CN111944086B - Polyacrylic acid thickener and preparation method thereof - Google Patents

Polyacrylic acid thickener and preparation method thereof Download PDF

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CN111944086B
CN111944086B CN202010922835.8A CN202010922835A CN111944086B CN 111944086 B CN111944086 B CN 111944086B CN 202010922835 A CN202010922835 A CN 202010922835A CN 111944086 B CN111944086 B CN 111944086B
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polyacrylic acid
acid thickener
thickener
emulsion
vinyl ether
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CN111944086A (en
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权衡
刘小川
卫增峰
倪丽杰
李青
陈学俊
邹春梅
张恒凤
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Hubei Daya Biological Technology Co ltd
Wuhan Textile University
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Wuhan Textile University
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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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid

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Abstract

The invention relates to an associative polyacrylic acid thickener used in the processing fields of water-based coating, textile printing, water-based resin coating and the like, and discloses a polyacrylic acid thickener and a preparation method thereof. The method comprises the following steps: raw material preparation, water phase preparation, oil phase preparation, pre-emulsion preparation, inverse emulsion polymerization and emulsion phase inversion. The method effectively improves the electrolyte resistance, acid resistance and alkali resistance of the thickening agent; the intermolecular association of the thickening agent is improved; the copolymerization of the short-chain alkyl ether or hydroxyalkyl ether and acrylic acid is good, the intramolecular association of the thickener cannot be obviously caused, and the ion shielding effect of the thickener can be obviously reduced; the short-chain polyether side chain and the polyether cross-linking are beneficial to improving the hydrophilicity of the thickener molecules and the spreadability of molecular chains of the thickener molecules; the quaternary ammonium cation structure enables the thickener to have certain reverse electrolyte performance and good salt tolerance.

Description

Polyacrylic acid thickener and preparation method thereof
Technical Field
The invention relates to an associative polyacrylic acid thickener used in the processing fields of water-based coating, textile printing, water-based resin coating and the like, in particular to a polyacrylic acid thickener and a preparation method thereof.
Background
In recent years, technologies such as textile printing, water-based coating, water-based resin coating and the like and applications thereof have been rapidly developed, and an indispensable polymer thickener is always a focus of attention. However, as the most important class of synthetic thickeners, the problems of high dosage, poor acid and alkali resistance, and no salt tolerance of polyacrylic acid polymer thickeners are not solved well all the time. At present, the main methods for modifying polyacrylic acid thickeners are: the introduction of nonionic monomers and the moderate introduction of nonionic chain links or neutral groups can improve the electrolyte resistance and water absorption performance of the thickening agent; the hydrophilicity is improved, so that not only the thickening force of the thickening agent can be improved, but also the electrolyte resistance of the thickening agent can be improved; the long-chain hydrophobic monomer is introduced, and the salt tolerance of the polyacrylic acid thickener can be improved by introducing the hydrophobic long chain to the thickener polymer; an amphoteric polymer is prepared, which has reverse electrolyte behavior. Nevertheless, the following related art problems have not been well solved: innovations of the associative structure of the thickening agent and the innovative application of a new monomer are realized, so that the comprehensive performance of the thickening agent is effectively regulated and controlled; the access technology of long-chain polyether, long-chain alkyl and polyether cross-linking and the copolymerization technology of modified monomers and acrylic monomers; the difference of the reaction between monomers with larger difference of physical and chemical properties (such as long-chain alkyl monomers and acrylic monomers) is also larger, and a technical method for controlling the distribution of hydrophilic and hydrophobic structures of thickener molecules needs to be solved; the selection and the proportion of strong acid groups and mixed anion groups (sulfonic acid groups, carboxylic acid groups, monocarboxylic acid, polycarboxylic acid and the like) and the relationship between the strong acid groups and the mixed anion groups and the main application performance of the thickening agent.
At present, the preparation method of polyacrylic acid thickener comprises the following steps:
1. the raw materials of the preparation method comprise a polymerized monomer, a modified monomer and an auxiliary agent, wherein: the polymerized monomer is alpha-methacrylic acid; the modified monomer is ethyl acrylate, butyl acrylate, octadecyl methacrylate and diallyl phthalate; the auxiliary agent is potassium persulfate, sodium dodecyl sulfate, Tween 60, etc.
For example, the synthesis of a hydrophobically modified polyacrylic acid thickener, disclosed in guoyegu (Shandong chemical industry, vol. 40, No. 3), discloses a preparation method of a polyacrylic acid salt-tolerant thickener modified by long-chain alkyl groups and neutral side groups, wherein in the molecular structure of the polyacrylic acid thickener, the long-chain alkyl groups are introduced by octadecyl acrylate, the neutral side groups are introduced by ethyl acrylate and butyl acrylate, and the cross-linking structure is introduced by diallyl phthalate, so that the salt-tolerant polyacrylic acid thickener is synthesized.
The salt-tolerant polyacrylic acid thickener prepared by the method has good performance and certain salt tolerance. However, because octadecyl acrylate is a strong hydrophobic monomer, the octadecyl acrylate is difficult to be effectively copolymerized with a strong hydrophilic monomer alpha-methacrylic acid by using a preparation technology and a process reflected by documents, and the distribution of the octadecyl acrylate on the molecular structure of the thickener cannot be controlled, so that the structure of the thickener is diversified, and the comprehensive performance is poor; in addition, the side chain alkyl chain segment introduced by the octadecyl acrylate is longer and lacks dispersibility, which can cause intramolecular association of the thickener and the intermolecular association structure thereof has certain defects; meanwhile, neutral side groups are introduced to the molecules of the thickener by ethyl acrylate and butyl acrylate, and simultaneously more ester groups are introduced laterally, so that the intramolecular association of the thickener is enhanced; finally, a great amount of methyl is introduced laterally into the thickener molecule by the polymerized main monomer alpha-methacrylic acid, so that the shielding effect on carboxyl is too strong, and the thickening capability is reduced.
2. The raw materials of the polyacrylic acid salt-tolerant thickening agent modified by long-chain alkyl and neutral and cationic side groups comprise a polymerized monomer, a modified monomer and an auxiliary agent, wherein: the polymerized monomer is acrylic acid; the modified monomer is butyl acrylate, acrylamide, octadecyl acrylate, methacryloyloxyethyl trimethyl ammonium chloride and N, N' -methylene bisacrylamide; the auxiliary agent is Span80, Tween 80, ammonium persulfate, sodium hydroxide and the like.
For example, the preparation method of the polyacrylic acid salt-resistant thickener modified by long-chain alkyl and neutral and cationic side groups, which is disclosed by Chengdanghui, Zhangzhi, Zhang Qiliang and the like ("dyeing & printing" 20 th year) discloses a preparation method of a salt-resistant synthetic thickener for printing, wherein the salt-resistant polyacrylic acid thickener is synthesized by introducing long-chain alkyl by octadecyl acrylate, introducing neutral side groups by butyl acrylate, introducing cationic side groups by methacryloyloxyethyltrimethyl ammonium chloride and introducing a cross-linking structure by N, N' -methylenebisacrylamide into the molecular structure of the polyacrylic acid thickener.
The salt-tolerant polyacrylic acid thickening agent prepared by the method has good thickening performance and certain salt tolerance and anti-electrolyte performance. However, because octadecyl acrylate is a strong hydrophobic monomer, the octadecyl acrylate is difficult to be effectively copolymerized with a strong hydrophilic monomer acrylic acid by using a preparation technology and a process reflected by documents, and the distribution of the octadecyl acrylate on the molecular structure of the thickener cannot be controlled, so that the structure of the thickener is diversified, and the comprehensive performance is poor; in addition, the side chain alkyl chain segment introduced by the octadecyl acrylate is longer and lacks dispersibility, which can cause intramolecular association of the thickener and the intermolecular association structure thereof has certain defects; meanwhile, neutral side groups are introduced to the thickener molecules from butyl acrylate, and meanwhile, more ester groups are introduced laterally, so that intramolecular association due to hydrogen bond action is enhanced; finally, the pendant long chain structures of the thickener are monotonous and unevenly distributed, and thus the "ionic effect" of the thickener cannot be sufficiently masked.
3. The raw materials of the polyacrylic acid salt-tolerant thickening agent modified by long-chain alkyl, polyether side chain and neutral side group comprise a polymerized monomer, a modified monomer and an auxiliary agent, wherein: the polymerization monomer is acrylic acid and methacrylic acid; the modified monomer is N, N' -methylene bisacrylamide, acrylamide, methyl acrylate, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate and alkyl vinyl ether; the auxiliary agent is fatty alcohol-polyoxyethylene ether, sodium hydroxide, potassium hydroxide, ammonium persulfate, potassium persulfate, sodium sulfite, sodium bisulfite, azodiisobutyronitrile, etc.
For example, the development of a novel dye printing thickener such as Korean silk, Luoyanghui, and Liangjuan (the 11 th stage of 2018) discloses a preparation method of a polyacrylic acid salt-resistant thickener modified by long-chain alkyl, polyether side chains and neutral side groups, wherein a cross-linking structure is introduced into a molecular structure of the polyacrylic acid thickener by N, N' -methylene bisacrylamide, a neutral side group is introduced by alkyl acrylate, and lateral polyether and alkyl long chains are introduced by alkyl vinyl ether, so that the salt-resistant polyacrylic acid thickener is synthesized.
The salt-tolerant polyacrylic acid thickener prepared by the method has the advantages of good copolymerization of modified monomers, strong impermeability, strong electrolyte resistance and soft handfeel of printed fabrics. However, the neutral side group is introduced to the thickener molecule by the alkyl acrylate, and simultaneously, more ester groups are introduced to the side direction of the thickener molecule, so that the intramolecular association due to the hydrogen bond action is strengthened; furthermore, from the polymerization techniques and processes known from the literature, the distribution of the polyethers and long alkyl chains introduced via alkyl vinyl ethers in the lateral direction of the molecular structure of the thickener is not controllable.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: a polyacrylic acid thickener and a preparation method thereof are provided. The polyacrylic acid thickening agent product prepared by the method can be used for water-based coating, textile printing, water-based resin coating and the like. In the invention, lateral structures such as 'cluster-shaped' long-chain alkyl, short-chain alkyl ether or hydroxyalkyl ether, short-chain polyether and the like, polyether cross-linking structures and quaternary ammonium cation structures are introduced into the molecules of the traditional polyacrylic acid thickener, so that the electrolyte resistance, acid resistance and alkali resistance of the thickener are effectively improved. Due to the adoption of a plurality of special modified monomers, the thickener molecules do not contain lateral ester groups, and the intramolecular hydrogen bond action between hydroxyl and ester groups does not exist, so that the intermolecular association of the thickener is facilitated; the 'cluster' long-chain alkyl has stronger association effect and is mainly distributed at the tail end of the thickener molecule, thereby being beneficial to the association effect among the molecules; the copolymerization of the short-chain alkyl ether or hydroxyalkyl ether and acrylic acid is good, the intramolecular association of the thickener cannot be obviously caused, and the ion shielding effect of the thickener can be obviously reduced; the short-chain polyether side chain and the polyether cross-linking are beneficial to improving the hydrophilicity of the thickener molecules and the spreadability of molecular chains of the thickener molecules; the quaternary ammonium cation structure enables the thickener to have certain reverse electrolyte performance and good salt tolerance.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a polyacrylic acid thickener, the method comprising the steps of:
(1) preparing raw materials: the raw materials contain polymerized monomers, modified monomers and auxiliary agents;
the polymerized monomer is unsaturated monocarboxylic acid; the modified monomer comprises long-chain alkyl vinyl ether polymer, alkyl vinyl ether, vinyl-terminated polyether, unsaturated quaternary ammonium salt and unsaturated cross-linking agent; the auxiliary agents comprise pure water, ammonia water, kerosene, oleophylic emulsifier, oxidation initiator, reduction initiator, hydrophilic emulsifier, polymerization inhibitor and chain transfer agent;
the unsaturated monocarboxylic acid is acrylic acid;
the long-chain alkyl vinyl ether polymer is C12～141 or C of trimers of alkyl vinyl ethers15～181 of dimers of alkyl vinyl ethers;
the alkyl vinyl ether is 1 of butyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether and hydroxypropyl vinyl ether;
the vinyl-terminated polyether is 1 of the vinyl-terminated polyethers with the molecular weight of 200-400;
the unsaturated quaternary ammonium salt is methacryloyloxyethyl trimethyl ammonium chloride;
the unsaturated cross-linking agent is 1 of polyethylene glycol dimethacrylate with molecular weight of 200-800 or 1 of polyethylene glycol diacrylate with molecular weight of 200-800;
the ammonia water is 18-23 wt% ammonia water;
the lipophilic emulsifier is a mixture of 2 nonionic emulsifiers with HLB values of 4-7, and the hydrophilic lipophilic values of the two emulsifiers are different by 2-3;
the oxidation initiator is potassium persulfate or ammonium persulfate;
the reduction initiator is sodium bisulfite;
the hydrophilic emulsifier is a mixture of 2 nonionic emulsifiers with HLB value of 14-17, and the hydrophilic and lipophilic values of the two emulsifiers are different by 2-3;
the polymerization inhibitor is a dimethylbenzene solution of hydroquinone with the concentration of 0.8-1.2 g/L;
the chain transfer agent has an alkyl chain length of C10～161 of the aliphatic thiols of (1);
the dosage of each component is as follows: 100% of unsaturated monocarboxylic acid; the long-chain alkyl vinyl ether polymer accounts for 1-2% of the total mass of the polymerized monomers, the alkyl vinyl ether accounts for 3-6% of the total mass of the polymerized monomers, the vinyl-terminated polyether accounts for 2-4% of the total mass of the polymerized monomers, the unsaturated quaternary ammonium salt accounts for 3-6% of the total mass of the polymerized monomers, and the unsaturated cross-linking agent accounts for 0.1-0.3% of the total mass of the polymerized monomers;
the amount of the pure water is 1.5-2 times of the total mass of the polymerized monomer and the modified monomer;
the dosage of the ammonia water is 0.7-1.1 times of the total mass of the polymerization monomers or the pH of the mixture of the neutralization polymerization monomers is controlled to 6-7;
the amount of the kerosene is 0.6-0.9 times of the mass of the pure water;
the dosage of the lipophilic emulsifier is 10-13% of the total mass of the polymerized monomer and the modified monomer, and the ratio of the hydrophilic-lipophilic value HLB value in the lipophilic emulsifier is 20-30%;
the amount of the chain transfer agent is 10-20% of the mass of the oxidation initiator;
the dosage of the oxidation initiator is 0.4-0.7% of the total mass of the polymerization monomer and the modified monomer;
the using amount of the reduction initiator is 15-20% of the mass of the oxidation initiator;
the dosage of the hydrophilic emulsifier is 1.6-2 times of the total mass of the lipophilic emulsifier, and the ratio of the hydrophilic lipophilic value HLB value in the hydrophilic emulsifier is 30-40%;
the dosage of the polymerization inhibitor is 0.04-0.08% of the total mass of the polymerization monomer and the modified monomer.
(2) Preparation of the aqueous phase: mixing and uniformly stirring a polymerized monomer, part of pure water, ammonia water, vinyl-terminated polyether, an unsaturated cross-linking agent and unsaturated quaternary ammonium salt to prepare a polyacrylic acid thickener water phase;
(3) preparation of oil phase: mixing kerosene, lipophilic emulsifier, alkyl vinyl ether and long-chain alkyl vinyl ether polymer, and stirring uniformly to obtain polyacrylic acid thickener oil phase;
(4) preparation of pre-emulsion: mixing and emulsifying a polyacrylic acid thickener water phase, a polyacrylic acid thickener oil phase, a chain transfer agent, an oxidation initiator and part of pure water to prepare a polyacrylic acid thickener pre-emulsion;
(5) inverse emulsion polymerization: mixing and reacting the polyacrylic acid thickener pre-emulsion with a reduction initiator and the residual pure water to prepare polyacrylic acid thickener oily emulsion;
(6) phase inversion of emulsion: and mixing the polyacrylic acid thickener oily emulsion with a hydrophilic emulsifier and a polymerization inhibitor, and uniformly stirring to obtain the polyacrylic acid thickener aqueous emulsion.
Preferably, the step (2) is specifically:
(2.1) controlling the temperature of the system to be 35-40 ℃, dissolving all the polymerization monomers in pure water accounting for 85% of the total amount, and slowly dropwise adding ammonia water to neutralize the system to a pH value of 6-7;
and (2.2) adding vinyl-terminated polyether, unsaturated cross-linking agent and unsaturated quaternary ammonium salt, and fully and uniformly stirring to obtain the polyacrylic acid thickener aqueous phase.
Preferably, the step (3) is specifically:
(3.1) dissolving the lipophilic emulsifier, the alkyl vinyl ether and the long-chain alkyl vinyl ether polymer in kerosene at room temperature;
and (3.2) fully stirring and mixing at room temperature to prepare the polyacrylic acid thickener oil phase.
Preferably, the step (4) is specifically:
(4.1) controlling the system temperature to be 40-50 ℃, adding the polyacrylic acid thickener aqueous phase prepared in the step (2) into the polyacrylic acid thickener oil phase prepared in the step (3), and homogenizing and emulsifying for 20-30 min;
and (4.2) keeping the temperature of the system unchanged, adding a chain transfer agent and an oxidation initiator dissolved in pure water accounting for 4-6% of the total amount, and continuing homogenizing and emulsifying for 5-10 min to obtain the polyacrylic acid thickener pre-emulsion.
Preferably, the step (5) is specifically:
(5.1) stirring and gradually heating to 55-65 ℃, and introducing nitrogen into the polyacrylic acid thickener pre-emulsion to expel oxygen for 15-20 min;
(5.2) maintaining the temperature of the reaction system at 60-70 ℃, and uniformly adding the reduction initiator dissolved in the residual pure water into the reaction system within 80-100 min;
and (5.3) heating to 65-75 ℃, and continuing to perform heat preservation reaction for 70-100 min to obtain the polyacrylic acid thickener oily emulsion.
Preferably, the step (6) is specifically:
(6.1) closing the nitrogen, cooling to 60-65 ℃, adding a polymerization inhibitor, and uniformly stirring;
(6.2) cooling to 55-60 ℃, adding a hydrophilic emulsifier, and stirring for 20-30 min to obtain the polyacrylic acid thickener aqueous emulsion.
Preferably, the ammonia water is 21 wt% ammonia water.
Preferably, the polymerization inhibitor is a xylene solution of hydroquinone at a concentration of 1 g/L.
In a second aspect, the present invention provides a polyacrylic acid thickener prepared by the above method.
Compared with the prior art, the method has the following advantages and characteristics:
1. in the invention, "cluster-shaped" long-chain alkyl, short-chain alkyl ether or hydroxyalkyl ether, short-chain polyether and other lateral structures, polyether cross-linking structures and quaternary ammonium cation structures are introduced into the molecules of the traditional polyacrylic acid thickener. In the thickener molecule, various modified structures are rich, and the functions are complementary and synergistic, so that the electrolyte resistance, acid resistance and alkali resistance of the thickener are effectively improved.
2. In the invention, a long-chain alkyl vinyl ether polymer is used for replacing a traditional long-chain alkyl acrylate (such as octadecyl acrylate) to introduce lateral alkyl long chains into a polyacrylic acid thickener molecule, alkyl vinyl ether is used for replacing a traditional short-chain alkyl acrylate or a short-chain hydroxyalkyl acrylate and acrylamide to introduce smaller neutral groups into the polyacrylic acid thickener molecule, terminal vinyl polyether is used for introducing polyether chain links with proper length into the polyacrylic acid thickener molecule, and polyether type unsaturated cross-linking agent is used for replacing a traditional N, N-methylene bisacrylamide to introduce cross-linking into the polyacrylic acid thickener molecule. That is, the thickener molecules are modified without carrying ester groups and amide groups, and the thickener molecules do not contain lateral ester groups and amide groups, and do not have intramolecular hydrogen bonding between hydroxyl groups and the ester groups and the amide groups, so that the association caused by the intramolecular hydrogen bonding is remarkably inhibited, and the intermolecular association of the thickener is favorably enhanced.
3. In the invention, the long-chain alkyl distance introduced into the polyacrylic acid thickener molecule by the long-chain alkyl vinyl ether polymer is obviously smaller, namely the polyacrylic acid thickener molecule is in a 'cluster' form, so that the association effect of the long-chain alkyl is stronger. Meanwhile, the reactivity of the long-chain alkyl vinyl ether polymer is obviously weaker than that of the traditional octadecyl acrylate, and the long-chain alkyl vinyl ether polymer participates in the polymerization reaction and is relatively delayed as a whole, so that the long-chain alkyl vinyl ether polymer is mainly distributed at the tail end of the thickener molecule and contributes to the association between the molecules.
4. In the present invention, the modified monomer short-chain alkyl ether or short-chain hydroxyalkyl ether has "weak hydrophobic short side chains", and has better copolymerizability with acrylic acid than octadecyl acrylate. Meanwhile, compared with the traditional modified monomers of ethyl acrylate, methyl acrylate, hydroxyethyl acrylate and the like, the alkyl group of the short-chain alkyl ether or the short-chain hydroxyalkyl ether is relatively large, but the length of the short-chain alkyl ether or the short-chain hydroxyalkyl ether is not long enough to form a relatively stable mutual association structure. Therefore, the short side chain with weak hydrophobicity does not obviously cause the internal association of thickener molecules, and can more obviously reduce the ion shielding effect, and the salt tolerance of the thickener is better.
5. In the invention, the short-chain polyether side chain and polyether cross-linking chain introduced into the thickener molecule are beneficial to improving the hydrophilicity of the thickener molecule and reducing the ion shielding effect of the thickener molecule. Meanwhile, different from the traditional N, N-methylene bisacrylamide crosslinking agent, the polyether crosslinking agent adopted by the invention has polyether chain links with certain length, and has small limitation on the stretching of the thickening agent molecules in the thickening process, so that the thickening capability of the crosslinking agent is better.
6. In the invention, the quaternary ammonium cation structure introduced into the thickener molecule enables the polyacrylic acid thickener to have certain reverse electrolyte performance, the salt resistance is better, the alkali resistance of the thickener is favorably improved, and the comprehensive application performance of the thickener is improved.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a polyacrylic acid thickener, the method comprising the steps of:
(1) preparing raw materials: the raw materials contain polymerized monomers, modified monomers and auxiliary agents;
the polymerized monomer is unsaturated monocarboxylic acid; the modified monomer comprises long-chain alkyl vinyl ether polymer, alkyl vinyl ether, vinyl-terminated polyether, unsaturated quaternary ammonium salt and unsaturated cross-linking agent; the auxiliary agents comprise pure water, ammonia water, kerosene, oleophylic emulsifier, oxidation initiator, reduction initiator, hydrophilic emulsifier, polymerization inhibitor and chain transfer agent;
the unsaturated monocarboxylic acid is acrylic acid;
the long-chain alkyl vinyl ether polymer is C12～141 or C of trimers of alkyl vinyl ethers15～181 of dimers of alkyl vinyl ethers;
the alkyl vinyl ether is 1 of butyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether and hydroxypropyl vinyl ether;
the vinyl-terminated polyether is 1 of the vinyl-terminated polyethers with the molecular weight of 200-400;
the unsaturated quaternary ammonium salt is methacryloyloxyethyl trimethyl ammonium chloride;
the unsaturated cross-linking agent is 1 of polyethylene glycol dimethacrylate with molecular weight of 200-800 or 1 of polyethylene glycol diacrylate with molecular weight of 200-800;
the ammonia water is 18-23 wt% ammonia water;
the lipophilic emulsifier is a mixture of 2 nonionic emulsifiers with HLB values of 4-7, and the hydrophilic lipophilic values of the two emulsifiers are different by 2-3;
the oxidation initiator is potassium persulfate or ammonium persulfate;
the reduction initiator is sodium bisulfite;
the hydrophilic emulsifier is a mixture of 2 nonionic emulsifiers with HLB value of 14-17, and the hydrophilic and lipophilic values of the two emulsifiers are different by 2-3;
the polymerization inhibitor is a dimethylbenzene solution of hydroquinone with the concentration of 0.8-1.2 g/L;
the chain transfer agent has an alkyl chain length of C10～161 of the aliphatic thiols of (1);
the dosage of each component is as follows: 100% of unsaturated monocarboxylic acid; the long-chain alkyl vinyl ether polymer accounts for 1-2% of the total mass of the polymerized monomers, the alkyl vinyl ether accounts for 3-6% of the total mass of the polymerized monomers, the vinyl-terminated polyether accounts for 2-4% of the total mass of the polymerized monomers, the unsaturated quaternary ammonium salt accounts for 3-6% of the total mass of the polymerized monomers, and the unsaturated cross-linking agent accounts for 0.1-0.3% of the total mass of the polymerized monomers;
the amount of the pure water is 1.5-2 times of the total mass of the polymerized monomer and the modified monomer;
the dosage of the ammonia water is 0.7-1.1 times of the total mass of the polymerization monomers or the pH of the mixture of the neutralization polymerization monomers is controlled to 6-7;
the amount of the kerosene is 0.6-0.9 times of the mass of the pure water;
the dosage of the lipophilic emulsifier is 10-13% of the total mass of the polymerized monomer and the modified monomer, and the ratio of the hydrophilic-lipophilic value HLB value in the lipophilic emulsifier is 20-30%;
the amount of the chain transfer agent is 10-20% of the mass of the oxidation initiator;
the dosage of the oxidation initiator is 0.4-0.7% of the total mass of the polymerization monomer and the modified monomer;
the using amount of the reduction initiator is 15-20% of the mass of the oxidation initiator;
the dosage of the hydrophilic emulsifier is 1.6-2 times of the total mass of the lipophilic emulsifier, and the ratio of the hydrophilic lipophilic value HLB value in the hydrophilic emulsifier is 30-40%;
the dosage of the polymerization inhibitor is 0.04-0.08% of the total mass of the polymerization monomer and the modified monomer.
(2) Preparation of the aqueous phase: mixing and uniformly stirring a polymerized monomer, part of pure water, ammonia water, vinyl-terminated polyether, an unsaturated cross-linking agent and unsaturated quaternary ammonium salt to prepare a polyacrylic acid thickener water phase;
(3) preparation of oil phase: mixing kerosene, lipophilic emulsifier, alkyl vinyl ether and long-chain alkyl vinyl ether polymer, and stirring uniformly to obtain polyacrylic acid thickener oil phase;
(4) preparation of pre-emulsion: mixing and emulsifying a polyacrylic acid thickener water phase, a polyacrylic acid thickener oil phase, a chain transfer agent, an oxidation initiator and part of pure water to prepare a polyacrylic acid thickener pre-emulsion;
(5) inverse emulsion polymerization: mixing and reacting the polyacrylic acid thickener pre-emulsion with a reduction initiator and the residual pure water to prepare polyacrylic acid thickener oily emulsion;
(6) phase inversion of emulsion: and mixing the polyacrylic acid thickener oily emulsion with a hydrophilic emulsifier and a polymerization inhibitor, and uniformly stirring to obtain the polyacrylic acid thickener aqueous emulsion.
In a preferred embodiment, the lipophilic emulsifier is a mixture of Span80(HLB4.3) and Span40(HLB6.7), a mixture of Span60(HLB4.7) and Span40(HLB6.7), or a mixture of Span60(HLB4.7) and Span40(HLB 6.7).
In preferred embodiments, the hydrophilic emulsifier is a mixture of Tween20(HLB16.7) and peregal 15(HLB14.0), Tween20(HLB16.7) and isomeric alcohol ethers 1009(HLB 14.5), or peregal 25(HLB16.7) and peregal 15(HLB 14.0).
In particular embodiments, the chain transfer agent may be used in an amount of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% by mass of the oxidation initiator.
In particular embodiments, the reducing initiator may be used in an amount of 15%, 16%, 17%, 18%, 19%, or 20% by mass of the oxidizing initiator.
In a preferred embodiment, the step (2) is specifically:
(2.1) controlling the temperature of the system to be 35-40 ℃, dissolving all the polymerization monomers in pure water accounting for 85% of the total amount, and slowly dropwise adding ammonia water to neutralize the system to a pH value of 6-7;
and (2.2) adding vinyl-terminated polyether, unsaturated cross-linking agent and unsaturated quaternary ammonium salt, and fully and uniformly stirring to obtain the polyacrylic acid thickener aqueous phase.
In a preferred embodiment, the step (3) is specifically:
(3.1) dissolving the lipophilic emulsifier, the alkyl vinyl ether and the long-chain alkyl vinyl ether polymer in kerosene at room temperature;
and (3.2) fully stirring and mixing at room temperature to prepare the polyacrylic acid thickener oil phase.
In a preferred embodiment, the step (4) is specifically:
(4.1) controlling the system temperature to be 40-50 ℃, adding the polyacrylic acid thickener aqueous phase prepared in the step (2) into the polyacrylic acid thickener oil phase prepared in the step (3), and homogenizing and emulsifying for 20-30 min;
and (4.2) keeping the temperature of the system unchanged, adding a chain transfer agent and an oxidation initiator dissolved in pure water accounting for 4-6% of the total amount, and continuing homogenizing and emulsifying for 5-10 min to obtain the polyacrylic acid thickener pre-emulsion.
In a preferred embodiment, the step (5) is specifically:
(5.1) stirring and gradually heating to 55-65 ℃, and introducing nitrogen into the polyacrylic acid thickener pre-emulsion to expel oxygen for 15-20 min;
(5.2) maintaining the temperature of the reaction system at 60-70 ℃, and uniformly adding the reduction initiator dissolved in the residual pure water into the reaction system within 80-100 min;
and (5.3) heating to 65-75 ℃, and continuing to perform heat preservation reaction for 70-100 min to obtain the polyacrylic acid thickener oily emulsion.
In a preferred embodiment, step (6) is performed after step (5), and step (6) is specifically:
(6.1) closing nitrogen, cooling the polyacrylic acid thickener oily emulsion to 60-65 ℃, adding a polymerization inhibitor, and uniformly stirring;
(6.2) cooling to 55-60 ℃, adding a hydrophilic emulsifier, and stirring for 20-30 min to obtain the polyacrylic acid thickener aqueous emulsion.
In the method of the present invention, the ammonia water is specifically ammonia water with a mass percentage concentration of 18-23 wt%, and the mass percentage concentration may be 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt% or 23 wt%, and most preferably the ammonia water is ammonia water with a mass percentage concentration of 21 wt%.
In a preferred case, the polymerization inhibitor is a xylene solution of hydroquinone at a concentration of 1g/L
In a second aspect, the present invention provides a polyacrylic acid thickener prepared by the above method.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
TABLE 1
Figure GDA0003345510900000131
Figure GDA0003345510900000141
Example 1
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) a step of preparing a water phase, which is to mix and uniformly stir a polymerized monomer, part of pure water, ammonia water, vinyl-terminated polyether, an unsaturated cross-linking agent and unsaturated quaternary ammonium salt to prepare a polyacrylic acid thickener water phase;
(2.1) controlling the temperature of the system to be 35-40 ℃, dissolving all the polymerization monomers in pure water accounting for 85% of the total amount, and slowly dropwise adding ammonia water to neutralize the system to pH6.4 +/-0.1;
and (2.2) adding vinyl-terminated polyether, unsaturated cross-linking agent and unsaturated quaternary ammonium salt, and fully and uniformly stirring to obtain the polyacrylic acid thickener aqueous phase.
(3) Preparing an oil phase, namely mixing and uniformly stirring kerosene, a lipophilic emulsifier, alkyl vinyl ether and a long-chain alkyl vinyl ether polymer to prepare a polyacrylic acid thickener oil phase;
(3.1) dissolving the lipophilic emulsifier, the alkyl vinyl ether and the long-chain alkyl vinyl ether polymer in kerosene at room temperature;
and (3.2) fully stirring and mixing at room temperature to prepare the polyacrylic acid thickener oil phase.
(4) A step of preparing a pre-emulsion, which is to mix and emulsify a polyacrylic acid thickener water phase, a polyacrylic acid thickener oil phase, a chain transfer agent, an oxidation initiator and part of pure water to prepare the polyacrylic acid thickener pre-emulsion;
(4.1) controlling the temperature of the system to be 40-45 ℃, adding the polyacrylic acid thickener aqueous phase prepared in the step (2.2) into the polyacrylic acid thickener oil phase prepared in the step (3.2), and homogenizing and emulsifying for 25-30 min;
and (4.2) maintaining the temperature of the system unchanged, adding a chain transfer agent and an oxidation initiator dissolved in pure water with the total amount of 4.5%, and continuing homogenizing and emulsifying for 5-10 min to obtain the polyacrylic acid thickener pre-emulsion.
(5) Mixing and reacting the polyacrylic acid thickener pre-emulsion with a reduction initiator and the residual pure water to prepare polyacrylic acid thickener oily emulsion;
(5.1) stirring and gradually heating to 55-60 ℃, and introducing nitrogen into the polyacrylic acid thickener pre-emulsion to expel oxygen for 15-20 min;
(5.2) maintaining the temperature of the reaction system at 60-65 ℃, and uniformly adding the reduction initiator dissolved in the residual pure water into the reaction system within 80-90 min;
and (5.3) heating to 65-70 ℃, and continuing to perform heat preservation reaction for 70-80 min to obtain the polyacrylic acid thickener oily emulsion.
(6) And (3) phase inversion of the emulsion, namely mixing the oily emulsion of the polyacrylic acid thickener with a hydrophilic emulsifier and a polymerization inhibitor, and uniformly stirring to obtain the aqueous emulsion of the polyacrylic acid thickener.
(6.1) closing the nitrogen, cooling to 60-65 ℃, adding a polymerization inhibitor, and uniformly stirring;
(6.2) cooling to 55-60 ℃, adding a hydrophilic emulsifier, and stirring for 25-30 min to obtain the polyacrylic acid thickener aqueous emulsion.
Example 2
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) a step of preparing a water phase, which is to mix and uniformly stir a polymerized monomer, part of pure water, ammonia water, vinyl-terminated polyether, an unsaturated cross-linking agent and unsaturated quaternary ammonium salt to prepare a polyacrylic acid thickener water phase;
(2.1) controlling the temperature of the system to be 35-40 ℃, dissolving all the polymerization monomers in pure water accounting for 85% of the total amount, and slowly dropwise adding ammonia water to neutralize the system to pH6.5 +/-0.2;
and (2.2) adding vinyl-terminated polyether, unsaturated cross-linking agent and unsaturated quaternary ammonium salt, and fully and uniformly stirring to obtain the polyacrylic acid thickener aqueous phase.
(3) Preparing an oil phase, namely mixing and uniformly stirring kerosene, a lipophilic emulsifier, alkyl vinyl ether and a long-chain alkyl vinyl ether polymer to prepare a polyacrylic acid thickener oil phase;
(3.1) dissolving the lipophilic emulsifier, the alkyl vinyl ether and the long-chain alkyl vinyl ether polymer in kerosene at room temperature;
and (3.2) fully stirring and mixing at room temperature to prepare the polyacrylic acid thickener oil phase.
(4) A step of preparing a pre-emulsion, which is to mix and emulsify a polyacrylic acid thickener water phase, a polyacrylic acid thickener oil phase, a chain transfer agent, an oxidation initiator and part of pure water to prepare the polyacrylic acid thickener pre-emulsion;
(4.1) controlling the temperature of the system to be 40-45 ℃, adding the polyacrylic acid thickener aqueous phase prepared in the step (2.2) into the polyacrylic acid thickener oil phase prepared in the step (3.2), and homogenizing and emulsifying for 25-30 min;
and (4.2) maintaining the temperature of the system unchanged, adding a chain transfer agent and an oxidation initiator dissolved in pure water with the total amount of 5%, and continuing homogenizing and emulsifying for 5-10 min to obtain the polyacrylic acid thickener pre-emulsion.
(5) Mixing and reacting the polyacrylic acid thickener pre-emulsion with a reduction initiator and the residual pure water to prepare polyacrylic acid thickener oily emulsion;
(5.1) stirring and gradually heating to 60 +/-2 ℃, and introducing nitrogen into the polyacrylic acid thickener pre-emulsion to expel oxygen for 15-20 min;
(5.2) maintaining the temperature of the reaction system at 65 +/-2 ℃, and uniformly adding the reduction initiator dissolved in the residual pure water into the reaction system within 90 +/-5 min;
(5.3) heating to 70 +/-2 ℃, and continuing to perform heat preservation reaction for 85 +/-5 min to obtain the polyacrylic acid thickener oily emulsion.
(6) And (3) phase inversion of the emulsion, namely mixing the oily emulsion of the polyacrylic acid thickener with a hydrophilic emulsifier and a polymerization inhibitor, and uniformly stirring to obtain the aqueous emulsion of the polyacrylic acid thickener.
(6.1) closing the nitrogen, cooling to 60-65 ℃, adding a polymerization inhibitor, and uniformly stirring;
(6.2) cooling to 55-60 ℃, adding a hydrophilic emulsifier, and stirring for 25-30 min to obtain the polyacrylic acid thickener aqueous emulsion.
Example 3
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) a step of preparing a water phase, which is to mix and uniformly stir a polymerized monomer, part of pure water, ammonia water, vinyl-terminated polyether, an unsaturated cross-linking agent and unsaturated quaternary ammonium salt to prepare a polyacrylic acid thickener water phase;
(2.1) controlling the temperature of the system to be 35-40 ℃, dissolving all the polymerization monomers in pure water accounting for 85% of the total amount, and slowly dropwise adding ammonia water to neutralize the system to pH6.6 +/-0.1;
and (2.2) adding vinyl-terminated polyether, unsaturated cross-linking agent and unsaturated quaternary ammonium salt, and fully and uniformly stirring to obtain the polyacrylic acid thickener aqueous phase.
(3) Preparing an oil phase, namely mixing and uniformly stirring kerosene, a lipophilic emulsifier, alkyl vinyl ether and a long-chain alkyl vinyl ether polymer to prepare a polyacrylic acid thickener oil phase;
(3.1) dissolving the lipophilic emulsifier, the alkyl vinyl ether and the long-chain alkyl vinyl ether polymer in kerosene at room temperature;
and (3.2) fully stirring and mixing at room temperature to prepare the polyacrylic acid thickener oil phase.
(4) A step of preparing a pre-emulsion, which is to mix and emulsify a polyacrylic acid thickener water phase, a polyacrylic acid thickener oil phase, a chain transfer agent, an oxidation initiator and part of pure water to prepare the polyacrylic acid thickener pre-emulsion;
(4.1) controlling the temperature of the system to be 45-50 ℃, adding the polyacrylic acid thickener aqueous phase prepared in the step (2.2) into the polyacrylic acid thickener oil phase prepared in the step (3.2), and homogenizing and emulsifying for 25-30 min;
and (4.2) maintaining the temperature of the system unchanged, adding a chain transfer agent and an oxidation initiator dissolved in pure water with the total amount of 6%, and continuing homogenizing and emulsifying for 5-10 min to obtain the polyacrylic acid thickener pre-emulsion.
(5) Mixing and reacting the polyacrylic acid thickener pre-emulsion with a reduction initiator and the residual pure water to prepare polyacrylic acid thickener oily emulsion;
(5.1) stirring and gradually heating to 60-65 ℃, and introducing nitrogen into the polyacrylic acid thickener pre-emulsion to expel oxygen for 15-20 min;
(5.2) maintaining the temperature of the reaction system at 65-70 ℃, and uniformly adding the reduction initiator dissolved in the residual pure water into the reaction system within 90-100 min;
and (5.3) heating to 70-75 ℃, and continuing to perform heat preservation reaction for 70-80 min to obtain the polyacrylic acid thickener oily emulsion.
(6) And (3) phase inversion of the emulsion, namely mixing the oily emulsion of the polyacrylic acid thickener with a hydrophilic emulsifier and a polymerization inhibitor, and uniformly stirring to obtain the aqueous emulsion of the polyacrylic acid thickener.
(6.1) closing the nitrogen, cooling to 60-65 ℃, adding a polymerization inhibitor, and uniformly stirring;
(6.2) cooling to 55-60 ℃, adding a hydrophilic emulsifier, and stirring for 25-30 min to obtain the polyacrylic acid thickener aqueous emulsion.
Comparative example 1
The procedure is as described in example 1, except that instead of the 12-alkyl vinyl ether trimer, octadecyl acrylate is used in the same mass.
Comparative example 2
The procedure is as described in example 1, except that methacryloyloxyethyltrimethylammonium chloride is not present in the starting material.
Test example
1. Viscosity and Print Viscosity Index (PVI) testing
Post-salt viscosity and Print Viscosity Index (PVI) test solution formulation: 289.8g of water and 1.20g of sodium chloride are accurately weighed in a 500ml beaker, a dispersion disc is adjusted to be about 10mm away from the bottom of the beaker, stirring is started, the rotating speed of a dispersion stirrer is adjusted to be 500 r/min-800 r/min, and 9.00g of sample (calculated on a dry basis) is slowly and uniformly added under the stirring condition. After the sample is added, the rotation speed of the dispersion stirrer is adjusted to 1500r/min +/-50 r/min and the mixture is continuously stirred for 8min, and then if the paste which is not completely dissolved is found, the mixture is manually stirred until the paste is completely and uniformly dissolved, so that a sample solution A1 is prepared. Sample solution A1 was placed in a thermostatic water bath at 25 ℃. + -. 1 ℃ for 2 h.
Viscosity test solution preparation before salt: 291.0g of water is accurately weighed in a 500ml beaker, a dispersion disc is adjusted to be about 10mm away from the bottom of the beaker, stirring is started, the rotating speed of a dispersion stirrer is adjusted to be 500 r/min-800 r/min, and 9.00g of sample (calculated on a dry basis) is slowly and uniformly added under the stirring condition. After the sample is added, the rotation speed of the dispersion stirrer is adjusted to 1500r/min +/-50 r/min and the mixture is continuously stirred for 8min, and then if the paste which is not completely dissolved is found, the mixture is manually stirred until the paste is completely and uniformly dissolved, so that a sample solution A2 is prepared. Sample solution A2 was placed in a thermostatic water bath at 25 ℃. + -. 1 ℃ for 2 h.
Viscosity test method: a proper amount of sample solution A1 or A2 which is constant at the temperature of 25 +/-1 ℃ is taken and placed in a 150ml beaker, and the viscosity of the solution is measured by selecting a No. 4 or No. 64 rotor corresponding to an instrument and rotating at the speed of 30r/min according to the operating procedure of an NDJ-5S viscometer.
Printing viscosity index test method: taking a proper amount of sample solution A1 which is constant at the temperature of 25 +/-1 ℃, placing the sample solution in a 150ml beaker, and selecting a No. 4 or No. 64 rotor corresponding to an instrument to respectively test the viscosity of the solution at the rotating speeds of 60r/min and 6r/min according to the operating procedure of an NDJ-5S viscometer. The viscosity index is calculated according to formula (1):
Figure GDA0003345510900000191
in the formula: PVI — viscosity index of sample solution;
η60-the viscosity, mPa · s, of the sample measured at a rotor speed of 60 r/min;
η6the viscosity, mPas, of the sample measured at a rotor speed of 6 r/min.
The results of the viscosity and printing viscosity index tests are shown in table 2.
TABLE 2
Performance testing Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Viscosity mp · s before/after salt 18750/7585 18893/7200 17902/6905 17018/5102 18890/4066
Post-salt PVI 0.23 0.22 0.22 0.30 0.29
2. Depasting Rate test
Preparing a sample solution: weighing 475g of water in a 1000ml beaker, adjusting a dispersion disc to be about 10mm away from the bottom of the beaker, starting stirring, adjusting the rotating speed of a dispersion stirrer to be 500 r/min-800 r/min, and slowly and uniformly adding 25.00g of sample (calculated on a dry basis) under the stirring condition, wherein the sample adding time is not less than 2 min. After the sample is added, the rotating speed of the dispersion stirrer is adjusted to be 1500r/min +/-50 r/min and the mixture is continuously stirred for 8min to prepare the original paste. 4.00g of sodium bicarbonate, 3.00g of sodium hexametaphosphate, 2.00g of dye-resistant salt S and 16.00g of urea are accurately weighed in a 500ml beaker, 49.00g of water is added, and the mixture is stirred until the mixture is completely dissolved. Accurately weighing 120.00g of raw paste and 6.00g of dye, adjusting the rotating speed of a dispersion stirrer to 1000r/min +/-50 r/min, and continuously stirring for 5min to obtain a sample solution B.
Making a printed cloth sample: the printing machine selects a magnetic bar with the thickness of 10mm, the magnetic force is set to be 80%, and the printing speed is 5 m/min. And (3) printing by adopting a pretreated 400mm × 250mm cloth sample, a printing screen frame engraved with 200mm × 200mm square patterns and the sample solution B, and drying to obtain the printed cloth sample. And (3) carrying out steam curing, cold water washing, hot water washing, soaping and cold water washing on the printed cloth sample, drying at 105 +/-2 ℃, ironing and flattening to obtain the printed cloth sample A.
The method for testing the paste removal rate comprises the following steps: drying the pretreated cloth sample with the thickness of 400mm multiplied by 250mm at the temperature of 105 +/-2 ℃ for 10min, then putting the cloth sample into a dryer for balancing for 30min, and weighing the dry weight m of the cloth sample0. Preparing a printed cloth sample by using the cloth sample according to the method, drying the printed cloth sample at 105 +/-2 ℃ for 10min, then putting the dried cloth sample into a dryer for balancing for 30min, and weighing the dry weight m of the printed cloth sample1. Cleaning the printed cloth sample to obtain a printed cloth sample A, drying at 105 +/-2 ℃ for 10min, then placing the dried printed cloth sample into a dryer for balancing for 30min, and weighing the dry weight m of the cleaned printed cloth sample2. The paste removal rate was calculated according to formula (2):
Figure GDA0003345510900000201
in the formula: t-paste removal rate,%;
m0-dry weight of cloth sample, g;
m1-dry weight of printed cloth sample, g;
m2-dry weight of the cleaned printed cloth sample, g.
The results of the test for the degree of deliquoring are shown in table 3.
TABLE 3
Performance of application Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Percentage of burnt removal (%) 90.0 90.5 89.8 81.6 85.2
3. Salt resistance test
The test method comprises the following steps: the salt tolerance is judged by using the viscosity retention rate, wherein the viscosity retention rate is eta (after NaCl is added)/eta (before NaCl is added), and the higher the viscosity retention rate is, the better the electrolyte resistance is.
The test results are shown in table 4.
TABLE 4
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Viscosity Retention (%) 40.4 38.1 38.6 30.0 21.5
According to the detection results of the test examples, the polyacrylic acid thickener has the characteristics of strong thickening capacity, good rheological property, high elution rate and good salt resistance. Can be widely used in the fields of water-based coating, textile printing, water-based resin coating and the like. The product prepared by the method of the invention is stored: the finished product should be stored in a shady, cool and dry place in a sealed way.
The above description is only a preferred example of the present invention, and actually, the specific raw materials listed in the present invention, the upper and lower limits and interval values of each raw material, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.) can all implement the present invention, and the examples are not listed here.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (9)

1. A method of making a polyacrylic acid thickener, the method comprising the steps of:
(1) preparing raw materials: the raw materials contain polymerized monomers, modified monomers and auxiliary agents;
the polymerized monomer is unsaturated monocarboxylic acid; the modified monomer comprises long-chain alkyl vinyl ether polymer, alkyl vinyl ether, vinyl-terminated polyether, unsaturated quaternary ammonium salt and unsaturated cross-linking agent; the auxiliary agents comprise pure water, ammonia water, kerosene, oleophylic emulsifier, oxidation initiator, reduction initiator, hydrophilic emulsifier, polymerization inhibitor and chain transfer agent;
the unsaturated monocarboxylic acid is acrylic acid;
the long-chain alkyl vinyl ether polymer is C12～141 or C of trimers of alkyl vinyl ethers15～181 of dimers of alkyl vinyl ethers;
the alkyl vinyl ether is 1 of butyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether and hydroxypropyl vinyl ether;
the vinyl-terminated polyether is 1 of the vinyl-terminated polyethers with the molecular weight of 200-400;
the unsaturated quaternary ammonium salt is methacryloyloxyethyl trimethyl ammonium chloride;
the unsaturated cross-linking agent is 1 of polyethylene glycol dimethacrylate with molecular weight of 200-800 or 1 of polyethylene glycol diacrylate with molecular weight of 200-800;
the ammonia water is 18-23 wt% ammonia water;
the lipophilic emulsifier is a mixture of 2 nonionic emulsifiers with HLB values of 4-7, and the hydrophilic lipophilic values of the two emulsifiers are different by 2-3;
the oxidation initiator is potassium persulfate or ammonium persulfate;
the reduction initiator is sodium bisulfite;
the hydrophilic emulsifier is a mixture of 2 nonionic emulsifiers with HLB value of 14-17, and the hydrophilic and lipophilic values of the two emulsifiers are different by 2-3;
the polymerization inhibitor is a dimethylbenzene solution of hydroquinone with the concentration of 0.8-1.2 g/L;
the chain transfer agent has an alkyl chain length of C10～161 of the aliphatic thiols of (1);
the dosage of each component is as follows: 100% of unsaturated monocarboxylic acid; the long-chain alkyl vinyl ether polymer accounts for 1-2% of the total mass of the polymerized monomers, the alkyl vinyl ether accounts for 3-6% of the total mass of the polymerized monomers, the vinyl-terminated polyether accounts for 2-4% of the total mass of the polymerized monomers, the unsaturated quaternary ammonium salt accounts for 3-6% of the total mass of the polymerized monomers, and the unsaturated cross-linking agent accounts for 0.1-0.3% of the total mass of the polymerized monomers;
the amount of the pure water is 1.5-2 times of the total mass of the polymerized monomer and the modified monomer;
the dosage of the ammonia water is 0.7-1.1 times of the total mass of the polymerization monomers or the pH of the mixture of the neutralization polymerization monomers is controlled to 6-7;
the amount of the kerosene is 0.6-0.9 times of the mass of the pure water;
the dosage of the lipophilic emulsifier is 10-13% of the total mass of the polymerized monomer and the modified monomer, and the ratio of the hydrophilic-lipophilic value HLB value in the lipophilic emulsifier is 20-30%;
the amount of the chain transfer agent is 10-20% of the mass of the oxidation initiator;
the dosage of the oxidation initiator is 0.4-0.7% of the total mass of the polymerization monomer and the modified monomer;
the using amount of the reduction initiator is 15-20% of the mass of the oxidation initiator;
the dosage of the hydrophilic emulsifier is 1.6-2 times of the total mass of the lipophilic emulsifier, and the ratio of the hydrophilic lipophilic value HLB value in the hydrophilic emulsifier is 30-40%;
the using amount of the polymerization inhibitor is 0.04-0.08% of the total mass of the polymerization monomer and the modified monomer;
(2) preparation of the aqueous phase: mixing and uniformly stirring a polymerized monomer, part of pure water, ammonia water, vinyl-terminated polyether, an unsaturated cross-linking agent and unsaturated quaternary ammonium salt to prepare a polyacrylic acid thickener water phase;
(3) preparation of oil phase: mixing kerosene, lipophilic emulsifier, alkyl vinyl ether and long-chain alkyl vinyl ether polymer, and stirring uniformly to obtain polyacrylic acid thickener oil phase;
(4) preparation of pre-emulsion: mixing and emulsifying a polyacrylic acid thickener water phase, a polyacrylic acid thickener oil phase, a chain transfer agent, an oxidation initiator and part of pure water to prepare a polyacrylic acid thickener pre-emulsion;
(5) inverse emulsion polymerization: mixing and reacting the polyacrylic acid thickener pre-emulsion with a reduction initiator and the residual pure water to prepare polyacrylic acid thickener oily emulsion;
(6) phase inversion of emulsion: and mixing the polyacrylic acid thickener oily emulsion with a hydrophilic emulsifier and a polymerization inhibitor, and uniformly stirring to obtain the polyacrylic acid thickener aqueous emulsion.
2. The method for preparing a polyacrylic acid thickener according to claim 1, wherein the step (2) is specifically:
(2.1) controlling the temperature of the system to be 35-40 ℃, dissolving all the polymerization monomers in pure water accounting for 85% of the total amount, and slowly dropwise adding ammonia water to neutralize the system to a pH value of 6-7;
and (2.2) adding vinyl-terminated polyether, unsaturated cross-linking agent and unsaturated quaternary ammonium salt, and fully and uniformly stirring to obtain the polyacrylic acid thickener aqueous phase.
3. The method for preparing a polyacrylic acid thickener according to claim 1, wherein the step (3) is specifically:
(3.1) dissolving the lipophilic emulsifier, the alkyl vinyl ether and the long-chain alkyl vinyl ether polymer in kerosene at room temperature;
and (3.2) fully stirring and mixing at room temperature to prepare the polyacrylic acid thickener oil phase.
4. The method for preparing a polyacrylic acid thickener according to any one of claims 1 to 3, wherein the step (4) is specifically:
(4.1) controlling the system temperature to be 40-50 ℃, adding the polyacrylic acid thickener aqueous phase prepared in the step (2) into the polyacrylic acid thickener oil phase prepared in the step (3), and homogenizing and emulsifying for 20-30 min;
and (4.2) keeping the temperature of the system unchanged, adding a chain transfer agent and an oxidation initiator dissolved in pure water accounting for 4-6% of the total amount, and continuing homogenizing and emulsifying for 5-10 min to obtain the polyacrylic acid thickener pre-emulsion.
5. The method for preparing a polyacrylic acid thickener according to claim 1, wherein the step (5) is specifically:
(5.1) stirring and gradually heating to 55-65 ℃, and introducing nitrogen into the polyacrylic acid thickener pre-emulsion to expel oxygen for 15-20 min;
(5.2) maintaining the temperature of the reaction system at 60-70 ℃, and uniformly adding the reduction initiator dissolved in the residual pure water into the reaction system within 80-100 min;
and (5.3) heating to 65-75 ℃, and continuing to perform heat preservation reaction for 70-100 min to obtain the polyacrylic acid thickener oily emulsion.
6. The method for preparing a polyacrylic acid thickener according to claim 1 or 5, wherein the step (6) is specifically:
(6.1) closing the nitrogen, cooling to 60-65 ℃, adding a polymerization inhibitor, and uniformly stirring;
(6.2) cooling to 55-60 ℃, adding a hydrophilic emulsifier, and stirring for 20-30 min to obtain the polyacrylic acid thickener aqueous emulsion.
7. The method for producing a polyacrylic acid thickener according to claim 1, wherein the aqueous ammonia is 21 wt% aqueous ammonia in mass%.
8. The method for producing a polyacrylic acid thickener according to claim 1, wherein the polymerization inhibitor is a xylene solution of hydroquinone at a concentration of 1 g/L.
9. Polyacrylic acid thickener obtainable by the process according to any of claims 1 to 8.
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