CN108623745A - A kind of phosphorous polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of phosphorous polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN108623745A CN108623745A CN201810586582.4A CN201810586582A CN108623745A CN 108623745 A CN108623745 A CN 108623745A CN 201810586582 A CN201810586582 A CN 201810586582A CN 108623745 A CN108623745 A CN 108623745A
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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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
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- C04B24/246—Phosphorus-containing polymers 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 phosphorous polycarboxylate water-reducer and preparation method thereof, molecular weight is 10000~150000, and its structural formula is as follows：
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of phosphorous polycarboxylate water-reducer and its preparation side
Method.
Background technology
Polycarboxylate water-reducer is as novel high-performance water reducing agent, with volume is low, water-reducing rate is high, slump-retaining
It is good, shrinking percentage is small, it is opposite with cement and admixture adaptability preferably, a series of enhancing effect performances outstanding such as obviously.Meanwhile
Production process environmental protection, is widely used at present in every engineering field.But due to market of real estate and infrastructure
High speed development is built, a large amount of engineering construction consumes the cement of flood tide, sandstone, exacerbates the nervous office of sand and stone resources supply
Face, the natural sand in many areas in the whole nation, stone resource are increasingly deficient, and supply falls short of demand for sandstone material, causes sandstone material extremely unstable
And sandstone clay content is high and unstable, polycarboxylate water-reducer is applied to concrete, water-reducing rate deficiency occurs, guarantor collapse it is bad, it is quick
Perceptual problem becomes increasingly conspicuous.Therefore, a kind of high diminishing, high-thin arch dam are developed, and is anticipated to the insensitive water-reducing agent of material clay content
Justice is great.
Invention content
It is an object of the invention to overcome prior art defect, a kind of phosphorous polycarboxylate water-reducer is provided.
Another object of the present invention is to provide the preparation methods of above-mentioned phosphorous polycarboxylate water-reducer.
Technical scheme is as follows：
A kind of phosphorous polycarboxylate water-reducer, molecular weight is 10000~150000, and its structural formula is as follows：
Wherein, R1For H or CH3, R2For the alkyl of 1~4 carbon, R3For empty or 1~4 carbon alkyl, R4For sky or 1~4
The alkyl of a carbon, R5For H or COOM, R6For H or CH3, R7For H or COOM, R8For H or CH3, R9For empty or 1~4 carbon alkane
Base, R10For the naphthalene nucleus for having there are one alkyl carboxylate's substituent group, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring
For ortho position, meta or para position.
Above-mentioned phosphorous polycarboxylate water-reducer preparation method, includes the following steps：
(1) first esterification：Insatiable hunger polyethers and the first compound are mixed, under nitrogen protection, are warming up to 70~90
DEG C, catalyst is added, 0.5~3.0h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is tied
It is down to room temperature after beam, obtains the first mixture containing esterification products and unreacted insatiable hunger polyethers；Above-mentioned insatiable hunger polyethers is point
The allyl polyglycol, 3- methyl -3- butene-1s-polyethylene glycol, 2- methacrylic polyethylene glycol that son amount is 600~5000
At least one of；The structural formula of above-mentioned first compound is as follows：
(2) second esterifications：Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydroxyl naphthalene-carboxylic acid and polymerization inhibitor are mixed,
Under nitrogen protection, 90~120 DEG C are warming up to, adds catalyst, 0.5~3.0h of insulation reaction, during which with vacuumizing or lead to nitrogen
Method of the gas with water removes water, is down to room temperature after reaction, obtain containing esterification products and unreacted unsaturated carboxylic acid or
Second mixture of unsaturated carboxylic acid anhydrides；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are acrylic acid, methacrylic acid, Malaysia
At least one of acid, maleic anhydride；Above-mentioned hydroxyl naphthalene phosphoric acid is -4 phosphoric acid of 1- hydroxyl naphthalenes, -5 phosphoric acid of 1- hydroxyl naphthalenes, 1- hydroxyls
- 6 phosphoric acid of naphthalene, -7 phosphoric acid of 1- hydroxyl naphthalenes, -4 phosphoric acid of 2 hydroxy naphthalene, -5 phosphoric acid of 2 hydroxy naphthalene, -6 phosphoric acid of 2 hydroxy naphthalene, 2- hydroxyls
- 7 phosphoric acid of naphthalene, -4 phosphoric acid of 1- methylols naphthalene, -5 phosphoric acid of 1- methylols naphthalene, -6 phosphoric acid of 1- methylols naphthalene, -7 phosphoric acid of 1- methylols naphthalene,
- 4 phosphoric acid of 2- methylols naphthalene, -5 phosphoric acid of 2- methylols naphthalene, -6 phosphoric acid of 2- methylols naphthalene, -7 phosphoric acid of 2- methylols naphthalene, 1- hydroxyl naphthalenes -
4 methyl acid phosphates, -5 methyl acid phosphate of 1- hydroxyl naphthalenes, -6 methyl acid phosphate of 1- hydroxyl naphthalenes, -7 methyl acid phosphate of 1- hydroxyl naphthalenes, 2 hydroxy naphthalene -4
Methyl acid phosphate, -5 methyl acid phosphate of 2 hydroxy naphthalene, -6 methyl acid phosphate of 2 hydroxy naphthalene, -7 methyl acid phosphate of 2 hydroxy naphthalene, 1- methylols naphthalene -
4 methyl acid phosphates, -5 methyl acid phosphate of 1- methylols naphthalene, -6 methyl acid phosphate of 1- methylols naphthalene, -7 methyl acid phosphate of 1- methylols naphthalene, 2- hydroxyls
- 4 methyl acid phosphate of methyl naphthalene, -5 methyl acid phosphate of 2- methylols naphthalene, -6 methyl acid phosphate of 2- methylols naphthalene, -7 methyl phosphorus of 2- methylols naphthalene
At least one of acid：
(3) monomer blend：By the second mixture made from the first mixture made from step (1) and step (2) with 100: 6
~18 mass ratio mixing, and water is added and makes its dissolving, obtain copolymerized monomer mixture solution；
(4) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~60 DEG C, time for adding be 0.2~6.0h, after being added dropwise keep the temperature 0~
3.0h obtains copolymerization product；
(5) neutralization reaction：It is phosphorous to get described one kind that the alkali of copolymerization product made from step (3) is adjusted into pH to 5~7
Polycarboxylate water-reducer.
In a preferred embodiment of the invention, in the step (1), the insatiable hunger polyethers and the first compound
Molar ratio is 1~1.5: 1, and the dosage of catalyst is the 0.05~0.3% of insatiable hunger polyethers and the first compound gross mass.
In a preferred embodiment of the invention, in the step (2), the unsaturated carboxylic acid or unsaturated carboxylic acid
The molar ratio of acid anhydride and hydroxyl naphthalene-carboxylic acid is 2~7: 1, and the dosage of the catalyst is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and hydroxyl
The 0.03~0.3% of base naphthalene-carboxylic acid gross mass；The polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and hydroxyl naphthalene
The 0.2~3.0%% of carboxylic acid gross mass.
In a preferred embodiment of the invention, the total amount of water used in the step (3) and step (4) makes described
The mass concentration of copolymerization product is 20~70%, and the dosage of the initiator is solute in the copolymerized monomer mixture solution
The 0.5~3.0% of gross mass, the dosage of the molecular weight regulator are total matter of solute in the copolymerized monomer mixture solution
The 0.2~2.0% of amount.
It is further preferred that the catalyst is mellitic acid, at least one of nitrogen sulphur side acid and trinitrobenzene sulfonic acid.
It is further preferred that the polymerization inhibitor is at least one of hydroquinone, phenthazine and diphenylamines.
It is further preferred that the initiator, which is water soluble, redox, causes system or water-soluble azo initiator.
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：
1, the present invention by unsaturated polyether monomer and the esterification products of the first compound by being used for polycarboxylate water-reducer
The branch terminals synthesized in polycarboxylate water-reducer molecule introduce phenyl ring and phosphoric acid based structures, and benzene ring structure makes polycarboxylic acids diminishing
The space steric effect of agent molecule branch is enhanced, and phosphoric acid based structures make polycarboxylate water-reducer molecule branch not only have
Space steric effect also has electrostatic repulsive force so that the polycarboxylate water-reducer water-reducing rate higher of preparation.
2, the present invention by the esterification products of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and hydroxyl naphthalene phosphoric acid by being used for poly- carboxylic
The synthesis of sour water-reducing agent introduces naphthalene phosphoric acid side group on the main chain of polycarboxylate water-reducer molecule, changes polycarboxylate water-reducer and exists
Cement, mud, the adsorption effect on mountain flour so that the polycarboxylate water-reducer of preparation has to containing mud and powder containing quantity in aggregate
The low effect of sensibility.
3, the ester group structure in polycarboxylate water-reducer of the invention can also be hydrolyzed gradually under the alkaline environment of concrete releases
Discharge section has the carboxylic acid group of water-reducing effect so that the polycarboxylate water-reducer of preparation also there is certain guarantor to collapse effect.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
The molecular weight of phosphorous polycarboxylate water-reducer obtained by following embodiments is 10000~150000, and its structural formula
It is as follows：
Wherein, R1For H or CH3, R2For the alkyl of 1~4 carbon, R3For empty or 1~4 carbon alkyl, R4For sky or 1~4
The alkyl of a carbon, R5For H or COOM, R6For H or CH3, R7For H or COOM, R8For H or CH3, R9For empty or 1~4 carbon alkane
Base, R10For the naphthalene nucleus for having there are one alkyl carboxylate's substituent group, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring
For ortho position, meta or para position.
Embodiment 1
(1) first esterification：Allyl polyglycol and 100.00g that 600.00g molecular weight is 1000 are faced into carboxyl
Benzenephosphonic acid mixes, and under nitrogen protection, is warming up to 75 DEG C, adds 0.38g mellitic acids, insulation reaction 2.0h, during which with pumping
The method of vacuum or logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted alkene
First mixture of propyl polyethylene glycol.
(2) second esterifications：75.00g acrylic acid, -4 phosphoric acid of 100.00g1- hydroxyl naphthalenes and 1.80g hydroquinones are mixed
It closes, under nitrogen protection, is warming up to 105 DEG C, add 0.15g mellitic acids, insulation reaction 2.0h, during which with vacuumizing or lead to
Method of the nitrogen with water removes water, is down to room temperature after reaction, obtains the containing esterification products and unreacted acrylic acid
Two mixtures；
(3) monomer blend：It will be second made from the first mixture made from 100.00g steps (1), 11.00g steps (2)
Mixture mixes, and 40.00g water is added and makes its dissolving, obtains copolymerized monomer mixture solution；
(4) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein hydrogen peroxide 0.90g, water
10.00g), aqueous ascorbic acid (wherein 0.20g, water 10.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 0.70g,
Water 10.00g) it instills in 40.00g water and is reacted, reaction temperature is 40 DEG C, and time for adding 3.0h is kept the temperature after being added dropwise
1.5h obtains copolymerization product；
(5) neutralization reaction：The alkali of copolymerization product made from step (4) is adjusted into pH to 5~7 to get the phosphorous poly- carboxylic
Sour water-reducing agent PCE-1.
Embodiment 2
(1) first esterification：By 1050.00g molecular weight be 2000 3- methyl -3- butene-1s-polyethylene glycol and
Carboxymethyl benzenephosphonic acid mixes between 100.00g, under nitrogen protection, is warming up to 75 DEG C, adds 1.50g nitrogen sulphur side acid, and heat preservation 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 producing containing esterification
First mixture of object and unreacted 3- methyl -3- butene-1s-polyethylene glycol.
(2) second esterifications：By 88.00g methacrylic acids, -5 phosphoric acid of 100.00g1- hydroxyl naphthalenes and 1.60g phenthazine
Mixing, under nitrogen protection, is warming up to 100 DEG C, adds 0.30g nitrogen sulphur side acid, insulation reaction 2.0h, during which with vacuumizing or
Logical method of the nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted metering system
Second mixture of acid；
(3) monomer blend：It will be second made from the first mixture made from 100.00g steps (1), 13.00g steps (2)
Mixture mixes, and 40.00g water is added and makes its dissolving, obtains copolymerized monomer mixture solution；
(4) copolyreaction：(wherein by above-mentioned copolymerized monomer mixture solution, azo diisobutyl amidine hydrochloric acid saline solution
Azo diisobutyl amidine hydrochloride 1.20g, water 10.00g) and sodium hypophosphite aqueous solution (wherein sodium hypophosphite 0.90g, water
It 10.00g) instills in 40.00g water and is reacted, reaction temperature is 45 DEG C, and time for adding 2.0h is kept the temperature after being added dropwise
1.0h obtains copolymerization product；
(5) neutralization reaction：The alkali of copolymerization product made from step (4) is adjusted into pH to 5~7 to get the phosphorous poly- carboxylic
Sour water-reducing agent PCE-2.
Embodiment 3
(1) first esterification：The 2- methacrylics polyethylene glycol and 100.00g for being 2400 by 1140.00g molecular weight
Carboxyethyl benzenephosphonic acid is mixed, under nitrogen protection, 85 DEG C is warming up to, adds 2.80g trinitrobenzene sulfonic acid, insulation reaction
1.5h is down to room temperature, obtains containing esterification products after reaction during which with vacuumizing or leading to method removing water of the nitrogen with water
With the first mixture of unreacted 2- methacrylics polyethylene glycol.
(2) second esterifications：165.00g maleic acids, -6 phosphoric acid of 100.00g1- hydroxyl naphthalenes and 1.80g diphenylamines are mixed
It closes, under nitrogen protection, is warming up to 110 DEG C, add 0.60g trinitrobenzene sulfonic acid, insulation reaction 2.5h, during which with vacuumizing
Or method of the logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted maleic acid
The second mixture；
(3) monomer blend：It will be second made from the first mixture made from 100.00g steps (1), 15.00g steps (2)
Mixture mixes, and 40.00g water is added and makes its dissolving, obtains copolymerized monomer mixture solution；
(4) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein azo two
Cyanopentanoic acid 2.20g, water 10.00g) and trisodium phosphate aqueous solution (wherein tertiary sodium phosphate 1.60g, water 10.00g) instillation 40.00g
It is reacted in water, reaction temperature is 50 DEG C, and time for adding 2.0h keeps the temperature 0.5h after being added dropwise, obtains copolymerization product；
(5) neutralization reaction：The alkali of copolymerization product made from step (4) is adjusted into pH to 5~7 to get the phosphorous poly- carboxylic
Sour water-reducing agent PCE-3.
Embodiment 4
(1) first esterification：Allyl polyglycol and 100.00g that 1450.00g molecular weight is 3000 are faced into carboxyl
Benzyl phosphoric acid mixes, and under nitrogen protection, is warming up to 90 DEG C, adds 4.40g mellitic acids, insulation reaction 3.0h, during which
Water is removed with vacuumizing or leading to method of the nitrogen with water, room temperature is down to after reaction, obtains containing esterification products and unreacted
Allyl polyglycol the first mixture.
(2) second esterifications：By 170.00g maleic anhydrides, -7 phosphoric acid of 100.00g1- hydroxyl naphthalenes and 2.00g to benzene two
Phenol mixes, and under nitrogen protection, is warming up to 100 DEG C, adds 0.70g trinitrobenzene sulfonic acid, insulation reaction 1.5h, during which with pumping
The method of vacuum or logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted horse
Carry out the second mixture of acid anhydrides；
(3) monomer blend：It will be second made from the first mixture made from 100.00g steps (1), 16.00g steps (2)
Mixture mixes, and 40.00g water is added and makes its dissolving, obtains copolymerized monomer mixture solution；
(4) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.20g, water
10.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 1.00g, water 10.00g), aqueous ascorbic acid are (wherein, anti-bad
Hematic acid 0.20, water 10.00g) it instills in 40.00g water and is reacted, reaction temperature is 35 DEG C, and time for adding 2.5h is dripped
1.0h is kept the temperature after finishing, obtains copolymerization product；
(5) neutralization reaction：The alkali of copolymerization product made from step (4) is adjusted into pH to 5~7 to get the phosphorous poly- carboxylic
Sour water-reducing agent PCE-4.
Embodiment 5
(1) first esterification：By 1990.00g molecular weight be 4000 3- methyl -3- butene-1s-polyethylene glycol and
100.00g mixes carboxymethyl phenethyl phosphoric acid, under nitrogen protection, is warming up to 80 DEG C, adds 6.00g trinitrobenzen sulphurs
Acid, insulation reaction 3.0h are down to room temperature, obtain after reaction during which with vacuumizing or leading to method removing water of the nitrogen with water
The first mixture containing esterification products and unreacted 3- methyl -3- butene-1s-polyethylene glycol.
(2) second esterifications：99.00g acrylic acid, -4 phosphoric acid of 100.00g2- hydroxyl naphthalenes and 3.60g phenthazine are mixed
It closes, under nitrogen protection, is warming up to 115 DEG C, add 0.40g nitrogen sulphur side acid, insulation reaction 1.5h, during which with vacuumizing or lead to
Method of the nitrogen with water removes water, is down to room temperature after reaction, obtains the containing esterification products and unreacted acrylic acid
Two mixtures；
(3) monomer blend：It will be second made from the first mixture made from 100.00g steps (1), 13.00g steps (2)
Mixture mixes, and 40.00g water is added and makes its dissolving, obtains copolymerized monomer mixture solution；
(4) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein, azo two
Cyanopentanoic acid 1.80g, water 10.00g), sodium hypophosphite aqueous solution (wherein, sodium hypophosphite 1.40g, water 20.00g) instill 40.00g
It is reacted in water, reaction temperature is 40 DEG C, and time for adding 2.0h keeps the temperature 2.0h after being added dropwise, obtains copolymerization product；
(5) neutralization reaction：The alkali of copolymerization product made from step (4) is adjusted into pH to 5~7 to get the phosphorous poly- carboxylic
Sour water-reducing agent PCE-5.
The phosphorous polycarboxylate water-reducer obtained by embodiment 1 to embodiment 5 is tested according to GB/T8076-2008,
(relative to cement consumption) when the solid volume of folding is 0.2%, water-reducing rate is above 45%, 28d compressive strength rates and is all higher than 140%,
28d shrinkage ratios are respectively less than 110%.
Using 42.5 Portland cements of Fujian good fortune P.O, concrete mix is：Cement 300kg/m3, flyash
100kg/m3, miberal powder 100kg/m3, sand 690kg/m3, stone 1050kg/m3, water 160kg/m3, and add 3.5% (phase of bentonite
For cement consumption), phosphorous polycarboxylate water-reducer and the commercially available polycarboxylate water-reducer obtained by embodiment 5 are arrived to embodiment 1
(PCE) according to folding, volume 0.15% is tested for the property admittedly.Test concrete initial slump and divergence, the 2h slumps and expansion
The test result of the latitude of emulsion, different additives is as shown in table 1.
The different additive test results of table 1
As it can be seen from table 1 subtracting to comparing commercially available polycarboxylic acids mixed with the embodiment of bentonitic material, this patent synthesis
Aqua (PCE), water-reducing rate bigger, function of slump protection are more preferable, it can be seen that polycarboxylate water-reducer prepared by this patent is to clay content height
Material sensitivity it is relatively low, have anti-mud effect.
Those of ordinary skill in the art remain able to it is found that when technical scheme of the present invention changes in following ranges
To same as the previously described embodiments or similar technique effect, protection scope of the present invention is still fallen within：
A kind of phosphorous polycarboxylate water-reducer, molecular weight is 10000~150000, and its structural formula is as follows：
Wherein, R1For H or CH3, R2For the alkyl of 1~4 carbon, R3For empty or 1~4 carbon alkyl, R4For sky or 1~4
The alkyl of a carbon, R5For H or COOM, R6For H or CH3, R7For H or COOM, R8For H or CH3, R9For empty or 1~4 carbon alkane
Base, R10For the naphthalene nucleus for having there are one alkyl carboxylate's substituent group, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring
For ortho position, meta or para position.
Above-mentioned phosphorous polycarboxylate water-reducer preparation method, includes the following steps：
(1) first esterification：Insatiable hunger polyethers and the first compound are mixed, under nitrogen protection, are warming up to 70~90
DEG C, catalyst is added, 0.5~3.0h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is tied
It is down to room temperature after beam, obtains the first mixture containing esterification products and unreacted insatiable hunger polyethers；Above-mentioned insatiable hunger polyethers is point
The allyl polyglycol, 3- methyl -3- butene-1s-polyethylene glycol, 2- methacrylic polyethylene glycol that son amount is 600~5000
At least one of；The structural formula of above-mentioned first compound is as follows：
(2) second esterifications：Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydroxyl naphthalene-carboxylic acid and polymerization inhibitor are mixed,
Under nitrogen protection, 90~120 DEG C are warming up to, adds catalyst, 0.5~3.0h of insulation reaction, during which with vacuumizing or lead to nitrogen
Method of the gas with water removes water, is down to room temperature after reaction, obtain containing esterification products and unreacted unsaturated carboxylic acid or
Second mixture of unsaturated carboxylic acid anhydrides；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are acrylic acid, methacrylic acid, Malaysia
At least one of acid, maleic anhydride；Above-mentioned hydroxyl naphthalene phosphoric acid is -4 phosphoric acid of 1- hydroxyl naphthalenes, -5 phosphoric acid of 1- hydroxyl naphthalenes, 1- hydroxyls
- 6 phosphoric acid of naphthalene, -7 phosphoric acid of 1- hydroxyl naphthalenes, -4 phosphoric acid of 2 hydroxy naphthalene, -5 phosphoric acid of 2 hydroxy naphthalene, -6 phosphoric acid of 2 hydroxy naphthalene, 2- hydroxyls
- 7 phosphoric acid of naphthalene, -4 phosphoric acid of 1- methylols naphthalene, -5 phosphoric acid of 1- methylols naphthalene, -6 phosphoric acid of 1- methylols naphthalene, -7 phosphoric acid of 1- methylols naphthalene,
- 4 phosphoric acid of 2- methylols naphthalene, -5 phosphoric acid of 2- methylols naphthalene, -6 phosphoric acid of 2- methylols naphthalene, -7 phosphoric acid of 2- methylols naphthalene, 1- hydroxyl naphthalenes -
4 methyl acid phosphates, -5 methyl acid phosphate of 1- hydroxyl naphthalenes, -6 methyl acid phosphate of 1- hydroxyl naphthalenes, -7 methyl acid phosphate of 1- hydroxyl naphthalenes, 2 hydroxy naphthalene -4
Methyl acid phosphate, -5 methyl acid phosphate of 2 hydroxy naphthalene, -6 methyl acid phosphate of 2 hydroxy naphthalene, -7 methyl acid phosphate of 2 hydroxy naphthalene, 1- methylols naphthalene -
4 methyl acid phosphates, -5 methyl acid phosphate of 1- methylols naphthalene, -6 methyl acid phosphate of 1- methylols naphthalene, -7 methyl acid phosphate of 1- methylols naphthalene, 2- hydroxyls
- 4 methyl acid phosphate of methyl naphthalene, -5 methyl acid phosphate of 2- methylols naphthalene, -6 methyl acid phosphate of 2- methylols naphthalene, -7 methyl phosphorus of 2- methylols naphthalene
At least one of acid；
(3) monomer blend：By the second mixture made from the first mixture made from step (1) and step (2) with 100: 6
~18 mass ratio mixing, and water is added and makes its dissolving, obtain copolymerized monomer mixture solution；
(4) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~60 DEG C, time for adding be 0.2~6.0h, after being added dropwise keep the temperature 0~
3.0h obtains copolymerization product；
(5) neutralization reaction：It is phosphorous to get described one kind that the alkali of copolymerization product made from step (3) is adjusted into pH to 5~7
Polycarboxylate water-reducer.
In the step (1), the molar ratio of the insatiable hunger polyethers and the first compound is 1~1.5: 1, the dosage of catalyst
It is the 0.05~0.3% of insatiable hunger polyethers and the first compound gross mass.In the step (2), the unsaturated carboxylic acid or insatiable hunger
It is 2~7: 1 with the molar ratio of carboxylic acid anhydrides and hydroxyl naphthalene-carboxylic acid, the dosage of the catalyst is unsaturated carboxylic acid or unsaturated carboxylic acid
The 0.03~0.3% of acid anhydride and hydroxyl naphthalene-carboxylic acid gross mass；The polymerization inhibitor dosage be unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and
The 0.2~3.0%% of hydroxyl naphthalene-carboxylic acid gross mass.The total amount of water used in the step (3) and step (4) makes the copolymerization produce
The mass concentration of object is 20~70%, and the dosage of the initiator is the gross mass of solute in the copolymerized monomer mixture solution
0.5~3.0%, the dosage of the molecular weight regulator is the gross mass of solute in the copolymerized monomer mixture solution
0.2~2.0%.
The catalyst is mellitic acid, at least one of nitrogen sulphur side acid and trinitrobenzene sulfonic acid.The polymerization inhibitor is
At least one of hydroquinone, phenthazine and diphenylamines.The initiator is that water soluble, redox causes system or water-soluble
Property azo initiator.The molecular weight regulator is thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, phosphorus
At least one of sour trisodium, sodium formate, sodium acetate and lauryl mercaptan.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of phosphorous polycarboxylate water-reducer, it is characterised in that：Its molecular weight is 10000~150000, and its structural formula is as follows：
Wherein, R1For H or CH3, R2For the alkyl of 1~4 carbon, R3For empty or 1~4 carbon alkyl, R4For empty or 1~4 carbon
Alkyl, R5For H or COOM, R6For H or CH3, R7For H or COOM, R8For H or CH3, R9For empty or 1~4 carbon alkyl, R10
For the naphthalene nucleus for having there are one alkyl carboxylate's substituent group, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring is neighbour
Position, meta or para position.
2. phosphorous polycarboxylate water-reducer preparation method described in claim 1, it is characterised in that：Include the following steps：
(1) first esterification：Insatiable hunger polyethers and the first compound are mixed, under nitrogen protection, are warming up to 70~90 DEG C, then
Addition catalyst, 0.5~3.0h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, after reaction
It is down to room temperature, obtains the first mixture containing esterification products and unreacted insatiable hunger polyethers；Above-mentioned insatiable hunger polyethers is molecular weight
For in 600~5000 allyl polyglycol, 3- methyl -3- butene-1s-polyethylene glycol, 2- methacrylic polyethylene glycol
It is at least one；The structural formula of above-mentioned first compound is as follows：
(2) second esterifications：Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, hydroxyl naphthalene-carboxylic acid and polymerization inhibitor are mixed, in nitrogen
Under protection, 90~120 DEG C are warming up to, adds catalyst, 0.5~3.0h of insulation reaction, during which with vacuumizing or lead to nitrogen band
The method of water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted unsaturated carboxylic acid or insatiable hunger
With the second mixture of carboxylic acid anhydrides；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides be acrylic acid, methacrylic acid, maleic acid,
At least one of maleic anhydride；Above-mentioned hydroxyl naphthalene phosphoric acid is -4 phosphoric acid of 1- hydroxyl naphthalenes, -5 phosphoric acid of 1- hydroxyl naphthalenes, 1- hydroxyl naphthalenes -6
Phosphoric acid, -7 phosphoric acid of 1- hydroxyl naphthalenes, -4 phosphoric acid of 2 hydroxy naphthalene, -5 phosphoric acid of 2 hydroxy naphthalene, -6 phosphoric acid of 2 hydroxy naphthalene, -7 phosphorus of 2 hydroxy naphthalene
Acid, -4 phosphoric acid of 1- methylols naphthalene, -5 phosphoric acid of 1- methylols naphthalene, -6 phosphoric acid of 1- methylols naphthalene, -7 phosphoric acid of 1- methylols naphthalene, 2- hydroxyl first
- 4 phosphoric acid of base naphthalene, -5 phosphoric acid of 2- methylols naphthalene, -6 phosphoric acid of 2- methylols naphthalene, -7 phosphoric acid of 2- methylols naphthalene, -4 methyl of 1- hydroxyl naphthalenes
Phosphoric acid, -5 methyl acid phosphate of 1- hydroxyl naphthalenes, -6 methyl acid phosphate of 1- hydroxyl naphthalenes, -7 methyl acid phosphate of 1- hydroxyl naphthalenes, -4 methyl of 2 hydroxy naphthalene
Phosphoric acid, -5 methyl acid phosphate of 2 hydroxy naphthalene, -6 methyl acid phosphate of 2 hydroxy naphthalene, -7 methyl acid phosphate of 2 hydroxy naphthalene, -4 first of 1- methylols naphthalene
Base phosphoric acid, -5 methyl acid phosphate of 1- methylols naphthalene, -6 methyl acid phosphate of 1- methylols naphthalene, -7 methyl acid phosphate of 1- methylols naphthalene, 2- hydroxyl first
- 4 methyl acid phosphate of base naphthalene, -5 methyl acid phosphate of 2- methylols naphthalene, -6 methyl acid phosphate of 2- methylols naphthalene, -7 methyl acid phosphate of 2- methylols naphthalene
At least one of；
(3) monomer blend：By the second mixture made from the first mixture made from step (1) and step (2) with 100: 6~18
Mass ratio mixing, and water is added and makes its dissolving, obtain copolymerized monomer mixture solution；
(4) copolyreaction：Above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled
It is reacted in water, reaction temperature is 10~60 DEG C, and time for adding is 0.2~6.0h, and 0~3.0h is kept the temperature after being added dropwise, is obtained
Copolymerization product；
(5) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the phosphorous poly- carboxylic of described one kind
Sour water-reducing agent.
3. preparation method as claimed in claim 2, it is characterised in that：In the step (1), the insatiable hunger polyethers and first is changed
The molar ratio for closing object is 1~1.5: 1, and the dosage of catalyst is the 0.05~0.3% of insatiable hunger polyethers and the first compound gross mass.
4. preparation method as claimed in claim 2, it is characterised in that：In the step (2), the unsaturated carboxylic acid or insatiable hunger
It is 2~7: 1 with the molar ratio of carboxylic acid anhydrides and hydroxyl naphthalene-carboxylic acid, the dosage of the catalyst is unsaturated carboxylic acid or unsaturated carboxylic acid
The 0.03~0.3% of acid anhydride and hydroxyl naphthalene-carboxylic acid gross mass；The polymerization inhibitor dosage be unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and
The 0.2~3.0%% of hydroxyl naphthalene-carboxylic acid gross mass.
5. preparation method as claimed in claim 2, it is characterised in that：The total amount of water used in the step (3) and step (4) makes
The mass concentration for obtaining the copolymerization product is 20~70%, and the dosage of the initiator is in the copolymerized monomer mixture solution
The dosage of the 0.5~3.0% of the gross mass of solute, the molecular weight regulator is solute in the copolymerized monomer mixture solution
Gross mass 0.2~2.0%.
6. the preparation method as described in any claim in claim 2 to 5, it is characterised in that：The catalyst is benzene six
At least one of formic acid, nitrogen sulphur side acid and trinitrobenzene sulfonic acid.
7. the preparation method as described in any claim in claim 2 to 5, it is characterised in that：The polymerization inhibitor is to benzene
At least one of diphenol, phenthazine and diphenylamines.
8. the preparation method as described in any claim in claim 2 to 5, it is characterised in that：The initiator is water-soluble
Property redox initiation system or water-soluble azo initiator.
9. the preparation method as described in any claim in claim 2 to 5, 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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| CN201810586582.4A CN108623745B (en) | 2018-06-08 | 2018-06-08 | Phosphorus-containing polycarboxylate superplasticizer and preparation method thereof |
| PCT/CN2018/122569 WO2019233085A1 (en) | 2018-06-08 | 2018-12-21 | Phosphorus-containing polycarboxylate superplasticizer and preparation method therefor |
| MYPI2018002722A MY197439A (en) | 2018-06-08 | 2018-12-21 | Phosphorus?containing polycarboxylate superplasticizer and method for making same |
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| CN201810586582.4A CN108623745B (en) | 2018-06-08 | 2018-06-08 | Phosphorus-containing polycarboxylate superplasticizer and preparation method thereof |
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| CN110228962A (en) * | 2019-05-29 | 2019-09-13 | 科之杰新材料集团有限公司 | A kind of water-retaining type wet mixing mortar plasticizer and preparation method thereof |
| CN110255958A (en) * | 2019-05-29 | 2019-09-20 | 科之杰新材料集团有限公司 | A kind of wet mixing mortar surely moulds agent and preparation method thereof |
| CN110330600A (en) * | 2019-05-29 | 2019-10-15 | 科之杰新材料集团有限公司 | A kind of low responsive type wet mixing mortar plasticizer and preparation method thereof |
| CN110358021A (en) * | 2019-05-29 | 2019-10-22 | 科之杰新材料集团有限公司 | A kind of cross-linking type wet mixing mortar plasticity-maintaining agent and preparation method thereof |
| WO2019233085A1 (en) * | 2018-06-08 | 2019-12-12 | 科之杰新材料集团有限公司 | Phosphorus-containing polycarboxylate superplasticizer and preparation method therefor |
| CN113185185A (en) * | 2021-05-31 | 2021-07-30 | 扬州工业职业技术学院 | Multifunctional auxiliary agent for building material and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| MY197439A (en) | 2023-06-19 |
| CN108623745B (en) | 2020-03-06 |
| WO2019233085A1 (en) | 2019-12-12 |
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