CN105713207A - Set-retarding type efficient dispersant and preparation method thereof - Google Patents
Set-retarding type efficient dispersant and preparation method thereof 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
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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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- 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
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Abstract
The invention discloses a set-retarding type efficient dispersant. The set-retarding type efficient dispersant is characterized in that a melamine derivative serves as a core, -PO3H2 and polyoxyalkylene side chains serve as the periphery and are independent from each other, but the periphery cannot be -PO3H2 or the polyoxyalkylene side chains completely simultaneously; the weight-average molecular weight of every polyoxyalkylene side chain ranges from 1,000 to 3,000, one terminal of every polyoxyalkylene side chain is exposed-OH while the other terminal thereof is unexposed fatty group or aromatic group, and every polyoxyalkylene side chain is prepared by direct oxyalkylation of corresponding fatty alcohol or aromatic alcohol. The set-retarding type efficient dispersant has a certain water reducing and slump retaining performance and remarkable set-retarding effect, and is highly adaptable to current low-grade concrete raw materials, strong in market demand, advanced in preparation technology and low in cost, thereby being promising in prospect and hopefully being developed into core technology of the concrete water reducing agent field to lead industry development.
Description
Technical field
The invention belongs to chemical building material field, be specifically related to a kind of retardation setting type dispersant with high efficiency for middle low-slump concrete and preparation method thereof.
Background technology
Concrete admixture refers to the material for improving and regulate concrete performance and fill, it is possible to regulating and controlling concrete rheological property, improve mechanical property and improve durability, concrete admixture technology has become as the core technology of modern concrete.For requirements such as the high and low contraction of mass concrete desired strength such as nuclear power engineering, water conservancy project, long construction periods, exploitation have retardation setting type, in low water-reducing rate, the long-time concrete admixture protecting collapse (2～8h) have great importance.
Not yet find the concrete admixture special for large volume special concrete at present, investigated by substantial amounts of technical data, only find that existing data all simply modifiies on conventional water reducing agents molecular structure so that it is there is slow setting feature.
The preparation method that patent CN102153711B discloses a kind of slow-setting polycarboxylic acid water reducing agent, innovation is in that to be incorporated in polycarboxylic acids molecular skeleton by the beta-schardinger dextrin-side chain with slow setting function, the water reducer of preparation has retarding performance, micro-bleed performance and better mobile performance, but complicated process of preparation, practicality is not strong, only resides within laboratory and only starches testing level.
Patent CN102276182B discloses a kind of cement retarder, mainly by ammonia, dodecyl sodium sulfate and Polyethylene Glycol with certain proportioning mixing, being applied in portland cement, it is possible to significantly improve retarding effect, fluidity improves 5-6%, Difference between initial setting times extends 40-100 minute, within 7 days, compressive strength rate is more or less the same, but developed retarder does not have water-reducing property, can only composite use, need during composite use to consider the compatibility with water reducer, there is application risk.
Patent CN104119017A discloses a kind of high temperature modification retardation water reducing agent, main employing compounded technology means, sugar calcium, phosphate cpd and other inorganic or organic polymer and conventional fat race water reducer are simply mixed with, but it is more to there is material, complicated process of preparation, unstable properties, is limited to high pressure cementing operation.
US Patent No. 5879445 discloses a kind of little molecule water reducer, adopt the amino-polyether of strand, end is carried out a step Mannich reaction, introduce phosphorous acid functional group, there is diminishing, retarding effect, but raw material needs to adopt expensive amino-polyether, consider from cost of material, operability capable of being industrialized is strong, so far there are no in market Related product.
For mass concrete, index is required except needs meet workability, intensity and durability etc., also need to emphasis and consider temperature difference problem of Cracking, owing in mass concrete, hydrated cementitious to produce substantial amounts of heat, the heat of inside concrete is fast not as what scattered and disappeared in surface, causes internal-external temperature difference excessive, and temperature stress produced by it very easily causes concrete cracking, the internal-external temperature difference stress that concrete cement aquation produces, is the main reason causing mass concrete to ftracture.Therefore, when concrete keeps certain fluidity energy so that it is there is retarding performance, when total thermal discharge is constant, delay the rate of heat release of hydrated cementitious, reduce hydrated cementitious thermal peak, be the key solving Volume Concrete Cracks problem.
And the situation of raw materials of modern concrete is increasingly severe, industry by-product gypsum causes Binder Materials SO as the use of cement adjustable solidification agent4 2-Content is higher；The extensive use of large industrial solid castoffs such as flyash, slag powders, gangue so that the component of Binder Materials is more complicated；Particularly high-quality sand, stone resource are day by day deficient, aggregate clay content and water absorption rate increase, directly affect the adaptability between concrete admixture and material, cause that concrete initial flow degree and fluidity holding capacity are greatly reduced, strongly limit the application of the popularization and application of high efficiency water reducing agent, particularly mass concrete.
Therefore, develop and a kind of have that high water reducer, retarding effect be excellent, little loss of slump, cement and admixture adaptability can be improved and the extra retarded set high-performance dispersant of mechanical performance of concrete and endurance quality can be obviously improved, for mass concrete, there is very important practice significance.
Summary of the invention
For solving the complicated process of preparation of retarder, retarder does not possess water-reducing effect, and high efficiency water reducing agent adaptability is not strong, and therefore retarder is limited with the application of the composite use of high efficiency water reducing agent, fails to solve efficiently the problem of Cracking of mass concrete；The present invention is directed to mass concrete application performance index, exploitation one have water-reducing rate high, latent excellent, protect a kind of retardation setting type dispersant with high efficiency and preparation method thereof of time length (2-8h) of collapsing, it is low that described retardation setting type dispersant with high efficiency has good cement adaptability, clay and sulfate sensitivity, can use composite with other water reducer, preparation technology can industrialization, have a extensive future.
Retardation setting type dispersant with high efficiency of the present invention, its molecular structural formula is such as shown in following formula I:
Architectural feature: for hub-and-spoke configuration, core is melamine derivative (A), and periphery is polyoxy alkane alkenyl chain (B),
In described structural formula I, R1, R2, R3, R4, R5, R6Respectively-PO3H2With one of polyoxy alkane alkenyl chain, separate, but can not be simultaneously-PO entirely3H2Or polyoxy alkane alkenyl chain；
Described polyoxy alkane alkenyl chain, weight average molecular weight is 1000～3000；One end is exposed-OH, and the other end is aliphatic or aromatic group closing, is prepare with the direct alkoxylate of corresponding fatty alcohol or aromatic alcohol, and method is comparatively ripe in industry, specifically can refer to patent ZL200910027884.9 and ZL200910234991.9；
Described polyoxy alkane alkenyl chain, segment is polyoxyethylene and/or polyoxypropylene, but can not be polyoxypropylene entirely, and polyoxyethylene block number is 22～114, and polyoxyethylene block number is 17～86；
The structure of retardation setting type dispersant with high efficiency of the present invention, does preferably, and its structure meets following formula, and adsorption group is phosphorous acid functional group；
The weight average molecular weight of retardation setting type dispersant with high efficiency of the present invention is 1700～16000；
The preparation method of retardation setting type dispersant with high efficiency of the present invention, comprises the steps；
Step (1): the preparation of six phosphorous acidic group tripolycyanamide (A), under the existence of water, tripolycyanamide, formaldehyde and phosphorous acid, adds catalyst acid, sets corresponding reaction temperature and response time, prepare core texture A monomer.
Wherein, metaformaldehyde, formaldehyde (37% aqueous solution), phosphorous acid are Industrial raw material, without particular/special requirement；
Molar ratio of material: tripolycyanamide: phosphorous acid: formaldehyde=1:6.0～8.0:7.0～9.0；
Water is as reaction dissolvent, and water addition is 1～2 times of quality of material；
Reaction temperature: 100 DEG C～120 DEG C, response time: 2～6h；
Catalyst acid is the mixture of any one any of the above ratio in formic acid, acetic acid, oxalic acid, hydrochloric acid, phosphoric acid；
Catalyst acid adds 5.0～7.0 times that mol amount is tripolycyanamide；
Device needs to install condenser (pipe) reflux, it is prevented that system acid or water lost, affects reaction condition.
Step (2): the preparation of dispersant, esterification: monomer A and polyoxy alkane alkene ether are mixed, under the effect of water entrainer, is reacted by dehydration esterification, cooling, then dilute, separate water layer.
Material ratio: six phosphorous acidic group tripolycyanamide: polyoxy alkane alkene ether=1:1.0～5.0；
Described water entrainer is one or more the mixture among hexamethylene, toluene and dimethylbenzene；
Water entrainer addition is 1～2 times of inventory (quality)；
Reaction temperature: 110～150 DEG C, response time 4h～10h；
Amount of water is 1.0～2.3 times of inventory (quality)；
The water entrainer separated can recycle, and water layer enters and neutralizes still；
Device needs to install water knockout drum and condenser (pipe) reflux, it is prevented that scattering and disappearing of system water entrainer.
Step (3): neutralize, in the dispersant system of synthesis, adds aqueous slkali, and the pH value of regulation system is 6～8.
Described aqueous slkali is conventional metal hydroxides, one or both in sodium hydroxide or potassium hydroxide；
The Solute mass concentration of described aqueous slkali is 10%～30%；
Adjust the addition of amount of water and aqueous slkali, make to prepare dispersant concentration and be maintained at 40% ± 5.
In the preparation method of retardation setting type dispersant with high efficiency of the present invention, step one and step 2 " one kettle way " can be completed, then pass through segregation apparatus and separate water layer, enter neutralization still and carry out the dispersant that simple preparation can prepare about 40%.
Retardation setting type dispersant with high efficiency of the present invention, first with tripolycyanamide for main structure body, introducing phosphorous acid adsorption group and polyoxy alkane alkenyl chain, molecular structure is " star-like ", novel molecular structure imparts the application performance that this dispersant is prominent, has reached the innovation effect of following aspect:
1. high-adaptability.Introduce phosphitylation tripolycyanamide as adsorption group, breach traditional carboxyl, sulfonic group system, Phosphateadsorption ability is strong, it is low that this condensation polymer shows stronger cement and high-sulfate environmental suitability, clay sensitivity, this characteristic, under the market environment of current concrete admixture and aggregate inferior quality, there is great performance advantage, core technology can be developed into.
2. excellent combination property.Polymer is hub-and-spoke configuration, side chain introduces the polyoxy alkane alkene ether that structure differs, there is extremely strong space steric effect, certain diminishing and function of slump protection are embodied, this dispersant also has good retarding effect, reduce hydration heat of cement, reduce the temperature shrinkage of mass concrete, decrease the cracking risk of mass concrete.
3. preparation technology is advanced.The cost of material of this process choice is low, synthesis technique simple possible, and polycondensation efficiency is high, and energy consumption is little, and preparation technology has can industrial prospect.
The present invention provides retardation setting type dispersant with high efficiency, there is certain diminishing and function of slump protection, retarding effect is notable, meanwhile, the low-grade raw material of current concrete is had high adaptability, the market demand is strong, having a extensive future, and preparation technology is advanced, production cost is low, it is expected to make the core technology into cement water reducing agent field, leads industry development.
Detailed description of the invention
Following example have described in more detail molecular structure and the preparation process of a kind of retardation setting type dispersant with high efficiency provided by the invention, these embodiments provide by way of illustration, its object is to allow person skilled in the art will appreciate that present disclosure and to implement according to this, but these embodiments do not limit the scope of the invention absolutely.All equivalences made according to spirit of the invention change or modify, and all should be encompassed within protection scope of the present invention.
Molecular weight test condition: in the embodiment of the present invention, the molecular weight of all condensation polymers uses aqueous gel chromatograph (GPC) to be measured, and experiment condition is as follows:
Gel column: ShodexSB806+803 two root chromatogram column is connected；
Mobile phase: 0.1MNaNO3 aqueous solution；
Mobile phase speed: 1.01ml/min；
Injection: 20 μ l0.5% aqueous solutions；
Detector: ShodexRI-71 type differential refraction detector；
Reference material: Polyethylene Glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232).
Synthetic example 1
(1) preparation of monomer A
By tripolycyanamide 126.04g (1.0mol), phosphorous acid 574.05g (7.02mol) and water 1400ml is placed in 2000ml reaction bulb, add sulphuric acid 294.05g (3.0mol), it is warming up to 110 DEG C, keeps 10min, then drip 37% formalin 648.02g (8.0mol), condensing tube is installed, it is heated to reflux 4h, after cooling, stand-by.
(2) esterification
In 5000ml round-bottomed flask, add monomer B (polyethers) 600.1g (0.3mol, Mn=2000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 1004g, condenser is installed, it is warming up to 130 DEG C, reaction 6h, is then cooled to about 50 DEG C, adds water 1004g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 53.3g (0.4mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 42%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 6821.
Synthetic example 2
(1) preparation of monomer A
By tripolycyanamide 126.02g (1.0mol), phosphorous acid 533.06g (6.5mol) and water 1300ml is placed in 2000ml reaction bulb, add sulphuric acid 270.0g (2.8mol), it is warming up to 108 DEG C, keeps 10min, then drip 37% formalin 608.2g (7.5mol), condensing tube is installed, it is heated to reflux 5h, after cooling, stand-by.
(2) esterification
In 5000ml round-bottomed flask, add monomer B (polyethers) 400.2g (0.2mol, Mn=2000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 563g, condenser is installed, it is warming up to 120 DEG C, reaction 5h, is then cooled to about 50 DEG C, adds water 563g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 66.7g (0.9mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 41%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 4835.
Synthetic example 3
(1) preparation of monomer A
By tripolycyanamide 126.06g (1.0mol), phosphorous acid 615.03g (7.5mol) and water 1500ml is placed in 3000ml reaction bulb, add sulphuric acid 318.10g (3.3mol), it is warming up to 115 DEG C, keeps 10min, then drip 37% formalin 689.03g (8.5mol), condensing tube is installed, it is heated to reflux 4.5h, after cooling, stand-by.
(2) esterification
In 5000ml round-bottomed flask, add monomer B (polyethers) 800.2g (0.4mol, Mn=2000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 1564g, condenser is installed, it is warming up to 140 DEG C, reaction 6h, is then cooled to about 50 DEG C, adds water 1564g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 40.3g (0.3mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 43%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 4835.
Synthetic example 4
(1) preparation of monomer A
By tripolycyanamide 126.03g (1.0mol), phosphorous acid 492.05g (6.0mol) and water 1200ml is placed in 2000ml reaction bulb, add sulphuric acid 245.3g (2.5mol), it is warming up to 100 DEG C, keeps 10min, then drip 37% formalin 568.08g (7.0mol), condensing tube is installed, it is heated to reflux 6h, after cooling, stand-by.
(2) esterification
In 2000ml round-bottomed flask, add monomer B (polyethers) 200.1g (0.2mol, Mn=1000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 404g, condenser is installed, it is warming up to 110 DEG C, reaction 8h, is then cooled to about 50 DEG C, adds water 404g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 66.7g (0.5mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 38%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 2800.
Synthetic example 5
(1) preparation of monomer A
By tripolycyanamide 126.01g (1.0mol), phosphorous acid 656.07g (8.0mol) and water 1500ml is placed in 3000ml reaction bulb, add sulphuric acid 343.06g (3.5mol), it is warming up to 118 DEG C, keeps 10min, then drip 37% formalin 730.02g (9.0mol), condensing tube is installed, it is heated to reflux 3h, after cooling, stand-by.
(2) esterification
In 5000ml round-bottomed flask, add monomer B (polyethers) 600.1g (0.2mol, Mn=3000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 1004g, condenser is installed, it is warming up to 140 DEG C, reaction 10h, is then cooled to about 50 DEG C, adds water 1004g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 66.7g (0.5mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 39%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 6925.
Synthetic example 6
(1) preparation of monomer A
By tripolycyanamide 126.06g (1.0mol), phosphorous acid 508.0g (6.2mol) and water 2000ml is placed in 5000ml reaction bulb, add sulphuric acid 318.6g (3.3mol), it is warming up to 110 DEG C, keeps 10min, then drip 37% formalin 800.04g (8.0mol), condensing tube is installed, it is heated to reflux 5h, after cooling, stand-by.
(2) esterification
In 2000ml round-bottomed flask, add monomer B (polyethers) 300.0g (0.3mol, Mn=1000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 554g, condenser is installed, it is warming up to 130 DEG C, reaction 9h, is then cooled to about 50 DEG C, adds water 554g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 53.3g (0.4mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 40%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 3916.
Comparative example 1
(1) preparation of monomer A
By tripolycyanamide 126.03g (1.0mol), phosphorous acid 328.01g (4.0mol) and water 600ml is placed in 2000ml reaction bulb, add sulphuric acid 196.5g (2.0mol), it is warming up to 90 DEG C, keeps 10min, then drip 37% formalin 405.02g (5.08mol), condensing tube is installed, it is heated to reflux 1h, after cooling, stand-by.
(2) esterification
In 2000ml round-bottomed flask, add monomer B (polyethers) 100.2g (0.2mol, Mn=500), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 507g, condenser is installed, it is warming up to 90 DEG C, reaction 5h, is then cooled to about 50 DEG C, adds water 507g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 66.7g (0.5mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 40%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 1765.
Comparative example 2
(1) preparation of monomer A
By tripolycyanamide 126.02g (1.0mol), phosphorous acid 738.0g (9.0mol) and water 4000ml is placed in 8000ml reaction bulb, add sulphuric acid 392.2g (4.0mol), it is warming up to 130 DEG C, keeps 10min, then drip 37% formalin 811.0g (10.0mol), condensing tube is installed, it is heated to reflux 7h, after cooling, stand-by.
(2) esterification
In 3000ml round-bottomed flask, add monomer B (polyethers) 800.1g (0.4mol, Mn=2000), monomer A (six phosphorous acidic group tripolycyanamide) 69.0g (0.1mol) and water entrainer hexamethylene 434g, condenser is installed, it is warming up to 160 DEG C, reaction 6h, is then cooled to about 50 DEG C, adds water 434g, enter segregation apparatus, separating lower aqueous solution, upper strata is collected, and continues cycling through use.
(3) neutralize
By lower aqueous solution, adding 30% sodium hydroxide solution 66.7g (0.5mol), regulation system PH=8～9, prepared weight concentration is about the dispersant of 40%, for light brown clear thick liquid, aqueous gel chromatographic determination condensation polymer weight average molecular weight is 8900.
Application example 1
In Application Example of the present invention, except special instruction, the cement adopted is little wild field 52.5R.P.II cement, and sand is the medium sand of modulus of fineness Mx=2.6, and cobble-stone diameter is the rubble of 5～20mm continuous grading.The slump and slump-loss perform with reference to JC473-2001 " concrete pump-feed agent " relevant regulations.
Table 1 test concrete mix
| Raw material | Cement | Flyash | Mechanism mountain sand | 5-10mm stone | 10-20mm stone |
| Proportioning, Kg/m3 | 340 | 110 | 775 | 410 | 615 |
Table 2 condensation polymer water reducer the performance test results
In table 2, concrete flowability data show, when clay content is 1.8% mechanism mountain sand and stone that clay content is 0.6% is aggregate, this novel dispersant shows middle low slump value, long-time protects ability of collapsing and preferably retarding effect, temperature difference between inside and outside concrete more than 20 DEG C can be reduced, for the extraordinary mass concrete such as nuclear power, water conservancy project, there is important using value, and the higher Machine-made Sand of clay content, stone are had the ability of well adapting to by this dispersant, anti-mud effect is obvious.The application data of comparative example shows: when reaction condition and technological parameter are beyond this patent protection domain; dispersant molecule structure will be affected; and then its setting time, retarding effect and dispersion and dispersion maintenance performance can be changed, even can affect the intensity of concrete 28d.
Claims (3)
1. a retardation setting type dispersant with high efficiency, it is characterised in that its molecular structural formula is such as shown in following formula I:
Described retardation setting type dispersant with high efficiency is hub-and-spoke configuration, and core is melamine derivative (A), and periphery is polyoxy alkane alkenyl chain (B)；
In described structural formula I, R1, R2, R3, R4, R5, R6Respectively-PO3H2With one of polyoxy alkane alkenyl chain, separate, but can not be simultaneously-PO entirely3H2Or polyoxy alkane alkenyl chain；
The weight average molecular weight of described retardation setting type dispersant with high efficiency is 1700～16000；
Described polyoxy alkane alkenyl chain, weight average molecular weight is 1000～3000；One end is exposed-OH, and the other end is aliphatic or aromatic group closing, is prepare with the direct alkoxylate of corresponding fatty alcohol or aromatic alcohol；
Described polyoxy alkane alkenyl chain, segment is polyoxyethylene and/or polyoxypropylene, but can not be polyoxypropylene entirely, and polyoxyethylene block number is 22～114, and polyoxyethylene block number is 17～86.
2. retardation setting type dispersant with high efficiency according to claim 1, it is characterised in that its structure meets following formula, and adsorption group is phosphorous acid functional group；
3. the preparation method of retardation setting type dispersant with high efficiency described in claim 1 or 2, it is characterised in that comprise the steps；
Step (1): the preparation of six phosphorous acidic group tripolycyanamide (A),
Under the existence of water, tripolycyanamide, formaldehyde and phosphorous acid, add catalyst acid, set corresponding reaction temperature and response time, prepare core texture A monomer；
Wherein, metaformaldehyde, formaldehyde (37% aqueous solution), phosphorous acid are Industrial raw material；
Molar ratio of material: tripolycyanamide: phosphorous acid: formaldehyde=1:6.0～8.0:7.0～9.0；
Water is as reaction dissolvent, and water addition is 1～2 times of quality of material；
Reaction temperature: 100 DEG C～120 DEG C, response time: 2～6h；
Catalyst acid is the mixture of any one any of the above ratio in formic acid, acetic acid, oxalic acid, hydrochloric acid, phosphoric acid；
Catalyst acid adds 5.0～7.0 times that mol amount is tripolycyanamide；
Device need install condenser backflow device, it is prevented that system acid or water scatter and disappear, affect reaction condition；
Step (2): the preparation of dispersant, esterification:
Monomer A and polyoxy alkane alkene ether are mixed, under the effect of water entrainer, is reacted by dehydration esterification, cooling, then dilute, separate water layer；
Material ratio: six phosphorous acidic group tripolycyanamide: polyoxy alkane alkene ether=1:1.0～5.0；
Described water entrainer is one or more the mixture among hexamethylene, toluene and dimethylbenzene；
Water entrainer addition is 1～2 times of quality of material；
Reaction temperature: 110～150 DEG C, response time 4h～10h；
Amount of water is 1.0～2.3 times of quality of material；
The water entrainer separated can recycle, and water layer enters and neutralizes still；
Device needs to install water knockout drum and condenser backflow device, it is prevented that scattering and disappearing of system water entrainer；
Step (3): neutralize,
In the dispersant system of synthesis, adding aqueous slkali, the pH value of regulation system is 6～8；
Described aqueous slkali sodium hydroxide or potassium hydroxide solution, Solute mass concentration is 10%～30%；
Adjust the addition of amount of water and aqueous slkali, make to prepare dispersant concentration and be maintained at 40% ± 5, obtain described retardation setting type dispersant with high efficiency.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111377646A (en) * | 2018-12-31 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Retarding dispersant and preparation method thereof |
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