CN102443115B - Method for producing slow-release cement dispersing agents - Google Patents
Method for producing slow-release cement dispersing agents Download PDFInfo
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- CN102443115B CN102443115B CN201110312367.3A CN201110312367A CN102443115B CN 102443115 B CN102443115 B CN 102443115B CN 201110312367 A CN201110312367 A CN 201110312367A CN 102443115 B CN102443115 B CN 102443115B
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- 239000004568 cement Substances 0.000 title claims abstract description 35
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000004567 concrete Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 229920000570 polyether Polymers 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- -1 polyoxyethylene Polymers 0.000 claims description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000002605 large molecules Chemical class 0.000 claims description 19
- 229920002521 macromolecule Polymers 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 2
- YKXCWZVUWWQSAV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O YKXCWZVUWWQSAV-BTVCFUMJSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- UDYLZILYVRMCJW-UHFFFAOYSA-L disodium;oxido carbonate Chemical compound [Na+].[Na+].[O-]OC([O-])=O UDYLZILYVRMCJW-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
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 production method of slow-release cement dispersing agents, belong to chemical building material field for building.
Background technology
In concrete Application Areas, the use of admixture improves the most effective way such as concrete strength, serviceability, endurance quality.Carboxylic acid type cement dispersants is widelyd popularize by country on highway, railway, bridge in recent years, and then is able to fast development, and manufacturer emerges in multitude, and carboxylic acid type cement dispersants technology is also known gradually.Although existing conventional poly carboxylic acid additive has good workability to fresh mortar or concrete, but Slump Time losing of Large is still larger, can slightly be improved by composite traditional slow setting component such as glucose sodium etc., but this method also can be restricted, cause early age strength of concrete too low sometimes, also there is coagulation component and cement consistency and go wrong and the too fast and abnormal gelatin phenomenon of slump-loss occurs.
Summary of the invention
In order to solve the technical problem existed in prior art, the object of the present invention is to provide a kind of degree of mobilization retentivity and the dispersing property that can significantly improve cement, air content is less, improve the adaptability to cement, improve concrete slump retentivity, reduce the slow-release cement dispersing agents of concrete mix viscosity.
The technical solution used in the present invention is:
A kind of production method of slow-release cement dispersing agents, it is characterized in that, first carry out the first step condensation reaction by MALEIC ANHYDRIDE and polyoxyethylene polyethers (a) containing two hydroxy functional group, carry out second step condensation reaction with the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block again, obtain Large molecule active monomer X; Large molecule active monomer X and long-chain polyoxyethylene polyethers (c), function monomer (z) containing unsaturated ethylene thiazolinyl, under the initiation of initiator, carry out Raolical polymerizable, obtain the finished product Y.
Further,
The structural formula of described polyoxyethylene polyethers (a) containing two hydroxy functional group is:
H0-(CH
2-CH
2-0)
nwherein, subscript n is 12 ~ 25 to-H;
The structural formula of the oxygen ethene of described monohydroxy and the vinyl polyether (b) of oxypropylene block is:
CH
2=CH-0-(CH
2-CH
2-0)
m-(CH (CH
3)-CH
2-0-)
o-H wherein, subscript m, o is 3 ~ 15;
The structural formula of described long-chain polyoxyethylene polyethers (c) containing unsaturated ethylene thiazolinyl is:
CH
2=CH-0-(CH
2-CH
2-0)
nwherein, subscript n is 12 ~ 25 to-H;
The structural formula of described Large molecule active monomer X is:
The structural formula of described the finished product Y is:
(wherein, z is function monomer).
The preparation method of a kind of slow-release cement dispersing agents of the present invention, the oxygen ethene polyethers of the two hydroxyl of this slow-release cement dispersing agents application, the oxygen ethene of monohydroxy and the polyethers of oxypropylene block are condensed into important high reactivity macromonomer respectively not arrange on year-on-year basis with MALEIC ANHYDRIDE, again with carry out Raolical polymerizable containing unsaturated allylic long-chain polyoxyethylene polyethers and other function monomers, and carry out in specific pH reaction system, special surface-active macromonomer structure ensures that it can provide enough crosslinked slow release molecules structure to ensure the maintenance of cement flows degree and concrete slump, simultaneously this method not only can avoid polymerization system to cause a large amount of gel to produce because of too high reactive behavior, be polymerized unsuccessfully, and can ensure that the molecular weight distribution of final product is balanced.
Owing to there is oxygen ethene, the oxypropylene group of very a high proportion of ester group slowly-releasing cross-linking set, carboxyl and different ratios in slow-release cement dispersing agents structure of the present invention, these active groups dredge mechanism due to different affine water, and polar chemical key and cement molecule and aqueous phase mutual effect, degree of mobilization retentivity and the dispersing property of cement can be significantly improved, air content is less, improve the adaptability to cement, improve concrete slump retentivity, reduce concrete mix viscosity.
The concrete operation step of slow-release cement dispersing agents of the present invention is as follows:
1., by 18.5 ~ 34.8% (mass percentage, lower with) MALEIC ANHYDRIDE with 5 ~ 8% polyoxyethylene polyethers (a) containing pair hydroxy functional group put into reaction vessel, heat up, mix after add the stopper of 0.3 ~ 1.1% and the catalyzer of 1.4 ~ 3.8%, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 100 ~ 115 DEG C, reacts 3 ~ 5 hours;
2., in reaction vessel, add the oxygen ethene of the monohydroxy of 10 ~ 13% and the vinyl polyether (b) of oxypropylene block, be warming up to 120 ~ 135 DEG C, continue reaction 1 ~ 3 hour, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add solvent, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 80 ~ 95 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system;
5., long-chain polyoxyethylene polyethers (c) of unsaturated ethylene thiazolinyl that contains of 41 ~ 55% is become solution with the function monomer (z) of 2 ~ 21.2% by dissolution with solvents;
6., the initiator dissolution with solvents of 1 ~ 4% is become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 2 ~ 4 hours, and controlling dropping temperature is 80 ~ 95 DEG C;
8., dropping terminates rear insulation 1 ~ 3 hour;
9., lower the temperature, add the solution prepared by the sodium hydroxide of 4.5 ~ 7%, obtain the finished product Y.
Preferably, described catalyzer is tosic acid or the vitriol oil.
Preferably, described stopper is Resorcinol, thiodiphenylamine or MEHQ.
Preferably, the function monomer (z) that described Raolical polymerizable uses is methyl acrylate, one or more in hydroxyethyl methacrylate and sodium allyl sulfonate.
Preferably, the initiator of described Raolical polymerizable is Potassium Persulphate and hydrogen peroxide composite initiation system.
Preferably, the pH value of described Raolical polymerizable system remains 3 ~ 5.
Preferably, described Raolical polymerizable uses solvent to be water.
Preferably, described Raolical polymerizable uses solvent to be deionized water.
Embodiment
Embodiment 1
Charging capacity is with weight parts, as shown in the table,
Production craft step is as follows:
1., MALEIC ANHYDRIDE and polyoxyethylene polyethers (a) containing two hydroxy functional group are put into reaction vessel, heat up, mix after add stopper and catalyzer, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 107 DEG C, reacts 5 hours;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block, be warming up to 135 DEG C, continue reaction 1 hour, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add deionized water, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 90 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system to be 4.5;
5., long-chain polyoxyethylene polyethers (c) and function monomer (z) the 10 parts of deionized water dissolvings containing unsaturated ethylene thiazolinyl are become solution;
6., initiator 9 parts of deionized water dissolvings are become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 2 hours, and controlling dropping temperature is 88 DEG C;
8., dropping terminates rear insulation 1 hour;
9., lower the temperature, add sodium hydroxide solution, obtain the finished product Y (being denoted as PC-B1).
Embodiment 2
Charging capacity is with weight parts, as shown in the table,
Production craft step is as follows:
1., MALEIC ANHYDRIDE and polyoxyethylene polyethers (a) containing two hydroxy functional group are put into reaction vessel, heat up, mix after add stopper and catalyzer, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 100 DEG C, reacts 3.5 hours;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block, be warming up to 120 DEG C, continue reaction 2.5 hours, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add deionized water, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 87 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system to be 3;
5., long-chain polyoxyethylene polyethers (c) and function monomer (z) the 7.5 parts of deionized water dissolvings containing unsaturated ethylene thiazolinyl are become solution;
6., initiator 9 parts of deionized water dissolvings are become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 3.5 hours, and controlling dropping temperature is 80 DEG C;
8., dropping terminates rear insulation 1.5 hours;
9., lower the temperature, add sodium hydroxide solution, obtain the finished product Y (being denoted as PC-B2).
Embodiment 3
Charging capacity is with weight parts, as shown in the table,
Production craft step is as follows:
1., MALEIC ANHYDRIDE and polyoxyethylene polyethers (a) containing two hydroxy functional group are put into reaction vessel, heat up, mix after add stopper and catalyzer, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 103 DEG C, reacts 3 hours;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block, be warming up to 123 DEG C, continue reaction 1.5 hours, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add deionized water, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 80 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system to be 5;
5., long-chain polyoxyethylene polyethers (c) and function monomer (z) the 19 parts of deionized water dissolvings containing unsaturated ethylene thiazolinyl are become solution;
6., initiator 27 parts of deionized water dissolvings are become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 3 hours, and controlling dropping temperature is 93 DEG C;
8., dropping terminates rear insulation 3 hours;
9., lower the temperature, add sodium hydroxide solution, obtain the finished product Y (being denoted as PC-B3).
Embodiment 4
Charging capacity is with weight parts, as shown in the table,
Production craft step is as follows:
1., MALEIC ANHYDRIDE and polyoxyethylene polyethers (a) containing two hydroxy functional group are put into reaction vessel, heat up, mix after add stopper and catalyzer, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 115 DEG C, reacts 4.5 hours;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block, be warming up to 132 DEG C, continue reaction 3 hours, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add deionized water, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 85 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system to be 3.5;
5., long-chain polyoxyethylene polyethers (c) and function monomer (z) the 2.6 parts of deionized water dissolvings containing unsaturated ethylene thiazolinyl are become solution;
6., initiator 9 parts of deionized water dissolvings are become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 2.5 hours, and controlling dropping temperature is 95 DEG C;
8., dropping terminates rear insulation 2.5 hours;
9., lower the temperature, add sodium hydroxide solution, obtain the finished product Y (being denoted as PC-B4).
Embodiment 5
Charging capacity is with weight parts, as shown in the table,
Production craft step is as follows:
1., MALEIC ANHYDRIDE and polyoxyethylene polyethers (a) containing two hydroxy functional group are put into reaction vessel, heat up, mix after add stopper and catalyzer, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 113 DEG C, reacts 4 hours;
2., in reaction vessel, add the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block, be warming up to 125 DEG C, continue reaction 2 hours, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add deionized water, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 95 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system to be 4;
5., long-chain polyoxyethylene polyethers (c) and function monomer (z) the 4 parts of deionized water dissolvings containing unsaturated ethylene thiazolinyl are become solution;
6., initiator 36 parts of deionized water dissolvings are become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 4 hours, and controlling dropping temperature is 84 DEG C;
8., dropping terminates rear insulation 2 hours;
9., lower the temperature, add sodium hydroxide solution, obtain the finished product Y (being denoted as PC-B5).
Slow-release cement dispersing agents PC-B (1 ~ 5) prepared by embodiment 1 ~ 5 carries out concrete experiments with coventional type poly-carboxylic-acid cement admixture (being called for short PC-A), naphthalene water reducer (FDN), aminosulfonic water-reducing agent (ASPF), detect according to GB8076-2008 standard, table specific as follows:
As can be seen from the above table, slow-release cement dispersing agents of the present invention has relatively good concrete workability, dispersed close with other water reducers, but concrete slump-loss is also very little, the individual example slump through time also have growth.For high grade, high slump, the longer commerical ready-mixed concrete of shipment distance can use widely, and this is that naphthalene water reducer, aminosulfonic water-reducing agent etc. are beyond one's reach.
Meanwhile, the starting material adopted due to slow-release cement dispersing agents of the present invention are comparatively cheap and easy to get, and production technique is also fairly simple, and comprehensive cost performance is very high, and the market advantage is obvious.
The above example, is only ideal several in the preparation method that the present invention relates to, but is not limited thereto, not because the order difference of embodiment forms restriction to the present invention.Anyly know these those skilled in the art in the technical scope that the present invention mentions, can light facile change or replacement, all should contain 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 (8)
1. the production method of a slow-release cement dispersing agents, it is characterized in that, first carry out the first step condensation reaction with the MALEIC ANHYDRIDE of 18.5 ~ 34.8% and polyoxyethylene polyethers (a) containing two hydroxy functional group of 5 ~ 8%, again with 10 ~ 13% the oxygen ethene of monohydroxy and the vinyl polyether (b) of oxypropylene block carry out second step condensation reaction, obtain Large molecule active monomer X; Large molecule active monomer X and 41 ~ 55% contains long-chain polyoxyethylene polyethers (c) of unsaturated ethylene thiazolinyl, the function monomer (z) of 2 ~ 21.2%, under the initiation of initiator, carries out Raolical polymerizable, obtains the finished product Y;
Wherein, the structural formula of described polyoxyethylene polyethers (a) containing two hydroxy functional group is:
HO-(CH
2-CH
2-O)
nwherein, subscript n is 12 ~ 25 to-H;
The structural formula of the oxygen ethene of described monohydroxy and the vinyl polyether (b) of oxypropylene block is:
CH
2=CH-O-(CH
2-CH
2-O)
m-(CH (CH
3)-CH
2-O-)
o-H wherein, subscript m, o is 3 ~ 15;
The structural formula of described long-chain polyoxyethylene polyethers (c) containing unsaturated ethylene thiazolinyl is:
CH
2=CH-O-(CH
2-CH
2-O)
nwherein, subscript n is 12 ~ 25 to-H;
Function monomer (z) is methyl acrylate, one or more in hydroxyethyl methacrylate and sodium allyl sulfonate.
2. the production method of slow-release cement dispersing agents according to claim 1, is characterized in that, concrete operation step is as follows:
1., polyoxyethylene polyethers (a) containing two hydroxy functional group of the MALEIC ANHYDRIDE of 18.5 ~ 34.8% and 5 ~ 8% is put into reaction vessel, heat up, mix after add the stopper of 0.3 ~ 1.1% and the catalyzer of 1.4 ~ 3.8%, pass into nitrogen protection, and reflux with nitrogen atmosphere, the water produced in separating reaction process and lower boiling small-molecule substance, control temperature, at 100 ~ 115 DEG C, reacts 3 ~ 5 hours;
2., in reaction vessel, add the oxygen ethene of the monohydroxy of 10 ~ 13% and the vinyl polyether (b) of oxypropylene block, be warming up to 120 ~ 135 DEG C, continue reaction 1 ~ 3 hour, be obtained by reacting Large molecule active monomer X;
3., in reaction vessel, add solvent, after logical nitrogen excluding air, open condensation reflux unit, be warming up to 80 ~ 95 DEG C;
4., Large molecule active monomer X is placed in reaction vessel, adds pH buffered soln, regulate pH value of reaction system;
5., long-chain polyoxyethylene polyethers (c) of unsaturated ethylene thiazolinyl that contains of 41 ~ 55% is become solution with the function monomer (z) of 2 ~ 21.2% by dissolution with solvents;
6., the initiator dissolution with solvents of 1 ~ 4% is become solution;
7. the solution, by step 5. and 6. prepared drops in reaction vessel respectively, and controlling time for adding is 2 ~ 4 hours, and controlling dropping temperature is 80 ~ 95 DEG C;
8., dropping terminates rear insulation 1 ~ 3 hour;
9., lower the temperature, add the solution prepared by the sodium hydroxide of 4.5 ~ 7%, obtain the finished product Y.
3. the production method of slow-release cement dispersing agents according to claim 2, is characterized in that, described catalyzer is tosic acid or the vitriol oil.
4. the production method of slow-release cement dispersing agents according to claim 2, is characterized in that, described stopper is Resorcinol, thiodiphenylamine or MEHQ.
5. the production method of slow-release cement dispersing agents according to claim 2, is characterized in that, the initiator of described Raolical polymerizable is Potassium Persulphate and hydrogen peroxide composite initiation system.
6. the production method of slow-release cement dispersing agents according to claim 2, is characterized in that, the pH value of described Raolical polymerizable system remains 3 ~ 5.
7. the production method of slow-release cement dispersing agents according to claim 2, is characterized in that, described Raolical polymerizable uses solvent to be water.
8. according to the production method of slow-release cement dispersing agents according to claim 7, it is characterized in that, described Raolical polymerizable uses solvent to be deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110312367.3A CN102443115B (en) | 2011-10-14 | 2011-10-14 | Method for producing slow-release cement dispersing agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110312367.3A CN102443115B (en) | 2011-10-14 | 2011-10-14 | Method for producing slow-release cement dispersing agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102443115A CN102443115A (en) | 2012-05-09 |
| CN102443115B true CN102443115B (en) | 2015-04-15 |
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Citations (6)
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| 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 | Production method of 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 |
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2011
- 2011-10-14 CN CN201110312367.3A patent/CN102443115B/en not_active Expired - Fee Related
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| 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 | Production method of 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 |
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| 聚醚接枝聚羧酸系高效减水剂合成;朱琳俐,冯恩娟等;《南京工业大学学报(自然科学版)》;20100131;第32卷(第1期);106-110页 * |
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