CN114702683A - Hyperbranched polycarboxylic acid water reducer and preparation method thereof - Google Patents

Hyperbranched polycarboxylic acid water reducer and preparation method thereof Download PDF

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Publication number
CN114702683A
CN114702683A CN202111639084.XA CN202111639084A CN114702683A CN 114702683 A CN114702683 A CN 114702683A CN 202111639084 A CN202111639084 A CN 202111639084A CN 114702683 A CN114702683 A CN 114702683A
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hyperbranched
polycarboxylic acid
monomer
reducing agent
water reducing
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黄立军
王若臣
黄庆
周广军
孟祥瑞
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Jiangsu Chaoli Building Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002Dendritic macromolecules
    • C08G83/005Hyperbranched macromolecules
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/28Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/288Halogen containing polymers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to the technical field of concrete water reducing agents, in particular to a hyperbranched polycarboxylic acid water reducing agent and a preparation method thereof. Unsaturated carboxylic acid, fluorine-containing acrylate and hyperbranched monomer are copolymerized. The water-reducing agent contains fluorine elements, has the characteristics of high water-reducing rate, good dispersibility and the like, can ensure that cement particles have better dispersibility, can effectively prevent the agglomeration phenomenon of the cement particles, has good workability, and is insensitive to the mixing amount; the preparation method is simple to operate, green and pollution-free.

Description

Hyperbranched polycarboxylic acid water reducer and preparation method thereof
Technical Field
The invention relates to the technical field of concrete water reducing agents, in particular to a hyperbranched polycarboxylic acid water reducing agent and a preparation method thereof.
Background
A polycarboxylic acid water reducing agent (Polycarboxylate Superplasticizer) is a high-performance water reducing agent and is a cement dispersing agent in cement concrete application. The method is widely applied to projects such as highways, bridges, dams, tunnels, high-rise buildings and the like.
According to the difference of the main chain structure, the polycarboxylic acid high-efficiency water reducing agent products can be divided into two main classes, namely, one class uses acrylic acid or methacrylic acid as the main chain and grafts polyethers with different side chain lengths. The other type is polyether with different side chain lengths grafted by maleic anhydride as a main chain. Based on the water reducing agent, a series of high-performance water reducing agent products with different characteristics are derived.
Before the appearance of the polycarboxylic acid additive, there are lignin sulfonate type additives, naphthalene series sulfonate formaldehyde condensates, melamine formaldehyde condensates, acetone sulfonate formaldehyde condensates, sulfamate formaldehyde condensates, and the like. The polycarboxylic acid water reducing agent is successfully developed in Japan in the beginning of the 80 s in the 20 th century. The new generation of polycarboxylic acid high-efficiency water reducing agent overcomes the defects of the traditional water reducing agent, and has the outstanding advantages of low mixing amount, good slump keeping performance, low concrete shrinkage, strong adjustability on molecular structure, high potential of high performance, no use of formaldehyde in the production process and the like.
The Chinese polycarboxylate superplasticizer starts late, and the research is relatively lagged.
Disclosure of Invention
The invention provides a fluorine-containing hyperbranched polycarboxylic acid water reducer. Under the same fracture-fixation mixing amount and water-cement ratio, the water reducing agent has good workability and is insensitive to the mixing amount.
The invention also provides a preparation method of the polycarboxylic acid water reducing agent.
A hyperbranched polycarboxylic acid water reducer is prepared by copolymerizing unsaturated carboxylic acid, fluorine-containing acrylate and a hyperbranched monomer to obtain a hyperbranched polycarboxylic acid water reducer;
preferably, the molar ratio of the unsaturated carboxylic acid to the fluorine-containing acrylate to the hyperbranched monomer is 1: 0.5-1.5: 0.5-1.0.
Unsaturated carboxylic acids acrylic acid or methacrylic acid are preferred.
The preferred fluoroacrylate is perfluorobutylethyl acrylate.
Preferably, the hyperbranched monomer is obtained by the following steps: diethanolamine and methyl acrylate react to generate AB2Monomer, AB2The monomer reacts with allyl alcohol to obtain the hyperbranched monomer.
Preferably allyl alcohol and AB2The molar ratio of the monomers is 1: 1-15.
Preferably, the folding and fixing mixing amount of the polycarboxylic acid water reducing agent in concrete is 0.2-1.0%.
The invention has the beneficial effects that:
the polycarboxylic acid water reducing agent contains fluorine, has the characteristics of high water reducing rate, good dispersibility and the like, can ensure that cement particles have better dispersibility, can effectively prevent the agglomeration phenomenon of the cement particles, has good workability, and is insensitive to the mixing amount; the preparation method is simple to operate, green and pollution-free.
Detailed Description
Example 1
After nitrogen was purged into the three-necked flask for 10min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, after dropwise adding is finished, heating in a water bath to 40 ℃, keeping for 4 hours, and then distilling under reduced pressure to remove methanol to obtain AB2A type monomer. 57.37g of AB are taken2Adding 5.81G of propylene alcohol and 0.32G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G2-generation hyperbranched monomer.
Example 2
After nitrogen was purged into the three-necked flask for 10min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 66.93g of AB are taken2Putting the monomer into a three-neck flask filled with nitrogen, adding 2.90G of propylene alcohol and 0.35G of p-toluenesulfonic acid, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G3-generation hyperbranched monomer.
Example 3
Introducing nitrogen into a three-neck flask for 10min, adding 105.14g of diethanolamine and 50mL of methanol, and magnetically stirring at room temperature under continuous nitrogen protection until the mixture is stirred until the mixture is dissolvedThe diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 57.37g of AB are taken2Adding 1.16G of propylene alcohol and 0.29G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G4-generation hyperbranched monomer.
Example 4
Preparing sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; respectively preparing acrylic acid, perfluorobutyl ethyl acrylate and G2 substituted hyperbranched type monomers into 25 mass percent aqueous solutions and mixing; ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallyl sulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, respectively dropwise adding 1/4 initiator and monomer mixed solution, heating to 80 ℃, dropwise adding the initiator and monomer mixed solution every half an hour, after the three times of dropwise adding are finished, heating to 85-90 ℃, continuing stirring and reacting for 4 hours, and then adjusting the pH to 7-7.5 by using a NaOH solution with the mass fraction of 40% to obtain the hyperbranched polycarboxylic acid water reducer G21. Wherein the molar ratio of the acrylic acid to the fluorine-containing acrylate to the G2-substituted hyperbranched monomer is 1: 0.5: 1.0.
example 5
Preparing sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; respectively preparing acrylic acid, perfluorobutyl ethyl acrylate and a G2-substituted hyperbranched monomer into 25% aqueous solution by mass percent and mixing; ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 mixed solution of an initiator and a monomer, then heating to 80 ℃, dropwise adding the mixed solution of the initiator and the monomer every half an hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding are finished, continuing stirring and reacting for 4 hours, and then adjusting the pH to 7-7.5 by using a NaOH solution with the mass fraction of 40% to obtain the hyperbranched polycarboxylic acid water reducing agent G22. Wherein the molar ratio of the acrylic acid to the fluorine-containing acrylate to the G2-substituted hyperbranched monomer is 1: 1.5: 0.5.
example 6
Preparing sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; respectively preparing acrylic acid, perfluorobutyl ethyl acrylate and G3 substituted hyperbranched type monomers into 25 mass percent aqueous solutions and mixing; ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 mixed solution of an initiator and a monomer, then heating to 80 ℃, dropwise adding the mixed solution of the initiator and the monomer every half an hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding are finished, continuing stirring and reacting for 4 hours, and then adjusting the pH to 7-7.5 by using a NaOH solution with the mass fraction of 40% to obtain the hyperbranched polycarboxylic acid water reducing agent G31. Wherein the molar ratio of the acrylic acid to the fluorine-containing acrylate to the G3-substituted hyperbranched monomer is 1: 0.5: 1.0.
example 7
Preparing sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; respectively preparing acrylic acid, perfluorobutyl ethyl acrylate and G3 substituted hyperbranched type monomers into 25 mass percent aqueous solutions and mixing; ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 mixed solution of an initiator and a monomer, then heating to 80 ℃, dropwise adding the mixed solution of the initiator and the monomer every half an hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding are finished, continuing stirring and reacting for 4 hours, and then adjusting the pH to 7-7.5 by using a NaOH solution with the mass fraction of 40% to obtain the hyperbranched polycarboxylic acid water reducing agent G33. Wherein the molar ratio of the acrylic acid to the fluorine-containing acrylate to the G3-substituted hyperbranched monomer is 1: 1.5: 0.5.
example 8
Preparing sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; respectively preparing acrylic acid, perfluorobutyl ethyl acrylate and G4 substituted hyperbranched type monomers into 25 mass percent aqueous solutions and mixing; ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 mixed solution of an initiator and a monomer, then heating to 80 ℃, dropwise adding the mixed solution of the initiator and the monomer every half an hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding are finished, continuing stirring and reacting for 4 hours, and then adjusting the pH to 7-7.5 by using a NaOH solution with the mass fraction of 40% to obtain the hyperbranched polycarboxylic acid water reducing agent G41. Wherein the molar ratio of the acrylic acid to the fluorine-containing acrylate to the G4-substituted hyperbranched monomer is 1: 0.5: 1.0.
example 9
Preparing sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; respectively preparing acrylic acid, perfluorobutyl ethyl acrylate and G4 substituted hyperbranched type monomers into 25 mass percent aqueous solutions and mixing; ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 mixed solution of an initiator and a monomer, then heating to 80 ℃, dropwise adding the mixed solution of the initiator and the monomer every half an hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding are finished, continuing stirring and reacting for 4 hours, and then adjusting the pH to 7-7.5 by using a NaOH solution with the mass fraction of 40% to obtain the hyperbranched polycarboxylic acid water reducing agent G42. Wherein the molar ratio of the acrylic acid to the fluorine-containing acrylate to the G4-substituted hyperbranched monomer is 1: 1.5: 0.5.
comparative example 1
The same procedure as in example 8 was repeated except that perfluorobutyl ethyl acrylate was replaced with acrylic acid in the same manner as in example 8.
The polycarboxylic acid water reducing agents prepared in the above examples 4 to 8 and comparative example 1 were subjected to a cement paste test and a concrete performance test, respectively. Note: all tests refer to national standard GB/T8077-; the cement used was portland cement 42.5.
TABLE 1 Cement paste fluidity test results
Figure RE-GDA0003673936160000041
TABLE 2 concrete test results
Figure RE-GDA0003673936160000051
Therefore, the novel polycarboxylic acid water reducing agent synthesized by the invention has high water reducing rate, good dispersibility and fluidity and strong pressure resistance, and can be widely applied to various concretes.

Claims (7)

1. A hyperbranched polycarboxylic acid water reducer is characterized in that unsaturated carboxylic acid, fluorine-containing acrylate and a hyperbranched monomer are copolymerized to obtain the hyperbranched polycarboxylic acid water reducer.
2. The polycarboxylic acid water reducer according to claim 1, characterized in that the molar ratio of the unsaturated carboxylic acid, the fluorine-containing acrylate and the hyperbranched monomer is 1: 0.5-1.5: 0.5-1.0.
3. The polycarboxylic acid-based water reducing agent according to claim 2, characterized in that the unsaturated carboxylic acid is acrylic acid or methacrylic acid.
4. The polycarboxylic acid-based water reducing agent according to claim 1 or 2, characterized in that the fluorine-containing acrylate is perfluorobutylethyl acrylate.
5. The polycarboxylic acid-based water reducer according to claim 1 or 2, characterized in that the hyperbranched-type monomer is obtained by: diethanolamine and methyl acrylate react to generate AB2Monomer, AB2The monomer reacts with allyl alcohol to obtain the hyperbranched monomer.
6. The polycarboxylic acid water reducing agent according to claim 5, characterized in that the allyl alcohol and AB are2The molar ratio of the monomers is 1: 1-15.
7. The polycarboxylic acid-based water reducing agent according to any one of claims 1 to 6, characterized in that the broken solid content in concrete is 0.2 to 1.0%.
CN202111639084.XA 2021-12-30 2021-12-30 Hyperbranched polycarboxylic acid water reducer and preparation method thereof Pending CN114702683A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115449105A (en) * 2022-10-12 2022-12-09 嘉兴富瑞邦新材料科技有限公司 Preparation method and application of polytetrafluoroethylene stretched film

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Publication number Priority date Publication date Assignee Title
CN101367922A (en) * 2008-09-12 2009-02-18 中国科学技术大学 Fluorine-containing hyperbranched polyester acrylic ester and method of preparing the same
CN103608381A (en) * 2011-06-21 2014-02-26 帝斯曼知识产权资产管理有限公司 Polymer, process and use
CN107082891A (en) * 2017-05-23 2017-08-22 中国矿业大学 A kind of hyperbranched poly carboxylic acid water reducer and preparation method
CN107337790A (en) * 2016-12-30 2017-11-10 江苏苏博特新材料股份有限公司 The synthesis and application of a kind of hyperbranched polyether phosphate water reducer in end
CN110156944A (en) * 2019-04-26 2019-08-23 中科广化(重庆)新材料研究院有限公司 Four arm starblock polycarboxylic acid super-plasticizers of one kind and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101367922A (en) * 2008-09-12 2009-02-18 中国科学技术大学 Fluorine-containing hyperbranched polyester acrylic ester and method of preparing the same
CN103608381A (en) * 2011-06-21 2014-02-26 帝斯曼知识产权资产管理有限公司 Polymer, process and use
CN107337790A (en) * 2016-12-30 2017-11-10 江苏苏博特新材料股份有限公司 The synthesis and application of a kind of hyperbranched polyether phosphate water reducer in end
CN107082891A (en) * 2017-05-23 2017-08-22 中国矿业大学 A kind of hyperbranched poly carboxylic acid water reducer and preparation method
CN110156944A (en) * 2019-04-26 2019-08-23 中科广化(重庆)新材料研究院有限公司 Four arm starblock polycarboxylic acid super-plasticizers of one kind and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115449105A (en) * 2022-10-12 2022-12-09 嘉兴富瑞邦新材料科技有限公司 Preparation method and application of polytetrafluoroethylene stretched film
CN115449105B (en) * 2022-10-12 2023-08-18 嘉兴富瑞邦新材料科技有限公司 Preparation method and application of polytetrafluoroethylene stretched film

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