CN105566505A - Preparation method of starch sulfonate - Google Patents
Preparation method of starch sulfonate Download PDFInfo
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- CN105566505A CN105566505A CN201510942224.9A CN201510942224A CN105566505A CN 105566505 A CN105566505 A CN 105566505A CN 201510942224 A CN201510942224 A CN 201510942224A CN 105566505 A CN105566505 A CN 105566505A
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- starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/06—Esters of inorganic acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/168—Polysaccharide derivatives, e.g. starch sulfate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical fields of chemical industry and concrete construction materials. In order to solve the problems of high slump constant time loss and lower flowability in the concrete, the invention provides a preparation method of starch sulfonate. The preparation method comprises the following steps: dissolving dextrin prepared from starch or directly purchased dextrin in water, heating to react by using water as a dispersing agent and sodium bisulfite as a sulfonating agent, and regulating the pH value to 7 with sodium hydroxide to obtain a liquid which is the starch sulfonate. The invention uses the method for preparing starch sulfonate by using water as the medium and sodium bisulfite as the sulfonating agent for the first time, which is different from the preparation method by using dichloromethane or any other organic solvent as the medium in the prior art. The method has the advantages of simple technique, environment friendliness and no pollution emission, and is beneficial to industrial production. The product has favorable synergic dispersion properties for cement particles, solves the problems of poor slump retaining effect and poor workability in the existing retarder for concrete, use of toxic solvents in the preparation process, and difficulty in treating sulfonating agent byproduct chlorine ions. The invention provides a novel preparation method of starch sulfonate.
Description
Technical field
The invention belongs to chemical industry and concrete building material technical field, be specifically related to a kind of preparation method of starch sulphonate.
Background technology
In concrete construction, the diminishing that the tricalcium aluminate content of cement and alkali content, the loss on ignition of flyash, the silt content of sandstone all can have influence on poly carboxylic acid series water reducer protects the effect of collapsing, make concrete Slump Time losing of Large large, mobility is deteriorated, and affects engineering construction.At present conventional terms of settlement be consumption by increasing water reducer improve cement slurry initial flow degree through time hold facility, but water reducer cost can be increased.Some people is for following the line of least resistance, and directly add water in construction increase degree of mobilization, and water cement ratio increases, and affects construction quality.Therefore, the guarantor of poly carboxylic acid series water reducer is collapsed, the problem of anti-mud has good application prospect to solving to research and develop a kind of concrete slump retaining auxiliary agent.
Starch is a kind of high glycan, primarily of the sugared ring of glucosyl residue by a-D-(l → 4) glycosidic link is formed by connecting, chemical structure is (C6H10O5) n, water-fast glucose ring is considered as hydrophobic group, the strong sulfonic group of wetting ability as hydrophilic radical, sulfonic acid esterification starch the is possessed basic structure of tensio-active agent.Starch derivative, as in the study mechanism of cement water reducing agent, sterically hinderedly accounts for leading role, and therefore molecular weight is very large on the impact of performance.Full-bodied starch sulphonate due to winding degree mutual between molecular chain comparatively large, the network structure formed in the solution is huge, and it is comparatively strong to embrace water-based, and cause free-water in system significantly to reduce, therefore it does not have dispersion effect to cement granules.And with the starch sulphonate of degraded starch synthesis because molecular chain is shorter, thus there is the dispersing property to cement granules, therefore, preparing low-viscosity starch sulphonate is precondition as concrete slump retaining auxiliary agent.
Current synthetic starch sulphonate is mainly glycosyl with dextrin, with organic solvent dichloromethane or DMF (DMF) for dispersion agent, and the synthetic route being sulphonating agent with chlorsulfonic acid or thionamic acid; Its dispersion agent DMF used is unfavorable for the sulfonation reaction of starch, and the irritating smell having ammonia due to DMF, be not easy to actually operating.And the boiling point of methylene dichloride is low, is only beneficial to and adopts half-dried legal system water reducer.Adopt chlorsulfonic acid as sulphonating agent, because chlorsulfonic acid has severe corrosive, in reaction, be attended by side reaction:
, the hydrochloric acid of generation has severe corrosive to production unit, and chlorsulfonic acid is expensive, further limit its application as sulphonating agent; The aqueous solution of thionamic acid has the strongly-acid equal with hydrochloric acid, sulfuric acid etc., therefore another name is solid sulphuric acid again, and it has non-volatile, odorless and the feature minimum to human toxicity.Aqueous sulfamic acid is comparatively slow to corrosion of metal effects such as iron, can add some sodium-chlor, make it to be equivalent to be converted into hydrochloric acid, thus dissolved iron is dirty effectively.Aqueous sulfamic acid can remove the water scale and corrosion product of the equipment surface that the materials such as iron, steel, copper, stainless steel manufacture.Therefore the incrustation scale on production unit surface or corrosion product are added in the starch sulphonate of preparation by solution, thus affect the performance of product.
Summary of the invention
The present invention is large in order to solve concrete Slump Time losing of Large, and the problem that mobility is deteriorated provides a kind of preparation method of starch sulphonate.Prepare a kind of tensio-active agent as poly carboxylic acid series water reducer auxiliary agent, play protect collapse, the result of use of anti-mud.
The present invention adopts following technical scheme to realize: a kind of preparation method of starch sulphonate, the dextrin prepared by starch or the water-soluble water of the dextrin directly buied do dispersion agent Sodium Metabisulphate 65 and make sulphonating agent, be that 7 acquisition liquid are starch sulphonate by sodium hydroxide adjust ph after temperature reaction, comprise the steps:
(1) enzyme process prepares dextrin: modulation quality percentage concentration is the starch milk of 30% ~ 45%, add 0.2-0.5 part amylase, control temperature is 50 ~ 60 DEG C, and pH 3.5 ~ 5.0 reacts, reaction terminating when inspection DE value is 10 ~ 20, then 100 DEG C are heated 3 ~ 5min and to go out enzyme;
(2) starch sulphonate is prepared: add 140 ~ 220 parts of deionized waters in there-necked flask, dextrin prepared by 70 ~ 120 parts of starch or the dextrin directly buied and 50 ~ 100 parts of Sodium Metabisulphate 65s, be warming up to 75 ~ 95 DEG C, insulation reaction 1 ~ 3 hour, pH to 7 is regulated by the NaOH solution that massfraction is 35%, the liquid obtained is starch sulphonate, is spray-driedly opaque starch sulphonate.
Synthesis technique of the present invention is simple, environmental protection, non-pollutant discharge.For the feature of amylodextrin Sodium Metabisulphate 65 slowly-releasing generation addition reaction in aqueous phase, can with the Sodium Metabisulphate 65 of dextrin generation addition reaction as sulphonating agent under selecting condition of heating more than 75 DEG C, generate strong polar hydrophilic group and functional chain, change the molecular structure of dextrin.With water be medium, pioneering be the method that starch sulphonate prepared by sulphonating agent with Sodium Metabisulphate 65, be different from the preparation method that prior art is medium with methylene dichloride or other organic solvent, present invention process is simple, environmental protection, contamination-free is discharged, and is beneficial to suitability for industrialized production.
Preparation starch sulfonate ester surfactant good to the dispersing property of cement granules, 0.5% amount to the water-reducing effect that solid volume just can reach 35%.But because of by force latent, should not mix more, generally as concrete additives can with poly carboxylic acid series water reducer, the composite use of naphthalene water reducer, synergistic function is obvious, very strong to various sand material quality, sand silt content adaptability.
The concrete flowability stirred out, workability, pumpability are good, guarantor's time of collapsing is long, to temperature-insensitive, even if also can normally use in the southern summer high temperature time, the lifting of environmental-protecting performance, endurance quality and energy-efficient performance can be built to China and play the effect of actively promoting.
Embodiment
Embodiment 1: a kind of preparation method of starch sulphonate, does dispersion agent Sodium Metabisulphate 65 by water-soluble for the dextrin directly buied water and makees sulphonating agent, is that 7 acquisition liquid are starch sulphonate, comprises the steps: after temperature reaction by sodium hydroxide adjust ph
200 mass parts deionized waters, 120 mass parts dextrin and 80 parts of Sodium Metabisulphate 65s are added in there-necked flask, be warming up to 75 DEG C, insulation reaction 2 hours, pH to 7 is regulated by the NaOH solution that mass percent concentration is 35%, the liquid obtained is starch sulphonate, is spray-driedly opaque starch sulphonate.
Embodiment 2: a kind of preparation method of starch sulphonate, the water-soluble water of the dextrin prepared by starch does dispersion agent Sodium Metabisulphate 65 and makees sulphonating agent, is that 7 acquisition liquid are starch sulphonate, comprises the steps: after temperature reaction by sodium hydroxide adjust ph
(1) enzyme process prepares dextrin: modulation concentration is the starch milk of 30%, and add 0.3 part of amylase, control temperature is 50 DEG C, and pH 4.0 reacts, reaction terminating when inspection DE value is 10 ~ 20, and then 100 DEG C are heated 3 ~ 5min and to go out enzyme;
(2) 220 mass parts deionized waters, 100 mass parts dextrin and 100 parts of Sodium Metabisulphate 65s are added in there-necked flask, be warming up to 95 DEG C, insulation reaction 3 hours, pH to 7 is regulated by the NaOH solution that mass percent concentration is 35%, the liquid obtained is starch sulphonate, is spray-driedly opaque starch sulphonate.
Embodiment 3: a kind of preparation method of starch sulphonate, the water-soluble water of the dextrin prepared by starch does dispersion agent Sodium Metabisulphate 65 and makees sulphonating agent, is that 7 acquisition liquid are starch sulphonate, comprises the steps: after temperature reaction by sodium hydroxide adjust ph
(1) enzyme process prepares dextrin: modulation concentration is the starch milk of 45%, and add 0.5 part of amylase, control temperature is 60 DEG C, and pH 5.0 reacts, reaction terminating when inspection DE value is 10 ~ 20, and then 100 DEG C are heated 3 ~ 5min and to go out enzyme;
(2) 140 mass parts deionized waters, 70 mass parts dextrin and 50 parts of Sodium Metabisulphate 65s are added in there-necked flask, be warming up to 85 DEG C, insulation reaction 1 hour, pH to 7 is regulated by the NaOH solution that mass percent concentration is 35%, the liquid obtained is starch sulphonate, is spray-driedly opaque starch sulphonate.
Embodiment 4: a kind of preparation method of starch sulphonate, the water-soluble water of the dextrin prepared by starch does dispersion agent Sodium Metabisulphate 65 and makees sulphonating agent, is that 7 acquisition liquid are starch sulphonate, comprises the steps: after temperature reaction by sodium hydroxide adjust ph
(1) enzyme process prepares dextrin: modulation concentration is the starch milk of 30%, and add 0.2 part of amylase, control temperature is 55 DEG C, and pH 3.5 reacts, reaction terminating when inspection DE value is 10 ~ 20, and then 100 DEG C are heated 3 ~ 5min and to go out enzyme;
(2) 210 mass parts deionized waters, 70 mass parts dextrin and 50 parts of Sodium Metabisulphate 65s are added in there-necked flask, be warming up to 85 DEG C, insulation reaction 1 hour, pH to 7 is regulated by the NaOH solution that mass percent concentration is 35%, the liquid obtained is starch sulphonate, is spray-driedly opaque starch sulphonate.
Experimental example 1: according to method described in embodiment 1, change different synthesis temperature, detects the impact of different temperature on the flowing degree of net paste of cement of product, and detected result is in table 1, and the flowing degree of net paste of cement of 75 DEG C after testing ~ 85 DEG C of products reaches the highest.
The flowing degree of net paste of cement of the different synthesis temperature product of table 1
According to method described in embodiment 1, change different generated time, detect the impact of different time on the flowing degree of net paste of cement of product, detected result is in table 2, and more than 2.0h product paste flowing degree reaches the highest after testing.
The flowing degree of net paste of cement of the different generated time product of table 2
According to method described in embodiment 1, change different synthesis pH, detect the impact of different pH on the flowing degree of net paste of cement of product, detected result is in table 3, and pH6.5 product paste flowing degree reaches the highest after testing.
The flowing degree of net paste of cement of table 3 difference synthesis pH product
Experimental example 2: product compliance test result: under the different addition quantity of starch sulphonate in cement, pulp flowage and slow setting time affect testing inspection, detected result is in table 4, within the moderate dosage of result display starch sulphonate accounts for 0.1% of cement consumption, exceed not solidify and not there is using value.
The pulp flowage of table 4 starch sulphonate under different addition quantity and slow setting time
Experimental example 3: polycarboxylate water-reducer solid content 20%, the starch sulphonate inside mixing solid content 2 ~ 5% does concrete slump loss testing inspection, detect formula in table 5, detected result is in table 6, and result shows: the polycarboxylate water-reducer not mixing retardant is less than 160mm 1 hour inner concrete slump; Starch sulphonate 2 hours inner concrete slumps of mixing 3% solid content in polycarboxylate water-reducer are not less than 160mm.The Sunmorl N 60S 1.5 hours concrete slumps mixing 3% solid content in polycarboxylate water-reducer are less than 160mm, and starch sulphonate slump retaining is better than Sunmorl N 60S.
Table 5 admixture formula (gross weight 400g, starch sulphonate volume accounts for admixture gross weight 2%)
Table 6 polycarboxylic admixture admixture glucose sulphonate and Sunmorl N 60S different addition quantity contrast at concrete slump loss
Experimental example 4: concrete water bleeding, the pumpability of starch sulphonate and Sunmorl N 60S are verified, comparing result is in table 7.
Concrete water bleeding, the pumpability of table 7 starch sulphonate and Sunmorl N 60S contrast
Experimental example 5: to the experimental verification of temperature-insensitive etc., the results are shown in Table 8.
The experimental result of table 8 pair temperature-insensitive etc.
The analysis of result: starch sulfonate ester surfactant is to temperature-insensitive, and guaranteeing role is played in concrete construction under high ambient conditions, is with high ferro construction to walk out to South Subtropical Area of China to promotion China one tunnel one and has pushing effect.
Experimental example 6: to the adaptive experiment of sand material silt content, experimental result is in table 9, and result shows: starch sulphonate is stronger than Sunmorl N 60S to various sand material quality, sand silt content adaptability.。
The table 9 pair adaptive experimental result of sand material silt content
Experimental example 7: with the experimental verification of poly carboxylic acid series water reducer, naphthalene water reducer composite use synergistic function effect, the results are shown in Table 10, result show: starch sulphonate as concrete retarder can with poly carboxylic acid series water reducer, the composite use of naphthalene water reducer, synergistic function is obvious.
Table 10 starch sulphonate and poly carboxylic acid series water reducer, the composite use synergistic function of naphthalene water reducer
Experimental example 8: the concrete strength contrast experiment of starch sulphonate and Sunmorl N 60S verifies, the result is in table 11, and result shows: the concrete mixing starch sulphonate is higher by 7% than the 28 days concrete strengths mixing Sunmorl N 60S.
The concrete strength contrast experiment of table 11 starch sulphonate and Sunmorl N 60S
Experimental example 9: the antiseptic property contrast experiment in admixture of starch sulphonate and Sunmorl N 60S verifies, the result is in table 12, and result shows: the polycarboxylic admixture mixing Sunmorl N 60S produces rancid flavor in 3 days, and degree of mobilization reduces.Mix the polycarboxylic admixture of starch sulphonate without rancid flavor, degree of mobilization remains unchanged.Therefore, starch sulphonate has antibacterial anti-corrosion function, can keep concrete admixture effect for a long time.
The antiseptic property contrast experiment (20 DEG C) in admixture of table 12 starch sulphonate and Sunmorl N 60S
| Cement type | Retardant accounts for cement consumption (%) | Presetting period (h) | Admixture smell | 3 days initial extension degree (mm) |
| Starch sulphonate | 0.02 | 8：40 | Tasteless | 500 |
| Sunmorl N 60S | 0.02 | 8：20 | Rancid flavor | 400 |
Claims (1)
1. the preparation method of a starch sulphonate, the dextrin prepared by starch or the water-soluble water of the dextrin directly buied do dispersion agent Sodium Metabisulphate 65 and make sulphonating agent, be that 7 acquisition liquid are starch sulphonate by sodium hydroxide adjust ph after temperature reaction, it is characterized in that: comprise the steps:
(1) enzyme process prepares dextrin: modulation concentration is the starch milk of 30% ~ 45%, add 0.2-0.5 part amylase, control temperature is 50 ~ 60 DEG C, and pH 3.5 ~ 5.0 reacts, reaction terminating when inspection DE value is 10 ~ 20, then 100 DEG C are heated 3 ~ min and to go out enzyme;
(2) starch sulphonate is prepared: add 140 ~ 220 parts of deionized waters in there-necked flask, dextrin prepared by 70 ~ 120 parts of starch or the dextrin directly buied and 50 ~ 100 parts of Sodium Metabisulphate 65s, be warming up to 75 ~ 95 DEG C, insulation reaction 1 ~ 3 hour, pH to 7 is regulated by the NaOH solution that massfraction is 35%, the liquid obtained is starch sulphonate, is spray-driedly opaque starch sulphonate.
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Cited By (3)
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| CN106749704A (en) * | 2016-11-03 | 2017-05-31 | 裘武军 | Sulfo-fatty acid sodium starch and preparation method thereof |
| CN111072788A (en) * | 2019-11-29 | 2020-04-28 | 娈烽附 | Preparation method of starch sulfate and application of starch sulfate as cement additive |
| CN115745468A (en) * | 2023-01-06 | 2023-03-07 | 石家庄市长安育才建材有限公司 | Starch-based slump retaining water reducer and preparation method thereof |
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| CN115745468A (en) * | 2023-01-06 | 2023-03-07 | 石家庄市长安育才建材有限公司 | Starch-based slump retaining water reducer and preparation method thereof |
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