CN107043227A - A kind of anti-stick soil type polymeric dispersant and preparation method thereof - Google Patents
A kind of anti-stick soil type polymeric dispersant and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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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- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0225—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing oxygen
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- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0231—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing nitrogen
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- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0237—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing sulfur
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- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0243—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/18—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenols substituted by carboxylic or sulfonic acid groups
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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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Abstract
The present invention discloses anti-stick soil type polymeric dispersant of a kind of anti-stick soil type and preparation method thereof, the anti-stick soil type polymeric dispersant of anti-stick soil type is polymerized by monomer A, B, E, monomer A is the aromatic series with carboxylic acid or phosphate group, monomer B is aldehyde, and it is the aromatic compounds with sulfonic acid group or hydroxyl that monomer E, which is,.The anti-stick soil type polymeric dispersant has remarkable anti-mud effect.
Description
Technical field
The present invention relates to a kind of anti-stick soil type polymeric dispersant and preparation method thereof and its application, belong to concrete admixture
Technical field.
Background technology
Water reducer is a kind of polymeric dispersant, but is a kind of surfactant in essence, mainly improves concrete
Mobility, control condensation or firm time, raising concrete strength etc..In the preparation process of concrete, it usually needs add
The mixing water more much more than water required for hydration or hardening process, concrete base substrate can be caused however as extra water evaporation
Long-living gap, so that mechanical strength and tolerance are significantly deteriorated, therefore concrete admixture is mainly water reducer
Addition is very important.
Polycarboxylate water-reducer is a kind of high-performance water reducing agent, and since the eighties in last century, no matter is poly carboxylic acid series water reducer
It is that research or application all have made great progress.Polycarboxylate water-reducer is made up of from structure two parts, and one is on main chain
Adsorption group be mainly hydroxy-acid group, two be that there is provided steric hindrance for the side chain that constitutes of polyether macromonomer.At present on polycarboxylic acids
Water reducer property modification patent report is a lot, relates generally to aspect strong for the scattered of polycarboxylic acids, function of slump protection and early stage
The raising of degree, and corresponding strategy is usually the ratio for changing monomer and adsorption group, or by changing polyether macromonomer
Weight average molecular weight change side chain lengths, and targetedly change the report of adsorption group and few.
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 oxypropylene units of oiliness, so that part by changing the component units of polyether structure
Reduce suction-operated of the soil to diminishing agent molecule in concrete.The patent has the disadvantage, the synthesized anti-mud effect of polymer
Not substantially, and initial dispersion decreases.
Patent document CN103596993A discloses a kind of copolymer having together with bis phosphoric acid ester group, and the copolymer has master
Hydrocarbon chain and side base, side base not only include carboxyl and polyoxy alkyl, in addition to together with bis phosphoric acid ester group.Also exactly drawing by phosphate group
Enter so that such polymer phase is low quick to having to the clay and alkaline sulfides in sandstone for polycarboxylate water-reducer
Perception.But industrialization is limited to the source of raw material, and technique conversion ratio is not high, and chlorion residual etc..
Patent document US5879445A discloses a kind of small molecule water reducer, and using single-stranded amino-polyether, end is entered
The step Mannich reaction of row one, introduces phosphorous acid functional group, and with diminishing, retarding effect, but raw material is needed using expensive
Amino-polyether, consider that operability capable of being industrialized is strong from cost of material.
Patent document EP0444542A1 reports a kind of phosphoric acid micromolecular of polyethylene as cement dispersants, but
Volume is higher, and equally faces the expensive shortcoming of cost of material.
And the situation of raw materials of modern concrete is increasingly severe, industry by-product gypsum is led as the use of cement adjustable solidification agent
Cause binder materials SO4 2-Content is higher；The extensive use of large industrial solid castoff such as flyash, slag powders, gangue, makes
The component for obtaining binder materials is more complicated；Particularly high-quality sand, stone resource are increasingly deficient, aggregate clay content and water absorption rate increase,
The adaptability between concrete admixture and material is directly affected, causes concrete initial flow degree and fluidity holding capacity big
Width is reduced, and strongly limit the popularization and application of high efficiency water reducing agent.
Therefore, develop it is a kind of have high diminishing, in mud-containing aggregates little loss of slump, cement and admixture can be improved fit
The high-performance dispersant of answering property, has very important practice significance for the application for expanding high efficiency water reducing agent.
The content of the invention
Anti- Property of Clay for the existing cement concrete dispersant of solution is poor, or with anti-Property of Clay, but because
A variety of causes makes the problem of industrialization is limited, and the present invention provides a kind of anti-stick soil type polymeric dispersant and preparation method thereof and should
With the anti-stick soil type polymeric dispersant can be used as the aqueous dispersion of hydraulic binding agent and/or latent hydraulicity cementing agent
Dispersant.
Anti-stick soil type polymeric dispersant of the present invention has following architectural features：
Main to be made up of monomer A, monomer E and aldehyde the B segment changed into, each monomer is arranged in random fashion in the segment
Row, can also block form arrangement, and non-fully by shown in formula.The weight average molecular weight of the anti-stick soil type polymeric dispersant
Preferably 8000~30000.
Wherein monomer A is aromatic series, with carboxylic acid or phosphate group, there is three aspect effects in the structure, and one is constituted
The basic framework of polymer, secondly with adsorption group, can be reached poly- with the calcium and magnesium plasmon structures in hydraulicity cement
The purpose of compound absorption, the 3rd is that part carboxyl or phosphate group on monomer can carry out esterification, polyether lateral chain with polyethers
Freely stretched there is provided steric hindrance in dispersion, be conducive to improving peptizaiton of the polymer in cement system.With gathering
Carboxylic acid water reducer is compared, and main polymer chain is more rigid in the invention, therefore the adsorption capacity of early stage is stronger.
Monomer E addition can adjust the pliability of main chain, have certain help to the adaptability of polymer.
The monomer A both can be P-hydroxybenzoic acid, septichen, p-aminobenzoic acid, ortho-aminobenzoic acid
In a kind of monomer as shown in (Ia) or (Ib) of one kind or structural formula：
Wherein, G is COOH, OPO3H2, OPO2H2；R1For H, C1~C5 alkyl；K is C1~C10 alkylidenes；X=NR2Or O,
Y is OH or OR3, R3、R2It is C1~C5 alkyl independently of each other；
The monomer A can also be structural formula such as (Ic) or (Id) or (Ie)；
The structural formula of the aldehyde B is such as shown in (II)：
R4CHO (II)
Wherein, R4For H, COOH, C1~C5 alkyl, phenyl, benzyl or phenethyl.The monomer E is to carry sulfonic acid
The aromatic compounds of group or hydroxyl, such as p-aminobenzene sulfonic acid, orthanilic acid, p-hydroxybenzenyl sulfonate, o-hydroxy sulphur
Acid, beta-naphthalenesulfonic-acid, phenol, Phenoxyethanol, betanaphthol, 4- methylphenols.
Monomer E effect, if the monomer of sulphonic acids, can provide adsorption group, enhancing polymer is integrally to cement
Adsorption capacity, be conducive to improving dispersibility, if hydroxy kind aromatic series, then be conducive to improving the soft of the overall chain of polymer
Property, it is easy to conformation to unfold in cement solution.
It is preferred that,
G is OPO3H2, OPO2H2, R1For H or C1~C3 alkyl；X is NR2Or O；R2For C1~C3 alkyl, more preferably first
Base or ethyl；Y is OH or OR3；R3Preferably C1~C3 alkyl, K is C1~C3 alkylidenes；R4For H, COOH or C1~C3 alkane
Base.
R2More preferably methyl or ethyl；R3More preferably methyl or ethyl, R4More preferably H or COOH.
R3Most preferably methyl；R4Most preferably H.
So preferred beneficial effect is preferably to go out optimal monomer structure above, especially when adsorption group G is
OPO3H2, OPO2H2When, its adsorption capacity is better than carboxylic acid and sulfonic acid group, is conducive to improving the initial water-reducing property of polymer,
And to the better adaptability of argillaceous aggregate.
The preparation method of anti-stick soil type polymeric dispersant of the present invention, comprises the following steps：
A. by monomer A, second comonomer E and aldehyde B carry out polycondensation reaction under catalyst C effects, form performed polymer；
B. add polyether monomer D and occur esterification with above-mentioned performed polymer；
One end of the polyether macromonomer D is OH, and the other end is that aliphatic or aromatic group are closed, typically with corresponding
Fatty alcohol or the direct alkoxylate of aromatic alcohol are made, and method is more ripe in industry；Its weight average molecular weight be 1000~
10000, more preferably 1000~3000.
The polyether chain of block structure or disordered structure may be selected in polyether macromonomer；Using pure ethylene oxide or oxirane and
The mixture of expoxy propane is prepared, wherein the mass percent of the mixture ethylene oxide is at least 80%.
The polyether macromonomer D and monomer A mol ratio is 1:(0.5~6.0), polyether macromonomer D and monomer E mole
Than for 1:(0~2.0), the aldehyde B and (monomer A+ polyether macromonomer D) mol ratio are 1.0~2.0.
In the present invention, the Alkyl means straight or branched alkyl, for example, C1~C5 alkyl can be methyl, ethyl, just
Propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,1- diformazans
Base propyl group, 1,2- dimethyl propyls.
Monomer A containing phosphorous acid or phosphate group then refers to prior art and made by oneself by known method.
When G is OPO3H2, OPO3H2When, then take following method：Using corresponding alcohols substrate such as propane diols phenylate, plus
Enter equivalent or the excessive Phosphoric Acid no more than 10%, esterification is carried out, using toluene or dimethylbenzene as solvent, in 110-130
Flow back 24-48h at DEG C, and after reaction terminates, unnecessary toluene is fallen in vacuum distillation, obtains corresponding phosphate ester monomer.
The aldehyde B can be formaldehyde, acetaldehyde, the alkyl aldehydes such as propionic aldehyde, benzaldehyde, and the aromatic aldehyde such as phenylacetaldehyde, can also be second
Aldehydic acid.
The polycondensation reaction is the polycondensation reaction between monomer A, monomer E and aldehyde B, and esterification is performed polymer and monomer D
Between reaction, be reaction type well known to those skilled in the art, wherein also needed to after terminating due to esterification use alkali in
Be 6-8 or so to pH, at this moment acids adsorption group contained in polymer can be converted into salt.The conversion will not be to Weight-average molecular
Amount generation significantly affect, the present invention to ignore.
The universal experience that specific reactions steps and condition can combine prior art is tests determined.Usual esterification knot
Also need to adjust pH value after beam.Preparation process is specifically included：
Aldehyde B is added dropwise into monomer A and catalyst C mixture for step (1), carries out polycondensation reaction, the polycondensation reaction
Condition is that reaction temperature is 80~140 DEG C, and the reaction time is 1-12 hours；
Usually selected according to this area, the polycondensation reaction using acid as catalyst, the catalyst C be the concentrated sulfuric acid, phosphoric acid,
Any one in methanesulfonic acid, p-methyl benzenesulfonic acid, oxalic acid, concentrated hydrochloric acid.Catalyst C consumption is that polyether monomer D is preferably 0.5
~2.0 times.
Step (2) adds polyether macromonomer D into mixture obtained by step (1), and water entrainer carries out esterification, described
Esterification reaction temperature is 80~150 DEG C, and the reaction time is 6~36 hours；The water entrainer be hexamethylene, toluene and dimethylbenzene it
In one or more of mixtures, water entrainer addition is 1~2 times of polyethers quality of material；
After step (3) reaction terminates, regulation pH value to 6-8；It is diluted with water, upper strata is organic phase, i.e. water entrainer layer, separates
Lower aqueous layer, lower aqueous layer is end product；The upstream water system can be recycled.The last production concentration of adjustment
To being no more than 40%, preferably 30%~40%, the percentage is mass percent.
Step (1) is preferred, and reaction temperature is 100~130 DEG C, the reaction time is 2~8 hours.
Step (2) is preferred, and reaction temperature is 110~140 DEG C, the reaction time is 12~24 hours.
PH value is adjusted to 6-8, in order to obtain preferable storage stability.
So preferred beneficial effect is by optimizing reaction temperature and reaction time above, it is ensured that polymer turns
Rate will not cause because monomer polymerization conversion not exclusively causes polymer less efficient dispersal more than 80%.
It is preferred that, the mol ratio (hereinafter referred to as D/A) of the polyether macromonomer D and monomer A are 1:(1.0~4.5).
It is preferred that, the mol ratio (hereinafter referred to as D/E) of the polyether macromonomer D and monomer E are 1:(0.5~2.0).
It is preferred that, the aldehyde B and (monomer A+ monomer D) mol ratio (hereinafter referred to as B/ (A+D)) are 1.0~2.0.
So preferred beneficial effect is above, by the optimization to molar ratio between each monomer, can make to gather
Adduct molecule structure is in a suitable regulatable scope, and the performance of performance has in terms of this collapses to polymer diminishing and guarantor
There is important influence.
The anti-stick soil type polymeric dispersant dissipates as the moisture of hydraulic binding agent and/or latent hydraulicity cementing agent
The application of the dispersant of body.Generally, the hydraulic binding agent is at least one of cement, lime, gypsum, anhydrous gypsum,
The latent hydraulicity cementing agent is volcanic ash, flyash or blast-furnace cinder.Based on the hydraulic binding agent and/or potential water
Rigid cementing agent, the volume of anti-stick soil type polymeric dispersant of the present invention is in 0.01% weight to 10% weight, especially
0.05% weight is best to 5% weight effects.
It should be noted that in the present invention, most of monomer A, monomer E and polyether monomer D take part in reaction, be converted into poly-
Compound, conversion ratio is more than 80%.But unreacted monomer and accessory substance can be applied directly without separation, will not be to it
Dispersion effect causes to significantly affect.
Beneficial effects of the present invention：
1. being prepared for a kind of new polymer architecture, one end is the adsorption group of polycondensation, and one section is polyethers, is effectively enhanced
The adsorption capacity of polymer.2. especially, as cement water reducing agent, anti-mud can be improved when adsorption group is phosphorus-containing groups
Can, further improve the adaptability problem of water reducer and clay；3. methods described herein synthesis technique is simple, by an one-step polycondensation
Reaction and a step esterification, with industrial applications prospect.
Embodiment
The present invention is described in detail below by example, these examples are merely illustrative, the limitation present invention is not represented
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 weight average molecular weight of polymer is determined using gel permeation chromatograph (abbreviation GPC), Weight-average molecular of the present invention
Measure counterpoise average molecular weight (hereinafter referred to as Mw) of attaching most importance to；
Reaction conversion ratio is tested by GPC, calculates polyether macromonomer surplus, you can obtained, it is clear that conversion ratio refers to herein
Polyether macromonomer D 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 NaNO3Solution；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, weight average molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,
232)。
In Application Example of the present invention, except special instruction, the cement used 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 2.0.Flowing degree of net paste of cement is surveyed
Examination is carried out with reference to GB/T8077-2000 standards, and cement 300g, amount of water is 87g, and water is determined on plate glass after stirring 3min
Cement paste fluidity, the results are shown in Table 1.0.With reference to JC473-2001《Concrete pump-feed agent》Relevant regulations test incorporation institute of the present invention
State the concrete performance of polymer.
Polyether macromonomer is prepared as ethoxylation process, herein with polyether macromonomer poly glycol monomethyl ether (Mw=2000)
Preparation exemplified by be described.Initiator glycol monoethyl ether, catalyst sodium hydroxide.Weigh glycol monoethyl ether 76g, hydrogen-oxygen
Change sodium 3g, above-mentioned material is added into reactor, reactor is evacuated to -0.1MPa at room temperature.Then reactor is warming up to 100
DEG C, pressure decline, temperature in oxirane 50g, question response kettle are passed through into reactor and is risen, illustrates that polymerisation starts.After
Continue be passed through into reactor during oxirane 1874g, charging maintenance reaction kettle temperature degree between 100~120 DEG C, pressure exists
Between 0.2~0.4MPa, after oxirane charging terminates, 100 DEG C are incubated 1h or so.Untill question response kettle pressure is no longer reduced,
Temperature of reaction kettle is reduced to 80 DEG C or so, atmospheric valve is opened and reacting kettle inner pressure is reduced to normal pressure, reactor discharging is opened, obtains
To sundown liquid, tested through GPC, weight average molecular weight is 1939, and weight average molecular weight is distributed as 1.06.
Embodiment 1
In the present embodiment, B/ (A+D)=1:1, A/D=2.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, para hydroxybenzene first is added
Sour A 27.6g (0.2mol), sulfuric acid C 12.5g (0.125mol), it is a uniform phase to stir to it.Then it is slowly added dropwise 37%
Formalin B 24.3g (0.3mol).After completion of dropping, reacted 8 hours at 100 DEG C.After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 2
In the present embodiment, B/ (A+D)=1:1, A/D=2.0, E/D=1.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, para hydroxybenzene first is added
Sour A 27.6g (0.2mol), p-hydroxybenzenyl sulfonate 17.4g (0.1mol), sulfuric acid C 10g (0.1mol), stirring are uniform to it
One phase.37% formalin B 24.3g (0.3mol) are then slowly added dropwise.After completion of dropping, reacted 2 hours at 130 DEG C.
After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 3
In the present embodiment, B/ (A+D)=1:1, A/D=1.0, E/D=1.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, Phenoxyethanol phosphorus is added
Acid esters A 43.6g (0.2mol), Phenoxyethanol 27.6g (0.2mol), sulfuric acid C 12.5g (0.125mol), stirring are equal to it
An even phase.37% formalin B 24.3g (0.3mol) are then slowly added dropwise.It is small in 115 DEG C of reactions 6 after completion of dropping
When.After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 600g (poly glycol monomethyl ethers are added
3000,0.2mol), water entrainer toluene 600g, installs condenser, is warming up to 140 DEG C, reacts 12h, is cooled to 60 DEG C or so, plus
Enter 200g water, into separator, separate lower aqueous solution, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 4
In the present embodiment, B/ (A+D)=1.125:1, A/D=3.0, E/D=2.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, phosphate (1a) A is added
65.1g (0.3mol), phenol 18.8g (0.2mol) sulfuric acid C 12.5g (0.125mol), it is a uniform phase to stir to it.Then
37% formalin B 36.4g (0.45mol) are slowly added dropwise.After completion of dropping, reacted 8 hours at 100 DEG C.After reaction,
Cooling is stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 5
In the present embodiment, B/ (A+D)=1.5:1, A/D=3.0, E/D=0.5.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, phosphate (2a) A is added
69.6g (0.3mol), Phenoxyethanol 6.9g (0.05mol), sulfuric acid C 12.5g (0.125mol), it is a uniform phase to stir to it.
37% formalin B 48.6g (0.6mol) are then slowly added dropwise.After completion of dropping, reacted 5 hours at 120 DEG C.Reaction
Afterwards, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (polyethylene glycol monophenyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 6
In the present embodiment, B/ (A+D)=1.8:1, A/D=4.5, E/D=1.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, benzene oxygen second is added
Alcohol phosphite ester A 98.1g (0.45mol), p-aminobenzene sulfonic acid 17.3g (0.1mol), sulfuric acid C 20g (0.2mol), stirring
It is a uniform phase to it.37% formalin B 72.8g (0.9mol) are then slowly added dropwise.After completion of dropping, at 110 DEG C
Reaction 8 hours.After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer toluene 236g, installs condenser, is warming up to 150 DEG C, reacts 6h, is cooled to 60 DEG C or so, addition
200g water, into separator, separates lower aqueous solution, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 7
In the present embodiment, B/ (A+D)=2:1, A/D=1.0, E/D=2.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, Phenoxyethanol phosphorus is added
(0.125mol, 50% is water-soluble by acid esters A 43.6g (0.2mol), o hydroxybenzenesulfonic acid 34.8g (0.2mol), methanesulfonic acid C 24g
Liquid), it is a uniform phase to stir to it.Aldehyde B mixed solution (37% formalin B-1 24.3g are then slowly added dropwise
(0.3mol) and 50% glyoxalic acid solution B-2 44.4g (0.3mol)).After completion of dropping, reacted 8 hours at 110 DEG C.Instead
Ying Hou, is cooled down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 100g (poly glycol monomethyl ethers are added
1000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 80 DEG C, reacts 16h, is cooled to 60 DEG C or so, plus
Enter 200g water, into separator, separate lower aqueous solution, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 8
In the present embodiment, B/ (A+D)=1.07:1, A/D=2.5, E/D=1.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, 2- naphthalene mono phosphoric acid esters are added
Sodium (1e) A 61.5g (0.25mol), p-hydroxybenzenyl sulfonate 17.4g (0.1mol), sulfuric acid C 12.5g (0.125mol), stirring is extremely
It is a uniform phase.37% formalin B 30.3g (0.375mol) are then slowly added dropwise.After completion of dropping, at 120 DEG C
Reaction 5 hours.After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 9
In the present embodiment, B/ (A+D)=1.5:1, A/D=3.0, E/D=1.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, 2- BNOAs A is added
60.6g (0.3mol), Phenoxyethanol 13.8g (0.1mol), sulfuric acid C 12.5g (0.125mol), it is a uniform phase to stir to it.
37% formalin B 48.6g (0.6mol) are then slowly added dropwise.After completion of dropping, reacted 5 hours at 120 DEG C.Reaction
Afterwards, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Embodiment 10
In the present embodiment, B/ (A+D)=1.5:1, A/D=3.0, E/D=1.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, Phenoxyethanol phosphorus is added
Acid esters A 65.4g (0.3mol), phenol E 9.4g (0.1mol), sulfuric acid C 12.5g (0.125mol), it is uniform one to stir to it
Phase.50% glyoxalic acid solution B 88.8g (0.6mol) are then slowly added dropwise.After completion of dropping, reacted 5 hours at 120 DEG C.
After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 200g (poly glycol monomethyl ethers are added
2000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Comparative example 1
In the present embodiment, B/ (A+D)=0.33:1, A/D=1.0, E/D=3.0.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, para hydroxybenzene first is added
Sour A 27.6g (0.2mol), phenol E 28.2g (0.3mol), sulfuric acid C 12.5g (0.125mol), it is uniform one to stir to it
Phase.37% formalin B 8.1g (0.1mol) are then slowly added dropwise.After completion of dropping, reacted 4 hours at 90 DEG C.Reaction
Afterwards, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 100g (poly glycol monomethyl ethers are added
1000,0.1mol), water entrainer hexamethylene 236g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
Comparative example 2
In the present embodiment, B/ (A+D)=3:1, A/D=0.5.
(1) polycondensation reaction
At one equipped with motor machine stirring, the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, Phenoxyethanol phosphorus is added
Acid esters A 43.6g (0.2mol), sulfuric acid C 12.5g (0.125mol), it is a uniform phase to stir to it.Then it is slowly added dropwise 37%
Formalin B 145.8g (1.8mol).After completion of dropping, reacted 8 hours at 140 DEG C.After reaction, cool down stand-by.
(2) esterification
In 2L round-bottomed flask, (1) reacted condensation polymer is added, polyethers D 400g (poly glycol monomethyl ethers are added
1000,0.4mol), water entrainer hexamethylene 450g, installs condenser, is warming up to 100 DEG C, reacts 16h, is cooled to 60 DEG C or so,
200g water is added, into separator, lower aqueous solution is separated, upper strata is collected, continues cycling through and use.
(3) neutralization reaction
Reaction is cooled to room temperature after terminating, and is diluted to pH to 6-8 or so with 30% alkali lye, is diluted with water to 30%-
40% or so.
The polymerisation conversion of table 1.0 and paste flowing degree
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 is 0.29.Polymer GPC, weight average molecular weight distribution PDI and polyethers
Conversion results are as shown in table 1.0, compared with control sample 1 and control sample 2, and other embodiments weight average molecular weight is in this patent institute
Defined scope, polymer shows to show preferably to starch effect only under the conditions of compared with low-dosage, and control sample 1 and control sample
2 weight average molecular weight are respectively 3182 and 65919, are not optimized in this patent in weight average molecular weight range, net slurry effect performance compared with
Difference.With reference to JC473-2001《Concrete pump-feed agent》The concrete performance of relevant regulations test incorporation polymer of the present invention.
As a result as shown in table 2.0.
The concrete test result of table 2.0
Concrete mix：Cement：Flyash：It is husky：Stone=4.2kg：0.8kg：12kg：13kg
From table 2.0, the diminishing for the anti-stick soil type polymeric dispersant reported with comparative example condition ratio, the present invention and
Function of slump protection is all more excellent.Especially, volume used in sulfonic acid and phosphoric acid class product is relatively low (embodiment 2-8,10), and effect is substantially excellent
In comparative example (comparative example 1 and 2) and carboxylic acids sample (embodiment 1 and embodiment 9).Pass through the intensity to 3d, 7d and 28d
Numerical value contrast finds that institute's invention sample has no adverse effect to later stage concrete strength, and 28d intensity can reach 40Mpa, can be with
Meet requirement of engineering.
Illustrate the hydroxy-acid group that is better than of phosphoric acid and sulfonic acid adsorption group at this, this is relevant with foregoing preferred group
The sensitivity experiments of clay
Anti-stick soil type polymeric dispersant sample in order to evaluate the present invention is tested containing clay to the sensitiveness of clay
Sand configuration mortar fluidity.Wherein the divergence test of mortar is with reference to GB/T17671-1999《Cement mortar flows
The assay method of degree》Tested, wherein cement on the basis of cement used, cement mortar rate is 1：3；The quality of clay substitution sand
0.5%；The ratio of mud is 0.44.Determine product fresh mortar of the present invention fluidity and 60min, 120min through when fluidity
Change.
The mortar test of table 3 (anti-stick soil experiment)
Above-mentioned experiment shows, anti-stick soil type polymeric dispersant of the invention compared with low-dosage for the clay in sand
Illustrate low sensitiveness, it is especially desirable to, it is noted that in the mortar containing clay, the stronger phosphoric acid polymerization thing of adsorption capacity
(embodiment 2-8,10), carboxylic acid sample (embodiment 1 and 9) and the He of comparative example 1 will be significantly better than in ability by being collapsed in diminishing and guarantor
Comparative example 2.For tackling the problem of sandstone aggregate increasingly serious in current concrete is poor, there is provided a possible solution for this
Scheme.
Claims (10)
1. a kind of anti-stick soil type polymeric dispersant, it is characterised in that with following architectural features：
The anti-stick soil type polymeric dispersant is made up of monomer A, monomer E and aldehyde the B segment changed into, and the segment is with nothing
Rule mode is arranged, or is arranged with block form, and non-fully by shown in formula；The weight of the anti-stick soil type polymeric dispersant is equal
Molecular weight is preferably 8000~30000；
Wherein monomer A is aromatic series, with carboxylic acid or phosphate group；
The monomer E is the aromatic compounds with sulfonic acid group or hydroxyl, selected from p-aminobenzene sulfonic acid, adjacent amino phenyl sulfonyl
Acid, p-hydroxybenzenyl sulfonate, o hydroxybenzenesulfonic acid, beta-naphthalenesulfonic-acid, phenol, Phenoxyethanol, betanaphthol, 4- methylphenols.
2. anti-stick soil type polymeric dispersant according to claim 1, it is characterised in that the monomer A is para hydroxybenzene
One kind in formic acid, septichen, p-aminobenzoic acid, ortho-aminobenzoic acid, or structural formula such as (Ia) or (Ib) institute
A kind of monomer shown, or structural formula such as (Ic) or (Id) or (Ie)；
Wherein, G is COOH, OPO3H2, OPO2H2；R1For H, C1~C5 alkyl；K is C1~C10 alkylidenes；X=NR2Or O, Y are
OH or OR3, R3、R2It is C1~C5 alkyl independently of each other；
The structural formula of the aldehyde B is such as shown in (II)：
R4CHO (II)
Wherein, R4For H, COOH, C1~C5 alkyl, benzyl or phenethyl.
3. anti-stick soil type polymeric dispersant according to claim 2, it is characterised in that G is OPO3H2, OPO2H2, R1For H or
C1~C3 alkyl；X is NR2Or O；R2For C1~C3 alkyl；Y is OH or OR3；R3For C1~C3 alkyl, K is C1~C3 alkylidenes；
R4For H, COOH or C1~C3 alkyl.
4. anti-stick soil type polymeric dispersant according to claim 3, it is characterised in that R2For methyl or ethyl；R3For methyl
Or ethyl, R4For H or COOH.
5. anti-stick soil type polymeric dispersant according to claim 4, it is characterised in that R2For methyl；R3For methyl, R4For
H。
6. the preparation method of the anti-stick soil type polymeric dispersant described in any one of claim 1 to 5, it is characterised in that
Comprise the following steps：
A. by monomer A, second comonomer E and aldehyde B carry out polycondensation reaction under catalyst C effects, form performed polymer；
B. add polyether monomer D and occur esterification with above-mentioned performed polymer；
One end of the polyether macromonomer D is OH, and the other end is that aliphatic or aromatic group are closed, and its weight average molecular weight is
1000~10000,
The polyether macromonomer D and monomer A mol ratio is 1:(0.5~6.0), polyether macromonomer D and monomer E mol ratio is
1:(0~2.0), the aldehyde B and (monomer A+ polyether macromonomer D) mol ratio are 1.0~2.0.
7. method according to claim 6, it is characterised in that the weight average molecular weight of the polyether macromonomer D is 1000~
3000。
8. according to the methods described of claim 6 or 7, it is characterised in that preparation process is specifically included：
Aldehyde B is added dropwise into monomer A and catalyst C mixture for step (1), carries out polycondensation reaction, the condition of the polycondensation reaction
For reaction temperature is 80~140 DEG C, and the reaction time is 1-12 hours；
The catalyst C is any one in the concentrated sulfuric acid, phosphoric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, oxalic acid, concentrated hydrochloric acid.Catalyst
C consumption is that polyether monomer D is preferably 0.5~2.0 times；
Step (2) adds polyether macromonomer D into mixture obtained by step (1), and water entrainer carries out esterification, the esterification
Reaction temperature is 80~150 DEG C, and the reaction time is 6~36 hours；The water entrainer is among hexamethylene, toluene and dimethylbenzene
The mixture of more than one arbitrary proportions, water entrainer addition is 1~2 times of polyethers quality of material；
After step (3) reaction terminates, regulation pH value to 6-8；It is diluted with water, upper strata is organic phase, i.e. water entrainer layer, separates lower floor
Water layer, lower aqueous layer is end product；The upstream water system can be recycled；
Adjustment end product concentration produces the anti-stick soil type polymeric dispersant to 30%~40%, and the percentage is quality
Percentage.
9. method according to claim 8, it is characterised in that step (1) reaction temperature is 100~130 DEG C, the reaction time is
2~8 hours；Step (2) reaction temperature is 110~140 DEG C, and the reaction time is 12~24 hours.
10. method according to claim 8, it is characterised in that the mol ratio of the polyether macromonomer D and monomer A are 1:
(1.0~4.5)；The mol ratio of the polyether macromonomer D and monomer E are 1:(0.5~2.0)；The aldehyde B and (monomer A+ monomers
D mol ratio) is 1.0~2.0.
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| CN107936209A (en) * | 2017-12-13 | 2018-04-20 | 江苏苏博特新材料股份有限公司 | A kind of high-adaptability disperses phosphonate group water-reducing agent and preparation method thereof soon |
| CN108059718A (en) * | 2017-12-20 | 2018-05-22 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the cement dispersants with clay adaptability and viscosity reducing effect |
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| CN108129625B (en) * | 2017-12-20 | 2020-06-26 | 江苏苏博特新材料股份有限公司 | Phosphonic acid-based water reducing agent, and preparation method and application thereof |
| CN111072883A (en) * | 2019-11-27 | 2020-04-28 | 江苏苏博特新材料股份有限公司 | Novel slump-retaining water reducer containing ester group and preparation method thereof |
| CN111072883B (en) * | 2019-11-27 | 2023-03-14 | 江苏苏博特新材料股份有限公司 | Ester-group-containing slump-retaining water reducer and preparation method thereof |
| CN113831487A (en) * | 2020-06-24 | 2021-12-24 | 江苏苏博特新材料股份有限公司 | Aromatic carboxylate intermediate, preparation method thereof and application thereof in ester type polycarboxylate superplasticizer |
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