CN104177561A - Polycarboxylate water reducing agent with slow-release property and mud resistance as well as preparation method and application of polycarboxylate water reducing agent - Google Patents
Polycarboxylate water reducing agent with slow-release property and mud resistance as well as preparation method and application of polycarboxylate water reducing agent Download PDFInfo
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- CN104177561A CN104177561A CN201410366490.7A CN201410366490A CN104177561A CN 104177561 A CN104177561 A CN 104177561A CN 201410366490 A CN201410366490 A CN 201410366490A CN 104177561 A CN104177561 A CN 104177561A
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- mud
- reducer
- polycarboxylate water
- slow
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 108
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 amine cation Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 abstract description 35
- 230000000694 effects Effects 0.000 abstract description 20
- 239000008187 granular material Substances 0.000 abstract description 12
- 125000003368 amide group Chemical group 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 230000008719 thickening Effects 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 230000032683 aging Effects 0.000 abstract 1
- 230000003111 delayed effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 239000004927 clay Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 125000004185 ester group Chemical group 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a polycarboxylate water reducing agent with slow-release property and mud resistance. According to the preparation method, a macromolecular structure design principle is adopted to synthesize a mud-resisting ester ether copolymerized polycarboxylate water reducing agent product which can release positive and negative non-ions slowly. The invention further discloses application of the polycarboxylate water reducing agent which is prepared by using the method and has slow-release property and mud resistance in concrete. Compared with the prior art, the polycarboxylate water reducing agent has the advantages that firstly, the molecular structure of the product has ester and amide groups which are not stable in a strong base cement environment; secondly, the amine cation generated from hydrolysis of amide groups has a sealing function for mud with negative charges, and thus a mud-resisting effect is achieved; thirdly, a thickening effect is achieved for cement paste, and hydration of cement granules is delayed; and fourthly, the product is high in water reduction rate, good in slump aging retentivity and high in tolerance for mud.
Description
Technical field
The present invention relates to concrete admixture field, relate in particular to the non-ionic ether-ether of the resistance to chamotte mould copolymerization of a kind of slow release negative and positive polycarboxylate water-reducer and preparation method thereof and the application in concrete.
Background technology
Water reducer is one of requisite component of modern concrete, is mainly used to disperse the cement granules in concrete, reduces water consumption, improves the workability of concrete mix, improves intensity and the weather resistance of maturing.The dispersion water-reduction of water reducer is realized in the absorption on cement granules and hydrated product surface thereof by water reducer.The absorption of water reducer has changed the form of character, aquation kinetics and the hydrated product of cement-aqueous dispersion solid-liquid interface.Water reducer molecular structure difference, its characterization of adsorption difference is also different on the impact of solid-liquid interface.The dissemination mechanism of water reducer has electrostatic repulsion effect, sterically hindered effect, hydration shell lubrication, cause isolation " ball " effect, wherein by well accepted be electrostatic repulsion effect and sterically hindered effect.
Electrostatic repulsion effect: mix in fresh concrete after water reducer, water reducer molecular orientation is adsorbed on cement particle surface, segment polarity group points to liquid phase.Due to the ionizing event of hydrophilic polar group, make electric charge identical on cement particle surface band, and the quantity of electric charge increases with water reducer concentration, thereby make to produce between cement granules electrostatic repulsion, cement granules flucculation structure is disintegrated, particle disperses mutually, discharges the free water being wrapped in floc sedimentation, thereby effectively increases the mobility of mixture.
Between steric hindrance: polyalcohol water reducing agent is adsorbed on cement particle surface, cement particle surface form one deck have certain thickness polymer molecule adsorption layer.Close when cement granules, adsorption layer starts overlapping, between particle, produces repulsion effect, and overlapping more, repulsion is larger, and sterically hindered repulsion is larger.Line style ionic polymer water reducer, as naphthalenesulfonate formaldehyde condensation compound, taking electrostatic repulsion as main dispersion cement granules; And comb type polycarboxylate water-reducer is adsorbed on cement particle surface, its main chain is connected with cement particle surface, and side chain extends into liquid phase and forms thicker polymer molecule adsorption layer, thereby has larger sterically hindered repulsion effect.
Aggregate is concrete main component, accounts for the 70-80% of volume of concrete total amount, and the quality of its character will directly have influence on fresh concrete and the rear concrete performance of sclerosis, as workability, intensity, weather resistance etc.Existing bibliographical information, polycarboxylate water-reducer is very responsive to aggregate silt content, can affect the concrete slump and slump-loss, in the time that aggregate silt content exceedes 3%, also can produce great effect to intensity.The mechanism of action of polycarboxylate water-reducer and earth comprises adsorption and chain intercalation.Silt particle interlayer structure can adsorb water reducer molecule in a large number, causes water reducer after absorption, to be reduced for the part of disperseing cement granules in a large number by silt particle, dispersed variation.
Constantly deteriorated along with a large amount of uses of admixture and sand material quality, there are many problems in water reducer, mainly contain in concrete production application process:
1, polycarboxylate water-reducer is very responsive to earth.
In the time that sandstone silt content is higher, concrete mix poor fluidity, or simply do not flow.In order to make concrete mix meet pumping construction requirement, some units are multiplied the volume of admixture, and concrete production cost is increased greatly, affect production cost and the direct economic benefit of Concrete Enterprises; Some units adopts the way of adding water to solve the problem of concrete mix illiquidity, causes the actual water-cement ratio of concrete to become greatly, has a strong impact on concrete intensity.
2, with the bad adaptability of cement, flyash etc.
Along with high performance water reducing agent of polyocarboxy acid promoting the use of in different engineerings, also expose problems, wherein aggregate silt content is one of distinct issues the most on the impact of its water-reducing effect.
Experts and scholars have carried out a large amount of research to polycarboxylate water-reducer to silt content sensitive issue both at home and abroad.J. Plank etc. is artificial, the impurity such as clay contain complicated mineralogical composition, the entirety of polycarboxylate water-reducer or a part can be adsorbed onto between clay seam, reduce for disperseing the poly carboxylic acid molecular amounts of cement, thereby reduced the dispersion rate of polycarboxylate water-reducer to cement granules.Clay generally by silicate minerals at the earth's surface weathering form, contained mineralogical composition mainly comprises kaolinite, montmorillonite, illite etc., there is very big-difference in the clay component under different geological conditions.Polycarboxylate water-reducer joins in mortar architecture, cement minerals is by absorption polycarboxylate water-reducer molecules such as intermolecular forces, chemical bonding force, hydrogen bond, electrostatic attractions, low surface energy falls, in its chemical molecular structure, the negative ions such as carboxyl (COOH) mainly provide electrostatic repulsion, and polyoxyethylene groups side chain mainly plays sterically hindered effect.The water reducer adsorbing on cement particle surface is heap bunch shape more.While containing clay in cement slurry, the side chain of polycarboxylate water-reducer molecule can enter between clay seam by intercalation, and clay particle preferentially adsorbs a certain amount of water reducer, causes its dispersion effect to cement granules to reduce, and does not reach original water-reducing effect.
How to use a kind of admixture, in the situation that sandstone silt content is higher, both can improve the state of fresh concrete, can meet again the requirement such as intensity, weather resistance of maturing, suitable admixture again economically, becomes Yi Ge center topic in recent years.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part and a kind of polycarboxylate water-reducer that has slow-releasing and resistance to mud concurrently is provided; Meanwhile, the preparation method of polycarboxylate water-reducer of slow-releasing and resistance to mud and the application in concrete thereof are provided concurrently described in also providing in the present invention.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of the polycarboxylate water-reducer with slow-releasing and resistance to mud, said method comprising the steps of:
(1) in the 1000ml four-hole boiling flask that agitator, thermometer and reflux condensing tube are housed, add successively deionized water, molecular weight regulator, monomer A, monomers B, the large monomer C of polymkeric substance, polyethylene glycol methacrylate-styrene polymer and monomer D, after fully stirring, obtain mixed solution, wherein, the add-on of each component is:
Deionized water 300 ~ 500ml
Molecular weight regulator mole number is 0.5 ~ 5% of total monomer mole number
Monomer A 0.2 ~ 3mol
Monomers B 0.2 ~ 3mol
The large monomer C of polymkeric substance 0.2 ~ 2mol
Polyethylene glycol methacrylate-styrene polymer 0.3 ~ 2mol
Monomer D 0.5 ~ 3mol
Wherein total monomer mole number is the mole number sum of monomer A, monomers B, the large monomer C of polymkeric substance, polyethylene glycol methacrylate-styrene polymer and monomer D;
(2) mixed solution described in step (1) is warming up to 85-95 DEG C, drips the aqueous solution of initiator, time for adding is 2-3h, after dropwising, insulation reaction 2-4h, is cooled to 50-45 DEG C, adjusting pH is 5-7, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, in described step (1), the add-on of each component is:
Deionized water 400ml
Molecular weight regulator mole number is 3% of total monomer mole number
Monomer A 1mol
Monomers B 1mol
The large monomer C of polymkeric substance 0.5mol
Polyethylene glycol methacrylate-styrene polymer 0.5mol
Monomer D 1mol.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, the molecular weight regulator in described step (1) is at least one in 3-thiohydracrylic acid, 3-mercaprol, Thiovanic acid, mercaptoethanol, Virahol.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, in described step (1), monomer A is N,N-DMAA, CH
2=CH-CONR
1r
2in at least one, wherein: R
1, R
2for C
nh
2n+1, the integer that n is 1-4.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, in described step (1), monomers B is at least one in methacrylic acid, vinylformic acid, sodium allyl sulfonate.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, in described step (1), the large monomer C of polymkeric substance is one or both the multipolymer in allyl group polyethylene oxide, allyl group poly(propylene oxide).
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, the molecular weight of described allyl group polyethylene oxide is 300-10000, and the molecular weight of described allyl group poly(propylene oxide) is 300-10000.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, in described step (1), monomer D is Hydroxyethyl acrylate, CH
2=CR-COO (CH
2) at least one in n-OH, wherein: R is H or CH
3, the integer that n is 2-5.
As the preparation method's of the polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention preferred implementation, in described step (2), initiator is at least one in ammonium persulphate, Potassium Persulphate, benzoyl peroxide.
In addition, the present invention also provides a kind of polycarboxylate water-reducer with slow-releasing and resistance to mud that adopts method described above to prepare, there is slow release negatively charged ion, positively charged ion and non-ionic type small molecules, thereby reach the characteristic of slow release water reducer effect and mud particles is had repellency and reaches the characteristic that reduces the susceptibility to earth.The innovation key point of described polycarboxylate water-reducer is to utilize the principle of macromolecular structure design, introduces ester group and amide group in poly carboxylic acid molecular structure, and under the strong alkali environment of cement, ester group and amide group are hydrolyzed, Xu's playing function small molecules.Hydrolysis of ester group produces negatively charged ion (on main chain), and discharges non-ionic type small molecules, and the hydroxyl on these molecules and water generation hydrogen bond action delay the aquation of cement granules, increase cement slurry viscosity, the retention of the raising slump.And amide group is hydrolyzed, Xu emits with the carboxyl of negative charge with the amido of positive charge.Negatively charged ion carboxyl can be adsorbed in cement particle surface effectively, and repels clay, reaches resistance to mud effect.And the amine positively charged ion discharging is preferentially adsorbed on the mud particles surface with negative charge, earth is played to sealing process, reduce earth to the adsorption of Soxylat A 25-7 side chain and connected intercalation, greatly reduce the susceptibility of polycarboxylate water-reducer to earth.
Finally, the present invention also provides the application of the above-mentioned polycarboxylate water-reducer with slow-releasing and resistance to mud in concrete.The polycarboxylate water-reducer with slow-releasing and resistance to mud of the present invention is applied in concrete, and water-reducing rate is high, the slump through time retentivity good, insensitive to earth, to the strong adaptability such as cement, flyash.
A kind of polycarboxylate water-reducer with slow-releasing and resistance to mud provided by the invention, compared with prior art, has the following advantages: in (1) products molecule structure, contain unsettled ester group and amide group under cement strong alkali environment; (2) the amine positively charged ion that amide group hydrolysis produces has sealing process to the earth with negative charge, reaches resistance to mud effect; (3) the nonionic small molecules that hydrolysis of ester group discharges, due to the hydrogen bond action of water molecules, cement slurry is had to thickening effectiveness, and delays the aquation of cement granules, to the concrete mix slump through time maintain good result; (4) this product water-reducing rate is high, the slump through time retentivity good, high to the tolerance of earth, be the collapse protective poly-carboxylic acid water reducing agent of resistance to mud.
Embodiment
For the object, technical solutions and advantages of the present invention are better described, below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The present invention is a kind of embodiment of a kind of preparation method of the polycarboxylate water-reducer with slow-releasing and resistance to mud, and the present embodiment said method comprising the steps of:
(1) being equipped with in agitator, thermometer and the 1000ml four-hole boiling flask with reflux condensing tube, add successively 400ml deionized water, 0.12mol 3-thiohydracrylic acid (mole number be total monomer mole number 3%), 1mol N, N-DMAA, 1mol methacrylic acid, 0.5mol allyl group polyethylene oxide, 0.5mol polyethylene glycol methacrylate-styrene polymer and 1mol Hydroxyethyl acrylate, obtain mixed solution after fully stirring;
(2) above-mentioned mixed solution is warming up to 90 DEG C, drips the aqueous solution of ammonium persulphate, time for adding is 2.5h, and after dropwising, insulation reaction 3h, is cooled to 48 DEG C, and regulating pH is 6, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
Embodiment 2
The present invention is a kind of embodiment of a kind of preparation method of the polycarboxylate water-reducer with slow-releasing and resistance to mud, and the present embodiment said method comprising the steps of:
(1), being equipped with in agitator, thermometer and the 1000ml four-hole boiling flask with reflux condensing tube, add successively 300ml deionized water, 0.006 mol3-mercaprol (mole number be total monomer mole number 0.5%), 0.2mol CH
2=CH-CONR
1r
2(R
1for CH
3, R
2for C
4h
9), 0.2mol vinylformic acid, 0.2mol allyl group poly(propylene oxide), 0.5mol CH
2=CR-COO (CH
2) n-OH(R is H, n is 2) and 0.3mol polyethylene glycol methacrylate-styrene polymer, after fully stirring mixed solution;
(2) above-mentioned mixed solution is warming up to 85 DEG C, drips the aqueous solution of Potassium Persulphate, time for adding is 2h, and after dropwising, insulation reaction 2h, is cooled to 45 DEG C, and regulating pH is 5, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
Embodiment 3
The present invention is a kind of embodiment of a kind of preparation method of the polycarboxylate water-reducer with slow-releasing and resistance to mud, and the present embodiment said method comprising the steps of:
(1), being equipped with in agitator, thermometer and the 1000ml four-hole boiling flask with reflux condensing tube, add successively 500ml deionized water, 0.68mol Thiovanic acid (mole number be total monomer mole number 5%), 3mol CH
2=CH-CONR
1r
2(R
1for C
2h
5, R
2for C
3h
7), 3mol sodium allyl sulfonate, 2mol allyl group (epoxy ethane-epoxy propane) multipolymer, 3mol CH
2=CR-COO (CH
2) n-OH(R is CH
3, n is 5) and 2mol polyethylene glycol methacrylate-styrene polymer, after fully stirring, obtain mixed solution;
(2) above-mentioned mixed solution is warming up to 95 DEG C, drips the aqueous solution of benzoyl peroxide, time for adding is 3h, and after dropwising, insulation reaction 4h, is cooled to 50 DEG C, and regulating pH is 7, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
Embodiment 4
The present invention is a kind of embodiment of a kind of preparation method of the polycarboxylate water-reducer with slow-releasing and resistance to mud, and the present embodiment said method comprising the steps of:
(1), being equipped with in agitator, thermometer and the 1000ml four-hole boiling flask with reflux condensing tube, add successively 350ml deionized water, 0.13mol mercaptoethanol (mole number be total monomer mole number 5%), 0.5mol CH
2=CH-CONR
1r
2(R
1for CH
3, R
2for C
3h
7), 0.5mol methacrylic acid, 0.3mol allyl group polyethylene oxide, 0.8mol CH
2=CR-COO (CH
2) n-OH(R is CH
3, n is 3) and 0.4mol polyethylene glycol methacrylate-styrene polymer, after fully stirring, obtain mixed solution;
(2) above-mentioned mixed solution is warming up to 90 DEG C, drips the aqueous solution of ammonium persulphate, time for adding is 2.5h, and after dropwising, insulation reaction 3h, is cooled to 48 DEG C, and regulating pH is 6, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
Embodiment 5
The present invention is a kind of embodiment of a kind of preparation method of the polycarboxylate water-reducer with slow-releasing and resistance to mud, and the present embodiment said method comprising the steps of:
(1), being equipped with in agitator, thermometer and the 1000ml four-hole boiling flask with reflux condensing tube, add successively 450ml deionized water, 0.42mol Virahol (mole number be total monomer mole number 5%), 2mol CH
2=CH-CONR
1r
2(R
1for C
2h
5, R
2for C
4h
9), 2mol vinylformic acid, 1mol allyl group poly(propylene oxide), 2mol CH
2=CR-COO (CH
2) n-OH(R is CH
3, n is 4) and 1mol polyethylene glycol methacrylate-styrene polymer, after fully stirring, obtain mixed solution;
(2) above-mentioned mixed solution is warming up to 90 DEG C, drips the aqueous solution of Potassium Persulphate, time for adding is 2.5h, and after dropwising, insulation reaction 3h, is cooled to 48 DEG C, and regulating pH is 6, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
Test example 1
The present invention has the polycarboxylate water-reducer effect test of slow-releasing and resistance to mud, and the polycarboxylate water-reducer described in test example 1 with slow-releasing and resistance to mud adopts method described in embodiment 1 to be prepared from.
Test arranges control group and test group, and control group and test group are all the concrete that adds water reducer, and wherein, concrete is made up of the raw material of following mass fraction proportioning:
Cement: flyash: breeze: river sand: rubble: water=200: 90: 60: 800: 1080: 165.
The water reducer of control group adopts polyethers polycarboxylate water-reducer, and in molecule, not containing ester group and amide group, the composition of control group ratio is:
Cement: flyash: breeze: river sand: rubble: water: polyethers polycarboxylate water-reducer=200: 90: 60: 800: 1080: 165:7
Prepared by water reducer employing the method for the invention of test group has slow release positively charged ion, negatively charged ion and non-ionic small molecules and has the polycarboxylate water-reducer of resistance to mud effect, and the composition of test group ratio is:
Cement: flyash: breeze: river sand: rubble: water: polyethers polycarboxylate water-reducer: polycarboxylate water-reducer=200 with slow-releasing and resistance to mud: 90: 60: 800: 1080: 165:7 × (1-X): 7 × X, wherein: weight ratio X=has polycarboxylate water-reducer/(having polycarboxylate water-reducer+polyethers polycarboxylate water-reducer of slow-releasing and resistance to mud) × 100% of slow-releasing and resistance to mud, 0%<X≤100%.
Test group is divided into test group 1 ~ 4, and test group 1 ~ 4 is respectively:
The polycarboxylate water-reducer that test group 1 adopts the present invention to have slow-releasing and resistance to mud replaces control group 10%(part by weight) polyethers polycarboxylate water-reducer be the concrete that X=10% prepares;
The polycarboxylate water-reducer that test group 2 adopts the present invention to have slow-releasing and resistance to mud replaces control group 35%(part by weight) polyethers polycarboxylate water-reducer be the concrete that X=35% prepares;
The polycarboxylate water-reducer that test group 3 adopts the present invention to have slow-releasing and resistance to mud replaces control group 70%(part by weight) polyethers polycarboxylate water-reducer be the concrete that X=70% prepares;
The polycarboxylate water-reducer that test group 4 adopts the present invention to have slow-releasing and resistance to mud replaces control group 100%(part by weight) polyethers polycarboxylate water-reducer be the concrete that X=100% prepares.
Detect respectively the collapse water-reducing rate of time, slump-loss and water reducer of control group and the concrete guarantor of test group 1 ~ 4, result is as follows:
Control group, guarantor's time of collapsing of fresh concrete is 1 ~ 2h, and 2h slump-loss is 35%, and the water-reducing rate of water reducer is 18%;
Test group 1 is X=10%, and guarantor's time of collapsing of fresh concrete is 2 ~ 3h, and 2h slump-loss is that 15%, 3h slump-loss is 20%, and the water-reducing rate of water reducer is 23%;
Test group 2 is X=35%, and guarantor's time of collapsing of fresh concrete is 3 ~ 5h, and 2h slump-loss is 2-5%, and 5h slump-loss is 20-30%, and the water-reducing rate of water reducer is 25%;
Test group 3 is X=70%, and guarantor's time of collapsing of fresh concrete is 5 ~ 7h, and 2h slump-loss is 0-3%, and 5h slump-loss is 25%, and the water-reducing rate of water reducer is 25-30%;
Test group 4 is X=100%, and guarantor's time of collapsing of fresh concrete is 6 ~ 10h, and 2h slump-loss is that 0,5h slump-loss is that 8%, 8h slump-loss is 25%, and the water-reducing rate of water reducer is 30-35%.
From above result, along with the present invention has the raising of the polycarboxylate water-reducer add-on of slow-releasing and resistance to mud, concrete guarantor progressively extends the time of collapsing, and the water-reducing rate of water reducer improves 5-17%, and Slump Time losing of Large rate reduces 20-30%.In addition, for the concrete to high silt content (aggregate silt content 3%, 5%), compared with common polycarboxylate water-reducer, add the water reducer of identical volume, the water-reducing rate of water reducer of the present invention improves 5-20%, and 2h Slump Time losing of Large rate reduces 20-100%.
Last institute should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although the present invention is explained in detail with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a preparation method with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, said method comprising the steps of:
(1) in the 1000ml four-hole boiling flask that agitator, thermometer and reflux condensing tube are housed, add successively deionized water, molecular weight regulator, monomer A, monomers B, the large monomer C of polymkeric substance, polyethylene glycol methacrylate-styrene polymer and monomer D, after fully stirring, obtain mixed solution, wherein, the add-on of each component is:
Deionized water 300 ~ 500ml
Molecular weight regulator mole number is 0.5 ~ 5% of total monomer mole number
Monomer A 0.2 ~ 3mol
Monomers B 0.2 ~ 3mol
The large monomer C of polymkeric substance 0.2 ~ 2mol
Polyethylene glycol methacrylate-styrene polymer 0.3 ~ 2mol
Monomer D 0.5 ~ 3mol
Wherein total monomer mole number is the mole number sum of monomer A, monomers B, the large monomer C of polymkeric substance, polyethylene glycol methacrylate-styrene polymer and monomer D;
(2) mixed solution described in step (1) is warming up to 85-95 DEG C, drips the aqueous solution of initiator, time for adding is 2-3h, after dropwising, insulation reaction 2-4h, is cooled to 50-45 DEG C, adjusting pH is 5-7, must have the polycarboxylate water-reducer of slow-releasing and resistance to mud.
2. there is as claimed in claim 1 the preparation method of the polycarboxylate water-reducer of slow-releasing and resistance to mud, it is characterized in that, the molecular weight regulator in described step (1) is at least one in 3-thiohydracrylic acid, 3-mercaprol, Thiovanic acid, mercaptoethanol, Virahol.
3. the preparation method as claimed in claim 1 with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, in described step (1), monomer A is N,N-DMAA, CH
2=CH-CONR
1r
2in at least one, wherein: R
1, R
2for C
nh
2n+1, the integer that n is 1-4.
4. the preparation method as claimed in claim 1 with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, in described step (1), monomers B is at least one in methacrylic acid, vinylformic acid, sodium allyl sulfonate.
5. the preparation method as claimed in claim 1 with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, the large monomer C of polymkeric substance is one or both the multipolymer in allyl group polyethylene oxide, allyl group poly(propylene oxide) in described step (1).
6. the preparation method as claimed in claim 5 with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, the molecular weight of described allyl group polyethylene oxide is 300-10000, and the molecular weight of described allyl group poly(propylene oxide) is 300-10000.
7. the preparation method as claimed in claim 1 with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, in described step (1), monomer D is Hydroxyethyl acrylate, CH
2=CR-COO (CH
2) at least one in n-OH, wherein: R is H or CH
3, the integer that n is 2-5.
8. the preparation method as claimed in claim 1 with the polycarboxylate water-reducer of slow-releasing and resistance to mud, is characterized in that, in described step (2), initiator is at least one in ammonium persulphate, Potassium Persulphate, benzoyl peroxide.
An employing as arbitrary in claim 1-8 as described in the polycarboxylate water-reducer with slow-releasing and resistance to mud for preparing of method.
10. a polycarboxylate water-reducer as claimed in claim 9 with slow-releasing and the resistance to mud application in concrete.
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| CN105621930A (en) * | 2015-12-24 | 2016-06-01 | 湖南中岩建材科技有限公司 | Mud-resistant and low-sensitive water reducer |
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| CN104910389A (en) * | 2015-05-21 | 2015-09-16 | 南京理工大学 | Anti-soil hyperbranched dispersing agent and preparation method thereof |
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| CN105330795A (en) * | 2015-10-14 | 2016-02-17 | 广东红墙新材料股份有限公司 | Super early strength polycarboxylate water-reducer, and preparation method thereof |
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| CN106186787A (en) * | 2016-06-27 | 2016-12-07 | 浙江吉盛化学建材有限公司 | A kind of production method of water reducer |
| CN108440721A (en) * | 2018-04-27 | 2018-08-24 | 江苏百瑞吉新材料有限公司 | A kind of production method of high-performance water reducing agent |
| CN109503772A (en) * | 2018-09-10 | 2019-03-22 | 河北科讯新能源开发有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof |
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