CN104231183A - Preparation method for polycarboxylate-type water reducer - Google Patents
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Abstract
The invention discloses a preparation method for a polycarboxylate-type water reducer. The preparation method comprises the following steps: firstly, performing acylation reaction on an unsaturated polyacid small monomer containing two or more carboxyls and alcohol amine organic compounds containing at least one terminal amino group under the action of a catalyst to obtain an acylate; secondly, performing aqueous-phase free radical polymerization on the acylate, the unsaturated polyacid small monomers, unsaturated acid small monomers, unsaturated polyether monomers, ester macromonomers and water under the joint action of an initiator and a chain transfer agent to obtain a copolymerization product; after the reaction is finished, adjusting the pH value, and adding water to obtain the polycarboxylate-type water reducer. According to the preparation method disclosed by the invention, the product performance is adjusted by controlling the molecular structure of the copolymerization product; the preparation method is quick in response, high in efficiency and simple for operation; no organic solvents is used, so toxicity and pollution are avoided. The polycarboxylate-type water reducer prepared by the preparation method disclosed by the invention is a polycarboxylate-type high-efficiency water reducer with high functional slump loss resistance; the slump loss resistance is improved on the premise of high water reducing property; the product performance is stable.
Description
Technical field
The present invention relates to a kind of technical field of cement concrete poly carboxylic acid series water reducer, be related specifically to a kind of preparation method adopting the poly carboxylic acid series water reducer of amidate action and radical polymerization.
Background technology
Poly carboxylic acid series concrete high-performance water reducing agent is continue being that the ordinary water-reducing agent of representative and the third generation new concrete high-performance that grows up after being the high efficiency water reducing agent of representative subtract agent with xylogen with naphthalene.Compared with traditional formaldehyde condensation class water reducer (naphthalene system, melamine system, sulfamate system), polycarboxylic acid series high efficiency water reducing agent has comb shaped molecular structure, better with the adaptability of gelling material, volume is low, pollution-free, cost is low, high diminishing, function of slump protection are excellent and time of coagulation is adjustable, shrinking percentage is low, Surface Quality of Concrete is good, alkali content and the advantage such as chloride ion content is low.Become the focus of domestic and international concrete admixture research and development gradually.
Along with the construction of national large-scale basis facility nuclear power, water conservancy, bridge, high ferro, tunnel and various heavy construction makes premixed concrete industry obtain great-leap-forward development, developing by leaps and bounds of high performance concrete admixture is also impelled to concrete intensity and improving constantly of performance requriements.Although the water-reducing property of polycarboxylate water-reducer excellence and good slump retention performance oneself extensively approved by industry, when high temperature, long-distance transportation, concrete slump loss is larger.Change blending craft, retemper, repeatedly method such as interpolation water reducer and composite slow setting composition etc. can produce severe side effect to concrete intensity and weather resistance while increase production cost.So high collapse protection type polycarboxylate water-reducer becomes study hotspot at present.
The development of collapse protective poly-carboxylic acid analog high efficiency water reducing agent is the breakthrough to conventional water reducing agents technology, the designability of molecular structure aspect determines the seriation product with better performance can developing different performance feature or novel texture, meet the diversified requirement of construction work to concrete admixture, can affirm that it will have wide development potentiality and market outlook.
Summary of the invention
The object of the invention is the preparation method providing a kind of poly carboxylic acid series water reducer in order to improve the deficiencies in the prior art, it turn improves slump retaining under the prerequisite of high diminishing.
Technical scheme of the present invention is: a kind of preparation method of poly carboxylic acid series water reducer, and its concrete steps are as follows:
1) by the unsaturated polyprotonic acid minor comonomer containing two or more carboxyls with at least hold the alcamines organic compound 85 ~ 140 DEG C of amido under catalyzer and stopper effect, carry out acylation reaction to obtain acylate in 3 ~ 10 hours containing one; The mol ratio of the unsaturated polyprotonic acid minor comonomer of two or more carboxyls wherein said, end amido alcamines organic compound, stopper and catalyzer is 1:(1 ~ 4): (0.01 ~ 0.1): (0.05 ~ 0.1);
2) by step 1) obtained acylate in initiator and chain-transfer agent acting in conjunction with unsaturated hydroxy ester class minor comonomer, unsaturated sulfonic acid class minor comonomer, unsaturated polyether polymeric monomer or unsaturated ester class polymeric monomer, carries out 3 ~ 5 hours aqueous phase Raolical polymerizables and namely obtains copolymerization product under remaining on the temperature of 35 ~ 80 DEG C; With alkali lye, the pH value of above-mentioned copolymerization product is adjusted to 6 ~ 7, adds water and obtain the poly carboxylic acid series water reducer of 5 ~ 60wt% concentration; The mass ratio of wherein said acylate, unsaturated hydroxy ester class minor comonomer, unsaturated sulfonic acid class minor comonomer, unsaturated polyether polymeric monomer or unsaturated ester class polymeric monomer, initiator and chain-transfer agent is 1:(0.1 ~ 4): (0.1 ~ 3): (12 ~ 30): (0.03 ~ 0.5): (0.01 ~ 0.1).
Preferred steps 1) described in catalyzer be Lewis acid or protonic acid; Described stopper is one or more combinations of para benzoquinone, Resorcinol, MEHQ, toluhydroquinone, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone.More preferably described step 1) described in catalyzer be anhydrous zinc dichloride, phosphoric acid, the vitriol oil, polyphosphoric acid or boron trifluoride one or more combination.
Preferred steps 1) described in containing the unsaturated polyprotonic acid minor comonomer general formula of two or more carboxyls: R
1(COOH)
xrepresent, wherein R
1be the ethylenic unsaturation alkyl of 3 ~ 10 carbon atoms, x is the integer of 2 ~ 6; The alcamines organic compound general formula of described end amido: HOR
2(NH
2)
yrepresent, wherein R
2be the alkyl of 2 ~ 6 carbon atoms, phenyl or alkoxyl group, y is the integer of 1 ~ 2.
More preferably step 1) described in be equisetic acid, toxilic acid, methylene-succinic acid, dimethyl maleic acid, 2 containing the unsaturated polyprotonic acid minor comonomer of two or more carboxyls, 2-dimethyl-succsinic acid, allyl succinic acid, 2-butylene-1-base succsinic acid or 1,2, one or more combinations of 3,4-cyclopentenes tetracarboxylic acid; The alcamines organic compound of described end amido is one or more combinations of diglycolamine, Monoethanolamine MEA BASF, monopropylene glycol amine, monoisopropanolamine, dihydroxyl Ursol D, isobutyl hydramine or butylethanolamine.
Preferred steps 2) described in unsaturated hydroxy ester class minor comonomer general formula: R
3cOOR
4oH represents, wherein R
3be the ethylenic unsaturation alkyl of 3 ~ 8 carbon atoms, R
4be alkyl or the alkoxyl group of 1 ~ 4 carbon atom; Described unsaturated sulfonic acid class minor comonomer general formula: R
5sO
3m represents, wherein R
5be the unsaturated olefin substrate of 3 ~ 8 carbon atoms, M is H or metal ion, ammonium or organic amino group; Described unsaturated polyether polymeric monomer general formula: R
6o (EO)
n(PO)
moR
7represent, wherein R
6be the ethylenic unsaturation alkyl of 3 ~ 8 carbon atoms, R
7for the alkyl of H or 1 ~ 6 carbon atom, n is 15 ~ 100, m is 0 ~ 100; Described unsaturated ester class polymeric monomer general formula: R
8cOO (EO)
n(PO)
moR
9represent, wherein R
8be the ethylenic unsaturation alkyl of 2 ~ 8 carbon atoms, R
9for the alkyl of H or 1 ~ 6 carbon atom, n is 15 ~ 100, m is 0 ~ 100.
Preferred steps 2) described in unsaturated hydroxy ester class minor comonomer be acrylate, Hydroxyethyl acrylate or the positive butyl ester of vinylformic acid hydroxyl one or more combination, described unsaturated sulfonic acid class minor comonomer is sodium allyl sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate, methallylsulfonic acid sodium, methyl allyloxy sodium sulfonate, allyl sulphonic acid amine, styrene sulfonic acid amine, vinyl sulfonic acid amine, methallylsulfonic acid amine, methyl allyloxy sulfanilic acid, allyl sulphonic acid potassium, styrene sulfonic acid potassium, vinyl sulfonic acid potassium, methallylsulfonic acid potassium, the one or more combination of methyl allyloxy potassium sulfonate or 2-acrylamide-2-methylpro panesulfonic acid, described unsaturated polyether polymeric monomer is one or more combinations of allyl polyglycol, methacrylic polyoxyethylene glycol, 3-methyl-3-butene-1-polyoxyethylene glycol or 2-methacrylic polyoxyethylene glycol, and its molecular weight is 300 ~ 8000, described unsaturated ester class polymeric monomer is one or more combinations of methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer, and its molecular weight is 300 ~ 8000.
Preferred described step 2) in initiator be persulfuric acid thing or superoxide, more preferably hydrogen peroxide, ammonium persulphate, Sodium Persulfate or Potassium Persulphate one or more combination; Preferably described chain-transfer agent is one or more combinations of Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, methylpropenyl sodium sulfonate or Dodecyl Mercaptan.
Preferred steps 3) described in alkali lye be potassium hydroxide, sodium hydroxide or calcium hydroxide one or more combination.
The inventive method adopts amidate action and radical polymerization synthesis high performance water reducing agent of polyocarboxy acid, and technique is simple, and imparts the new function of water reducer, improves concrete slump retaining.
Beneficial effect:
1. the abundant raw material source that utilizes of the inventive method.
2. the inventive method by controlling the molecular structure of acylation reaction and the incompatible adjustment product of radical polymerization, thus can obtain excellent performance.
3. the polycarboxylate water-reducer product prepared of the inventive method, has high-collapse-retentivity again under the prerequisite of high diminishing.
4. the polycarboxylate water-reducer product that prepared by the inventive method is made into stable performance after the aqueous solution, not stratified during storage, do not precipitate.
5. the polycarboxylate water-reducer product prepared of the inventive method, adapts to wide, and has transport advantage.
6. the inventive method is safe and reliable in the whole preparation process of polycarboxylate water-reducer product of preparation, operation steps is simple and convenient, not with an organic solvent, and nontoxic pollution-free, the advantage such as environmentally safe.
Embodiment
Below by embodiment, technical solution of the present invention is described in further detail.
Embodiment 1
Step 1) synthesis of acylate: the Monoethanolamine MEA BASF of the toxilic acid of 116.07g (1mol) and 61.1g (1mol) is added in reactor and stirs; under nitrogen protection; add hydroquinone of polymerization retarder 0.01mol; add 0.05mol polyphosphoric acid; heat up 85 DEG C; in reaction process, removing generates water, constant temperature 3h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 20g, acrylate 2g, sodium allyl sulfonate 30g and allyl polyglycol (M
n=300g/mol) 300g first adds in reactor and stirs, then drip 0.6g hydrogen peroxide and the 0.6g thiohydracrylic acid aqueous solution respectively, keep temperature 35 DEG C, react after 3 hours, obtain copolymerization product; Regulate pH to 6 with sodium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 5wt% concentration.
Embodiment 2
Step 1) synthesis of acylate: the monopropylene glycol amine of the equisetic acid of 174g (1mol) and 150.22g (2mol) is added in reactor and stirs; under nitrogen protection; add stopper para benzoquinone 0.02mol; add 0.1mol phosphoric acid; heat up 90 DEG C; in reaction process, removing generates water, constant temperature 4h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 30g, Hydroxyethyl acrylate 10g, Sodium styrene sulfonate 4g and methacrylic polyoxyethylene glycol (M
n=800g/mol) 360g first adds in reactor, stirs, and then drips ammonium persulphate 0.9g and the 3g2-thiohydracrylic acid aqueous solution respectively, and keep temperature 45 C, react after 4 hours, obtain copolymerization product; Regulate pH to 6 with potassium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 15wt% concentration.
Embodiment 3:
Step 1) synthesis of acylate: the diglycolamine of the dimethyl maleic acid of 126g (1mol) and 105.11g (1mol) is added in reactor and stirs; under nitrogen protection; add stopper MEHQ 0.1mol; add the 0.05mol vitriol oil; heat up 95 DEG C; in reaction process, removing generates water, constant temperature 5h, and cooling obtains acylate.Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 10g, the positive butyl ester 40g of vinylformic acid hydroxyl, sodium vinyl sulfonate 30g and 3-methyl-3-butene-1-polyoxyethylene glycol (M
n=1000g/mol) 300g first adds in reactor, stirs, and then drips Potassium Persulphate 0.5g and the 0.1g3-thiohydracrylic acid aqueous solution respectively, and keep temperature 50 C, react after 4.5 hours, obtain copolymerization product; Regulate pH to 7 with sodium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 20wt% concentration.
Embodiment 4:
Step 1) synthesis of acylate: the monopropylene glycol amine of the methylene-succinic acid of 130g (1mol) and 75.11g (1mol) is added in reactor and stirs; under nitrogen protection; add stopper toluhydroquinone 0.1mol; add 0.1mol phosphoric acid; heat up 100 DEG C; in reaction process, removing generates water, constant temperature 5h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 5g, acrylate 10g, Hydroxyethyl acrylate 5g, methylpropene sodium sulfonate 10g and, 2-methacrylic polyoxyethylene glycol 150g first adds in reactor, stir, then Potassium Persulphate 0.25g and the Thiovanic acid 0.05g aqueous solution is dripped respectively, keep temperature 55 DEG C, react after 5 hours, obtain copolymerization product; Regulate pH to 6 with sodium hydroxide and aqua calcis, add water and obtain the polycarboxylate high performance water-reducing agent of 25wt% concentration.
Embodiment 5:
Step 1) synthesis of acylate: the monoisopropanolamine of the allyl succinic acid of 158g (1mol) and 75.11g (1mol) is added in reactor and stirs; under nitrogen protection; add stopper 2-Tert. Butyl Hydroquinone 0.05mol; add the anhydrous zinc dichloride of 0.1mol; heat up 105 DEG C; in reaction process, removing generates water, constant temperature 6h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 5g, acrylate 5g, positive butyl ester 5g, 2-acrylamide-2-methylpro panesulfonic acid 15g of vinylformic acid hydroxyl and 2-methacrylic polyoxyethylene glycol (M
n=500g/mol) 135g first adds in reactor, stir, then drip Sodium Persulfate 0.11g, Potassium Persulphate 0.08g, methylpropenyl sodium sulfonate 0.1g and the Dodecyl Mercaptan 0.2g aqueous solution respectively, keep temperature 60 C, react after 3 hours, obtain copolymerization product; Regulate pH to 7 with sodium hydroxide and potassium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 30wt% concentration.
Embodiment 6:
Step 1) synthesis of acylate: by 2 of 146.13 (1mol) g; the isobutyl hydramine of 2-methyl-succsinic acid and 89.14g (1mol) adds in reactor and stirs; under nitrogen protection; add stopper 2,5 di tert butyl hydroquinone 0.1mol, add 0.05mol polyphosphoric acid; heat up 110 DEG C; in reaction process, removing generates water, constant temperature 7h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 20g, acrylate 10g, 2-acrylamide-2-methylpro panesulfonic acid 15g, methylpropene sodium sulfonate 10g, polyethylene glycol acrylate (M
n=1200g/mol) 260g and polyethylene glycol methacrylate-styrene polymer 15g first adds in reactor, stirs, and then drips hydrogen peroxide 0.6g and the Dodecyl Mercaptan 1.9g aqueous solution respectively, and keep temperature 65 DEG C, react after 3.5 hours, obtain copolymerization product; Regulate pH to 7 with potassium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 35wt% concentration.
Embodiment 7:
Step 1) synthesis of acylate: by 244.17g (1mol) 1,2,3; the Monoethanolamine MEA BASF of 4-cyclopentenes tetracarboxylic acid and 24.44g (0.4mol); 378.504g (3.6mol) diglycolamine, adds in reactor and stirs, under nitrogen protection; add stopper para benzoquinone 0.01mol, Resorcinol 0.01mol; add 0.06mol phosphoric acid, heat up 115 DEG C, in reaction process, removing generates water; constant temperature 8h, cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 10g, Hydroxyethyl acrylate 10g, 2-acrylamide-2-methylpro panesulfonic acid 15g and polyethylene glycol methacrylate-styrene polymer (M
n=2400g/mol) 200g first adds in reactor, stirs, and then drips Potassium Persulphate 4g and the methylpropenyl sodium sulfonate 0.8g aqueous solution respectively, and keep temperature 70 C, react after 4 hours, obtain copolymerization product; Regulate pH to 6 with sodium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 40wt% concentration.
Embodiment 8:
Basic procedure is with embodiment 3, and difference is:
Step 1) synthesis of acylate: by the toxilic acid of 87g (0.5mol) equisetic acid and 58g (0.5mol); the 4-hydroxyl O-Phenylene Diamine of 102g (1mol) adds in reactor and stirs; under nitrogen protection; add stopper MEHQ 0.02mol, toluhydroquinone 0.02mol; add 0.07mol polyphosphoric acid, heat up 120 DEG C, in reaction process, removing generates water; constant temperature 3h, cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 6g, the positive butyl ester 24g of vinylformic acid hydroxyl, methyl allyloxy sodium sulfonate 10g, 2-acrylamide-2-methylpro panesulfonic acid 5g and polyethylene glycol acrylate (M
n=300g/mol) 150g first adds in reactor, stirs, and then drips ammonium persulphate 0.21g and the methylpropenyl sodium sulfonate 0.6g aqueous solution respectively, and keep temperature 75 DEG C, react after 4.5 hours, obtain copolymerization product; Regulate pH to 6 with aqua calcis, add water and obtain the polycarboxylate high performance water-reducing agent of 45wt% concentration.
Embodiment 9:
Step 1) synthesis of acylate: by the toxilic acid of 130g (1mol) methylene-succinic acid and 116.07g (1mol); the Monoethanolamine MEA BASF of 61.1g (1mol); 75.11g (1mol) monopropylene glycol amine adds in reactor and stirs; under nitrogen protection; add stopper 2-Tert. Butyl Hydroquinone 0.02mol; 2; 5-di-tert-butyl hydroquinone 0.02mol; add 0.1mol boron trifluoride; heat up 125 DEG C; in reaction process, removing generates water, constant temperature 9h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 5g, Hydroxyethyl acrylate 10g, the positive butyl ester 5g of vinylformic acid hydroxyl, sodium vinyl sulfonate 5g, methallylsulfonic acid sodium 10g and methoxy polyethylene glycol acrylate (M
n=8000g/mol) 150g first adds in reactor, stirs, and then drips Potassium Persulphate 0.15g and the thiohydracrylic acid 0.5g aqueous solution respectively, and keep temperature 80 DEG C, react after 5 hours, obtain copolymerization product; Regulate pH to 7 with potassium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 50wt% concentration.
Embodiment 10:
Step 1) synthesis of acylate: by 130g (1mol) methylene-succinic acid; the toxilic acid of 61g (0.5mol) dimethyl maleic acid and 116g (1mol); the isobutyl hydramine of 89.14 (1mol); 52.67g (0.5mol) diglycolamine; 61.1g (1mol) Monoethanolamine MEA BASF adds in reactor and stirs; under nitrogen protection; add hydroquinone of polymerization retarder 0.25mol; add 0.25mol phosphoric acid; heat up 130 DEG C; in reaction process, removing generates water, constant temperature 10h, and cooling obtains acylate.
Step 2) synthesis of poly carboxylic acid series water reducer: by acylate 10g, the positive butyl ester 5g of vinylformic acid hydroxyl, sodium allyl sulfonate 10g, Sodium styrene sulfonate 5g and methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylate (M
n=2400g/mol) 200g first adds in reactor, stirs, and then drips Potassium Persulphate 0.4g and the Thiovanic acid 1g aqueous solution respectively, and keep temperature 80 DEG C, react after 5 hours, obtain copolymerization product; Regulate pH to 6 with sodium hydroxide solution, add water and obtain the polycarboxylate high performance water-reducing agent of 60wt% concentration.
Paste flowing degree is tested: with reference to GB8077-2000 " Methods for testing uniformity of concrete admixture ", carry out paste flowing degree test to embodiment 1 to embodiment 10 gained sample.W/C is 0.29, and the solid volume of admixture folding is 0.11% of cement consumption, and paste flowing degree is all greater than 175mm, loses hardly in 2 hours;
The paste flowing degree of the different sample of table 1 and gradual loss
Testing concrete performance: to embodiment 10 gained sample, slump-loss, concrete strength inspection are carried out to embodiment 1 with reference to GB8076-2008 " concrete admixture ".When the solid volume of admixture folding is 1.5wt% (relative to cement consumption), water-reducing rate is all higher than 40%, and ultimate compression strength raising in 3 days is all greater than 85%, and ultimate compression strength raising in 7 days is all greater than 70%, and ultimate compression strength raising in 28 days is all greater than 75%.
The concrete slump retaining performance of the different sample of table 2 and mechanical property
Claims (9)
1. a preparation method for poly carboxylic acid series water reducer, its concrete steps are as follows:
1) by the unsaturated polyprotonic acid minor comonomer containing two or more carboxyls with at least hold the alcamines organic compound 85 ~ 140 DEG C of amido under catalyzer and stopper effect, carry out acylation reaction to obtain acylate in 3 ~ 10 hours containing one; The mol ratio of the unsaturated polyprotonic acid minor comonomer of two or more carboxyls wherein said, end amido alcamines organic compound, stopper and catalyzer is 1:(1 ~ 4): (0.01 ~ 0.1): (0.05 ~ 0.1);
2) by step 1) obtained acylate in initiator and chain-transfer agent acting in conjunction with unsaturated hydroxy ester class minor comonomer, unsaturated sulfonic acid class minor comonomer, unsaturated polyether polymeric monomer or unsaturated ester class polymeric monomer, carries out 3 ~ 5 hours aqueous phase Raolical polymerizables and namely obtains copolymerization product under remaining on the temperature of 35 ~ 80 DEG C; With alkali lye, the pH value of copolymerization product is adjusted to 6 ~ 7, adds water and obtain the poly carboxylic acid series water reducer of 5 ~ 60wt% concentration; The mass ratio of wherein said acylate, unsaturated hydroxy ester class minor comonomer, unsaturated sulfonic acid class minor comonomer, unsaturated polyether polymeric monomer or unsaturated ester class polymeric monomer, initiator and chain-transfer agent is 1:(0.1 ~ 4): (0.1 ~ 3): (12 ~ 30): (0.03 ~ 0.5): (0.01 ~ 0.1).
2. preparation method according to claim 1, is characterized in that, step 1) described in catalyzer be Lewis acid or protonic acid; Described stopper is one or more combinations of para benzoquinone, Resorcinol, MEHQ, toluhydroquinone, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone.
3. preparation method according to claim 1, is characterized in that, described step 1) described in catalyzer be anhydrous zinc dichloride, phosphoric acid, the vitriol oil, polyphosphoric acid or boron trifluoride one or more combination.
4. preparation method according to claim 1, is characterized in that, step 1) described in containing the unsaturated polyprotonic acid minor comonomer general formula of two or more carboxyls: R
1(COOH)
xrepresent, wherein R
1be the ethylenic unsaturation alkyl of 3 ~ 10 carbon atoms, x is the integer of 2 ~ 6; The alcamines organic compound general formula of described end amido: HOR
2(NH
2)
yrepresent, wherein R
2be the alkyl of 2 ~ 6 carbon atoms, phenyl or alkoxyl group, y is the integer of 1 ~ 2.
5. preparation method according to claim 1, it is characterized in that, step 1) described in be equisetic acid, toxilic acid, methylene-succinic acid, dimethyl maleic acid, 2 containing the unsaturated polyprotonic acid minor comonomer of two or more carboxyls, 2-dimethyl-succsinic acid, allyl succinic acid, 2-butylene-1-base succsinic acid or 1,2, one or more combinations of 3,4-cyclopentenes tetracarboxylic acid; The alcamines organic compound of described end amido is one or more combinations of diglycolamine, Monoethanolamine MEA BASF, monopropylene glycol amine, monoisopropanolamine, dihydroxyl Ursol D, isobutyl hydramine or butylethanolamine.
6. preparation method according to claim 1, is characterized in that, step 2) described in unsaturated hydroxy ester class minor comonomer general formula: R
3cOOR
4oH represents, wherein R
3be the ethylenic unsaturation alkyl of 3 ~ 8 carbon atoms, R
4be alkyl or the alkoxyl group of 1 ~ 4 carbon atom; Described unsaturated sulfonic acid class minor comonomer general formula: R
5sO
3m represents, wherein R
5be the unsaturated olefin substrate of 3 ~ 8 carbon atoms, M is H or metal ion, ammonium or organic amino group; Described unsaturated polyether polymeric monomer general formula: R
6o (EO)
n(PO)
moR
7represent, wherein R
6be the ethylenic unsaturation alkyl of 3 ~ 8 carbon atoms, R
7for the alkyl of H or 1 ~ 6 carbon atom, n is 15 ~ 100, m is 0 ~ 100; Described unsaturated ester class polymeric monomer general formula: R
8cOO (EO)
n(PO)
moR
9represent, wherein R
8be the ethylenic unsaturation alkyl of 2 ~ 8 carbon atoms, R
9for the alkyl of H or 1 ~ 6 carbon atom, n is 15 ~ 100, m is 0 ~ 100.
7. preparation method according to claim 1, is characterized in that, step 2) described in unsaturated hydroxy ester class minor comonomer be acrylate, Hydroxyethyl acrylate or the positive butyl ester of vinylformic acid hydroxyl one or more combination, described unsaturated sulfonic acid class minor comonomer is sodium allyl sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate, methallylsulfonic acid sodium, methyl allyloxy sodium sulfonate, allyl sulphonic acid amine, styrene sulfonic acid amine, vinyl sulfonic acid amine, methallylsulfonic acid amine, methyl allyloxy sulfanilic acid, allyl sulphonic acid potassium, styrene sulfonic acid potassium, vinyl sulfonic acid potassium, methallylsulfonic acid potassium, the one or more combination of methyl allyloxy potassium sulfonate or 2-acrylamide-2-methylpro panesulfonic acid, described unsaturated polyether polymeric monomer is one or more combinations of allyl polyglycol, methacrylic polyoxyethylene glycol, 3-methyl-3-butene-1-polyoxyethylene glycol or 2-methacrylic polyoxyethylene glycol, and its molecular weight is 300 ~ 8000, described unsaturated ester class polymeric monomer is one or more combinations of methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer, and its molecular weight is 300 ~ 8000.
8. preparation method according to claim 1, is characterized in that, described step 2) in initiator be persulfuric acid thing or superoxide, preferably: one or more combinations of hydrogen peroxide, ammonium persulphate, Sodium Persulfate or Potassium Persulphate; Described chain-transfer agent is one or more combinations of Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, methylpropenyl sodium sulfonate or Dodecyl Mercaptan.
9. preparation method according to claim 1, is characterized in that, step 3) described in alkali lye be potassium hydroxide, sodium hydroxide or calcium hydroxide one or more combination.
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| CN105622863A (en) * | 2016-02-24 | 2016-06-01 | 泸州国豪混凝土外加剂有限公司 | Preparation method of polycarboxylate water reducing agent |
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| CN106397682A (en) * | 2016-08-29 | 2017-02-15 | 江苏中铁奥莱特新材料股份有限公司 | Preparation method of slump loss resistant polycarboxylate water reducer |
| CN108129053A (en) * | 2017-12-26 | 2018-06-08 | 江苏苏博特新材料股份有限公司 | A kind of preparation method and applications of the concrete plasticiser with improved clay adaptability |
| CN109096448A (en) * | 2018-07-06 | 2018-12-28 | 西南科技大学 | A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer |
| CN109251279A (en) * | 2018-08-16 | 2019-01-22 | 科之杰新材料集团有限公司 | A kind of shrinkage type polycarboxylate water-reducer and preparation method thereof |
| CN109265052A (en) * | 2018-09-07 | 2019-01-25 | 科之杰新材料集团有限公司 | A kind of preparation method being crosslinked viscosity reduction type polycarboxylate water-reducer |
| CN109776722A (en) * | 2019-02-11 | 2019-05-21 | 山东理工大学 | Ternary graft copolymer and its preparation method and application |
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| CN104945634A (en) * | 2015-06-02 | 2015-09-30 | 江苏奥莱特新材料有限公司 | Preparation method of amine-ester slow-setting polycarboxylic acid type water-reducer |
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| CN105668665B (en) * | 2016-04-13 | 2018-09-04 | 湖南中大建设工程检测技术有限公司 | A method of it is administered in chromyl waste water and is separated by solid-liquid separation using mineral |
| CN105668665A (en) * | 2016-04-13 | 2016-06-15 | 湖南中大建设工程检测技术有限公司 | Solid and liquid separation method for treating waste water containing hexavalent chromium through minerals |
| CN106397682A (en) * | 2016-08-29 | 2017-02-15 | 江苏中铁奥莱特新材料股份有限公司 | Preparation method of slump loss resistant polycarboxylate water reducer |
| CN106397682B (en) * | 2016-08-29 | 2018-07-17 | 江苏中铁奥莱特新材料股份有限公司 | The preparation method of collapse protective poly-carboxylic acid water reducing agent |
| CN108129053A (en) * | 2017-12-26 | 2018-06-08 | 江苏苏博特新材料股份有限公司 | A kind of preparation method and applications of the concrete plasticiser with improved clay adaptability |
| CN109096448A (en) * | 2018-07-06 | 2018-12-28 | 西南科技大学 | A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer |
| CN109251279A (en) * | 2018-08-16 | 2019-01-22 | 科之杰新材料集团有限公司 | A kind of shrinkage type polycarboxylate water-reducer and preparation method thereof |
| CN109251279B (en) * | 2018-08-16 | 2020-09-04 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN109265052A (en) * | 2018-09-07 | 2019-01-25 | 科之杰新材料集团有限公司 | A kind of preparation method being crosslinked viscosity reduction type polycarboxylate water-reducer |
| WO2020087866A1 (en) * | 2018-10-29 | 2020-05-07 | 科之杰新材料集团有限公司 | Long-acting sustained-release polycarboxylic acid set-retarding agent and preparation method therefor |
| CN109776722A (en) * | 2019-02-11 | 2019-05-21 | 山东理工大学 | Ternary graft copolymer and its preparation method and application |
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Application publication date: 20141224 |