CN103214209A - Portland cement fluidizing agent preparation method - Google Patents
Portland cement fluidizing agent preparation method Download PDFInfo
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- CN103214209A CN103214209A CN2013100224864A CN201310022486A CN103214209A CN 103214209 A CN103214209 A CN 103214209A CN 2013100224864 A CN2013100224864 A CN 2013100224864A CN 201310022486 A CN201310022486 A CN 201310022486A CN 103214209 A CN103214209 A CN 103214209A
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- diacetone
- acryloamide
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- liquid agent
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Abstract
The invention relates to a Portland cement fluidizing agent. According to the invention, the fluidizing agent is prepared through straight-chain alkylene oxide ether and diacetone acrylamide polymerization under the catalyzing of oil-soluble peroxide and according to a free radical polymerization mechanism. One component of the fluidizing agent is a product obtained by a copolymerization reaction of straight-chain alkenyl ether with an oxyalkylene average addition molar number of 20-40 and diacetoneacrylamide, wherein a molar ratio is 12-15%:88-85%. The other component of the fluidizing agent is a product obtained by a copolymerization reaction of straight-chain alkenyl ether with an oxyalkylene average addition molar number of 50-100 and diacetoneacrylamide, wherein a molar ratio is 10-13%:90-87%. The Portland cement fluidizing agent provided by the invention is applied in construction engineering. With the fluidizing agent provided by the invention, cement concrete can be provided with high fluidity, cement condensation and curing are not significantly retarded, and cement mechanical strength is not reduced.
Description
Technical field
The present invention relates to a kind of cement liquid agent.Specifically, the present invention is a kind of liquid agent composition that is used for the silicate cement mixture, thereby said composition is significantly improved its workability and flowability by stoping mobile decline of mortar or concrete mix.
Background technology
Mobile loss is the subject matter that cement industry exists.People wish to obtain a kind of cement liquid agent very much all the time, and this liquid agent can keep the concrete mortar flowability in the long time.Synthesized various chemical substances in order to address this problem people, but these chemical substances can not make fully performances such as coagulability, flowability and mechanical strength be met simultaneously.The objective of the invention is synthetic a kind ofly can significantly improve the silicate cement flowability, significantly do not change the cement setting performance again and do not reduce the silicate cement liquid agent of cement mechanical strength.
Summary of the invention
Find to have following described some polymkeric substance and combination thereof not cause that for stoping cement flows decline the reduction of cement retardative and mechanical strength has significant effect after deliberation with specific molecular structure.
The present invention relates to a kind of composition of cement liquid agent, said composition has been used the multipolymer of certain straight-chain alkenyl ether and diacetone-acryloamide(DAA) polyreaction.Specifically, the present invention makes up liquid agent and is had the straight chain oxidative chain alkene ether of 20～40 oxyalkylene group units and copolymer A that diacetone-acryloamide(DAA) carries out free radical reaction and carried out the combination of free radical reaction multipolymer B with straight chain oxidative chain alkene ether and diacetone-acryloamide(DAA) that (II) has 50～100 oxyalkylene nuit(s)s by (I).
Cement liquid agent involved in the present invention and composition thereof comprise certain straight-chain alkenyl ether and biacetone acrylamide copolymer.Find after deliberation, have two kinds of specific copolymer when using, can realize the combination of characteristics such as desirable flowability, coagulability and intensity according to the method for the invention.Every kind of multipolymer has the straight-chain alkenyl ether comonomer that is shown below respectively:
R
1O(AO)
nR
2 (I)
R
1O(AO)
mR
2 (II)
Wherein above-mentioned various in
R
1Expression C
2-5Alkenyl;
R
2Expression C
1-4Alkyl;
AO represents C
2-20Oxyalkylene group, O represention oxygen atom wherein, A represents a kind of alkyl;
N represents that the oxyalkylene group number is 20 to 40 moles, also is that the average addition mole number of oxyalkylene group is 20-40;
M represents 50 to 100 the average addition mole number of oxyalkylene group;
" copolymer A " is meant the multipolymer of straight-chain alkenyl ether I and diacetone-acryloamide(DAA) among the present invention, perhaps hydrolysate partially or completely, and the molar percentage of straight-chain alkenyl ether I and diacetone-acryloamide(DAA) is 12: 88 to 15: 85.
" multipolymer B " is meant the multipolymer of straight-chain alkenyl ether II and diacetone-acryloamide(DAA), perhaps hydrolysate partially or completely, and the mol ratio of straight-chain alkenyl ether II and diacetone-acryloamide(DAA) is 10: 90 to 13: 87.
In above-mentioned formula (I), (II) are various, by R
1The C of expression
2-5Straight-chain alkenyl comprises vinyl, propenyl, methacrylic, 1, and 1-dimethyl-2-propenyl and 3-methyl-3-butenyl etc. in these groups, preferably use allyl group or methylpropenyl.
In above-mentioned formula (I), (II) are various, the C that represents by AO
2-20Oxyalkylene group comprises ethylene oxide, propylene oxide, oxybutylene, oxidation dodecylene, oxidation tetradecene, oxidation cetene, oxidation vaccenic acid and oxidation eicosylene etc.Wherein preferred C
2-4Oxyalkylene group such as ethylene oxide or propylene oxide.AO can comprise the oxyalkylene part of two or more types.
In above-mentioned formula (I), (II) are various, by R
2The C of expression
1-4Alkyl comprises as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-and the tertiary butyl.The preferential C that selects
1-2Alkyl.
Cement liquid agent involved in the present invention has been applied in the construction work, has realized making cement concrete to obtain higher flowability and the not obvious effect that delays cement setting curing and do not reduce mechanical strength.
Similar to traditional water mud liquid agent such as naphthalene sulfonic acidformaldehyde condensation product class, sulfonated melamine compound condenses class liquid agent, cement liquid agent of the present invention has the characteristic that influence comprises cement concrete combination particle thing dispersiveness, and this polymkeric substance improves the effect of sand-cement slurry flowability in addition certainly.The additive of being made up of copolymer A still all has the effect that increases the grout flowability in the later stage at the aquation initial stage.
Copolymer A of the present invention is compared with traditional fluidity regulator of use, can more effective raising sand-cement slurry or concrete composition particulate dispersiveness.This multipolymer can form hydration layer around being adsorbed on the lip-deep many oxyalkylene groups of particulate matter, this hydration layer has sterically hindered effect, keeps the dispersiveness of cement granules in the long time period.Therefore, cement granules can disperse admirably and can more effectively prevent mobile decline.
According to the type of cement mixture, the cement liquid agent of copolymer A can also contain the multipolymer B of a small amount of its quality 5-20% and their hydrolysate.This can need determine the ratio of admixture multipolymer B by the test to performances such as special cement slurry flowability, intensity.
The cement liquid agent that contains the mixture of copolymer A of the present invention and multipolymer B thereof is owing to these multipolymers and cement granules interphase interaction keep degree of mobilization not descend strongly.The major cause that increases considerably in starting stage cement granules dispersiveness is the effect by copolymer A, keeps the grout flowability not descend jointly and multipolymer B can work in coordination with polymer A.Equally, form a hydration layer at the also extended many oxyalkylene groups of main chain of the multipolymer B of cement particle surface absorption, this hydration layer is one to the copolymer A hydration layer and effectively replenishes, and can keep the flowability of grout in the longer time.
Copolymer A of the present invention, B can press radical polymerization mechanism under the effect of oil soluble peroxide catalyzed, through type (I), (II) straight-chain alkenyl ether and diacetone-acryloamide(DAA) polymerization prepare.Formula (I) straight-chain alkenyl ether and diacetone-acryloamide(DAA) mol ratio are generally 12-15%: 88-85%, preferred proportion are 13%: 87%.Formula (II) straight-chain alkenyl ether and diacetone-acryloamide(DAA) mol ratio are generally 10-13%: 90-87%, preferred proportion are 12%: 88%.
The hydrolysate of copolymer A and B is a kind of salt that is formed by diacetone-acryloamide(DAA), is generally an alkali metal salt such as sodium salt or sylvite.
The cement liquid agent consumption that reaches the desired effect of the present invention is generally the 0.03-1.0% of cement quality, and the preferred mass mark is 0.1-0.5%.
Traditional cement additire such as air entrapment agent, water-resisting agent, defoamer, hardening accelerator can use simultaneously with this additive.These additives can mix with cement liquid agent of the present invention and cement concrete composition earlier, perhaps in the end add liquid agent of the present invention.
Liquid agent of the present invention is applicable to portland-type cement, as ordinary Portland cement, Portland blast, Portland fly ash cement etc.
Embodiment
1, copolymer A prepares embodiment
Each component recited above is packed in the reactor, and this reactor is equipped with condenser, nitrogen input tube, thermometer and agitator.Under nitrogen atmosphere temperature is increased to 90-100 ℃ then, 2-4.5h carries out copolyreaction continuously under nitrogen protection.
After reaction finished, toluene distillation was come out in underpressure distillation under 100 conditions, obtains the brown viscous liquid copolymer A.
2, multipolymer B prepares embodiment
Each component recited above is packed in the reactor, and this reactor is equipped with condenser, nitrogen input tube, thermometer and agitator.Under nitrogen atmosphere temperature is increased to 100 ℃ then, 5-6h carries out copolyreaction continuously under nitrogen protection.
After reaction is finished, toluene distillation is come out, obtain being under the normal temperature brown viscous liquid multipolymer B 100 ℃ of following underpressure distillation.
3, batching embodiment
Table 1 batching embodiment
| The prescription number | The cement additire combination | With cement quality is basic addition/% |
| 1 | Copolymer A | 0.10 |
| 2 | Copolymer A | 0.15 |
| 3 | Multipolymer B | 0.10 |
| 4 | Multipolymer B | 0.15 |
| 5 | Copolymer A/multipolymer B | 0.25/0.05 |
| 6 | Copolymer A/multipolymer B | 0.25/0.05 |
4, detect embodiment
1 six prescriptions of his-and-hers watches manufactured samples detects result such as table 2.
Table 2
Claims (6)
1. silicate cement liquid agent and preparation method, this liquid agent has used the multipolymer of some straight-chain alkenyl ether and diacetone-acryloamide(DAA) polyreaction, specifically, the present invention makes up liquid agent and contains the combination that the straight chain oxidative chain alkene ether of 20～40 oxyalkylene group units and diacetone-acryloamide(DAA) carry out the copolymer A of free radical reaction and (II) contain the straight chain oxidative chain alkene ether and the multipolymer B that diacetone-acryloamide(DAA) carries out free radical reaction of 50～100 oxyalkylene nuit(s)s by (I).
The copolymer A of claim 1 silicate cement liquid agent, B can be under the effect of oil soluble peroxide catalyzed, press radical polymerization mechanism, through type (I), (II) straight-chain alkenyl ether and diacetone-acryloamide(DAA) polymerization prepare, and its Chinese style (I) straight-chain alkenyl ether and diacetone-acryloamide(DAA) mol ratio are 12-15%: 88-85%; Formula (II) straight-chain alkenyl ether and diacetone-acryloamide(DAA) mol ratio are 10-13%: 90-87%.
3. the concrete synthesis step of claim 1 silicate cement liquid agent is: (1) is packed top described each component into respectively and is had in the reactor of condenser, nitrogen input tube, thermometer and agitator; (2) preparation condition of copolymer A is: under nitrogen atmosphere temperature is increased to 90-100 ℃, 2-4.5h carries out copolyreaction continuously; The preparation condition of multipolymer B is: under nitrogen atmosphere temperature is increased to 100 ℃, 5-6h carries out copolyreaction continuously; (3) after reaction finished, toluene distillation was come out in underpressure distillation under 100 ℃ of conditions, obtains two kinds of light yellow viscous liquid copolymer A and B respectively; (4) respectively copolymer A, the B that obtains carried out alkaline hydrolysis and obtain silicate cement liquid agent composition.
4. the silicate cement liquid agent of claim 1, this liquid agent contains at least a alkenyl ether that is shown below
R
1O(A O)nR
2 (I)
Wherein
R
1Expression C
2-5Alkenyl;
R
2Expression C
1-4Alkyl;
A O represents C
2-20Oxyalkylene group, wherein O represention oxygen atom, A represent a kind of alkyl;
It is 20 to 40 straight-chain alkenyl ether and diacetone-acryloamide(DAA) copolymerization that n represents to have the average addition mole number of oxyalkylene group, said alkenyl ether (I) is 12～15: 88～85 with the mole of said diacetone-acryloamide(DAA), and its multipolymer is the salt of hydrolysate or hydrolysate.
5. the silicate cement liquid agent of claim 1, this liquid agent contains:
(1) at least a, by formula R
1O (AO) mR
2(II)
The straight-chain alkenyl ether of expression, wherein R
1Expression C
2-5Alkenyl;
R
2Expression C
1-4Alkyl;
AO represents C
2-20Oxyalkylene group, wherein O represention oxygen atom, A represent alkyl;
M represent to have oxyalkylene group average addition mole number 50 to 100 alkenyl ether and the copolymerization of diacetone-acryloamide(DAA).Said alkenyl ether (II) is 10～13: 90～87 with the mol ratio of said diacetone-acryloamide(DAA).
6. the silicate cement liquid agent of claim 1 also contains 5～20% (weight) (based on 100 parts heavy copolymer A), by formula (II): R
1O (AO) mR
2The hydrolysate of the straight-chain alkenyl ether of expression and the multipolymer of diacetone-acryloamide(DAA) or the salt of hydrolysate.
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| CN2013100224864A CN103214209A (en) | 2013-01-07 | 2013-01-07 | Portland cement fluidizing agent preparation method |
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|---|---|---|---|
| CN2013100224864A CN103214209A (en) | 2013-01-07 | 2013-01-07 | Portland cement fluidizing agent preparation method |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077181A (en) * | 1992-02-14 | 1993-10-13 | 格雷斯公司 | Cement admixture composition |
| CN1215034A (en) * | 1993-04-05 | 1999-04-28 | 格雷斯公司 | Improved cement compositions capable of exhibiting inhibition to slump loss with respect to time |
| CN1916053A (en) * | 2002-03-25 | 2007-02-21 | 塞卡施韦茨股份公司 | Polymers in a solid state |
| CN101333092A (en) * | 2007-06-25 | 2008-12-31 | 深圳市海川实业股份有限公司 | Cement concrete superplasticizer and method for preparing same |
| US7670426B2 (en) * | 2005-09-09 | 2010-03-02 | Jack B. Parson Companies | Concrete mixtures having aqueous foam admixtures |
| CN101786824A (en) * | 2010-02-26 | 2010-07-28 | 北京新中岩建材科技有限公司 | Plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent and preparation method thereof |
| CN102149737A (en) * | 2008-09-11 | 2011-08-10 | 建筑研究和技术有限公司 | Dynamic copolymers for workability retention of cementitious composition |
| CN102432776A (en) * | 2011-09-30 | 2012-05-02 | 南京瑞迪高新技术有限公司 | Method for preparing early strength type polycarboxylic acid water-reducing agent |
-
2013
- 2013-01-07 CN CN2013100224864A patent/CN103214209A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077181A (en) * | 1992-02-14 | 1993-10-13 | 格雷斯公司 | Cement admixture composition |
| CN1215034A (en) * | 1993-04-05 | 1999-04-28 | 格雷斯公司 | Improved cement compositions capable of exhibiting inhibition to slump loss with respect to time |
| CN1916053A (en) * | 2002-03-25 | 2007-02-21 | 塞卡施韦茨股份公司 | Polymers in a solid state |
| US7670426B2 (en) * | 2005-09-09 | 2010-03-02 | Jack B. Parson Companies | Concrete mixtures having aqueous foam admixtures |
| CN101333092A (en) * | 2007-06-25 | 2008-12-31 | 深圳市海川实业股份有限公司 | Cement concrete superplasticizer and method for preparing same |
| CN102149737A (en) * | 2008-09-11 | 2011-08-10 | 建筑研究和技术有限公司 | Dynamic copolymers for workability retention of cementitious composition |
| CN101786824A (en) * | 2010-02-26 | 2010-07-28 | 北京新中岩建材科技有限公司 | Plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent and preparation method thereof |
| CN102432776A (en) * | 2011-09-30 | 2012-05-02 | 南京瑞迪高新技术有限公司 | Method for preparing early strength type polycarboxylic acid water-reducing agent |
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Application publication date: 20130724 |