CN107337789A - A kind of preparation method and applications of small molecule phosphate dispersant - Google Patents
A kind of preparation method and applications of small molecule phosphate dispersant Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
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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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of small molecule phosphoric acid dispersant, and it has following architectural features：Contain one or more amide groups in its structure（‑CO‑NH‑）, one or more bidentate phosphorous acids are contained in the end in its structure（‑CH(OH)(PO3H2)2）, have polyether segment, amide group link polyether segment and end group in structure, the polyethers section weight average molecular weight is between 200 to 5000.The function of slump protection of the small molecule phosphoric acid dispersant is good, can be adsorbed onto cement particle surface faster, and this is beneficial to the adaptability problem for solving current water reducer and clay.And having the ability for delaying hydrated cementitious, this has preferable benefit to concrete hot weather construction, pumping construction.
Description
Technical field
The present invention relates to a kind of preparation method and applications of small molecule phosphate dispersant, belong to concrete admixture technology
Field.
Background technology
With the fast development of China's economy, various novel building constantly lands, and shows Super High, large span
Development trend, undoubtedly the intensity to concrete and durability propose higher requirement for this.And current maximally effective coping style,
Polyalcohol water reducing agent is exactly mixed in concrete admixture, water reducer is a kind of surfactant in essence, is mainly changed
Kind concrete flowability, control condensation or firm time, improve concrete strength etc..
What polycarboxylate water-reducer was applied at present is the most extensive, but polycarboxylic acids diminishing is found from theoretical research and practical application
There is consistency problem in agent and some concrete materials, this shows particularly evident, master in the higher aggregate environment of clay content
Showing as volume will substantially increase, and concrete slump loss is fast, easily cross and mix isolation.Therefore solve carboxylic acid water reducer containing
It is necessary and anxious to be resolved in academia and Practical Project field that adaptability problem in mud aggregate has become pendulum at present
Problem.
Patent document CN103508696A reports anti-mud water reducer of a kind of polycarboxylic acids and preparation method thereof.Gather with traditional
Carboxylic acid water reducer is compared, and author introduces the propylene oxide units of oiliness, so as to portion by changing the component units of polyether structure
Divide suction-operated of the soil to diminishing agent molecule reduced in concrete.The patent shortcoming is the synthesized anti-mud effect of polymer
Fruit unobvious, and initial dispersion decreases.
Patent US2014/0039098 discloses a kind of synthetic method of bis phosphoric acid base water reducer.In 175 DEG C and 20mBar
Prepared under vacuum degree condition by poly glycol monomethyl ether, polyacrylic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid reaction.Although this kind of bis phosphoric acid
Base water reducer is provided with certain sulfur resistive acid ion and anti-stick soil characteristics, but the method reaction time is grown, industrialized condition
Harshness, esterification yield is not high, and early stage, equipment of industrial product investment was high.
Chinese patent CN 103467670A report a kind of preparation side of the anti-stick soil type polycarboxylate water-reducer of phosphorous acid groups
Method.The water reducer is by isoamyl alcohol polyoxyethylene ether, quaternary ammonium salt oligomer, aminotrimethylene phosphoric acid and unsaturated carboxylic acid etc.
Copolymerization.The water reducer is insensitive to the clay content problem of aggregate.Patent CN 103641963A, CN
104031217A, CN 105236806A also disclose the anti-Property of Clay of similar phosphorous acid groups water reducer.On but
The preparation method for stating type water reducer is generally synthetic the unsaturated monomer of phosphorous acidic groups, and then is amounted to by radical polymerization
Aggregate into, therefore cause synthesis step cumbersome, and technology controlling and process is difficult.
Polycarboxylate water-reducer has stronger adsorption tendency in clay mineral, there is high sensitivity to aggregate clay content
Degree, this all brings very big influence to concrete transportation, working condition and intensity.Do not have for clay adaptability problem at present yet
The solution having had, in addition to patent described above, middle compounding some small molecules such as sodium gluconate, sucrose, lemon can only be passed through
Lemon acid, sylvite etc. improve concrete properties, can not fundamentally solve polycarboxylate water-reducer in the suitable of high clay content area
Answer sex chromosome mosaicism.Therefore developing one kind has more excellent diminishing and retardation capability, and can improve the high-performance water reducing agent of clay adaptability
With very important practical significance.
The content of the invention
It is too high to clay content sensitiveness in aggregate in unresolved existing polycarboxylate water-reducer, and anti-chamotte mould polycarboxylic acids diminishing
The problem of processing step of agent is more numerous and diverse, the present invention provide a kind of preparation method of small molecule phosphate dispersant and its answered
With.
Small molecule phosphate dispersant of the present invention has following architectural features：The primary of its structure is characterized in containing 1-
3 amide groups (- CO-NH-), secondly, one or more bidentate phosphorous acids are contained in the end in the type molecular structure
(-CH(OH)(PO3H2)2), and the bidentate phosphate group is located at the end in molecule, and this bidentate phosphorous acid has very
Strong adsorptivity；Again, there are polyether segment, amide group link polyether segment and end group, institute in the type molecular structure
Polyethers section weight average molecular weight is stated between 200 to 5000,
The polyether chain can be polymerized by different alkyleneoxide randoms or block polymerization, or pure alkylene oxide, and this is right
The hydrophobic and hydrophily for adjusting its structure plays an important role.
Compared with ester bond, amido link not facile hydrolysis, stability of the structure in cement system may advantageously facilitate；
The molecular structural formula of small molecule phosphate dispersant of the present invention is as follows, there is two kinds of structures of III a and III b：
R1And R2Each independent expression alkyl, alkylene or cycloalkyl.
The preparation method of small molecule phosphate dispersant of the present invention, comprises the following steps：
A. amidation process is carried out under catalytic amount peroxide agent C effects by amine terminated polyether A and monomer acid anhydrides B, generated
Intermediate product D, react and carried out under the conditions of cushioning liquid F；
B. the hydroxy-acid group of the product D ends is carried out phosphitylation, obtain final goal product E.
Amido link is that amido after small molecule anhydride reaction with forming in polyetheramine, its one end link polyethers section, the other end
For the carboxylic acid product after acid anhydrides open loop, exposed carboxylic acid functional can next step phosphitylation reaction.
R in the small molecule phosphate dispersant1And R2It is to be brought by monomer acid anhydrides B reactions, is that acid anhydrides is removed in its structure
Outer part, i.e. R1And R2Structure depend on monomer acid anhydrides B used structure.
The synthetic route of small molecule phosphate dispersant of the present invention is as follows：
The amine terminated polyether A is that the alcohol substituted using alkyl or aryl is obtained for corresponding initiator, and its structural formula is such as
Be single-ended amino-polyether shown in (I a), or be double-end amino polyethers as shown (I b), or be triamido polyethers, the Amino End Group
Polyethers A weight average molecular weight range is between 200~5000.
Wherein, R1For H or with C1~C10 alkyl, or the alcoholic extract hydroxyl group of aryl substitution
Q be C2~C24 alkylidene, m=4~112, n=4~112；
The amine terminated polyether A both include commercialization purchase, polyetheramine type as follows, comprising M series, ED series with
And T series commercially produced products, can also be by testing self-control synthesis.
Single-ended amino-polyether therein, contain a primary amine group in its molecular structure, and the amido is located at molecular structure
End, the other end are polyether segment, including commercially available M600, M1000, M2005, M2070.
Described double-end amino polyethers, contain two primary amine groups in its molecular structure, be respectively at the two of molecular structure
End, polyether segment are among two amidos, this such as commercially available HK511, ED600, ED900, ED2003.
Described polyamino polyethers, there is the amido of 3 and the above in molecular structure, the position of amido is located at molecular structure
End, polyether chain are between amido, such as commercially available T403, T3000, T5000.
The amine terminated polyether A is that the alcohol substituted using alkyl or aryl is corresponding initiator, is total to epoxyalkane QO
It is poly- to obtain.
Preferable epoxyalkane QO is oxirane, expoxy propane, 1- epoxy butanes, 2,3- epoxy butanes, 2- methyl isophthalic acids,
At least one of 2- expoxy propane (epoxy iso-butane), 1- epoxypentanes.
More preferably oxirane and/or expoxy propane are used in the present invention.
The structural formula of the monomer B is such as shown in (II a)：
Wherein, IIa is containing double bond structure such as maleic anhydride, citraconic anhydride, itaconic anhydride etc., corresponding gained in structural formula
R in small molecule phosphoric acid dispersant2As following structure：
IIa or in structural formula without double bond structure such as succinic anhydride, 2- methyl succinic acid anhydrides, corresponding gained small molecule
R in phosphoric acid dispersant2As following structure
The step (a) is amidation process, and polyetheramine A generates amide-type intermediate product D with the reaction of anhydrides substrate B.
The cushioning liquid E can be sodium dihydrogen phosphate or potassium dihydrogen phosphate or sodium dihydrogen phosphate and disodium hydrogen phosphate mixing
The mixture of thing or potassium dihydrogen phosphate and dipotassium hydrogen phosphate, it is necessary to control pH value of solution in 7-9 during reaction.
Reaction temperature is 55~85 DEG C in the step (a), reaction time 2-6h.
Per-compound C can be Ammonium Persulfate 98.5, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, mistake in the step (a)
The per-compound such as sodium oxide molybdena, unlimited and example noted earlier.
It should be noted that in the present invention, most of amine terminated polyether A take part in reaction, and conversion ratio is more than 80%.But
Unreacted monomer and accessory substance can directly be applied without separation, its dispersion effect will not be caused to significantly affect.
Phosphitylation in the step (b) is the hydroxy-acid group (- COOH) in intermediate product D is converted into C (OH)
(PO3H2)2。
Chlorinating agent and phosphitylation reagent are additionally added in step (b) makes hydroxy-acid group (COOH) be converted into C (OH)
(PO3H2)2, wherein chlorinating agent makes hydroxy-acid group (COOH) be changed into COCl, and phosphitylation reagent makes COCl be changed into phosphorous acid
Group.
It is preferred that the chlorinating agent is phosphorus trichloride, thionyl chloride or phosphorus pentachloride, phosphitylation reagent is phosphorous acid, three
Phosphorus chloride, three (trimethyl silane) phosphite esters or Trimethyl phosphite.
More preferably described chlorinating agent is phosphorus trichloride, and phosphitylation reagent is phosphorus trichloride or phosphorous acid；It is preferred that chloro
The dosage of reagent is 1.0-1.1 times of equivalent of hydroxy-acid group (COOH), and the dosage of phosphitylation reagent is hydroxy-acid group (COOH)
2.0-3.0 times of equivalent.
More preferably chlorinating agent is phosphorus trichloride, and phosphitylation reagent is phosphorus trichloride or phosphorous acid.
The phosphitylation reaction is known response type, and those skilled in the art generally know its reaction principle and reaction
Condition.
Specifically, the condition of phosphitylation reaction is：60-100 DEG C is warming up to, 1-24 hours is reacted, is more preferably warming up to
60-90 DEG C, 4-24 hours are reacted, after question response terminates, add a certain amount of water, 100 DEG C of hydrolysis 1-2 hours.
In the present invention, the Alkyl means straight or branched alkyl, for example, C1~C10 alkyl can be methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,1- bis-
Methyl-propyl, 1,2- dimethyl propyls, n-hexyl, isohesyl, Sec-Hexyl, new hexyl, 3- methyl amyls, 1,1- dimethyl butyrates
Base, 1,3- dimethylbutyls, 1- ethyl-butyls, 1- methyl isophthalic acids-ethyl propyl, n-heptyl and its isomers, n-octyl and its different
Structure body, n-nonyl and its isomers or positive decyl and its isomers.
The aryl represents monocyclic aryl or condensed ring together and the cyclophane base containing 6 to 10 carbon atoms in ring, such as benzene
Base, o-tolyl, a tolyl, p-methylphenyl, 1- naphthyls, 2- naphthyls or indenyl.
In order to obtain preferable storage stability, generally also need to adjust last production concentration extremely no more than 40%, it is excellent
30%~40% is selected, the percentage is mass percent.
Small molecule phosphoric acid dispersant of the present invention is as hydraulic binding agent and/or the moisture of latent hydraulicity cementing agent
The application of the dispersant of granular media.Generally, the hydraulic binding agent is at least one in cement, lime, gypsum, anhydrous gypsum
Kind, preferably cement, the latent hydraulicity cementing agent are volcanic ash, flyash or blast-furnace cinder.It is cementing based on the hydraulicity
Agent and/or latent hydraulicity cementing agent, the volume of small molecule phosphoric acid dispersant of the present invention is in 0.01% weight to 10% weight
Amount, especially 0.05% weight to 5% weight.
Beneficial effects of the present invention：
1. phosphate can be hydrolyzed rapidly as adsorption group under strong alkali environment, so as to cause water reducer water reducing ability
Rapid loss, and P and C atoms are joined directly together the present invention as adsorption group, in phosphorous acid using bidentate phosphorous acid, can be with
Avoid hydrolyzing, function of slump protection is good.
2. bidentate phosphorous acid has stronger coordination ability, cement particle surface can be adsorbed onto faster, this is beneficial to
Solves the adaptability problem of current water reducer and clay.
3. compared with conventional carboxylic acid's water reducer, the polymeric additive of bidentate phosphorous acids of the invention is of the present invention
Two class formations show certain ability for delaying hydrated cementitious, this has preferable to concrete hot weather construction, pumping construction
Benefit.
Embodiment
The present invention is described in detail below by example, and these examples are merely illustrative, do not represent the limitation present invention
The scope of application, medicine or reagent used are that general analysis are pure in embodiment, can be bought by usual channel.
In the embodiment of the present invention, the molecular weight of polymer is determined using gel permeation chromatograph (abbreviation GPC), institute of the present invention
It is weight average molecular weight (hereinafter referred to as Mw) to state molecular weight；
Reaction conversion ratio is tested by GPC, calculates polyether macromonomer surplus, you can is obtained, it is clear that conversion ratio refers to herein
Polyether macromonomer A conversion ratio.
The above-mentioned test GPC produces for Wyatt Technology of the U.S., wherein gel column：Shodex SB806+803 two
Root chromatogram column is connected；Elutriant：0.1M NaNO3 solution；Flow phase velocity：0.8ml/min；Injection：20 μ l 0.5% are water-soluble
Liquid；Detector：Shodex RI-71 type differential refraction detectors；Reference material：Polyethylene glycol GPC standard specimens (Sigma of U.S. Order
Ritchie company, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232).
In Application Example of the present invention, except special instruction, used cement is the south of the River-small wild water in field mud
(P.O42.5), stone is the rubble that particle diameter is 5~20mm continuous gradings.Sand is as shown in table 1.1.Flowing degree of net paste of cement is surveyed
Examination is carried out with reference to GB/T8077-2000 standards, cement 300g, amount of water 87g, and water is determined on plate glass after stirring 3min
Cement paste fluidity, the results are shown in Table 1.0.
The preparation method of polyetheramine is known to industry.It can be obtained by following three kinds of modes, first, numerous amino
Polyethers can be bought from commercial company, second, in industry usually through PPG end under the conditions of high temperature Gao Ya, with
Terminal amido is realized in hydrogen and ammonia reaction.3rd, can also be in laboratory using leaving away method, by by PPG end
Easy leaving group such as sulfonic group, halogen group etc. are first changed into, then is realized by amination.
Embodiment 1
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M2070 (EO/
PO=31:10, Mw=2000,0.1mol) 200g, it is warming up to 70 DEG C, adds 10ml sodium dihydrogen phosphates as cushioning liquid,
Ammonium Persulfate 98.5 0.585g.Take maleic anhydride (0.12mol) 11.7g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), delay
Slowly it is added dropwise in polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add the regulation of 1mol/L sodium hydroxide solutions
9~10,70 DEG C of insulation reaction 4h of pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 75
DEG C reaction 12h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 2
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M1000 (EO/
PO=19:3, Mw=1000,0.1mol) 100g, it is warming up to 70 DEG C, adds 10ml sodium dihydrogen phosphates as cushioning liquid,
Ammonium Persulfate 98.5 0.585g.Take maleic anhydride (0.12mol) 11.7g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), delay
Slowly it is added dropwise in polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add the regulation of 1mol/L sodium hydroxide solutions
9~10,70 DEG C of insulation reaction 4h of pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 75
DEG C reaction 12h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 3
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M600 (EO/
PO=1:9, Mw=600,0.1mol) 60g, 55 DEG C are warming up to, adds 10ml sodium dihydrogen phosphates as cushioning liquid, over cure
Acid amide 0.585g.Maleic anhydride (0.12mol) 11.7g is taken to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), slowly drop
Add in polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, it is molten to add the regulation of 1mol/L sodium hydroxide solutions
9~10,55 DEG C of insulation reaction 6h of liquid pH.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 75
DEG C reaction 12h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 4
In the present embodiment, polyetheramine used is double amino-polyether amine ED600, stirred equipped with motor machine, heated at constant temperature
In the 1000ml four-hole boiling flasks of oil bath, polyetheramine ED600 (EO/PO=9.0 are added:3.6, Mw=600,0.1mol) 60g, heating
To 70 DEG C, 10ml sodium dihydrogen phosphates are added as cushioning liquid, Ammonium Persulfate 98.5 1.17g.Take maleic anhydride (0.24mol)
23.4g is dissolved in 25ml methanol (acid anhydrides facile hydrolysis, matching while using), is slowly added dropwise into polyetheramine noted earlier, stirs to it
For a uniform phase, if pH<8, add 9~10,70 DEG C of insulation reaction 4h of 1mol/L sodium hydroxide solutions regulation pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 109.8g (0.8mol) is added in 30min, is warming up to
90 DEG C of reaction 4h, then add water 167.4g (9.3mol), are warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 5
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine ED2003
(EO/PO=39:6, Mw=2000,0.1mol) 200g, 70 DEG C are warming up to, it is molten as buffering to add 10ml sodium dihydrogen phosphates
Liquid, potassium peroxydisulfate 1.17g.Maleic anhydride (0.24mol) 23.4g is taken to be dissolved in 25ml methanol (acid anhydrides facile hydrolysis, matching while using),
It is slowly added dropwise into polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add 1mol/L sodium hydroxide solutions and adjust
Save 9~10,60 DEG C of insulation reaction 4h of pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 109.8g (0.8mol) is added in 30min, is warming up to
75 DEG C of reaction 12h, then add water 167.4g (9.3mol), are warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction cooling
To room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 6
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M2070 (EO/
PO=31:10, Mw=2000,0.1mol) 200g, it is warming up to 70 DEG C, adds 10ml sodium dihydrogen phosphates as cushioning liquid,
Potassium peroxydisulfate 0.585g.Take succinic anhydride (0.12mol) 12.0g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), delay
Slowly it is added dropwise in polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add the regulation of 1mol/L sodium hydroxide solutions
9~10,70 DEG C of insulation reaction 4h of pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 75
DEG C reaction 12h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 7
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M2070 (EO/
PO=31:10, Mw=2000,0.1mol) 200g, it is warming up to 85 DEG C, adds 10ml sodium dihydrogen phosphates as cushioning liquid,
Ammonium Persulfate 98.5 0.585g.Take 2- methyl succinics acid anhydrides (0.12mol) 13.7g to be dissolved in 20ml methanol, be slowly added dropwise to above institute
State in polyetheramine, it is a uniform phase to stir to it, if pH<8,1mol/L sodium hydroxide solutions regulation pH value of solution 9~10 is added,
85 DEG C of insulation reaction 2h.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 60
DEG C reaction 24h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 2h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 8
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M2070 (EO/
PO=31:10, Mw=2000,0.1mol) 200g, 70 DEG C are warming up to, it is molten as buffering to add 10ml sodium dihydrogen phosphates
Liquid, Ammonium Persulfate 98.5 0.585g.Take citraconic anhydride (0.12mol) 13.4g be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, it is current existing
With), it is slowly added dropwise into polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, it is molten to add 1mol/L sodium hydroxides
9~10,70 DEG C of insulation reaction 4h of liquid regulation pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 75
DEG C reaction 12h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 9
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine T3000 (Mw
=3000,0.1mol) 300g, 70 DEG C are warming up to, adds 10ml sodium dihydrogen phosphates as cushioning liquid, Ammonium Persulfate 98.5
0.585g.Take maleic anhydride (0.12mol) 11.7g to be dissolved in 20ml methanol, be slowly added dropwise into polyetheramine noted earlier, stir
It is a uniform phase to it, if pH<8, add 9~10,70 DEG C of insulation reaction 4h of 1mol/L sodium hydroxide solutions regulation pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4mol) is added in 30min, is warming up to 75
DEG C reaction 12h, then add water 83.7g (4.65mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, uses
30% alkali lye is neutralized to pH to 10 or so, and 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction is cooled to
Room temperature, solution concentration is diluted with water to as 30%-40% or so.
Embodiment 10
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine T5000 (Mw
=5000,0.1mol) 500g, 60 DEG C are warming up to, adds 10ml sodium dihydrogen phosphates as cushioning liquid, Ammonium Persulfate 98.5
0.585g.Take maleic anhydride (0.12mol) 11.7g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), be slowly added dropwise to
In polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add 1mol/L sodium hydroxide solutions regulation pH value of solution 9
~10,85 DEG C of insulation reaction 6h.
After acylation reaction terminates, 25 DEG C are cooled to, thionyl chloride 13.1g (0.11mol) and tri-chlorination are added in 30min
Phosphorus 41.1g (0.3mol), 75 DEG C of reaction 12h are warming up to, then add water 83.7g (4.65mol), it is anti-to be warming up to 105 DEG C of hydrolysis
Answer 1h.Reaction is cooled to room temperature, is neutralized to pH to 10 or so with 30% alkali lye, 110 DEG C are continued to react 0.5-1 hours, are removed
Unreacted formaldehyde.Reaction is cooled to room temperature, is diluted with water to solution concentration as 30%-40% or so.
Embodiment 11
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine T3000 (Mw
=3000,0.1mol) 300g, 70 DEG C are warming up to, adds 10ml sodium dihydrogen phosphates as cushioning liquid, Ammonium Persulfate 98.5
0.585g.Take maleic anhydride (0.12mol) 11.7g to be dissolved in 20ml methanol, be slowly added dropwise into polyetheramine noted earlier, stir
It is a uniform phase to it, if pH<8, add 9~10,70 DEG C of insulation reaction 4h of 1mol/L sodium hydroxide solutions regulation pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 27.4g (0.2mol) and phosphorous acid are added in 30min
16.4g (0.2mol), 75 DEG C of reaction 12h are warming up to, water 83.7g (4.65mol) is then added, is warming up to 105 DEG C of hydrolysis
1h.Reaction is cooled to room temperature, is neutralized to pH to 10 or so with 30% alkali lye, 110 DEG C are continued to react 0.5-1 hours, are removed not
The formaldehyde of reaction.Reaction is cooled to room temperature, is diluted with water to solution concentration as 30%-40% or so.
Embodiment 12
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M2070 (EO/
PO=31:10, Mw=2000,0.1mol) 200g, it is warming up to 70 DEG C, adds 10ml sodium dihydrogen phosphates as cushioning liquid,
Ammonium Persulfate 98.5 0.585g.Take citraconic anhydride (0.12mol) 13.4g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), delay
Slowly it is added dropwise in polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add the regulation of 1mol/L sodium hydroxide solutions
9~10,70 DEG C of insulation reaction 4h of pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus pentachloride 22.9g (0.11mol) and phosphorous acid are added in 30min
24.6g (0.3mol), 75 DEG C of reaction 12h are warming up to, water 83.7g (4.65mol) is then added, is warming up to 105 DEG C of hydrolysis
1h.Reaction is cooled to room temperature, is neutralized to pH to 10 or so with 30% alkali lye, 110 DEG C are continued to react 0.5-1 hours, are removed not
The formaldehyde of reaction.Reaction is cooled to room temperature, is diluted with water to solution concentration as 30%-40% or so.
Comparative example 1 (while maleic anhydride amount reduces)
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M1000 (EO/
PO=19:3, Mw=1000,0.1mol) 100g, it is warming up to 60 DEG C, adds 10ml sodium dihydrogen phosphates as cushioning liquid,
Ammonium Persulfate 98.5 0.585g.Take maleic anhydride (0.04mol) 4.0g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), delay
Slowly it is added dropwise in polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, add the regulation of 1mol/L sodium hydroxide solutions
9~10,85 DEG C of insulation reaction 6h of pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 27.4g (0.2mol) and phosphorous acid are added in 30min
16.4g (0.2mol), 75 DEG C of reaction 12h are warming up to, water 83.7g (4.65mol) is then added, is warming up to 105 DEG C of hydrolysis
1h.Reaction is cooled to room temperature, is neutralized to pH to 10 or so with 30% alkali lye, 110 DEG C are continued to react 0.5-1 hours, are removed not
The formaldehyde of reaction.Reaction is cooled to room temperature, is diluted with water to solution concentration as 30%-40% or so.
(5000) polyetheramine molecular weight 10000, overruns comparative example 2
Stirred equipped with motor machine, in the 3000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M10000
(EO/PO=20:5, Mw=10000,0.1mol) 1000g, 60 DEG C are warming up to, adds 10ml sodium dihydrogen phosphates as buffering
Solution, Ammonium Persulfate 98.5 0.585g.Take maleic anhydride (0.12mol) 11.7g be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, it is current existing
With), it is slowly added dropwise into polyetheramine noted earlier, it is a uniform phase to stir to it, if pH<8, it is molten to add 1mol/L sodium hydroxides
9~10,85 DEG C of insulation reaction 6h of liquid regulation pH value of solution.
After acylation reaction terminates, 25 DEG C are cooled to, phosphorus pentachloride 22.9g (0.11mol) and phosphorous acid are added in 30min
24.6g (0.3mol), 75 DEG C of reaction 12h are warming up to, water 83.7g (4.65mol) is then added, is warming up to 105 DEG C of hydrolysis
1h.Reaction is cooled to room temperature, is neutralized to pH to 10 or so with 30% alkali lye, 110 DEG C are continued to react 0.5-1 hours, are removed not
The formaldehyde of reaction.Reaction is cooled to room temperature, is diluted with water to solution concentration as 30%-40% or so.
Comparative example 3 (is not added with peroxide)
Stirred equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, adding polyetheramine M1000 (EO/
PO=19:3, Mw=1000,0.1mol) 100g, 60 DEG C are warming up to, adds 10ml sodium dihydrogen phosphates as cushioning liquid.
Take maleic anhydride (0.12 mol) 11.7g to be dissolved in 20ml methanol (acid anhydrides facile hydrolysis, matching while using), be slowly added dropwise to above institute
State in polyetheramine, it is a uniform phase to stir to it, if pH<8,1 mol/L sodium hydroxide solutions regulation pH value of solution 9~10 is added,
85 DEG C of insulation reaction 6h.After acylation reaction terminates, 25 DEG C are cooled to, phosphorus trichloride 54.9g (0.4 mol) is added in 30min,
75 DEG C of reaction 12h are warming up to, water 83.7g (4.65mol) is then added, is warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room
Temperature, pH to 10 or so is neutralized to 30% alkali lye, 110 DEG C are continued to react 0.5-1 hours, remove unreacted formaldehyde.Reaction
Room temperature is cooled to, is diluted with water to solution concentration as 30%-40% or so.
Application examples：
Flowing degree of net paste of cement presses GB/T 8077-2000《Concrete admixture is even to property experimental method》Tested, its
In cement used be small wild water in field mud (300g), the ratio of mud 0.29.
Montmorillonite is purchased from Aladdin reagent (Shanghai) Co., Ltd., and its content is more than 95% (mass fraction), specific surface area
10.86 m2/ g, average grain diameter are 1.52 μm, montmorillonite primary chemical composition such as following table：
The montmorillonite primary chemical of table 1.1 forms
| SiO2 | Al2O3 | Fe2O3 | CaO | MgO | Na2O | K2O |
| 54.0 | 17.0 | 5.2 | 1.5 | 2.5 | 0.4 | 1.5 |
The polymerisation conversion of table 1.0 and paste flowing degree
As shown in table 1.0, compared with control sample 1-3, under the conditions of 2.0 ‰ volumes, synthesized sample in embodiment 1-12
For paste flowing degree between 236mm to 258mm, this shows that it has preferable initial dispersion.After 0.5% montmorillonite is added
(cement quality fraction), it will be seen that control sample 1-3, paste flowing degree declines substantially, decline 27mm to 45mm, and phase
Embodiment sample 1-12 is answered only to decline 2-15mm, this shows that synthesized sample has good anti-Property of Clay.
Table 1.2 is starched guarantor and collapsed and setting time test only
Compared with comparative example 1-3, this patent newly synthesizes water reducer sample, in filling in the case of montmorillonite, cement paste
Fluidity initial abstraction is substantially small compared with comparative sample, illustrates that this patent water reducer has good clay adaptability.Simultaneously with it is right
Compared than sample, the new water reducer of this patent, which has, certain delays the effect of hydrated cementitious and guarantor is collapsed effect, average initial set and final set
Time delays 1-2h compared with control sample.
Claims (12)
1. a kind of small molecule phosphate dispersant, it is characterised in that there are following architectural features：Contain 1-3 acyl in its structure
One or more bidentate phosphorous acids (- CH (OH) (PO is contained in amine groups (- CO-NH-), the end in its structure3H2)2), knot
There are polyether segment, amide group link polyether segment and end group in structure, the polyethers section weight average molecular weight is 200 to 5000
Between；
The polyether chain is polymerized by different alkyleneoxide randoms or block polymerization, or for pure alkylene oxide.
2. small molecule phosphate dispersant according to claim 1, it is characterised in that the small molecule phosphate dispersant
Molecular structural formula it is as follows, have two kinds of structures of III a and III b：
R1And R2Each independent expression alkyl, alkylene or cycloalkyl.
3. the preparation method of the small molecule phosphate dispersant of claim 1 or 2, it is characterised in that comprise the following steps：
A. amidation process is carried out under catalytic amount peroxide agent C effects by amine terminated polyether A and monomer acid anhydrides B, generation is middle
Product D, react and carried out under the conditions of cushioning liquid F；
B. the hydroxy-acid group of the end of the intermediate product D is carried out phosphitylation, obtain final goal product E.
Amido link is that amido after small molecule anhydride reaction with forming in polyetheramine, and its one end link polyethers section, the other end is acid
Carboxylic acid product after acid anhydride open loop, exposed carboxylic acid functional can next step phosphitylation reaction；
R in the small molecule phosphate dispersant1And R2Be by monomer acid anhydrides B reaction brought, be in its structure in addition to acid anhydrides
Part, i.e. R1And R2Structure depend on monomer acid anhydrides B used structure；
The synthetic route of the small molecule phosphate dispersant is as follows：
The amine terminated polyether A is that the alcohol substituted using alkyl or aryl is obtained for corresponding initiator, its structural formula such as (I a)
It is shown, it is single-ended amino-polyether, or as being double-end amino polyethers shown in (I b), or be triamido polyethers, the amine terminated polyether
A weight average molecular weight range is between 200~5000；
Wherein, R1For H or with C1~C10 alkyl, or the alcoholic extract hydroxyl group of aryl substitution；
Q be C2~C24 alkylidene, m=4~112, n=4~112；
The structural formula of the monomer acid anhydrides B is such as shown in (II a)：
Wherein, IIa is containing double bond structure such as maleic anhydride, citraconic anhydride, itaconic anhydride etc., corresponding small point of gained in structural formula
R in sub- phosphoric acid dispersant2As following structure：
IIa or in structural formula without double bond structure such as succinic anhydride, 2- methyl succinic acid anhydrides, corresponding gained small molecule phosphoric acid
R in dispersant2As following structure：
Per-compound C is in Ammonium Persulfate 98.5, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, sodium peroxide in the step (a)
Any one.
The cushioning liquid E can be sodium dihydrogen phosphate or potassium dihydrogen phosphate or sodium dihydrogen phosphate and disodium hydrogen phosphate mixture or
The mixture of potassium dihydrogen phosphate and dipotassium hydrogen phosphate, it is necessary to control pH value of solution in 7-9 during reaction.
4. according to the method for claim 3, it is characterised in that
Described single-ended amino-polyether, contain a primary amine group in its molecular structure, and the amido is located at molecular structure end,
The other end is polyether segment；
Described double-end amino polyethers, contain two primary amine groups in its molecular structure, be respectively at the both ends of molecular structure, gather
Ether segment is among two amidos；
Described polyamino polyethers, there is the amido of 3 and the above in molecular structure, the position of amido is located at the end of molecular structure
End, polyether chain are between amido.
5. the method according to claim 3 or 4, it is characterised in that the amine terminated polyether A is taken using alkyl or aryl
The alcohol in generation is corresponding initiator, is copolymerized and obtains with epoxyalkane QO；
The epoxyalkane QO is oxirane, expoxy propane, 1- epoxy butanes, 2,3- epoxy butanes, 2- methyl isophthalic acids, 2- epoxies
At least one of propane (epoxy iso-butane), 1- epoxypentanes.
6. according to the method for claim 5, it is characterised in that the epoxyalkane QO is oxirane and/or epoxy third
Alkane.
7. according to the method described in any one of claim 3-6, it is characterised in that reaction temperature is in the step (a)
55~85 DEG C, reaction time 2-6h.
8. according to the method described in any one of claim 3-7, it is characterised in that be additionally added chlorinating agent in step (b)
Hydroxy-acid group (COOH) is set to be converted into C (OH) (PO with phosphitylation reagent3H2)2, wherein chlorinating agent makes hydroxy-acid group (COOH)
It is changed into COCl, phosphitylation reagent makes COCl be changed into phosphorous acid；The dosage of chlorinating agent is hydroxy-acid group (COOH)
1.0-1.1 times of equivalent, the dosage of phosphitylation reagent is 2.0-3.0 times of equivalent of hydroxy-acid group (COOH).
9. according to the method for claim 8, it is characterised in that the chlorinating agent is phosphorus trichloride, thionyl chloride or five
Phosphorus chloride, phosphitylation reagent are phosphorous acid, phosphorus trichloride, three (trimethyl silane) phosphite esters or Trimethyl phosphite.
10. according to the method for claim 9, it is characterised in that the chlorinating agent is phosphorus trichloride, phosphitylation reagent
For phosphorus trichloride or phosphorous acid.
11. the method according to claim 9 or 10, it is characterised in that the chlorinating agent is phosphorus trichloride, phosphitylation
Reagent is phosphorus trichloride or phosphorous acid.
12. the application of the small molecule phosphoric acid dispersant described in claim 1 or 2, it is characterised in that as hydraulic binding agent
And/or the application of the dispersant of the aqueous dispersion of latent hydraulicity cementing agent；The hydraulic binding agent is cement, lime, stone
At least one of cream, anhydrous gypsum, the latent hydraulicity cementing agent are volcanic ash, flyash or blast-furnace cinder；Based on institute
Hydraulic binding agent and/or latent hydraulicity cementing agent are stated, the volume of the small molecule phosphoric acid dispersant is in 0.01%-10% weights
Amount ratio.
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