CN107987235A - A kind of preparation method of low hydration heat crack resistance type polycarboxylate water-reducer - Google Patents
A kind of preparation method of low hydration heat crack resistance type polycarboxylate water-reducer Download PDFInfo
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- CN107987235A CN107987235A CN201711290313.5A CN201711290313A CN107987235A CN 107987235 A CN107987235 A CN 107987235A CN 201711290313 A CN201711290313 A CN 201711290313A CN 107987235 A CN107987235 A CN 107987235A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention discloses a kind of preparation method of low hydration heat crack resistance type polycarboxylate water-reducer, include the following steps：(1) acylated esterification；(2) monomer blend；(3) copolyreaction；(4) neutralization reaction.Contain ester group, phenyl and phosphate group in diminishing agent molecule made from the preparation method of the present invention, applied in concrete, hydrolyzed under basic conditions of the ester group in concrete, gradually discharge the carboxyl with diminishing and the hydroxy phenyl phosphate group with the reduction heat of hydration, hydration heat of concrete can be effectively reduced, extend the heat dissipation time, so as to can effectively prevent concrete cracking problem to a certain extent, the durability of concrete can be improved.Simultaneously because polyether lateral chain is connected with main chain by ester bond, water membrane can be formed in concrete surface, reduction concrete surface dehydration is too fast, effectively reduces the contraction of concrete, advantageously reduces the cracking of concrete.
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of low hydration heat crack resistance type polycarboxylate water-reducer
Preparation method.
Background technology
From the twenties in 19th century Portland cement come out since, concrete material with its practicality and cheap cost and
As indispensable material in civil engineering, the structures such as bridge, dam, highway, industry and civil buildings are widely used in
In.Polycarboxylate water-reducer is as new high-performance water reducing agent, with volume is low, water-reducing rate is high, slump-retaining good, contraction
Rate is small, it is opposite with cement and admixture adaptability preferably, a series of performance for protrusions such as enhancing effect is obvious, answer extensively at present
For in every engineering field.
With the quickening of concrete works project construction, China is increasingly carried for the durability of concrete and apparent requirement
High causes the major influence factors of distress in concrete to have unfreezing, the burn into steel bar corrosion of aggressive chemistries, temperature
Stress crack and alkali-aggregate reaction.In order to solve Durability of Concrete, our countries also take huge financial resources thing
Power, researchs and develops a kind of polycarboxylate water-reducer with effect of prestressed with reduction heat of hydration double properties, to improving concrete
Durability is very significant and value.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of low hydration heat crack resistance type polycarboxylate water-reducer
Preparation method.
Technical scheme is as follows：
A kind of preparation method of low hydration heat crack resistance type polycarboxylate water-reducer, includes the following steps：
(1) acylated esterification：By unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, molecular weight be 400~5000 it is poly-
Glycol monoethyl ether, compound A and polymerization inhibitor mixing, under nitrogen protection, are warming up to 63~86 DEG C, add catalyst, protect
Temperature 0.5~3.5h of reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, is down to room temperature, obtains after reaction
Acylated esterification products and the first mixture of unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid or unsaturation
Carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, the molar ratio of compound A are 5~20: 0.2~1.2: 0.2~1.2: 0.5~2, are urged
The dosage of agent is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.2~
4.3%, polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses
0.1~3.2%；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides for maleic anhydride, acrylic acid, methacrylic acid, fumaric acid,
At least one of itaconic acid, above-mentioned hydramine are at least one in monoethanolamine, diethanol amine, triethanolamine, triisopropanolamine
Kind, above-claimed cpd A is (2- hydroxy phenyls) phosphoric acid, (3- hydroxy phenyls) phosphoric acid, (4- hydroxy phenyls) phosphoric acid, (2- methylols
Phenyl) phosphoric acid, (3- hydroxymethyl phenyls) phosphoric acid, (4- hydroxymethyl phenyls) phosphoric acid, (2- hydroxyphenylmethyls) phosphoric acid, (3- hydroxy benzenes
Methyl) phosphoric acid, (4- hydroxyphenylmethyls) phosphoric acid, (2- methylols benzyl) phosphoric acid, (3- methylols benzyl) phosphoric acid, (4- hydroxyls
Methylbenzyl) at least one of phosphoric acid, above-mentioned catalyst is periodic acid, dinitrobenzoic acid, in ethylenediamine tetra-acetic acid
It is at least one；
(2) monomer blend：By the first mixture, unsaturated sulfonic acid salt made from step (1) with 180~220: 1~7 matter
Amount adds water and causes its dissolving than mixing, obtains copolymerized monomer mixture solution, above-mentioned unsaturated sulfonic acid salt is pi-allyl sulphur
In sour sodium, sodium styrene sulfonate, sodium vinyl sulfonate, methylpropene sodium sulfonate, 2- acrylamide-2-methylpro panesulfonic acids extremely
Few one kind；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~62 DEG C, time for adding be 0.2~6.5h, after being added dropwise insulation 0~
3.5h, obtains copolymerization product；The total amount of water used in the step and step (2) cause the mass concentration of the copolymerization product for 20~
80%, the dosage of initiator is 0.5~3.5% of the gross mass of solute in copolymerized monomer mixture solution, molecular weight regulator
Dosage be copolymerized monomer mixture solution in solute gross mass 0.2~3.0%；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to a kind of low water
Change hot crack resistance type polycarboxylate water-reducer.
In a preferred embodiment of the invention, the step (1) is：By unsaturated carboxylic acid or unsaturated carboxylic acid
Acid anhydride, hydramine, poly glycol monomethyl ether, compound A and polymerization inhibitor mixing, under nitrogen protection, are warming up to 65~85 DEG C, add
Catalyst, 0.5~3h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, is down to room after reaction
Temperature, obtains acylated esterification products and the first mixture of unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid
Or the molar ratio of unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A are 5~20: 1: 1: 0.5~2, catalyst
Dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, the 0.3~4.0% of compound A gross masses,
Polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.1~
3.0%；
In a preferred embodiment of the invention, the step (2) is：By the first mixture made from step (1),
Unsaturated sulfonic acid salt is mixed with 200: 1~5 mass ratio, and is added water and caused its dissolving, obtains copolymerized monomer mixture solution.
In a preferred embodiment of the invention, the step (3) is：By above-mentioned copolymerized monomer mixture solution with
Initiator solution and molecular weight regulator aqueous solution, which are instilled in water, to be reacted, and reaction temperature is 10~60 DEG C, time for adding
For 0.2~6.0h, 0~3.0h is kept the temperature after being added dropwise, obtains copolymerization product；The total amount of water causes used in the step and step (2)
The mass concentration of the copolymerization product is 20~70%, and the dosage of initiator is the gross mass of solute in copolymerized monomer mixture solution
0.5~3.0%, the dosage of the molecular weight regulator be the gross mass of solute in copolymerized monomer mixture solution 0.2~
2.0%.
It is further preferred that the polymerization inhibitor is at least one of hydroquinone, phenthazine and diphenylamines.
It is further preferred that the initiator triggers system or water-soluble azo initiator for water soluble, redox.
It is further preferred that the molecular weight regulator is thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, secondary phosphorus
At least one of sour sodium, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
The beneficial effects of the invention are as follows：
1st, preparation method of the invention by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and hydramine, poly glycol monomethyl ether,
Compound A is acylated esterification and prepares the unsaturated minor comonomer with amide group, the unsaturated small list with amino group at the same time
Body, the unsaturated polymeric monomer with polyether lateral chain and with phenyl ring and phosphate group unsaturation minor comonomer, then during with acylated being esterified
Excessive unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, the copolymerization of unsaturated sulfonic acid salt, introduce amide group, amino in the molecular structure
Group, phosphate group, carboxylic acid group, sulfonic acid group, amide group and polyether lateral chain and phenyl ring so that product have it is higher just
Beginning water-reducing rate.
2nd, ester group, phenyl and phosphate group are contained in diminishing agent molecule made from preparation method of the invention, applied to mixed
In solidifying soil, ester group gradually discharges the carboxyl with diminishing and with reducing water in the hydrolyzed under basic conditions of concrete
Change the hydroxy phenyl phosphate group of heat, hydration heat of concrete can be effectively reduced, extend the heat dissipation time, so as to a certain degree
On can effectively prevent concrete cracking problem, the durability of concrete can be improved.Simultaneously because polyether lateral chain is to pass through with main chain
Ester bond connection, water membrane can be formed in concrete surface, reduction concrete surface dehydration is too fast, effectively reduces concrete
Shrink, advantageously reduce the cracking of concrete.
3rd, phosphinylidyne-containing amine group in water-reducing agent molecular structure made from preparation method of the invention, applied in concrete, energy
The early strength of concrete is enough improved, and 28 days intensity is not influenced.
4th, preparation method of the invention is catalyzed by introducing effective catalyst so that acylated esterification temperature is relatively low, drop
Low energy consumption, has saved production cost, and double bond retention rate is higher, and the conversion ratio of product further improves, and can be lifted
The comprehensive performance of product.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
(1) acylated esterification：By 147.00g maleic anhydrides, 2.20g monoethanolamines, 29.00g (4- hydroxy phenyls) phosphorus
Poly glycol monomethyl ether, 2.00g hydroquinones and 2.00g the phenthazine mixing that acid, 100.00g molecular weight are 600, are protected in nitrogen
Under shield, 65 DEG C are warming up to, adds 2.00g periodic acid and 5.00g dinitrobenzoic acids, insulation reaction 2.0h is during which true with taking out
Method of the empty or logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing acylation esterification products and unreacted
First mixture of maleic anhydride；
(2) monomer blend：First mixture, 4.00g sodium styrene sulfonate made from 200.00g steps (1) are mixed, and
Add 70.00g water and cause its dissolving, obtain copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein hydrogen peroxide 1.60g, water
20.00g), aqueous ascorbic acid (wherein 0.40g, water 20.00g) and tertiary sodium phosphate (wherein tertiary sodium phosphate 2.00g, water
20.00g) instill in 60.00g water and reacted, reaction temperature is 30 DEG C, and time for adding 4.0h, keeps the temperature after being added dropwise
3.0h, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to the low hydration heat
Crack resistance type polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) acylated esterification：By 36.00g acrylic acid, 4300g methacrylic acids, 4.00g diethanol amine, 24.00g
(3- hydroxymethyl phenyls) phosphoric acid, poly glycol monomethyl ether, 1.00g hydroquinones and the 2.00g bis- that 100.00g molecular weight is 800
Aniline mixes, and under nitrogen protection, is warming up to 70 DEG C, adds 3.00g dinitrobenzoic acids and 3.00g ethylenediamine tetra-acetic acids,
Insulation reaction 3h, during which with vacuumizing or leading to method removing water of the nitrogen with water, is down to room temperature, obtains containing acyl after reaction
Change esterification products and unreacted acrylic acid, the first mixture of methacrylic acid；
(2) monomer blend：By the first mixture, 1.00g Sodium Allyl Sulfonate and 4.00 made from 200.00g steps (1)
Sodium vinyl sulfonate mixes, and adds 70.00g water and cause its dissolving, obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo diisobutyl amidine hydrochloric acid saline solution (wherein
Azo diisobutyl amidine hydrochloride 2.00g, water 40.00g) and sodium hypophosphite aqueous solution (wherein sodium hypophosphite 3.00g, water
20.00g) instill in 60.00g water and reacted, reaction temperature is 40 DEG C, and time for adding 4.0h, keeps the temperature after being added dropwise
2.0h, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to the low hydration heat
Crack resistance type polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) acylated esterification：By 58.00g acrylic acid, 23.00g fumaric acid, 3.00g diethanol amine, 14.00g (3- hydroxyls
Base phenyl) poly glycol monomethyl ether, the 3.00g of phosphoric acid, 4.00g (4- hydroxyphenylmethyls) phosphoric acid, 100.00g molecular weight for 1000
Hydroquinone and the mixing of 1.00g phenthazine, under nitrogen protection, are warming up to 75 DEG C, add 2.00g periodic acid and 2.00g second
Ethylenediamine tetraacetic acid (EDTA), insulation reaction 2.0h, during which with vacuumizing or leading to method removing water of the nitrogen with water, is down to room after reaction
Temperature, obtains containing acylated esterification products and unreacted acrylic acid, the first mixture of fumaric acid；
(2) monomer blend：By the first mixture, 2.00g sodium styrene sulfonate and 1.00g made from 200.00g steps (1)
Methylpropene sodium sulfonate mixes, and adds 70.00g water and cause its dissolving, obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein azo two
Cyanopentanoic acid 3.00g, water 40.00g) and trisodium phosphate aqueous solution (wherein tertiary sodium phosphate 1.00g, water 20.00g) instillation 60.00g
Reacted in water, reaction temperature is 45 DEG C, and time for adding 3.0h, keeps the temperature 1.0h after being added dropwise, obtain copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to the low hydration heat
Crack resistance type polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) acylated esterification：By 98.00g maleic anhydrides, 43.00g itaconic acids, 4.50g triethanolamines, 15.00g (3-
Hydroxy phenyl) phosphoric acid, 100.00g molecular weight be 1200 poly glycol monomethyl ether, 2.00g hydroquinones and 3.00g phenthazine
Mixing, under nitrogen protection, is warming up to 80 DEG C, adds 1.00g periodic acid and 2.00g dinitrobenzoic acids, insulation reaction
1.0h, during which with vacuumizing or leading to method removing water of the nitrogen with water, is down to room temperature, obtains being esterified containing acylated after reaction
Product and unreacted maleic anhydride, the first mixture of itaconic acid；
(2) monomer blend：By the first mixture, 1.00g Sodium Allyl Sulfonate and 1.00g made from 200.00g steps (1)
Sodium styrene sulfonate, and add 70.00g water and cause its dissolving, obtain copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 2.20g, water
20.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 1.80g, water 20.00g), aqueous ascorbic acid are (wherein, anti-bad
Hematic acid 0.80, water 20.00g) instill in 60.00g water and reacted, reaction temperature is 50 DEG C, and time for adding 5.0h, drips
5.0h is kept the temperature after finishing, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to the low hydration heat
Crack resistance type polycarboxylate water-reducer PCE-4.
Embodiment 5
(1) acylated esterification：By 14.00g acrylic acid, 35.00g methacrylic acids, 1.20g diethanol amine, 9.00g
(4- hydroxyphenylmethyls) phosphoric acid, poly glycol monomethyl ether, 3.00g hydroquinones and the 3.00g bis- that 100.00g molecular weight is 2000
Aniline mixes, and under nitrogen protection, is warming up to 85 DEG C, adds 2.00g periodic acid and 3.00g dinitrobenzoic acids, and insulation is anti-
1.5h is answered, during which with vacuumizing or leading to method removing water of the nitrogen with water, room temperature is down to after reaction, obtains containing acylated ester
Change product and unreacted acrylic acid, the first mixture of methacrylic acid；
(2) monomer blend：By the first mixture, 2.00g Sodium Allyl Sulfonate and 2.00g made from 200.00g steps (1)
Sodium styrene sulfonate mixes, and adds 70.0 water and cause its dissolving, obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein, azo two
Cyanopentanoic acid 2.00g, water 40.00g), sodium hypophosphite aqueous solution (wherein, sodium hypophosphite 3.00g, water 20.00g) instill 60.00g
Reacted in water, reaction temperature is 60 DEG C, and time for adding 1.5h, keeps the temperature 2.0h after being added dropwise, obtain copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to the low hydration heat
Crack resistance type polycarboxylate water-reducer PCE-5.
Embodiment 6
(1) acylated esterification：By 20.00g maleic anhydrides, 36.00g itaconic acids, 1.30g triethanolamines, 3.00g (4-
Hydroxy phenyl) phosphoric acid, 5.00g (4- methylols benzyl) phosphoric acid, 100.00g molecular weight be 2400 poly glycol monomethyl ether,
1.00g phenthazine and the mixing of 1.00g diphenylamines, under nitrogen protection, are warming up to 80 DEG C, add 2.00g ethylenediamine tetra-acetic acids
With 1.00g dinitrobenzoic acids, insulation reaction 2.0h, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is tied
Room temperature is down to after beam, is obtained containing acylated esterification products and unreacted maleic anhydride, the first mixture of itaconic acid；
(2) monomer blend：By the first mixture, 1.00g Sodium Allyl Sulfonate and 2.00g made from 200.00g steps (1)
Sodium vinyl sulfonate mixes, and adds 70.00g water and cause its dissolving, obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo diisobutyl amidine hydrochloric acid saline solution (wherein,
Azo diisobutyl amidine hydrochloride 4.00g, water 40.00g), aqueous sodium acetate solution (wherein, sodium acetate 2.00g, water 20.00g) drop
Enter and reacted in 60.00g water, reaction temperature is 20 DEG C, and time for adding 6.0h, 1.0h is kept the temperature after being added dropwise, and must be copolymerized
Product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to the low hydration heat
Crack resistance type polycarboxylate water-reducer PCE-6.
According to GB/T8076-2008 to the low hydration heat crack resistance type polycarboxylate water-reducer obtained by embodiment 1 to embodiment 6
Tested, (relative to cement consumption, it is equal that water-reducing rate is above 25%, 1d compressive strength rates when the solid volume of folding is 0.12wt%
140%, 28d shrinkage ratios, which are all higher than, more than 180%, 28d compressive strength rates is respectively less than 90%, concrete 28d shrinking percentages are smaller,
The effectively volume stability of lifting concrete, reduces the cracking of concrete, and product effect of prestressed is preferable.
Using China Resources P.O42.5 Portland cements, concrete mix is：Cement 300kg/m3, flyash 80kg/
M3, miberal powder 80kg/m3, sand 735kg/m3, stone 1040kg/m3, water 165kg/m3, it is made to embodiment 6 to embodiment 1 respectively
The concrete flowability stabilizer and commercially available polycarboxylate water-reducer (PCE) obtained carries out performance survey according to the solid volume 0.12% of folding
Examination, the heat of hydration test result of different additives are as shown in table 1.
The heat of hydration test result of the different additives of table 1
| Test number | Additive species | TL0(mm) | TL2(mm) | tmax/h | Tmax/℃ |
| 1 | PCE | 200 | 150 | 16 | 73 |
| 2 | PCE-1 | 210 | 210 | 28 | 61 |
| 3 | PCE-2 | 210 | 205 | 27 | 60 |
| 4 | PCE-3 | 210 | 200 | 29 | 59 |
| 5 | PCE-4 | 205 | 200 | 28 | 61 |
| 6 | PCE-5 | 210 | 205 | 27 | 61 |
| 7 | PCE-6 | 215 | 215 | 30 | 58 |
tmax：Cement slurry hydration heat reaches corresponding time during maximum temperature；
Tmax：Cement slurry hydration heat reaches corresponding temperature during maximum temperature；
As it can be seen from table 1 the embodiment of this patent synthesis contrasts commercially available polycarboxylate water-reducer (PCE, Control Measures for Concrete Slump
Degree holding capacity is more preferable, and hydration heat speed is slower, and the heat of hydration is considerably lower.
Those of ordinary skill in the art understand, when the present invention is raw materials used and parameter changes in following ranges, still can
Same as the previously described embodiments or similar technique effect is accessed, still falls within protection scope of the present invention：
A kind of preparation method of low hydration heat crack resistance type polycarboxylate water-reducer, includes the following steps：
(1) acylated esterification：By unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, molecular weight be 400~5000 it is poly-
Glycol monoethyl ether, compound A and polymerization inhibitor mixing, under nitrogen protection, are warming up to 63~86 DEG C (preferably 65~85 DEG C), then
Add catalyst, 0.5~3.5h of insulation reaction (preferably 0.5~3h), is during which removed with vacuumizing or lead to method of the nitrogen with water
Water, is down to room temperature after reaction, obtains the of acylated esterification products and unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides
One mixture, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, the molar ratio of compound A are 5~20:
0.2~1.2: 0.2~1.2: 0.5~2 (preferably 5~20: 1: 1: 0.5~2), the dosage of catalyst is unsaturated carboxylic acid or insatiable hunger
With carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.2~4.3% (preferably 0.3~4.0%), polymerization inhibitor
Dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, the 0.1~3.2% of compound A gross masses
(preferably 0.1~3.0%)；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are maleic anhydride, acrylic acid, methacrylic acid, richness
Horse acid, at least one of itaconic acid, above-mentioned hydramine is monoethanolamine, in diethanol amine, triethanolamine, triisopropanolamine extremely
Few one kind, above-claimed cpd A is (2- hydroxy phenyls) phosphoric acid, (3- hydroxy phenyls) phosphoric acid, (4- hydroxy phenyls) phosphoric acid, (2- hydroxyls
Aminomethyl phenyl) phosphoric acid, (3- hydroxymethyl phenyls) phosphoric acid, (4- hydroxymethyl phenyls) phosphoric acid, (2- hydroxyphenylmethyls) phosphoric acid, (3- hydroxyls
Base benzyl) phosphoric acid, (4- hydroxyphenylmethyls) phosphoric acid, (2- methylols benzyl) phosphoric acid, (3- methylols benzyl) phosphoric acid,
At least one of (4- methylols benzyl) phosphoric acid, above-mentioned catalyst are periodic acid, dinitrobenzoic acid, ethylenediamine tetra-acetic acid
At least one of；
(2) monomer blend：By the first mixture, unsaturated sulfonic acid salt made from step (1) with 180~220: 1~7 matter
Amount adds water and causes its dissolving than mixing (preferably 200: 1~5), obtains copolymerized monomer mixture solution, above-mentioned unsaturation sulphur
Hydrochlorate is Sodium Allyl Sulfonate, sodium styrene sulfonate, sodium vinyl sulfonate, methylpropene sodium sulfonate, 2- acrylamido -2- first
At least one of base propane sulfonic acid；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill in water and reacted, reaction temperature is 10~62 DEG C (preferably 10~60 DEG C), and time for adding is 0.2~6.5h (preferably 0.2
~6.0h), 0~3.5h (preferably 0~3.0h) is kept the temperature after being added dropwise, obtains copolymerization product；Water used in the step and step (2)
Total amount make it that the mass concentration of the copolymerization product is 20~80% (preferably 20~70%), and the dosage of initiator is mixed for comonomer
0.5~3.5% (preferably 0.5~3.0%) of the gross mass of solute in polymer solution, the dosage of molecular weight regulator are single for copolymerization
0.2~3.0% (preferably 0.2~2.0%) of the gross mass of solute in body mixture solution；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to a kind of low water
Change hot crack resistance type polycarboxylate water-reducer.
The polymerization inhibitor is at least one of hydroquinone, phenthazine and diphenylamines.The initiator is water-soluble oxygen
Change reduction initiating system or water-soluble azo initiator.The molecular weight regulator is thioacetic acid, mercaptopropionic acid, sulfydryl second
At least one of alcohol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (7)
- A kind of 1. preparation method of low hydration heat crack resistance type polycarboxylate water-reducer, it is characterised in that：Include the following steps：(1) acylated esterification：By unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, the poly- second two that molecular weight is 400~5000 Alcohol monomethyl ether, compound A and polymerization inhibitor mixing, under nitrogen protection, are warming up to 63~86 DEG C, add catalyst, and insulation is anti- 0.5~3.5h is answered, during which with vacuumizing or leading to method removing water of the nitrogen with water, room temperature is down to after reaction, is acylated First mixture of esterification products and unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid or unsaturated carboxylic acid Acid anhydride, hydramine, poly glycol monomethyl ether, the molar ratio of compound A are 5~20: 0.2~1.2: 0.2~1.2: 0.5~2, catalyst Dosage be unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.2~ 4.3%, polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.1~3.2%；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides for maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, At least one of itaconic acid, above-mentioned hydramine are at least one in monoethanolamine, diethanol amine, triethanolamine, triisopropanolamine Kind, above-claimed cpd A is (2- hydroxy phenyls) phosphoric acid, (3- hydroxy phenyls) phosphoric acid, (4- hydroxy phenyls) phosphoric acid, (2- methylols Phenyl) phosphoric acid, (3- hydroxymethyl phenyls) phosphoric acid, (4- hydroxymethyl phenyls) phosphoric acid, (2- hydroxyphenylmethyls) phosphoric acid, (3- hydroxy benzenes Methyl) phosphoric acid, (4- hydroxyphenylmethyls) phosphoric acid, (2- methylols benzyl) phosphoric acid, (3- methylols benzyl) phosphoric acid, (4- hydroxyls Methylbenzyl) at least one of phosphoric acid, above-mentioned catalyst is periodic acid, dinitrobenzoic acid, in ethylenediamine tetra-acetic acid It is at least one；(2) monomer blend：By the first mixture, unsaturated sulfonic acid salt made from step (1) with 180~220: 1~7 mass ratio Mixing, and add water and cause its dissolving, copolymerized monomer mixture solution is obtained, above-mentioned unsaturated sulfonic acid salt is allyl sulphonic acid In sodium, sodium styrene sulfonate, sodium vinyl sulfonate, methylpropene sodium sulfonate, 2- acrylamide-2-methylpro panesulfonic acids at least It is a kind of；(3) copolyreaction：Above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled Reacted in water, reaction temperature is 10~62 DEG C, and time for adding is 0.2~6.5h, and 0~3.5h is kept the temperature after being added dropwise, is obtained Copolymerization product；The total amount of water used in the step and step (2) make it that the mass concentration of the copolymerization product is 20~80%, initiator Dosage be 0.5~3.5% of the gross mass of solute in copolymerized monomer mixture solution, the dosage of molecular weight regulator is copolymerization The 0.2~3.0% of the gross mass of solute in monomer mixture solution；(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7, up to a kind of low hydration heat Crack resistance type polycarboxylate water-reducer.
- 2. preparation method as claimed in claim 1, it is characterised in that：The step (1) is：By unsaturated carboxylic acid or unsaturation Carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A and polymerization inhibitor mixing, under nitrogen protection, are warming up to 65~85 DEG C, then Catalyst is added, 0.5~3h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, drops after reaction To room temperature, acylated esterification products and the first mixture of unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are obtained, it is unsaturated Carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, the molar ratio of compound A are 5~20: 1: 1: 0.5~2, catalysis The dosage of agent is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.3~ 4.0%, polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydramine, poly glycol monomethyl ether, compound A gross masses 0.1~3.0%.
- 3. preparation method as claimed in claim 1, it is characterised in that：The step (2) is：By first made from step (1) Mixture, unsaturated sulfonic acid salt are mixed with 200: 1~5 mass ratio, and add water and cause its dissolving, obtain comonomer mixing Thing solution.
- 4. preparation method as claimed in claim 1, it is characterised in that：The step (3) is：By above-mentioned copolymerized monomer mixture Solution is instilled in water with initiator solution and molecular weight regulator aqueous solution to be reacted, and reaction temperature is 10~60 DEG C, drop It is 0.2~6.0h between added-time, 0~3.0h is kept the temperature after being added dropwise, obtains copolymerization product；Water is total used in the step and step (2) For amount so that the mass concentration of the copolymerization product is 20~70%, the dosage of initiator is solute in copolymerized monomer mixture solution The 0.5~3.0% of gross mass, the dosage of the molecular weight regulator is the gross mass of solute in copolymerized monomer mixture solution 0.2~2.0%.
- 5. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The polymerization inhibitor is to benzene At least one of diphenol, phenthazine and diphenylamines.
- 6. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The initiator is water-soluble Property redox initiation system or water-soluble azo initiator.
- 7. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The molecular weight regulator For thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan At least one of.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108864389A (en) * | 2018-07-27 | 2018-11-23 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type sulfamate water reducer |
| CN110451839A (en) * | 2019-08-20 | 2019-11-15 | 重庆腾治科技有限公司 | A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application |
| WO2020001169A1 (en) * | 2018-06-26 | 2020-01-02 | 科之杰新材料集团有限公司 | Preparation method for retarding ether type polycarboxylic acid water reducing agent |
| CN112708054A (en) * | 2020-10-30 | 2021-04-27 | 科之杰新材料集团河南有限公司 | Polycarboxylate superplasticizer for concrete member and preparation method thereof |
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| CN107200817A (en) * | 2017-07-07 | 2017-09-26 | 科之杰新材料集团有限公司 | A kind of preparation method of stable type concrete slump controlling agent |
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| CN107200817A (en) * | 2017-07-07 | 2017-09-26 | 科之杰新材料集团有限公司 | A kind of preparation method of stable type concrete slump controlling agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020001169A1 (en) * | 2018-06-26 | 2020-01-02 | 科之杰新材料集团有限公司 | Preparation method for retarding ether type polycarboxylic acid water reducing agent |
| CN108864389A (en) * | 2018-07-27 | 2018-11-23 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type sulfamate water reducer |
| CN108864389B (en) * | 2018-07-27 | 2020-09-04 | 科之杰新材料集团有限公司 | Preparation method of viscosity-reducing sulfamate water reducer |
| CN110451839A (en) * | 2019-08-20 | 2019-11-15 | 重庆腾治科技有限公司 | A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN112708054A (en) * | 2020-10-30 | 2021-04-27 | 科之杰新材料集团河南有限公司 | Polycarboxylate superplasticizer for concrete member and preparation method thereof |
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