CN114656188B - Composite gypsum retarder and preparation method thereof - Google Patents

Composite gypsum retarder and preparation method thereof Download PDF

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CN114656188B
CN114656188B CN202210444018.5A CN202210444018A CN114656188B CN 114656188 B CN114656188 B CN 114656188B CN 202210444018 A CN202210444018 A CN 202210444018A CN 114656188 B CN114656188 B CN 114656188B
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phosphoric acid
parts
itaconic acid
reaction
gypsum
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CN114656188A (en
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田民格
高德超
马祥棣
郏瑞花
曾俊
曾志农
孟伟康
田沛霖
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Sciengreen Shandong Environment Technology Co ltd
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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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Ceramic Engineering (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention belongs to the field of gypsum building materials, and relates to a composite gypsum retarder which comprises the following raw materials in parts by weight: 30-50 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 15-25 parts of magnesium salt, 13-20 parts of organic acid salt and 5-25 parts of sulfamate. The invention also discloses a preparation method of the compound gypsum retarder. Compared with the prior art, the invention has the following advantages: from two macroscopic indexes of the setting time and the strength loss, compared with other inorganic salt retarders, the retarder has the advantages of long setting retarding time and small strength loss; the retarder time of the invention does not generate mutation phenomenon due to the change of the mixing amount, the mixing amount and the retarding time are in linear relation, and the setting time of the gypsum can be adjusted arbitrarily according to the operation time.

Description

Composite gypsum retarder and preparation method thereof
Technical Field
The invention belongs to the field of gypsum building materials, and particularly relates to a composite gypsum retarder and a preparation method thereof.
Background
As an excellent green building material, gypsum is widely used in products such as plastering gypsum, gypsum products and other decorative parts. In practical application, the gypsum material is mixed with water and then is set for a short time, and the fluidity of the gypsum material can be lost in a few minutes, so that the gypsum material cannot meet the requirements of normal construction. Only by adding the retarder to reform the gypsum-based product, the gypsum-based product really has use value, so the gypsum-based retarder has important significance for the application of the gypsum-based building material.
Suitable set retarders can delay the initial setting time of the gypsum material to a suitable range while maintaining the strength of the gypsum product.
There are three main types of retarders commonly used at present: organic acid and its soluble salt, alkaline phosphate and protein retarder. The organic acid and its soluble salt retarder mainly includes citric acid, sodium citrate, tartaric acid, potassium tartrate, etc.
Citric acid: when the mixing amount is low, a strong retarding effect is achieved, but the strength of the gypsum is obviously reduced, and the strength is reduced more greatly when the mixing amount is larger. Borax: the slow setting effect is not obvious at low mixing amount, and the dosage is large. Sodium polyphosphate: the growth habit of gypsum crystals is changed through adsorption, so that the crystals are coarsened, the lap joints among the crystals are weakened, the pore structure is deteriorated due to the increase of macropores, and the strength is reduced.
Proteins: the calcium phosphate slow-setting adhesive comprises bone glue, peptone and synthetic amino acids, the slow-setting effect is derived from the adsorption and protection of protein colloid, the influence on the crystal morphology of the dihydrate gypsum is small, and the strength loss is small. In recent years, bone glue and natural protein products also appear, but only simple physical composition of components is involved, the mixing amount is large, the slow setting time is not easy to control, and the gypsum product is not satisfactory in the aspect of comprehensive application performance, especially in the aspect of strength loss of the gypsum product.
Disclosure of Invention
The composite gypsum retarder is used for adjusting the retardation time of building gypsum and has the characteristics of low doping amount, linear relation between the doping amount and the retardation time, good retardation effect and small strength loss.
The technical scheme of the invention is realized as follows:
a composite gypsum retarder comprises the following raw materials in parts by weight:
30-50 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 15-25 parts of magnesium salt, 13-20 parts of organic acid salt and 5-25 parts of sulfamate.
Preferably, the invention discloses a composite gypsum retarder which is prepared from the following components in parts by weight: 28 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 15 parts of magnesium salt, 15 parts of organic acid salt and 20 parts of sulfamate.
Preferably, the preparation method of the itaconic acid-p-amino styrene phosphoric acid copolymer comprises the following steps:
1) Sequentially adding itaconic acid, p-aminophenylethylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylethylene phosphoric acid, adding a sodium hydroxide solution to keep the pH value at 8-9, and obtaining a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 70-95 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
The synthetic chemical reaction of the itaconic acid-p-amino styrene phosphoric acid copolymer is as follows:
Figure DEST_PATH_IMAGE002
in the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the mass ratio of the itaconic acid to the p-aminophenylethylene phosphate is 1.5-2.5:1, the catalyst accounts for 8-12% of the total mass of the itaconic acid and the p-amino styrene phosphoric acid, and the mass ratio of the deionized water to the reaction monomer is 4-7:1.
in the step 2), the initiator accounts for 3% of the mass sum of the itaconic acid and the p-amino styrene phosphoric acid;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the continuous heat preservation reaction time is 1 to 4h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
Preferably, the catalyst is titanium tetrachloride and the initiator is potassium persulfate.
Preferably, the magnesium salt is one of magnesium nitrate, magnesium ammonium phosphate, magnesium tartrate and magnesium dihydrogen phosphate.
Preferably, the organic acid salt is one of disodium hydroxyethylidene diphosphonate, tetrasodium hydroxyethylidene diphosphonate and tetrasodium 2-phosphonobutane-1, 2, 4-tricarboxylate.
Preferably, the sulfamate is one or two of sodium sulfamate, potassium sulfamate, sodium sulfanilate, sodium metanilic sulfonate and calcium metanilic sulfonate;
the invention also discloses a preparation method of the composite gypsum retarder, which comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
Compared with the prior art, the invention has the following advantages:
1) From two macroscopic indexes of the setting time and the strength loss, compared with other inorganic salt retarders, the retarder has the advantages of long setting retarding time and small strength loss;
2) The retarder time of the invention does not generate mutation phenomenon due to the change of the mixing amount, the mixing amount and the retarding time are in linear relation, and the setting time of the gypsum can be adjusted arbitrarily according to the operation time.
Drawings
FIG. 1 shows the linear trend of the addition amount and the retardation time of the high-efficiency gypsum retarder in example 6 of the invention;
the specific implementation mode is as follows:
the present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Example 1:
the embodiment discloses a composite gypsum retarder which is prepared from the following components in percentage by mass: 28 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 15 parts of magnesium nitrate, 15 parts of hydroxy ethylidene diphosphonic acid disodium and 20 parts of sodium sulfamate.
In this embodiment, the preparation method of the itaconic acid-p-aminophenylethylene phosphoric acid copolymer includes the following steps:
1) Sequentially adding itaconic acid, p-aminophenylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylene phosphoric acid, adding a sodium hydroxide solution to keep the pH value at 8.5, and obtaining a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 75 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
In the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the amount ratio of the itaconic acid to the p-aminophenylethylene phosphate substance is 1.5:1, the catalyst accounts for 8% of the mass sum of itaconic acid and p-amino styrene phosphoric acid, and the mass ratio of deionized water to reaction monomers is 4:1.
in the step 2), the initiator accounts for 3% of the total mass of the itaconic acid and the p-aminophenylethylene phosphoric acid, the catalyst is titanium tetrachloride, and the initiator is potassium persulfate;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 2h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
In the embodiment, the preparation method of the compound gypsum retarder comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
1000 parts of building gypsum and 0.1 part of composite gypsum retarder are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time and the strength performance are tested.
Example 2:
the embodiment discloses a composite gypsum retarder which is prepared from the following components in percentage by mass: 50 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 15 parts of magnesium ammonium phosphate, 13 parts of tetra sodium hydroxy ethylidene diphosphonate and 25 parts of sodium m-amino benzene sulfonate.
In this embodiment, the preparation method of the itaconic acid-p-aminophenylethylene phosphoric acid copolymer includes the following steps:
1) Sequentially adding itaconic acid, p-aminophenylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylene phosphoric acid, adding a sodium hydroxide solution to keep the pH value at 8.5, and obtaining a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 75 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
In the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the ratio of the amount of itaconic acid to the amount of p-aminophenylethylene phosphate is 2.5:1, the catalyst accounts for 10% of the total mass of itaconic acid and p-amino styrene phosphoric acid, and the mass ratio of deionized water to reaction monomers is 7:1.
in the step 2), the initiator accounts for 3% of the total mass of the itaconic acid and the p-aminophenylethylene phosphoric acid, the catalyst is titanium tetrachloride, and the initiator is potassium persulfate;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 4h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
In the embodiment, the preparation method of the compound gypsum retarder comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
1000 parts of building gypsum and 0.5 part of composite gypsum retarder are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time and the strength performance are tested.
Example 3:
the embodiment discloses a composite defluorinating agent which is prepared from the following components in percentage by mass: 30 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 25 parts of magnesium tartrate, 20 parts of 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid tetrasodium salt and 5 parts of potassium sulfamate.
In this embodiment, the preparation method of the itaconic acid-p-aminophenylethylene phosphoric acid copolymer includes the following steps:
1) Sequentially adding itaconic acid, p-amino styrene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-amino styrene phosphoric acid, adding a sodium hydroxide solution to obtain a pH value, and keeping the pH value at 8.5 to obtain a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 75 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
In the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the amount ratio of the itaconic acid to the p-aminophenylethylene phosphate substance is 1.5:1, the catalyst accounts for 12% of the total mass of itaconic acid and p-amino styrene phosphoric acid, and the mass ratio of deionized water to reaction monomers is 7:1.
in the step 2), the initiator accounts for 3% of the total mass of the itaconic acid and the p-aminophenylethylene phosphoric acid, the catalyst is titanium tetrachloride, and the initiator is potassium persulfate;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 2h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
In the embodiment, the preparation method of the compound gypsum retarder comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
1000 parts of building gypsum and 5 parts of composite gypsum retarder are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time and the strength performance are tested.
Example 4
The embodiment discloses a composite gypsum retarder which is prepared from the following components in percentage by mass: 44 parts of itaconic acid-p-aminophenylethylene phosphoric acid copolymer, 15 parts of magnesium dihydrogen phosphate, 10 parts of hydroxyl ethylidene diphosphonic acid tetrasodium salt and 20 parts of o-sulfamic acid.
In this embodiment, the preparation method of the itaconic acid-p-aminophenylethylene phosphoric acid copolymer includes the following steps:
1) Sequentially adding itaconic acid, p-aminophenylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylene phosphoric acid, adding a sodium hydroxide solution to keep the pH value at 8.5, and obtaining a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 75 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
In the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the amount ratio of the itaconic acid to the p-aminophenylethylene phosphate substance is 2.0:1, the catalyst accounts for 8% of the total mass of the itaconic acid and the p-amino styrene phosphoric acid, and the mass ratio of the deionized water to the reaction monomer is 5:1.
in the step 2), the initiator accounts for 3% of the total mass of the itaconic acid and the p-aminophenylethylene phosphoric acid, the catalyst is titanium tetrachloride, and the initiator is potassium persulfate;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 1h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
In the embodiment, the preparation method of the compound gypsum retarder comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
1000 parts of building gypsum and 2 parts of compound gypsum retarder are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time and the strength performance are tested.
Example 5
The embodiment discloses a composite gypsum retarder which is prepared from the following components in percentage by mass: 30 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 19 parts of magnesium tartrate, 18 parts of hydroxy ethylidene diphosphonic acid tetrasodium and 25 parts of calcium m-amino benzene sulfonate.
In this embodiment, the preparation method of the itaconic acid-p-aminophenylethylene phosphoric acid copolymer includes the following steps:
1) Sequentially adding itaconic acid, p-aminophenylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylene phosphoric acid, adding a sodium hydroxide solution to keep the pH value at 8.5, and obtaining a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 75 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
In the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the amount ratio of the itaconic acid to the p-aminophenylethylene phosphate substance is 1.5:1, the catalyst accounts for 9% of the total mass of the itaconic acid and the p-amino styrene phosphoric acid, and the mass ratio of the deionized water to the reaction monomer is 6:1.
in the step 2), the initiator accounts for 3% of the total mass of the itaconic acid and the p-aminophenylethylene phosphoric acid, the catalyst is titanium tetrachloride, and the initiator is potassium persulfate;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 4h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
In the embodiment, the preparation method of the composite gypsum retarder comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
1000 parts of building gypsum and 1 part of composite gypsum retarder are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time and the strength performance are tested.
Table 1 test results of the high efficiency composite gypsum retarder according to embodiments 1-5 of the present invention are as follows:
table 1:
Figure DEST_PATH_IMAGE004
example 6
The embodiment discloses a composite gypsum retarder which is prepared from the following components in percentage by mass: 35 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 18 parts of magnesium tartrate, 20 parts of tetra sodium hydroxy ethylidene diphosphonate and 19 parts of calcium m-amino benzene sulfonate.
In this embodiment, the preparation method of the itaconic acid-p-aminophenylethylene phosphoric acid copolymer includes the following steps:
1) Sequentially adding itaconic acid, p-aminophenylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylene phosphoric acid, adding a sodium hydroxide solution to keep the pH value at 8.5, and obtaining a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 75 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) And cooling after the reaction is finished, and stopping stirring to obtain the itaconic acid-p-aminophenylethylene phosphoric acid copolymer.
In the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer.
In the step 1), the quantity ratio of the itaconic acid to the p-aminophenylethylene phosphate substance is 1.8:1, the catalyst accounts for 8% of the total mass of the itaconic acid and the p-amino styrene phosphoric acid, and the mass ratio of the deionized water to the reaction monomer is 5:1.
in the step 2), the initiator accounts for 3% of the total mass of the itaconic acid and the p-amino styrene phosphoric acid, the catalyst is titanium tetrachloride, and the initiator is potassium persulfate;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 3h.
In the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
In the embodiment, the preparation method of the compound gypsum retarder comprises the steps of stirring and mixing the components in proportion in a mixing kettle at normal temperature for 30min, and discharging.
1000 parts of building gypsum and 0.25 part of the composite gypsum retarder of the embodiment are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time test is carried out.
1000 parts of building gypsum and 0.5 part of the composite gypsum retarder of the embodiment are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time test is carried out.
1000 parts of building gypsum and 0.75 part of the composite gypsum retarder of the embodiment are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time test is carried out.
1000 parts of building gypsum and 1 part of the composite gypsum retarder of the embodiment are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time test is carried out.
1000 parts of building gypsum and 2 parts of the composite gypsum retarder are prepared into a mixture, the water-material ratio is 0.65, the mixture is molded, and the setting time test is carried out.
Table 2 the test results of the high efficiency composite gypsum retarder of example 6 of the present invention are as follows:
Figure DEST_PATH_IMAGE006
FIG. 1 shows the linear trend of the addition amount and the retardation time of the high-efficiency gypsum retarder of example 6 of the invention;
table 3 comparative tests the results are as follows:
Figure DEST_PATH_IMAGE008
comparative examples 1 to 6: chemical reagents are doped externally in equal amount, the water-material ratio is 0.65, and the common single gypsum retarder has the problems of low retarding efficiency and large strength loss.
By combining the data analysis, 1) from two macroscopic indexes of the setting time and the strength loss, the retarder has the advantages of long retarding time and small strength loss compared with other inorganic salt retarders; 2) The retarder time of the invention does not generate mutation phenomenon due to the change of the mixing amount, the mixing amount and the retarding time are in linear relation, and the setting time of the gypsum can be adjusted arbitrarily according to the operation time.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention, and the technical solutions are all covered in the scope of the claims and the specification of the present invention; it will be apparent to those skilled in the art that any alternative modifications or variations to the embodiments of the present invention may be made without departing from the scope of the invention.
The present invention is not described in detail, but is known to those skilled in the art.

Claims (6)

1. A compound gypsum retarder is characterized in that: according to the weight portion, the material comprises 30-50 portions of itaconic acid-p-amino styrene phosphoric acid copolymer, 15-25 portions of magnesium salt, 13-20 portions of organic acid salt and 5-25 portions of sulfamate;
the preparation method of the itaconic acid-p-amino styrene phosphoric acid copolymer comprises the following steps,
1) Sequentially adding itaconic acid, p-aminophenylethylene phosphoric acid, deionized water and a catalyst into a reactor, heating in a constant-temperature water bath kettle, stirring to dissolve the itaconic acid and the p-aminophenylethylene phosphoric acid, adding a sodium hydroxide solution to adjust the pH value, and keeping the pH value at 8-9 to obtain a reaction solution;
2) Under the nitrogen atmosphere, maintaining the temperature at 70-90 ℃, dropwise adding an initiator into the reaction liquid at a constant speed, heating, refluxing, mechanically stirring, and continuing to perform heat preservation reaction after dropwise adding is finished;
3) Cooling after the reaction is finished, stopping stirring, and drying at 80 ℃ to obtain an itaconic acid-p-aminophenylethylene phosphoric acid copolymer;
in the step 1), the reactor is a three-neck flask provided with a reflux condenser, a constant pressure dropping funnel and a stirrer;
in the step 1), the mass ratio of the itaconic acid to the p-aminophenylethylene phosphoric acid is 1.5-2.5:1, the catalyst accounts for 8-12% of the total mass of the itaconic acid and the p-amino styrene phosphoric acid, and the mass ratio of the deionized water to the reaction monomer is 4-7:1;
in the step 2), the initiator accounts for 3% of the mass sum of the itaconic acid and the p-aminophenylethylene phosphoric acid;
in the step 2), the dropping time of dropping the initiator at a constant speed is 0.5h, and the reaction time is kept for 1-4h;
in the step 3), after the reaction is finished, stopping stirring to obtain a polymerization reactant solution; adding absolute ethyl alcohol into the polymerization reaction solution, stirring to obtain a polymerization reaction product precipitate, and drying in vacuum to constant weight to obtain the itaconic acid-p-amino styrene phosphoric acid copolymer.
2. The compound gypsum retarder of claim 1, wherein: the composition is prepared from the following components in parts by weight: 28 parts of itaconic acid-p-amino styrene phosphoric acid copolymer, 15 parts of magnesium salt, 15 parts of organic acid salt and 20 parts of sulfamate.
3. The composite gypsum retarder according to claim 1 or 2, wherein: the magnesium salt is one of magnesium ammonium phosphate, magnesium tartrate and magnesium dihydrogen phosphate.
4. The composite gypsum retarder according to claim 1 or 2, wherein: the organic acid salt is one of disodium hydroxyethylidene diphosphonate, tetrasodium hydroxyethylidene diphosphonate and tetrasodium 2-phosphonobutane-1, 2, 4-tricarboxylic acid.
5. The composite gypsum retarder according to claim 1 or 2, wherein: the sulfamate is one or two of sodium sulfamate, potassium sulfamate, sodium sulfanilate and calcium sulfanilate.
6. The preparation method of the compound gypsum retarder according to claim 1 or 2, which is characterized in that: the components are stirred and mixed in a mixing kettle for 30min at normal temperature according to a certain proportion, and then the materials are discharged.
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