CN105504136A - Quadripolymer and preparation method - Google Patents

Quadripolymer and preparation method Download PDF

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Publication number
CN105504136A
CN105504136A CN201511026680.5A CN201511026680A CN105504136A CN 105504136 A CN105504136 A CN 105504136A CN 201511026680 A CN201511026680 A CN 201511026680A CN 105504136 A CN105504136 A CN 105504136A
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CN
China
Prior art keywords
monomer
combinations
quadripolymer
acid
acrylamide
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201511026680.5A
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Chinese (zh)
Inventor
傅乐峰
徐健
冯中军
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Shanghai Sanrui High-Polymer Material Co Ltd
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Shanghai Sanrui High-Polymer Material Co Ltd
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Priority to CN201511026680.5A priority Critical patent/CN105504136A/en
Publication of CN105504136A publication Critical patent/CN105504136A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • 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
    • C04B2103/44—Thickening, gelling or viscosity increasing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate

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

Abstract

The invention discloses a quadripolymer and a preparation method. The quadripolymer is prepared by polymerizing a monomer A, a monomer B, a monomer C and a monomer D, wherein the monomer A is sodium vinylbenzenesulfonate, sodium allylsulfonate, 3-allyloxy-2-hydroxyl-1-propylsulfonate, 2-acryloyloxy-2-methylpropane sulfonic acid, 2-acrylamide-2-methylallyl sulfonic acid or sodium methylallyl sulfonate; the monomer B is N,N-dimethacrylamide, N,N-diethyl acrylamide, acrylamide or N-vinyl pyrrolidone; the monomer C is acrylic acid, methacrylic acid or itaconic acid; and the monomer D is methacrylatoethyl trimethyl ammonium chloride, dimethyldiallyl ammonium chloride or acryloyloxyethyltrimethyl ammonium chloride. The quadripolymer disclosed by the invention is a water-soluble polymer with a good development prospect; and due to the properties such as delayed coagulation, thickening and surface activity, the quadripolymer can be applied to chemical fiber, plastics, printing and dyeing, coating, surfactants, antistatic agents, ceramics, washing assistants, petroleum assistants, concrete and mortar assistants.

Description

A kind of quadripolymer and preparation method
Technical field
The present invention relates to polymkeric substance and preparation method, especially a kind of quadripolymer and preparation method.
Background technology
In mortar Application Areas, construction market use cellulose materials as thickening material, such as methyl cellulose ether, hydroxyethyl ether cellulose etc.Merely adding cellulose family tackifier easily causes water cement ratio in mortar to increase, reduce intensity, and be not suitable with polycarboxylate water-reducer, main manifestations is that both are difficult to mix, easily occur flocculation or precipitation after mixing, portion of cellulose ether also has a strong impact on diminishing, the function of slump protection of polycarboxylate water-reducer simultaneously.
Summary of the invention
The object of the invention is for the existing technical problem of thickening material for building, a kind of quadripolymer and preparation method are provided, this quadripolymer not only can improve concrete workability, good with the consistency of poly carboxylic acid mother liquor, improving concrete cohesiveness while, do not affect the performances such as the water-reducing rate of admixture, slump retention and time of coagulation.
The concrete technical scheme realizing the object of the invention is:
A kind of quadripolymer, feature is: be polymerized by the component of following weight percent, and each component is:
Monomer A is selected from one or both combinations in vinylbenzenesulfonic acid sodium, sodium allylsulfonate, 3-allyloxy-2-hydroxyl-1-propanesulfonate, 2-acryloxy-2-methyl propane sulfonic acid, 2-acrylamide-2 methacrylic sulfonic acid, methylpropene sodium sulfonate;
Monomers B is selected from one or both combinations in N,N-DMAA, N, N-acrylamide, acrylamide, N-vinylpyridine network alkane ketone;
Monomer C is selected from one or both combinations in vinylformic acid, methacrylic acid, methylene-succinic acid;
Monomer D is selected from one or both combinations in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac.
The weight-average molecular weight of described polymkeric substance is 40 ~ 3,000,000.
A preparation method for quadripolymer, the method comprises the following steps:
A, monomer A, monomers B, monomer C, monomer D to be joined in reactor successively, add water and stir;
B, sodium hydroxide solution with 30% join in reactor, regulation system pH to 7-10;
C, heated and stirred, to 40-50 DEG C, add initiator, and insulation 1-3 hour, obtains water white transparency or pale yellow viscous liquid, and thin up continues to stir 1-3 hour, and discharging, obtains described quadripolymer; Wherein:
Described monomer A is selected from one or both combinations in vinylbenzenesulfonic acid sodium, sodium allylsulfonate, 3-allyloxy-2-hydroxyl-1-propanesulfonate, 2-acryloxy-2-methyl propane sulfonic acid, 2-acrylamide-2 methacrylic sulfonic acid, methylpropene sodium sulfonate;
Monomers B is selected from one or both combinations in N,N-DMAA, N, N-acrylamide, acrylamide, N-vinylpyridine network alkane ketone;
Monomer C is selected from one or both combinations in vinylformic acid, methacrylic acid, methylene-succinic acid;
Monomer D is selected from one or both combinations in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac.
One or both combinations of ammonium persulphate, Sodium Persulfate, ammonium persulphate selected by described initiator.
Described initiator is the 0.01-0.5% of monomer total amount.
Quadripolymer of the present invention, overcomes the problem such as consistency, reduction intensity that thickening material for building occurs;
This base polymer is the water-soluble polymers that a class has good development prospect, because having the performances such as slow setting, thickening and surfactivity, can be used for chemical fibre, plastics, printing and dyeing, coating, tensio-active agent, static inhibitor, pottery, washing auxiliary detergent, petroleum assistant, concrete or mortar auxiliary agent etc.
Embodiment
Embodiment 1
By 30% vinylbenzenesulfonic acid sodium, 30%N, N-DMAA, 30% vinylformic acid, 10% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride join in reactor successively, add water and stir, the sodium hydroxide solution with 30% joins in reactor, regulation system pH to 7, heated and stirred to 45 DEG C, add 0.16g ammonium persulphate, be incubated 1.5 hours, obtain water white transparency or pale yellow viscous liquid, thin up continues stirring 1 hour, discharging.
Embodiment 2
By 60% sodium allylsulfonate, 20%N, N-DMAA, 10% methacrylic acid, 10% dimethyl diallyl ammonium chloride join in reactor successively, add water and stir, the sodium hydroxide solution with 30% joins in reactor, regulation system pH to 8, heated and stirred to 45 DEG C, add 0.20g ammonium persulphate, be incubated 2 hours, obtain water white transparency or pale yellow viscous liquid, thin up continues stirring 3 hours, discharging.
Embodiment 3
40%2-acryloxy-2-methyl propane sulfonic acid, 40%N-vinylpyridine network alkane ketone, 10% methylene-succinic acid, 10% dimethyl diallyl ammonium chloride are joined in reactor successively, add water and stir, sodium hydroxide solution with 30% joins in reactor, regulation system pH to 9, heated and stirred to 45 DEG C, adds 0.40g ammonium persulphate, be incubated 1.5 hours, obtain water white transparency or pale yellow viscous liquid, thin up continues stirring 1 hour, discharging.
Embodiment 4
By 25% methylpropene sodium sulfonate, 25%N, N-DMAA, 25% vinylformic acid, 25% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride join in reactor successively, add water and stir, the sodium hydroxide solution with 30% joins in reactor, regulation system pH to 7, heated and stirred to 50 DEG C, add 0.25g ammonium persulphate, be incubated 2.0 hours, obtain water white transparency or pale yellow viscous liquid, thin up continues stirring 2.0 hours, discharging.
Embodiment 5
50%2-acrylamide-2 methacrylic sulfonic acid, 20%N-vinylpyridine network alkane ketone, 15% vinylformic acid, 15% acrylyl oxy-ethyl-trimethyl salmiac are joined in reactor successively, add water and stir, sodium hydroxide solution with 30% joins in reactor, regulation system pH to 10, heated and stirred to 40 DEG C, adds 0.40g ammonium persulphate, be incubated 1.5 hours, obtain water white transparency or pale yellow viscous liquid, thin up continues stirring 3 hours, discharging.
Mortar result of use
Water retention according to JC/T517-2005 standard testing mortar:
Visible quadripolymer of the present invention is obviously better than the water retention of ether of cellulose, and quadripolymer of the present invention can change mixture flow sex change, obtains good stability, improve concrete anti-segregation, anti-bleeding performance by adjustment slurry viscosity.

Claims (5)

1. a quadripolymer, it is characterized in that being polymerized by the component of following weight percent, each component is:
Monomer A 20-60%
Monomers B 20-60%
Monomer C5-30%
Monomer D5-30%
Monomer A is selected from one or both combinations in vinylbenzenesulfonic acid sodium, sodium allylsulfonate, 3-allyloxy-2-hydroxyl-1-propanesulfonate, 2-acryloxy-2-methyl propane sulfonic acid, 2-acrylamide-2 methacrylic sulfonic acid, methylpropene sodium sulfonate;
Monomers B is selected from one or both combinations in N,N-DMAA, N, N-acrylamide, acrylamide, N-vinylpyridine network alkane ketone;
Monomer C is selected from one or both combinations in vinylformic acid, methacrylic acid, methylene-succinic acid;
Monomer D is selected from one or both combinations in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac.
2. quadripolymer according to claim 1, is characterized in that the weight-average molecular weight of described polymkeric substance is 40 ~ 3,000,000.
3. a preparation method for quadripolymer, is characterized in that the method comprises the following steps:
Monomer A, monomers B, monomer C, monomer D are joined in reactor successively, adds water and stir;
B, sodium hydroxide solution with 30% join in reactor, regulation system pH to 7-10;
C, heated and stirred, to 40-50 DEG C, add initiator, and insulation 1-3 hour, obtains water white transparency or pale yellow viscous liquid, and thin up continues to stir 1-3 hour, and discharging, obtains described quadripolymer; Wherein:
Monomer A 20-60%
Monomers B 20-60%
Monomer C5-30%
Monomer D5-30%
Described monomer A is selected from one or both combinations in vinylbenzenesulfonic acid sodium, sodium allylsulfonate, 3-allyloxy-2-hydroxyl-1-propanesulfonate, 2-acryloxy-2-methyl propane sulfonic acid, 2-acrylamide-2 methacrylic sulfonic acid, methylpropene sodium sulfonate;
Monomers B is selected from one or both combinations in N,N-DMAA, N, N-acrylamide, acrylamide, N-vinylpyridine network alkane ketone;
Monomer C is selected from one or both combinations in vinylformic acid, methacrylic acid, methylene-succinic acid;
Monomer D is selected from one or both combinations in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac.
4. preparation method according to claim 2, is characterized in that one or both combinations of ammonium persulphate, Sodium Persulfate, ammonium persulphate selected by described initiator.
5. preparation method according to claim 2, is characterized in that described initiator is the 0.01-0.5% of monomer total amount.
CN201511026680.5A 2015-12-31 2015-12-31 Quadripolymer and preparation method Pending CN105504136A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107286492A (en) * 2017-06-28 2017-10-24 常州欣彬纺织品有限公司 A kind of antistatic film and preparation method thereof
CN107649068A (en) * 2017-08-31 2018-02-02 湖北工业大学 A kind of wet-milling low molecular weight cationic type polymeric dispersant and preparation method thereof
CN111961212A (en) * 2020-08-28 2020-11-20 浙江九本环保技术有限公司 Novel rheological thickening water-retaining agent for papermaking, preparation method and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103509535A (en) * 2012-06-29 2014-01-15 中国石油化工股份有限公司 Filtrate loss reduction method for water-based drilling fluid, and preparation method for filtrate loss reducer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103509535A (en) * 2012-06-29 2014-01-15 中国石油化工股份有限公司 Filtrate loss reduction method for water-based drilling fluid, and preparation method for filtrate loss reducer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107286492A (en) * 2017-06-28 2017-10-24 常州欣彬纺织品有限公司 A kind of antistatic film and preparation method thereof
CN107649068A (en) * 2017-08-31 2018-02-02 湖北工业大学 A kind of wet-milling low molecular weight cationic type polymeric dispersant and preparation method thereof
CN107649068B (en) * 2017-08-31 2020-01-14 湖北工业大学 Low-molecular-weight cationic polymer dispersant for wet grinding and preparation method thereof
CN111961212A (en) * 2020-08-28 2020-11-20 浙江九本环保技术有限公司 Novel rheological thickening water-retaining agent for papermaking, preparation method and application

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Application publication date: 20160420