CN109553729A - A kind of anti-chamotte mould water-reducing agent of both sexes and preparation method thereof - Google Patents
A kind of anti-chamotte mould water-reducing agent of both sexes and preparation method thereof Download PDFInfo
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- CN109553729A CN109553729A CN201811434604.1A CN201811434604A CN109553729A CN 109553729 A CN109553729 A CN 109553729A CN 201811434604 A CN201811434604 A CN 201811434604A CN 109553729 A CN109553729 A CN 109553729A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- 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 present invention provides a kind of anti-chamotte mould water-reducing agent of both sexes, is prepared by following raw material: 15~60 parts of unsaturated polyether amine monomers E, 15~60 parts of unsaturated phosphine based polyether monomer G, 2~30 parts of unsaturated minor comonomer H, 0.1~7.5 part of oxidant, 0.2~8.5 part of reducing agent, 0.1~7.3 part of chain-transferring agent and 120~200 parts of deionized water；The present invention also provides a kind of preparation method of the anti-chamotte mould water-reducing agent of both sexes, include the following steps: that (1) prepares unsaturation end epoxidized polyether C；(2) unsaturated polyether amine monomers E is prepared；(3) unsaturated phosphine based polyether monomer G is prepared；(4) water-reducing agent is prepared；Present invention enhances the steric hindrance of water-reducing agent branch, inter-chain action power and end electrostatic forces, so that the water-reducing rate of polycarboxylate water-reducer, anti-mud and slump retaining are substantially improved.
Description
Technical field
The present invention relates to the technical field of building additive, the anti-chamotte mould water-reducing agent of especially a kind of both sexes and its preparation side
Method.
Background technique
Polycarboxylate water-reducer, which compares traditional naphthalene system, melamine series, amido sulfoacid series and fatty family water-reducing agent, to be had
Water-reducing rate is high, molecular structure designability is strong, simple production process, the advantages that low energy consumption, low in the pollution of the environment, but there is also pair
The disadvantage of sandstone aggregate clay content sensitivity.
Flourishing due to architectural engineering at present, sandstone aggregate best in quality supply not having to ask, and many engineering projects are adopted
With the higher sandstone aggregate of clay content, and soil has very strong suction-operated to polycarboxylate water-reducer, and water-reducing rate is caused to drop significantly
Low, slump-loss greatly improves, and improves volume and water consumption then will lead to concrete water bleeding isolation and volume contraction, give engineering
Construction and quality bring huge adverse effect.Continuous promotion with people to construction engineering quality and environmental requirement passes
Water-reducing agent of uniting gradually is replaced being trend of the times by polycarboxylate water-reducer, however the defect of the anti-mud difference of polycarboxylate water-reducer does not obtain
It is solved to effective, therefore limits extensive use of the polycarboxylate water-reducer in architectural engineering.
In view of this, the present inventor specially devises a kind of anti-chamotte mould water-reducing agent of both sexes and preparation method thereof, this case is thus
It generates.
Summary of the invention
To solve the above-mentioned problems, technical scheme is as follows:
The present invention provides a kind of anti-chamotte mould water-reducing agent of both sexes, is prepared by following raw material: 15~60 parts of unsaturation
Polyethers amine monomers E, 15~60 parts of unsaturated phosphine based polyether monomer G, 2~30 parts of unsaturated minor comonomer H, 0.1~7.5 part
Oxidant, 0.2~8.5 part of reducing agent, 0.1~7.3 part of chain-transferring agent and 120~200 parts of deionized water；
The unsaturated polyether amine monomers E is prepared by following raw material: unsaturated end epoxidized polyether C and amine chemical combination
Object D, wherein the molar ratio of the unsaturation end epoxidized polyether C and aminated compounds D is 1:1~1:6；
The unsaturation phosphine based polyether monomer G is prepared by following raw material: unsaturated end epoxidized polyether C and phosphine
Compound F, wherein the molar ratio of the unsaturation end epoxidized polyether C and phosphine compound F is 1:1~1:6；
The unsaturation end epoxidized polyether C is prepared by following raw material: unsaturated ether polymeric monomer A, end epoxy compound
Object B and catalyst, wherein the molar ratio of the unsaturated ether polymeric monomer A and end ring oxygen compound B is 1:1~1:4, it is described
Catalyst amount is the 0.3~3.5% of unsaturated ether polymeric monomer A and end ring oxygen compound B gross mass.
Further, the oxidizer be unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G, insatiable hunger
With the 0.2%~5% of minor comonomer H gross mass.
Further, the chain-transferring agent dosage be unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G, no
It is saturated the 0.3%~4.3% of minor comonomer H gross mass.
Further, the reducing agent dosage be unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G, insatiable hunger
With the 0.5%~5.5% of minor comonomer H gross mass.
Further, the unsaturated ether polymeric monomer A is allyl polyethenoxy ether, methacrylic polyoxyethylene
One of ether, isopentene group polyoxyethylene ether or any two kinds or more of mixture.
Further, the end ring oxygen compound B is bisphenol A type epoxy resin E51, bisphenol A type epoxy resin E44, second
Hexanediol diglycidyl ether, propylene glycol diglycidylether, butanediol diglycidyl ether, season neopentyl glycol diglycidyl glycerin ether,
2-glycidyl aniline, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, polypropylene glycol three-glycidyl
The mixture of one of ether, trihydroxymethylpropanyltri diglycidyl ether, T 55 or any two kinds or more.
Further, the aminated compounds D is ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, four ethylene
Five amine, pentaethylene hexamine, m-phenylene diamine (MPD), m-xylene diamine, isophorone diamine,One of alkane diamines, polyetheramine are appointed
The mixture of two kinds of meaning or more.
Further, the phosphine compound F is phosphoric acid, phosphorous acid, 2- phosphonobutane -1,2,4- tricarboxylic acids, amino three
The mixture of one of methylenephosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid or any two kinds or more.
Further, the unsaturation minor comonomer H is acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, third
Olefin(e) acid ethyl ester, methyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, Sodium Allyl Sulfonate,
The mixture of one of methylpropene sodium sulfonate or any two kinds or more.
Further, the catalyst be boron trifluoride/etherate, triphenylphosphine, N, N- dimethyl benzylamine, 2,4,
One of 6- tri- (dimethylamino methyl) phenol, triethylamine or any two kinds or more of mixture.
Further, the oxidant is one of hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate or any
Two kinds or more of mixture.
Further, the reducing agent is one of ascorbic acid, sodium hydrogensulfite, sodium formaldehyde sulfoxylate, ferrous sulfate or appoints
The mixture of two kinds of meaning or more.
Further, the chain-transferring agent is thioacetic acid, mercaptopropionic acid, mercaptoethanol, lauryl mercaptan, octadecyl sulphur
The mixture of one of alcohol or any two kinds or more.
The present invention also provides a kind of preparation methods of the anti-chamotte mould water-reducing agent of both sexes, include the following steps:
(1) in nitrogen after preparation unsaturation end epoxidized polyether C: unsaturated ether polymeric monomer A is mixed with end ring oxygen compound B
Under protection and catalyst, in 80 DEG C~150 DEG C generation epoxy ring opening reactions, 3~7h of isothermal reaction obtains unsaturated end ring
Oxygen polyethers C；
(2) it prepares unsaturated polyether amine monomers E: aminated compounds D being preheated to 40~80 DEG C under nitrogen protection, it will not
Saturation end epoxidized polyether C is added thereto carry out chain extension, and 3~5h of isothermal reaction obtains unsaturated polyether amine monomers E；
(3) it prepares unsaturated phosphine based polyether monomer G: phosphine compound F being preheated to 90 DEG C~140 under nitrogen protection
DEG C, unsaturated end epoxidized polyether C is added thereto, 3~5h of isothermal reaction, obtains unsaturated phosphine based polyether monomer G；
(4) prepare water-reducing agent: under nitrogen protection by unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G,
Part unsaturation minor comonomer H and oxidant co-dissolve in deionized water and are preheated to 25~50 DEG C, by remaining unsaturated
Minor comonomer H and chain-transferring agent are dissolved in the I material being made into deionized water and are dissolved in the II material being made into deionized water by reducing agent together
When be at the uniform velocity gradually added into and wherein reacted, I expects that 2~4h is added, and II material is later than I and expects that 0.5~1h is added, keep the temperature after 1~3h plus
Enter a certain amount of deionized water dilution, obtains the water-reducing agent of 40% solid content.
Beneficial effects of the present invention are as follows:
(1) chain extension is carried out to unsaturated ether polymeric monomer using end ring oxygen compound, aminated compounds and phosphine compound,
The more rigid radicals of water-reducing agent branch, polar group and xenogenesis charge are assigned, to strengthen the steric hindrance of water-reducing agent branch, interchain
Active force and end electrostatic force, so that the multilayer of Water-reducing Admixtures To Cements particle is adsorbed, steric hindrance is repelled between particle and electrostatic is arranged
Denounce effect enhancing, water-reducing rate is improved；
(2) steric hindrance of water-reducing agent branch and the enhancing of inter-chain action power, are not easy to improve anti-mud by soil Inter layer adsorption；
(3) structure of water-reducing agent strand upper end epoxide, aminated compounds and phosphine compound can play collaboration
Anti- mud effect.
Specific embodiment
Technical solution of the present invention is further elaborated below with reference to embodiment.Particular technique or item are not specified in embodiment
Part person described technology or conditions or carries out according to the literature in the art according to product description.Agents useful for same or instrument
Production firm person is not specified in device, and being can be with conventional products that are commercially available.
Embodiment 1
(1) allyl polyethenoxy ether (number-average molecular weight 2400) of 2mol and 2mol bisphenol A type epoxy resin E51 are mixed
After conjunction under nitrogen protection and 55.8g boron trifluoride/etherate catalysis, in 90 DEG C of generation epoxy ring opening reactions, constant temperature is anti-
5h is answered, the unsaturated single epoxidized polyether of 2mol is obtained；
(2) 1mol triethylene tetramine is preheated to 60 DEG C under nitrogen protection, the unsaturated single epoxidized polyether of 1mol is added
Chain extension is wherein carried out, isothermal reaction 4h obtains 1mol unsaturated polyether polyamine monomers；
(3) 1mol phosphoric acid is preheated to 100 DEG C under nitrogen protection, the unsaturated single epoxidized polyether of 1mol is added thereto,
Isothermal reaction 5h obtains the unsaturated single phosphine based polyether monomer of 1mol；
(4) under nitrogen protection by 160g unsaturated polyether polyamine monomers, the unsaturated single phosphine based polyether monomer of 590g,
The methacrylic acid and 5g hydrogen peroxide co-dissolve of 100g is in 680g deionized water and is preheated to 40 DEG C, by 150g methyl-prop
Olefin(e) acid and 3g mercaptopropionic acid are dissolved in the I material being made into 230g deionized water and are dissolved in 330g deionized water by 25g ascorbic acid
The II being made into expects while being at the uniform velocity gradually added into wherein to be reacted, and I material 3h is added, and II material 3.5h is added, and is added after keeping the temperature 1h
The dilution of 290g deionized water, obtains the water-reducing agent of 40% solid content.
Embodiment 2
(1) methyl allyl polyoxyethylene ether (number-average molecular weight 3000) of 2mol shrinks sweet with 4mol polypropylene glycol two
After oily ether (epoxide number is 0.28~0.36mol/100g) mixing under nitrogen protection and 144.4g triphenyl phosphine catalyst, in 140
DEG C epoxy ring opening reaction occurs, isothermal reaction 7h obtains 2mol unsaturation bis-epoxy polyethers；
(2) 2mol m-xylene diamine is preheated to 70 DEG C under nitrogen protection, 1mol unsaturation bis-epoxy polyethers is added
Chain extension is wherein carried out, isothermal reaction 3h obtains 1mol unsaturated polyether polyamine monomers；
(3) 2mol 1-hydroxy ethylidene-1,1-diphosphonic acid is preheated to 130 DEG C under nitrogen protection, by 1mol unsaturation bis-epoxy polyethers
It is added thereto, isothermal reaction 5h, obtains the unsaturated double phosphine based polyether monomers of 1mol；
(4) under nitrogen protection by 470g unsaturated polyether polyamine monomers, the unsaturated double phosphine based polyether monomers of 430g,
35g acrylic acid and 15g sodium peroxydisulfate co-dissolve in 720g deionized water and are preheated to 35 DEG C, by 65g acrylic acid and 8g
Thioacetic acid is dissolved in the I material being made into 300g deionized water and is dissolved in the II being made into 300g deionized water by 20g ascorbic acid
Material is at the uniform velocity gradually added into simultaneously wherein to be reacted, and I material 3h is added, and II material 4h is added, and 214.5g deionization is added after keeping the temperature 2h
Water dilution, obtains the water-reducing agent of 40% solid content.
Embodiment 3
(1) methyl allyl polyoxyethylene ether (number-average molecular weight 3000) of 2mol and 2mol trimethylolpropane tris contract
In nitrogen protection and 180.2gN after the mixing of water glycerin ether, under the catalysis of N- dimethyl benzylamine, in 120 DEG C of generation epoxy ring opening reactions,
Isothermal reaction 6h obtains 2mol unsaturation bis-epoxy polyethers；
(2) 2mol isophorone diamine is preheated to 70 DEG C under nitrogen protection, 1mol unsaturation bis-epoxy polyethers is added
Enter and wherein carry out chain extension, isothermal reaction 5h obtains 1mol unsaturated polyether polyamine monomers；
(3) 2mol aminotrimethylenephosphonic acid is preheated to 90 DEG C under nitrogen protection, by 1mol unsaturation bis-epoxy polyethers
It is added thereto, isothermal reaction 5h, obtains the unsaturated double phosphine based polyether monomers of 1mol；
(4) under nitrogen protection by 560g unsaturated polyether polyamine monomers, the unsaturated double phosphine based polyether monomers of 280g,
60g hydroxy-ethyl acrylate and 21g potassium peroxydisulfate co-dissolve in 730g deionized water and are preheated to 30 DEG C, by 100g propylene
Sour hydroxyl ethyl ester and 12g mercaptoethanol be dissolved in be made into 400g deionized water I material and by 32g sodium hydrogensulfite be dissolved in 350g go from
The II being made into sub- water expects while being at the uniform velocity gradually added into wherein to be reacted, and I material 4h is added, and II material 4.5h is added, after keeping the temperature 3h
The dilution of 117.5g deionized water is added, obtains the water-reducing agent of 40% solid content.
Embodiment 4
(1) the isopentene group polyoxyethylene ether (number-average molecular weight 2400) of 2mol and 4mol T 55 are mixed
It is anti-in 115 DEG C of generation epoxy additions after conjunction under nitrogen protection and 175.2g2, the catalysis of 4,6- tri- (dimethylamino methyl) phenol
It answers, isothermal reaction 7h, obtains 2mol unsaturated tetracyclic oxygen polyethers；
(2) 4mol polyetheramine D400 is preheated to 65 DEG C under nitrogen protection, 1mol unsaturated tetracyclic oxygen polyethers is added
Chain extension is wherein carried out, isothermal reaction 4.5h obtains 1mol unsaturated polyether polyamine monomers；
(3) 4mol phosphorous acid is preheated to 140 DEG C under nitrogen protection, it is added in 1mol unsaturated tetracyclic oxygen polyethers
In, isothermal reaction 4h obtains 1mol unsaturation tetraphosphine based polyether monomer；
(4) under nitrogen protection by 400g unsaturated polyether polyamine monomers, 400g unsaturation tetraphosphine based polyether monomer,
20g acrylic acid, 60g hydroxy-ethyl acrylate and 10g ammonium persulfate co-dissolve are in 730g deionized water and are preheated to 45 DEG C,
It is dissolved in the I material being made into 410g deionized water by 30g acrylic acid, 90g hydroxy-ethyl acrylate and 15g lauryl mercaptan and is hung by 24g
White piece is dissolved in the II being made into 240g deionized water and expects while being at the uniform velocity gradually added into wherein to be reacted, and I material 3.5h is added, II material
4h is added, and the dilution of 193.5g deionized water is added after keeping the temperature 2h, obtains the water-reducing agent of 40% solid content.
Embodiment 5
(1) the isopentene group polyoxyethylene ether (number-average molecular weight 2400) of 2mol is mixed with 2mol 2-glycidyl aniline
Afterwards under nitrogen protection and 94gN, the catalysis of N- dimethyl benzylamine, in 135 DEG C of generation epoxy ring opening reactions, isothermal reaction 4h is obtained
The unsaturated single epoxidized polyether of 2mol；
(2) 1mol polyetheramine D2000 is preheated to 80 DEG C under nitrogen protection, the unsaturated single epoxidized polyether of 1mol is added
Chain extension is wherein carried out, isothermal reaction 5h obtains 1mol unsaturated polyether polyamine monomers；
(3) 1mol aminotrimethylenephosphonic acid is preheated to 125 DEG C under nitrogen protection, by the unsaturated single epoxidized polyether of 1mol
It is added thereto, isothermal reaction 3h, obtains the unsaturated single phosphine based polyether monomer of 1mol；
(4) under nitrogen protection by 440g unsaturated polyether polyamine monomers, the unsaturated single phosphine based polyether monomer of 260g,
75g acrylic acid, 25g methylpropene sodium sulfonate and 40g ammonium persulfate co-dissolve are in 700g deionized water and are preheated to 30 DEG C,
Expect the I being made into 450g deionized water is dissolved in by 150g acrylic acid, 50g methylpropene sodium sulfonate and 15g Stearyl mercaptan
It is wherein reacted with being dissolved in the II material being made into 200g deionized water by 50g ferrous sulfate while being at the uniform velocity gradually added into, I expects 4h
It adds, II material 5h is added, and the dilution of 207.5g deionized water is added after keeping the temperature 3h, obtains the water-reducing agent of 40% solid content.
Water-reducing agent obtained by above-mentioned 5 embodiments is mixed in concrete and is mixed and stirred, according to GB8076-2008 " concrete
Additive " survey concrete water-reducing rate, the slump and Slump Time losing of Large, and with commercially available polycarboxylate water-reducer comparative sample ratio
Compared with the results are shown in Table 1, concrete mix are as follows: cement 360kg/m3, sand 720kg/m3, stone 950kg/m3, water-reducing agent
0.54kg/m3, sand clay content are 0% or 2%.
Table 1: the diminishing of each embodiment and comparative sample, anti-mud and slump retaining
As can be seen from Table 1, the anti-chamotte mould water-reducing agent of both sexes produced by the present invention is gathered around compared to commercially available polycarboxylate water-reducer
There are more excellent diminishing, anti-mud and guarantor to collapse effect.The present invention is using the hydroxyl and end epoxy compound on unsaturated ether polymeric monomer A
Epoxy ring opening reaction occurs for object B, and hydroxy radical content is constant in reaction process, and it is more can to prepare unsaturation using different mol ratio accordingly
Epoxidized polyether also can obtain insatiable hunger by control molar ratio when then reacting respectively with aminated compounds D, phosphine compound F
With polyether polyamine monomer, unsaturated more phosphine based polyether monomers, final water-reducing agent obtained draws money on credit chain end as polyamines and more phosphines
Perester radical, greatly strengthens the steric hindrance, inter-chain action power and end electrostatic force of branch, to be obviously improved diminishing, resist
Mud and guarantor are collapsed effect.
In conclusion the present invention is big to unsaturated ether using end ring oxygen compound, aminated compounds and phosphine compound
Monomer carries out chain extension, the more rigid radicals of water-reducing agent branch, polar group and xenogenesis charge is assigned, to strengthen water-reducing agent branch
Steric hindrance, inter-chain action power and the end electrostatic force of chain, so that the multilayer of Water-reducing Admixtures To Cements particle is adsorbed, steric hindrance between particle
Repel and the enhancing of electrostatic repulsion effect, water-reducing rate are improved；And steric hindrance and inter-chain action the power enhancing of water-reducing agent branch, no
Easily by soil Inter layer adsorption, anti-mud is improved；Water-reducing agent strand upper end epoxide, aminated compounds and phosphine simultaneously
The structure for closing object can play the role of the anti-mud of collaboration.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (9)
1. a kind of anti-chamotte mould water-reducing agent of both sexes, which is characterized in that it is prepared by following raw material: 15~60 parts of unsaturation is poly-
Ether amines monomer E, 15~60 parts of unsaturated phosphine based polyether monomer G, 2~30 parts of unsaturated minor comonomer H, 0.1~7.5 part
Oxidant, 0.2~8.5 part of reducing agent, 0.1~7.3 part of chain-transferring agent and 120~200 parts of deionized water；
The unsaturated polyether amine monomers E is prepared by following raw material: unsaturated end epoxidized polyether C and aminated compounds D,
Wherein the molar ratio of the unsaturation end epoxidized polyether C and aminated compounds D is 1:1~1:6；
The unsaturation phosphine based polyether monomer G is prepared by following raw material: unsaturated end epoxidized polyether C and phosphine chemical combination
Object F, wherein the molar ratio of the unsaturation end epoxidized polyether C and phosphine compound F is 1:1~1:6；
The unsaturation end epoxidized polyether C is prepared by following raw material: unsaturated ether polymeric monomer A, end ring oxygen compound B with
And catalyst, wherein the molar ratio of the unsaturated ether polymeric monomer A and end ring oxygen compound B is 1:1~1:4, the catalysis
Agent dosage is the 0.3~3.5% of unsaturated ether polymeric monomer A and end ring oxygen compound B gross mass.
2. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the oxidizer is insatiable hunger
With polyethers amine monomers E, unsaturated phosphine based polyether monomer G, unsaturated minor comonomer H gross mass 0.2%~5%；
The chain-transferring agent dosage is unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G, unsaturated minor comonomer H are total
The 0.3%~4.3% of quality；
The reducing agent dosage is unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G, the unsaturation total matter of minor comonomer H
The 0.5%~5.5% of amount.
3. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the unsaturated ether polymeric monomer
A is one of allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isopentene group polyoxyethylene ether or two kinds any
Or more mixture.
4. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the end ring oxygen compound B is
Bisphenol A type epoxy resin E51, bisphenol A type epoxy resin E44, ethylene glycol diglycidylether, propylene glycol diglycidylether,
Butanediol diglycidyl ether, season neopentyl glycol diglycidyl glycerin ether, 2-glycidyl aniline, polyethyleneglycol diglycidylether,
Polypropylene glycol diglycidyl ether, polypropylene glycol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerol three shrink
The mixture of one of glycerin ether or any two kinds or more.
5. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the aminated compounds D is second
Diamines, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine, m-phenylene diamine (MPD), m-xylene diamine,
Isophorone diamine,The mixture of one of alkane diamines, polyetheramine or any two kinds or more.
6. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the phosphine compound F is phosphorus
Acid, phosphorous acid, 2- phosphonobutane -1,2, one of 4- tricarboxylic acids, aminotrimethylenephosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid or any
Two kinds or more of mixture.
7. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the unsaturation minor comonomer H is
Acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, hydroxy-ethyl acrylate,
One of hydroxypropyl acrylate, hy-droxybutyl, Sodium Allyl Sulfonate, methylpropene sodium sulfonate or any two kinds or more
Mixture.
8. the anti-chamotte mould water-reducing agent of a kind of both sexes according to claim 1, which is characterized in that the catalyst is borontrifluoride
Boron/etherate, triphenylphosphine, N, N- dimethyl benzylamine, 2,4,6- tri- (dimethylamino methyl) phenol, one in triethylamine
Kind or any two kinds or more of mixture；
The oxidant is the mixed of one of hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate or any two kinds or more
Close object；
The reducing agent is one of ascorbic acid, sodium hydrogensulfite, sodium formaldehyde sulfoxylate, ferrous sulfate or any two kinds or more
Mixture；
The chain-transferring agent be one of thioacetic acid, mercaptopropionic acid, mercaptoethanol, lauryl mercaptan, Stearyl mercaptan or
Any two kinds or more of mixture.
9. a kind of preparation method of the anti-chamotte mould water-reducing agent of both sexes described in claim 1-8 any one, which is characterized in that including
Following steps:
(1) in nitrogen protection after preparation unsaturation end epoxidized polyether C: unsaturated ether polymeric monomer A is mixed with end ring oxygen compound B
Under catalyst, in 80 DEG C~150 DEG C generation epoxy ring opening reactions, it is poly- to obtain unsaturated end ring oxygen by 3~7h of isothermal reaction
Ether C；
(2) it prepares unsaturated polyether amine monomers E: aminated compounds D being preheated to 40~80 DEG C under nitrogen protection, it will be unsaturated
End epoxidized polyether C is added thereto carry out chain extension, and 3~5h of isothermal reaction obtains unsaturated polyether amine monomers E；
(3) it prepares unsaturated phosphine based polyether monomer G: phosphine compound F being preheated to 90 DEG C~140 DEG C under nitrogen protection,
Unsaturated end epoxidized polyether C is added thereto, 3~5h of isothermal reaction, obtains unsaturated phosphine based polyether monomer G；
(4) water-reducing agent is prepared: under nitrogen protection by unsaturated polyether amine monomers E, unsaturated phosphine based polyether monomer G, part
Unsaturated minor comonomer H and oxidant co-dissolve in deionized water and are preheated to 25~50 DEG C, by remaining unsaturated small list
Body H and chain-transferring agent be dissolved in be made into deionized water I material and be dissolved in by reducing agent be made into deionized water II material simultaneously it is even
Speed, which is gradually added into, is wherein reacted, and I expects that 2~4h is added, and II material is later than I and expects that 0.5~1h is added, and is added one after keeping the temperature 1~3h
Quantitative deionized water dilution, obtains the water-reducing agent of 40% solid content.
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| CN113773457A (en) * | 2021-08-26 | 2021-12-10 | 北京工业大学 | Low-creep high-efficiency polycarboxylate superplasticizer and preparation method thereof |
| CN117624580A (en) * | 2023-11-10 | 2024-03-01 | 江苏博思通新材料有限公司 | Nonionic anti-mud drag reducer and preparation method thereof |
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