Retarder for composite multi-component cementing material and preparation method thereof

Abstract

The invention discloses a preparation method of a retarder for compounding a multi-component cementing material, which comprises the following steps: by taking a polyalcohol acid organic matter as a raw material, introducing an active alkenyl monomer, grafting a protein component containing multi-amino carboxyl, and introducing a main functional group for adjusting the coagulation time of gypsum and a composite material, thereby obtaining the retarder. Through the mode, the retarder for the composite multi-element cementing material and the preparation method have the advantages that the retarding effect of a gypsum composite cementing material can be improved, the yield of condensation and polymerization reaction can be improved, the retarding degree difference can be effectively reduced, the adaptability and the sensitivity are better, and the application field is wider.

Description

Technical Field

[0001] The invention relates to the technical field of additives for building cementitious materials, in particular to a retarder for composite multi-component cementitious materials and a preparation method thereof. Background Art

[0002] At present, gypsum cementitious materials and their products in the field of building materials are widely used in plastering, painting and the manufacture of various gypsum products because of their low production cost, certain strength, simple process and good fireproof and heat insulation performance. The advantages of adding solid waste admixtures to gypsum are obvious. It can not only further improve the performance of gypsum, but also reduce production costs. Solid waste resources can also be reused. Among them, admixtures include cement, lime calcium, slag, fly ash, etc.

[0003] There are many types of gypsum, mainly including building gypsum, phosphogypsum, desulfurized gypsum and titanium gypsum, etc. Gypsum retarder is one of the indispensable materials in the production and use of gypsum. Most gypsum retarders on the market currently have ideal setting performance during construction for single-component gypsum materials, but for gypsum-based composite materials that introduce gypsum, lime lime, quicklime, etc., due to the complex composition, the control of setting time during construction will be more complicated, and the adaptability of ordinary retarders becomes poor. The setting effect fluctuates greatly and is unstable, which is prone to engineering accidents. It is far from meeting the current use needs, so it needs to be improved. Summary of the invention

[0004] In order to solve the above technical problems, a technical solution adopted by the present invention is: Provided is a retarder for composite multi-element gelling material and a preparation method thereof, the steps comprising: (1) Add the following components in a reaction kettle: 30-50 parts of a small molecule alkenyl carboxylic acid compound, 50-70 parts of a polyol acid organic compound, and 0.2-1 parts of a condensation catalyst, respectively; heat the reaction kettle to 90-115° C., stir the reaction for 1 h-3 h, and then cool the reaction kettle to room temperature to obtain a raw material A; (2) Add 30-50 parts of a small molecule alkenyl carboxylic acid compound, 50-70 parts of a polycarboxylic acid protein and 0.2-1 parts of a condensation catalyst into a reaction kettle, raise the temperature to 40-60° C., stir and react for a period of time, and then cool to room temperature to obtain raw material B; (3) Add 30-50 parts of water, 35-55 parts of raw material A and 30-45 parts of raw material B to the reactor, raise the temperature to 40-60°C, dropwise add the initiator catalyst to react, add the pH adjuster after the reaction is completed, keep the pH of the system at neutral, and keep the temperature for 1-2 hours; (4) After the stock solution obtained in step (3) is cooled to room temperature, it is powdered and dried in a centrifugal spray tower to obtain a retarder for a composite multi-component gelling material.

[0005] In a preferred embodiment of the present invention, in step (1) and step (2), the small molecule alkenyl carboxylic acid compound comprises one or two of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

[0006] In a preferred embodiment of the present invention, the polyol acid organic matter includes one or two of glucose, gluconic acid, gluconolactone and citric acid.

[0007] In a preferred embodiment of the present invention, in step (1) and step (2), the condensation catalyst includes one or two of concentrated sulfuric acid, p-toluenesulfonic acid, and DMAP.

[0008] In a preferred embodiment of the present invention, the polycarboxylic acid protein comprises one or two of glycine, glutamic acid, lysine and aspartic acid.

[0009] In a preferred embodiment of the present invention, the initiating catalyst includes one or two of hydrogen peroxide, ammonium persulfate, and ferrous sulfate.

[0010] In a preferred embodiment of the present invention, the pH adjuster includes one of sodium hydroxide, calcium hydroxide and quicklime.

[0011] In a preferred embodiment of the present invention, the dropwise addition time of the initiating catalyst is 30 to 60 minutes.

[0012] A retarder for composite multi-element gelling material is prepared by the above-mentioned preparation method.

[0013] The beneficial effects of the present invention are: not only can the retarding effect of the gypsum composite cementitious material be improved, but also the yield of condensation and polymerization reactions can be improved, and the difference in retarding degree can be effectively reduced, so that the adaptability and sensitivity are better and the application field is wider. DETAILED DESCRIPTION

[0014] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Embodiments of the present invention include: A retarder for composite multi-component cementitious materials (composite gypsum) is produced by using polyol acid organic matter as raw material, introducing active olefin monomers, grafting protein components containing polyamine carboxyl groups, polymerizing long chains, and introducing main functional groups for regulating the setting time of gypsum and composite materials, thereby utilizing a simple and efficient synthesis process to produce the retarder.

[0016] A method for preparing a retarder for composite multi-element gelling material, the specific steps of which include: (1) Add the following components in a reaction kettle: 30-50 parts of a small molecule alkenyl carboxylic acid compound, 50-70 parts of a polyol acid organic compound, and 0.2-1 part of a condensation catalyst. Heat the reaction kettle to 90-115°C, stir the reaction for 1-3 hours, and then cool the reaction kettle to room temperature to obtain raw material A.

[0017] More preferably, the small molecule alkenyl carboxylic acid compound includes one or two of acrylic acid, methacrylic acid, maleic acid and maleic anhydride.

[0018] More preferably, the polyol acid organic substance includes one or two of glucose, gluconic acid, gluconolactone and citric acid.

[0019] More preferably, the condensation catalyst includes one or two of concentrated sulfuric acid, p-toluenesulfonic acid, and DMAP.

[0020] (2) Add 50-80 parts of a small molecule alkenyl carboxylic acid compound, 30-70 parts of a polycarboxylic acid protein and 0.2-1 part of a condensation catalyst into a reaction kettle, heat to 40-60°C, stir and react for a period of time, then cool to room temperature to obtain raw material B.

[0021] More preferably, the small molecule alkenyl carboxylic acid compound includes one or two of acrylic acid, methacrylic acid, maleic acid and maleic anhydride.

[0022] More preferably, the polycarboxylic acid protein comprises one or two of glycine, glutamic acid, lysine and aspartic acid.

[0023] More preferably, the condensation catalyst includes one or two of concentrated sulfuric acid, p-toluenesulfonic acid, and DMAP.

[0024] (3) Add 60-100 parts of water, 35-55 parts of raw material A and 30-45 parts of raw material B to the reactor, heat it to 40-60°C, and then slowly drop 0.2-3.0 parts of initiator catalyst to react. After the reaction is completed, add a pH adjuster to keep the pH of the system at neutral, and keep warm for 1-2 hours.

[0025] More preferably, the initiating catalyst includes one or two of hydrogen peroxide, ammonium persulfate, and ferrous sulfate.

[0026] Further preferably, the pH adjuster includes one of sodium hydroxide or its solution, calcium hydroxide, and quicklime.

[0027] More preferably, the dropping time is 30 to 60 min.

[0028] (4) After the stock solution obtained in step 3 is cooled to room temperature, it is powdered and dried in a centrifugal spray tower to obtain a retarder for composite multi-element gypsum. Example

[0029] 1) Add 35 parts by weight of maleic anhydride to a reactor, heat it to 60°C, then add 65 parts of glucose and 0.5 parts of concentrated sulfuric acid, heat it to 110°C, react for 2 hours, and then cool it to room temperature to obtain raw material A; 2) Add 50 parts by weight of maleic anhydride, 40 parts by weight of glycine and 0.3 parts by weight of DMAP to a reaction kettle, then heat to 100°C, react for 2 hours, and then cool to room temperature to obtain raw material B; 3) Add 60 parts of water and 35 parts of raw material A and 30 parts of raw material B in the reaction kettle, raise the temperature to 60°C, slowly drop 2.5 parts of 30% ammonium persulfate solution for 60 minutes, and keep warm for 2 hours after completion; 4) Add 30% sodium hydroxide solution into the reactor, neutralize to neutrality, then cool to room temperature, and transport to a centrifugal spray drying tower for powder spraying and drying to obtain a composite gypsum retarder. Example

[0030] 1) Add 35 parts by weight of maleic anhydride to a reactor, heat it to 60°C, then add 65 parts of gluconic acid and 0.8 parts of p-toluenesulfonic acid, heat it to 110°C, react for 2 hours, and then cool to room temperature to obtain raw material A; 2) Add 65 parts by weight of maleic anhydride, 70 parts by weight of lysine and 0.5 parts by weight of DMAP into a reaction kettle, then heat to 105°C, react for 2 hours, and then cool to room temperature to obtain raw material B; 3) Add 60 parts by weight of water, 36 parts of raw material A and 40 parts of raw material in the above step into the reaction kettle, heat to 50°C, slowly drop 2.5 parts of 30% ammonium persulfate solution for 60 minutes, and keep warm for 2 hours after completion; 4) A 30% sodium hydroxide solution is added to the reaction kettle to neutralize it to neutrality, then cooled to room temperature, and transported to a centrifugal spray drying tower for powder spraying and drying to obtain a composite gypsum retarder. Example

[0031] 1) Add 40 parts by weight of maleic anhydride to a reactor, heat it to 60°C, then add 70 parts of gluconic acid and 0.5 parts of p-toluenesulfonic acid, heat it to 110°C, react for 2 hours, and then cool it to room temperature to obtain raw material A; 2) Add 65 parts by weight of maleic anhydride, 50 parts by weight of lysine and 0.6 parts by weight of p-toluenesulfonic acid into a reaction kettle, then heat to 105°C, react for 2 hours, and then cool to room temperature to obtain raw material B; 3) Add 70 parts by weight of water and 40 parts of raw material A and 35 parts of raw material B in the reaction kettle, raise the temperature to 50°C, and slowly drop a solution prepared by 3.2 parts of hydrogen peroxide and 20 parts of water and a solution prepared by 0.05 parts of ferrous sulfate and 30 parts of water. The dropping time is 60 minutes. After completion, keep warm for 2 hours; 4) A 30% sodium hydroxide solution is added to the reaction kettle to neutralize it to neutrality, then cooled to room temperature, and transported to a centrifugal spray drying tower for powder spraying and drying to obtain a composite gypsum retarder. Example

[0032] 1) Add 40 parts by weight of maleic anhydride to a reaction kettle, heat it to 60°C, then add 70 parts of citric acid and 0.9 parts of p-toluenesulfonic acid, heat it to 110°C, react for 2 hours, and then cool to room temperature to obtain raw material A; 2) Add 70 parts by weight of maleic anhydride, 45 parts by weight of glutamic acid and 0.7 parts by weight of DMAP to the reaction kettle, then heat to 105°C, react for 2 hours, and then cool to room temperature to obtain raw material B; 3) Add 60 parts by weight of water and 35 parts of raw material A and 45 parts of raw material B in the above step into the reaction kettle, heat to 60°C, slowly drop 1.5 parts of 30% ammonium persulfate solution for 60 minutes, and keep warm for 2 hours after completion; 4) A 30% sodium hydroxide solution is added to the reaction kettle to neutralize it to neutrality, then cooled to room temperature, and transported to a centrifugal spray drying tower for powder spraying and drying to obtain a composite gypsum retarder. Example

[0033] 1) Add 40 parts by weight of maleic anhydride to a reaction kettle, heat it to 60°C, then add 65 parts of gluconolactone and 0.9 parts of p-toluenesulfonic acid, heat it to 110°C, react for 2 hours, and then cool to room temperature to obtain raw material A; 2) Add 65 parts by weight of maleic anhydride, 45 parts by weight of lysine and 0.7 parts by weight of DMAP into a reaction kettle, then heat to 105°C, react for 2 hours, and then cool to room temperature to obtain raw material B; 3) Add 65 parts by weight of water and 40 parts of raw material A and 45 parts of raw material B in the above step into the reaction kettle, heat to 45°C, slowly drop 2.1 parts of 30% ammonium persulfate solution for 60 minutes, and keep warm for 2 hours after completion; 4) A 30% sodium hydroxide solution is added to the reaction kettle to neutralize it to neutrality, then cooled to room temperature, and transported to a centrifugal spray drying tower for powder spraying and drying to obtain a composite gypsum retarder.

[0034] Comparative Example 1 Sodium gluconate was used alone as a retarder in the retarding experiment of gypsum composite cementitious materials.

[0035] Comparative Example 2 The commercially available bone glue process multi-protein gypsum retarder was used as a retarder in the gypsum composite cementitious material retarding experiment.

[0036] In order to further evaluate the effect of the retarder for composite multi-element cementitious materials provided by the present invention on the setting time of gypsum, the gypsum retarder obtained in the above experimental examples and comparative examples was used in the gypsum retarding experiment, and the retarder dosage was 0.08% of the mass of gypsum. The setting time of gypsum after adding the retarder was measured according to GB / T17669.4-1994 "Determination of physical properties of building gypsum paste" and GB / T17669.3-1994 "Determination of physical properties of building gypsum paste". In addition, 2% lime and 2% cement were added to the gypsum to test the setting time of the above experimental examples and comparative examples under alkaline conditions.

[0037] The results are shown in Table 1.

[0038] The experimental results show that the retarder for composite multi-component cementitious materials prepared by the present invention has a better retarding effect under different alkaline conditions of gypsum composite cement and lime, and has a wider adaptability. Among them, the combination of polyol acid and amino acid used in Experimental Example 2 produces a more effective graft polymerization structure, and the retarding time is significantly improved.

[0039] Compared with Comparative Example 2, the present invention uses a reasonable molecular structure to make the retarder performance meet the requirements of gypsum construction with different composite admixtures, avoiding the problem that conventional organic acid small molecules have a long setting time in the gypsum of composite cement, but the performance is reduced and unstable in the lime-lime system.

[0040] Compared with Comparative Example 2, the performance of the present invention in the two gypsum composites is relatively stable and has good adaptability. Comparative Example 2 has good adaptability in cement composite gypsum materials, but in the more alkaline lime composite gypsum system, the performance is greatly reduced, the adaptability is reduced, and the construction is affected.

[0041] Compared with Comparative Examples 1 and 2, the retarder for composite multi-element cementitious materials prepared by the present invention has a stronger applicable scenario. After the specific polyhydroxy and carboxylic acid organic matter and protein amino acid are grafted and polymerized with active polyene carboxylic acid, the retarding adaptability effect is better than the effect of the retarder applicable to the cement system alone, and is even better than the collagen-based gypsum retarder. This project enables the addition of cement and other admixtures to gypsum to have a wider application, reduces production costs, recycles solid waste resources, improves the environment, and saves natural resources.

[0042] The beneficial effects of the retarder for composite multi-element gelling material and the preparation method of the present invention are: 1. Based on the structural design of polymerizing the monomer molecules of polytype grafted hydroxyl groups and carboxylic acid derivatives, it has more active gypsum calcium ion chelating groups and dispersing groups of cement, lime and other admixtures, so as to obtain better retarding effect and wider adaptability in the application of complex gypsum composite cementitious materials.

[0043] 2. Under the latest catalytic system, the yield of condensation and polymerization reactions is higher. More effective chelating groups and polymer molecules can better retain the active carboxylic acid ions and hydroxyl and amide condensation molecular structures under the strong alkaline conditions of gypsum composite materials, improve the retarding effect in gypsum, and also make it easier to reduce the difference in retarding degree of the product in desulfurized and phosphorus building gypsum composite materials, improve adaptability and sensitivity, and have a wider range of applications.

[0044] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a retarder for composite multi-element gelling material, characterized in that the steps include: (1) Add the following components in a reaction kettle: 30-50 parts of a small molecule alkenyl carboxylic acid compound, 50-70 parts of a polyol acid organic compound, and 0.2-1 parts of a condensation catalyst, respectively; heat the reaction kettle to 90-115° C., stir the reaction for 1 h-3 h, and then cool the reaction kettle to room temperature to obtain a raw material A; (2) Add 30-50 parts of a small molecule alkenyl carboxylic acid compound, 50-70 parts of a polycarboxylic acid protein and 0.2-1 parts of a condensation catalyst into a reaction kettle, raise the temperature to 40-60° C., stir and react for a period of time, and then cool to room temperature to obtain raw material B; (3) Add 30-50 parts of water, 35-55 parts of raw material A and 30-45 parts of raw material B to the reactor, raise the temperature to 40-60°C, dropwise add the initiator catalyst to react, add the pH adjuster after the reaction is completed, keep the pH of the system at neutral, and keep the temperature for 1-2 hours; (4) After the stock solution obtained in step (3) is cooled to room temperature, it is powdered and dried in a centrifugal spray tower to obtain a retarder for a composite multi-component gelling material.

2. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: In step (1) and step (2), the small molecule alkenyl carboxylic acid compound includes one or two of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

3. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: The polyol acid organic matter includes one or two of glucose, gluconic acid, gluconolactone and citric acid.

4. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: In step (1) and step (2), the condensation catalyst includes one or two of concentrated sulfuric acid, p-toluenesulfonic acid, and DMAP.

5. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: The polycarboxylic acid protein includes one or two of glycine, glutamic acid, lysine and aspartic acid.

6. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: The initiating catalyst includes one or two of hydrogen peroxide, ammonium persulfate and ferrous sulfate.

7. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: The pH adjuster includes one of sodium hydroxide, calcium hydroxide and quicklime.

8. The method for preparing a retarder for composite multi-component gelling material according to claim 1, characterized in that: The dropwise addition time of the initiating catalyst is 30 to 60 minutes.

9. A retarder for composite multi-component gelling material, characterized in that: Prepared by the preparation method described in any one of claims 1 to 8.

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