sodium hydroxide solution, promptly get the finished product Y (note is made PC-B4).
Embodiment 5
Charging capacity is in parts by weight, and is as shown in the table,
Production craft step is following:
1., MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups are put into reaction vessel; Heat up, mix the back and add stopper and catalyzer; Feed nitrogen protection, and reflux water that produces in the separating reaction process and lower boiling small-molecule substance with nitrogen atmosphere; Controlled temperature reacted 4 hours at 113 ℃;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 125 ℃, continue reaction 2 hours, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add deionized water, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 95 ℃;
4., macromole reactive monomer X is placed in the reaction vessel, add pH buffered soln, the conditioned reaction system pH is 4;
5., will contain unsaturated allylic long-chain polyoxy ethene polyethers (c) and become solution with 4 parts of deionized water dissolvings with function monomer (z);
6., initiator is become solution with 36 parts of deionized water dissolvings;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 4 hours, the control dropping temperature is 84 ℃;
8., drip end back insulation 2 hours;
9., cooling, add sodium hydroxide solution, promptly get the finished product Y (note is made PC-B5).
The slow release type cement dispersants PC-B (1～5) of embodiment 1～5 preparation carries out concrete experiments with coventional type poly-carboxylic-acid cement admixture (being called for short PC-A), naphthalene water reducer (FDN), thionamic acid based water reducer (ASPF); Detect table specific as follows according to the GB8076-2008 standard:
Can find out that from last table slow release type cement dispersants of the present invention has relatively good concrete workability, dispersed close, but concrete slump-loss is also very little with other water reducers, indivedual instance slumps through the time also have growth.For high grade, the long commerical ready-mixed concrete of high slump, shipment distance can use widely, and this is that institutes such as naphthalene water reducer, thionamic acid based water reducer are beyond one's reach.
Simultaneously, because the starting material that slow release type cement dispersants of the present invention is adopted are comparatively cheap and easy to get, production technique is also fairly simple, and comprehensive price ratio is very high, and the market advantage is apparent in view.
The above instance is merely among the preparation method who the present invention relates to comparatively several kinds of ideal, but is not limited thereto, and the order difference because of embodiment does not form restriction to the present invention.Anyly know these those skilled in the art in the technical scope that the present invention mentions, variation that can obtain easily or replacement all should be encompassed within the 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. the working method of a slow release type cement dispersants; It is characterized in that; Carry out the first step condensation reaction with MALEIC ANHYDRIDE and the polyoxy ethene polyethers (a) that contains two hydroxy functional groups earlier; Carry out the second step condensation reaction with the oxygen ethene of monohydroxy and the allyl polyether (b) of oxypropylene block again, obtain macromole reactive monomer X; Macromole reactive monomer X with contain unsaturated allylic long-chain polyoxy ethene polyethers (c), function monomer (z), under the initiation of initiator, carry out Raolical polymerizable, obtain the finished product Y.
2. the working method of slow release type cement dispersants according to claim 1 is characterized in that,
The said structural formula that contains the polyoxy ethene polyethers (a) of two hydroxy functional groups is:
HO-(CH2-CH2-O) n-H (n is 12～25);
The structural formula of the allyl polyether (b) of the oxygen ethene of said monohydroxy and oxypropylene block is:
CH2=CH-O-(CH2-CH2-O) m-(CH (CH3)-CH2-O-) o-H (m, o are 3～15);
The said structural formula that contains unsaturated allylic long-chain polyoxy ethene polyethers (c) is:
CH2=CH-O-(CH2-CH2-O) n-H (n is 12～25);
The structural formula of said macromole reactive monomer X is:
The structural formula of said the finished product Y is:
(wherein, z is a function monomer).
3. the working method of slow release type cement dispersants according to claim 1 is characterized in that, the concrete operations step is following:
1., the polyoxy ethene polyethers (a) that contains two hydroxy functional groups of 18.5～34.8% MALEIC ANHYDRIDE and 5～8% is put into reaction vessel; Heat up, mix the stopper of back adding 0.3～1.1% and 1.4～3.8% catalyzer; Feed nitrogen protection, and reflux water that produces in the separating reaction process and lower boiling small-molecule substance with nitrogen atmosphere; Controlled temperature reacted 3～5 hours at 100～115 ℃;
2., in reaction vessel, add the oxygen ethene of 10～13% monohydroxy and the allyl polyether (b) of oxypropylene block, be warming up to 120～135 ℃, continue reaction 1～3 hour, reaction obtains macromole reactive monomer X;
3., in reaction vessel, add solvent, behind the logical nitrogen excluding air, open condensation reflux unit, be warming up to 80～95 ℃;
4., macromole reactive monomer X is placed in the reaction vessel adding pH buffered soln, conditioned reaction system pH;
5., 41～55% the unsaturated allylic long-chain polyoxy ethene polyethers (c) that contains is become solution with 2～21.2% function monomer (z) with dissolution with solvents;
6., 1～4% initiator is become solution with dissolution with solvents;
7., with step 5. and 6. the solution of preparation drop to respectively in the reaction vessel, the control dropping time is 2～4 hours, the control dropping temperature is 80～95 ℃;
3., drip end back insulation 1～3 hour;
9., cooling, add solution by 4.5～7% sodium hydroxide preparation, promptly get the finished product Y.
4. the working method of slow release type cement dispersants according to claim 3 is characterized in that, said catalyzer is the tosic acid or the vitriol oil.
5. the working method of slow release type cement dispersants according to claim 3 is characterized in that, said stopper is Resorcinol, thiodiphenylamine or MEHQ.
6. the working method of slow release type cement dispersants according to claim 3 is characterized in that, the function monomer that said Raolical polymerizable uses (z) is in methyl acrylate, methylacrylic acid hydroxyl ethyl ester and the sodium allyl sulfonate one or more.
7. the working method of slow release type cement dispersants according to claim 3 is characterized in that, the initiator of said Raolical polymerizable is Potassium Persulphate and hydrogen peroxide composite initiation system.
8. the working method of slow release type cement dispersants according to claim 3 is characterized in that, the pH value of said Raolical polymerizable system remains 3～5.
9. the working method of slow release type cement dispersants according to claim 3 is characterized in that, said Raolical polymerizable uses solvent to be water.
10. according to the working method of slow release type cement dispersants according to claim 9, it is characterized in that said Raolical polymerizable uses solvent to be deionized water.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172780A (en) * | 1996-08-06 | 1998-02-11 | 大赛璐·赫斯株式会社 | Cement retarder and cement retardative sheet |
| US5739212A (en) * | 1992-12-08 | 1998-04-14 | Skw Trostberg Aktiengesellschaft | Water-soluble graft polymers |
| CN1412175A (en) * | 2001-10-16 | 2003-04-23 | 竹本油脂株式会社 | Method for producing allyl ether ester monomer and cement dispersant |
| EP1368849B1 (en) * | 2000-10-18 | 2006-04-05 | Du Pont-Mitsui Polychemicals Co., Ltd. | Gel-type polymer electrolyte and use thereof |
| CN101407386A (en) * | 2007-10-10 | 2009-04-15 | 黎思幸 | High dispersing plasticizing adulterating agent for cement concrete |
| CN101575188A (en) * | 2009-05-31 | 2009-11-11 | 上海三瑞化学有限公司 | Gypsum particle dispersing agent and preparation method thereof |
-
2011
- 2011-10-14 CN CN201110312367.3A patent/CN102443115B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5739212A (en) * | 1992-12-08 | 1998-04-14 | Skw Trostberg Aktiengesellschaft | Water-soluble graft polymers |
| CN1172780A (en) * | 1996-08-06 | 1998-02-11 | 大赛璐·赫斯株式会社 | Cement retarder and cement retardative sheet |
| EP1368849B1 (en) * | 2000-10-18 | 2006-04-05 | Du Pont-Mitsui Polychemicals Co., Ltd. | Gel-type polymer electrolyte and use thereof |
| CN1412175A (en) * | 2001-10-16 | 2003-04-23 | 竹本油脂株式会社 | Method for producing allyl ether ester monomer and cement dispersant |
| CN101407386A (en) * | 2007-10-10 | 2009-04-15 | 黎思幸 | High dispersing plasticizing adulterating agent for cement concrete |
| CN101575188A (en) * | 2009-05-31 | 2009-11-11 | 上海三瑞化学有限公司 | Gypsum particle dispersing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 朱琳俐,冯恩娟等: "聚醚接枝聚羧酸系高效减水剂合成", 《南京工业大学学报(自然科学版)》 * |
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