CN114134732A - Compound thickener and preparation method thereof - Google Patents

Compound thickener and preparation method thereof Download PDF

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Publication number
CN114134732A
CN114134732A CN202111403117.0A CN202111403117A CN114134732A CN 114134732 A CN114134732 A CN 114134732A CN 202111403117 A CN202111403117 A CN 202111403117A CN 114134732 A CN114134732 A CN 114134732A
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Prior art keywords
emulsion
cationic
temperature
parts
anionic
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CN202111403117.0A
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Inventor
于本成
柴宇伦
王静昌
卢奕江
袁国伟
陈八斤
姚从春
游爱鸳
王胜鹏
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Zhejiang Chuanhua Functional New Material Co ltd
Transfar Zhilian Co Ltd
Hangzhou Transfar Fine Chemicals Co Ltd
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Zhejiang Chuanhua Functional New Material Co ltd
Transfar Zhilian Co Ltd
Hangzhou Transfar Fine Chemicals Co Ltd
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Priority to CN202111403117.0A priority Critical patent/CN114134732A/en
Publication of CN114134732A publication Critical patent/CN114134732A/en
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    • 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
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • 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
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5221—Polymers of unsaturated hydrocarbons, e.g. polystyrene polyalkylene

Abstract

The invention belongs to the technical field of printing and dyeing auxiliaries, and particularly relates to a compound thickener and a preparation method thereof. According to the compound thickener provided by the invention, the cationic emulsion is introduced into the acrylic acid anionic emulsion, and the electrostatic interaction of the anionic and cationic interactions of the acrylic acid anionic emulsion and the cationic emulsion is utilized, so that the volume of aggregates after swelling of the anionic emulsion is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickener is improved. The method disclosed by the invention can avoid the phenomenon of emulsion breaking and instability generated in the conventional anion/cation compounding process, and the thickener emulsion obtained by compounding has good thickening and paste removing effects.

Description

Compound thickener and preparation method thereof
Technical Field
The invention belongs to the technical field of printing and dyeing auxiliaries, and particularly relates to a compound thickener and a preparation method thereof.
Background
The printing is a comprehensive processing process for obtaining colored patterns on local parts of the fabric, and the printing paste contains necessary chemical additives and also a very important component, namely a thickening agent. Thickeners are a class of hydrophilic substances that increase the viscosity of the system. There are many kinds of thickeners, including natural hydrophilic polymers and modified products thereof, emulsified pastes or galactized pastes, synthetic thickeners, and the like. Most of the prior printing and dyeing thickeners are natural hydrophilic polymers and modified products thereof, such as starch, cellulose, sodium alginate, xanthan gum and the like, but the thickeners have the defects of slow paste opening, large using amount, and great influence on sources, purity, cost, storage and the like. The synthetic thickening agent appeared in the early 70 s of the 20 th century, and has the advantages of quick paste opening, small using amount, low price, stable product and the like, so the synthetic thickening agent becomes an important thickening agent variety after decades of development, and is one of important ways for replacing the traditional natural thickening agent in a printing process.
The acrylic polymer thickener has the advantages of ideal comprehensive performance, and is widely applied to the fields of textile printing and dyeing, oil field chemical industry, leather, building, papermaking, food processing, cosmetics and the like. In the synthetic thickener, a large amount of sodium carboxylate exists in a molecular chain of an acrylic polymer, a large amount of carboxylate ions can be ionized in water, a strong electrostatic repulsion effect is generated, the originally curled molecular chain is expanded, the volume of the polymer molecules is increased, and large resistance is generated to fluid flow, so that the viscosity of the solution is improved, namely, the solution is thickened. The normal anion system is a fully extended system, the high crosslinking degree can cause the paste removal speed to become slow, the low crosslinking degree and the low paste forming efficiency, and the two contradict each other. The prior anionic thickening agent has the problems of unsatisfactory thickening effect and low paste removing efficiency, and can not well meet the requirements of printing and dyeing application. In order to solve the problem, many researchers improve the thickening effect and the paste removal efficiency of the synthetic thickener by changing the polymerization process, adding functional monomers, compounding and other means.
Patent CN 101619543A discloses a preparation method of acrylate synthetic thickener, which is characterized in that a special weak cationic (methyl) acrylate functional monomer is synthesized by adopting an ester exchange method, and the textile printing thickener is prepared by adopting the functional monomer and vinyl monomers such as acrylic acid, acrylamide and the like through inverse emulsion polymerization, and has the characteristics of high thickening capacity and good water holding capacity.
Patent CN 105484067a discloses a preparation method of a novel printing thickener, which comprises mixing unsaturated acidic monomers, inorganic thickening powder and hydroxymethyl cellulose as water phase, fully stirring with organic solvent under the action of emulsifier to obtain reversed phase emulsion, initiating polymerization reaction, and adding phase inversion emulsifier after the reaction is finished to obtain the final product. The printing thickener provided by the invention has good thickening effect, high viscosity and electrolyte resistance, can reduce the using amount of the thickener, and has no adverse effect on the color brightness, fastness to washing and handfeel softness of printed fabrics.
Patent CN107690494A discloses a process for preparing cationic polymer thickeners in particulate form, said polymers consisting of water swellable crosslinked cationic polymers consisting of cationic water soluble monomers and non-ionic water soluble monomers and/or anionic water soluble monomers, obtained by inverse emulsion polymerization, which have good dispersion characteristics in water as thickeners.
Patent CN102482619A discloses a thickener containing a crosslinked water-swellable cationic polymer containing at least one cationic monomer and optionally a nonionic or anionic monomer, said polymer containing less than 25% by weight of water-soluble polymer chains based on the total mass of said polymer, and a crosslinking agent of an epoxy compound such as ethylene glycol diacrylate. The thickener has the functions of combining with softening agent of clothes and improving rheological property.
The prior art mentioned above tries to improve the thickening effect and the paste removal efficiency of the acrylic polymer thickener by various means, however, the paste formation efficiency of the white slurry is not high enough, the hydration of the anionic thickener is easily damaged when the anionic thickener meets the electrolyte, the salt tolerance is not good, and the contradiction between the thickening efficiency and the paste removal efficiency is not solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a compound thickener and a preparation method thereof, and the compound thickener is prepared by introducing a cationic emulsion into the prior acrylic acid anionic emulsion for compounding, and improves the aggregate volume and the movement difficulty of the swollen anionic emulsion by utilizing the electrostatic interaction of the mutual attraction of anions and cations between the cationic emulsion and the anionic emulsion, thereby improving the thickening effect of the thickener and solving the technical problems of low pasting rate, poor salt tolerance, low pasting efficiency and the like of the acrylic acid anionic emulsion thickener in the prior art.
In order to achieve the above object, the present invention provides a complex thickener comprising an acrylic acid-based anionic emulsion and a cationic emulsion; the mass ratio of the cationic emulsion in the compound thickener is less than or equal to 20 percent;
when the thickening agent is used, the acrylic acid series anionic emulsion and the cationic emulsion are mutually attracted through the electrostatic action of anions and cations, the volume of an aggregate after the anionic emulsion is swelled is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickening agent is improved.
Preferably, the mass ratio of the cationic emulsion in the compound thickener is 3-15%;
the cationic emulsion is prepared from the following components in parts by weight: 1-40 parts of unsaturated cationic monomer, 5-70 parts of functional monomer, 1-10 parts of initiator, 0.1-5 parts of cross-linking agent, 2-5 parts of emulsifier, 15-30 parts of hydrocarbon solvent and 1-10 parts of phase inversion emulsifier.
Preferably, the cationic emulsion is prepared from the following components in parts by weight: 5-20 parts of unsaturated cationic monomer, 15-30 parts of functional monomer, 2-4 parts of initiator, 1-5 parts of cross-linking agent, 2-5 parts of emulsifier, 15-30 parts of hydrocarbon solvent and 3-5 parts of phase inversion emulsifier.
Preferably, the cationic emulsion is obtained by performing inverse suspension polymerization on the unsaturated cationic monomer, the crosslinking agent and the functional monomer in a hydrocarbon solvent under the action of the initiator and the emulsifier and then performing phase inversion; wherein the unsaturated cationic monomer is selected from one or more of dimethyl diallyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and acryloyloxyethyl dimethyl benzyl ammonium chloride.
Preferably, the particle size of the cationic emulsion is 1-10 μm, and the particle size of the acrylic anionic emulsion is less than 1 μm.
Preferably, the acrylic acid series anionic emulsion is obtained by performing inverse suspension polymerization on an unsaturated acidic monomer, a cross-linking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier and then performing phase inversion; the composition is prepared from the following components in parts by weight: 25-35 parts of unsaturated acidic monomer, 35-60 parts of liquid alkali, 0.2-0.5 part of initiator, 10-30 parts of deionized water, 0.01-0.1 part of cross-linking agent, 10-30 parts of functional monomer, 5-15 parts of emulsifier, 35-55 parts of hydrocarbon solvent and 3-5 parts of phase inversion emulsifier.
Preferably, the unsaturated acidic monomer is selected from one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid and fumaric acid.
Preferably, the initiator is selected from the group consisting of potassium persulfate, ammonium persulfate, sodium persulfate, azobisisobutyramidine hydrochloride, and azobisisobutyramidine oxazoline hydrochloride.
Preferably, the crosslinking agent is one or more of diallyl phthalate, divinylbenzene, ethylene glycol diacrylate, triethylene glycol diacrylate, polyvinyl alcohol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, butylene dimethacrylate, N' N-methylenebisacrylamide and pentaerythritol triacrylate.
Preferably, the functional monomer is one or more of acrylamide, methacrylamide, styrene, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.
According to another aspect of the present invention, there is provided a method for preparing the complex thickener, comprising the steps of:
(1) carrying out inverse suspension polymerization on an unsaturated cationic monomer, a cross-linking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier, and then carrying out phase inversion to obtain a cationic emulsion;
(2) unsaturated acidic monomers, cross-linking agents and functional monomers are subjected to reversed-phase suspension polymerization in a hydrocarbon solvent under the action of an initiator and an emulsifier and then phase inversion is carried out to generate acrylic acid series anionic emulsion;
(3) and (3) compounding the cationic emulsion obtained in the step (1) and the acrylic acid series anionic emulsion obtained in the step (2) to obtain the compound thickener.
Preferably, the method for preparing the cationic emulsion comprises the following substeps:
(1-1) dissolving unsaturated cationic monomers and functional monomers in water under the condition of stirring, adding an initiator and deionized water, and mixing to obtain a water phase substance;
(1-2) mixing the water phase substance prepared in the step (1) with an oil phase consisting of an emulsifier, a cross-linking agent and a hydrocarbon solvent under the stirring condition, and controlling the mechanical stirring speed at 600-800rpm for 10-30 minutes to obtain a stable pre-emulsion;
(1-3) heating the pre-emulsion obtained in the step (2) to 30-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after the reaction is finished, and preserving the temperature for 1-8 hours at 50-90 ℃ to obtain the polymerized emulsion, or
Controlling the temperature of the pre-emulsion in the step (2) to be 18-20 ℃, dropwise adding a sodium bisulfite aqueous solution into the pre-emulsion, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after the reaction is finished, and preserving the temperature at 50-90 ℃ for 1-8 hours to obtain a polymerized emulsion;
(1-4) cooling the polymerized emulsion to room temperature, adding a phase inversion emulsifier, and performing reverse emulsification for 10-20 minutes to obtain the cationic emulsion.
Preferably, the preparation method of the acrylic anionic emulsion comprises the following steps:
(2-1) neutralizing an unsaturated acidic monomer with liquid alkali under stirring to pH 5-7, adding an initiator and deionized water, and mixing to obtain an aqueous phase;
(2-2) mixing the water phase substance prepared in the step (2-1) with an oil phase consisting of an emulsifier, a cross-linking agent and a hydrocarbon solvent under the stirring condition, and emulsifying for 30-50 minutes at the stirring speed of 1000-1500rpm to obtain a stable pre-emulsion;
(2-3) heating the pre-emulsion obtained in the step (2-2) to 30-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 65-75 ℃ for 1.5-2 hours to obtain polymerized emulsion; or
Controlling the temperature of the pre-emulsion in the step (2-2) to be 18-20 ℃, dropwise adding a sodium bisulfite aqueous solution into the pre-emulsion, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 60-70 ℃ for 1.5-2 hours; obtaining polymerized emulsion;
and (2-4) cooling the polymerized emulsion to room temperature, adding a phase inversion emulsifier, and performing reverse emulsification for 10-20 minutes to obtain the acrylic acid series anionic emulsion.
According to another aspect of the invention, a method for improving the thickening effect of an acrylic acid type thickener is provided, wherein a cationic emulsion is introduced into an acrylic acid type anionic emulsion thickener to form a complex thickener, so that the mass ratio of the cationic emulsion in the complex thickener is less than or equal to 20%;
when the thickening agent is used, the acrylic acid series anionic emulsion and the cationic emulsion are mutually attracted through the electrostatic action of anions and cations, so that the volume of an aggregate after the anionic emulsion is swelled is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickening agent is improved.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) according to the compound thickener provided by the invention, the cationic emulsion is introduced into the acrylic acid anionic emulsion, and the electrostatic interaction of the anionic and cationic interactions of the acrylic acid anionic emulsion and the cationic emulsion is utilized, so that the volume of the aggregates after swelling of the anionic emulsion is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickener is improved.
(2) A large amount of sodium carboxylate exists in a molecular chain of a traditional acrylic acid series anionic emulsion thickener, a large amount of carboxylate ions can be ionized in water, a strong electrostatic repulsion effect is generated, an originally curled molecular chain is expanded, the volume of polymer molecules is increased, and large resistance is generated to fluid flow, namely thickening is performed, however, the expanded anionic molecular chain is easily damaged by cations in electrolyte, and the salt tolerance is poor. According to the invention, by compounding the cationic emulsion and the acrylic acid series anionic emulsion, on one hand, the cationic emulsion plays a role of a physical crosslinking point, so that the volume of an anionic aggregate is increased, and the thickening efficiency is improved; on the other hand, cations are crosslinked by anions and cations, and the cations contain more nonpolar groups, so that the whole system can play a role of skeleton support, and compared with a simple anionic thickener system, the cationic thickener system is influenced by electrolyte, has smaller compression degree and embodies better salt resistance.
(3) According to the invention, the cationic emulsion is introduced into the acrylic acid anionic thickener, the cationic emulsion plays a role of a cross-linking point, the cationic emulsion and the acrylic acid anionic thickener are mutually adsorbed through charges, and the size of an aggregate of the anionic emulsion is controlled. The anion-cation system compound with moderate molecular weight has stronger charge attraction effect under the condition of low temperature, the electrostatic interaction force is weakened under the conditions of high temperature and high shear force (paste removing process), the aggregate decomposition of the thickener of the compound system is reduced, the thickener is easy to remove paste and wash away, and the paste removing speed of the thickener is improved. The improvement of the pasting rate in the conventional anionic crosslinking system is realized by chemical crosslinking of covalent bonds, and the crosslinking mode cannot be destroyed under the conditions of high temperature and covalent bonds, so that the thickener aggregate is not easy to reduce. The invention is physical cross-linking due to electrostatic interaction, so under the conditions of high temperature and high shear force (paste removing process), the electrostatic interaction force is weakened, the decomposition of the thickener aggregate of the compound system is reduced, and the paste is easy to remove and wash.
(4) The complex thickener is obtained by simply compounding after the anionic emulsion and the cationic emulsion are respectively prepared, and the complex thickener is simple in preparation method and easy to apply in a large scale.
(5) The invention provides a method for improving the thickening effect of an acrylic acid type anionic emulsion polymer thickener, which can remarkably improve the white pulp viscosity of an anionic emulsion by compounding a certain mass fraction of cationic emulsion into the acrylic acid type anionic emulsion thickener.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a compound thickener, which comprises an acrylic acid series anionic emulsion and a cationic emulsion; the mass ratio of the cationic emulsion in the compound thickener is less than or equal to 20 percent; when the thickening agent is used, the acrylic acid series anionic emulsion and the cationic emulsion are mutually attracted through the electrostatic action of anions and cations, the volume of an aggregate after the anionic emulsion is swelled is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickening agent is improved.
In some embodiments, the mass ratio of the cationic emulsion in the complex thickener is 3-15%; the cationic emulsion is prepared from the following components in parts by weight: 1-40 parts of unsaturated cationic monomer, 5-70 parts of functional monomer, 1-10 parts of initiator, 0.1-5 parts of cross-linking agent, 2-5 parts of emulsifier, 15-30 parts of hydrocarbon solvent and 1-10 parts of phase inversion emulsifier.
In some preferred embodiments, the cationic emulsion is prepared from the following components in parts by mass: 5-20 parts of unsaturated cationic monomer, 15-30 parts of functional monomer, 2-4 parts of initiator, 1-5 parts of cross-linking agent, 2-5 parts of emulsifier, 15-30 parts of hydrocarbon solvent and 3-5 parts of phase inversion emulsifier.
In some embodiments, the cationic emulsion is obtained by performing inverse suspension polymerization on the unsaturated cationic monomer, the crosslinking agent and the functional monomer in a hydrocarbon solvent under the action of the initiator and the emulsifier, and then performing phase inversion; wherein the unsaturated cationic monomer is selected from one or more of dimethyl diallyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and acryloyloxyethyl dimethyl benzyl ammonium chloride.
In a preferred embodiment, the particle size of the cationic emulsion is 1-10 μm, preferably 2-8 μm, and more preferably 2-5 μm. The particle size of the acrylic acid series anion emulsion prepared by the invention is less than 1 μm, preferably 500nm-1 μm.
In some embodiments, the acrylic anionic emulsion is obtained by performing inverse suspension polymerization on an unsaturated acidic monomer, a crosslinking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier and then performing phase inversion; the composition is prepared from the following components in parts by weight: 25-35 parts of unsaturated acidic monomer, 35-60 parts of liquid alkali, 0.2-0.5 part of initiator, 10-30 parts of deionized water, 0.01-0.1 part of cross-linking agent, 10-30 parts of functional monomer, 5-15 parts of emulsifier, 35-55 parts of hydrocarbon solvent and 3-5 parts of phase inversion emulsifier.
In some embodiments, the unsaturated acidic monomer is selected from one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid.
In some embodiments, the initiator is selected from the group consisting of potassium persulfate, ammonium persulfate, sodium persulfate, azobisisobutyramidine hydrochloride, and azobisisobutyramidine oxazoline hydrochloride (KEXIN).
In some embodiments, the crosslinking agent is one or more of diallyl phthalate, divinylbenzene, ethylene glycol diacrylate, triethylene glycol diacrylate, polyvinyl alcohol (400) diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, butylene dimethacrylate, N' -N-methylenebisacrylamide, pentaerythritol triacrylate.
In some embodiments, the functional monomer is one or any combination of the following compounds: acrylamide, methacrylamide, styrene, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate.
In some embodiments, the emulsifier is selected from one or more of sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, propylene glycol monostearate, sorbitan sesquioleate, diethylene glycol monolaurate and tetraethylene glycol monostearate.
In the preparation of the cationic emulsion and the acrylic anionic emulsion, the hydrocarbon solvent used comprises but is not limited to one or more of kerosene, white oil and the like; the phase inversion emulsifier generally adopts nonionic emulsifier with HLB value between 9-12, including but not limited to fatty alcohol polyoxyethylene ether. The liquid alkali used for preparing the acrylic acid series anionic emulsion comprises but is not limited to one or more of ammonia water, organic amine, liquid alkali, potassium hydroxide solution and the like.
The invention also provides a preparation method of the compound thickener, which comprises the following steps:
(1) carrying out inverse suspension polymerization on an unsaturated cationic monomer, a cross-linking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier, and then carrying out phase inversion to obtain a cationic emulsion;
(2) unsaturated acidic monomers, cross-linking agents and functional monomers are subjected to reversed-phase suspension polymerization in a hydrocarbon solvent under the action of an initiator and an emulsifier and then phase inversion is carried out to generate acrylic acid series anionic emulsion;
(3) and (3) compounding the cationic emulsion obtained in the step (1) and the acrylic acid series anionic emulsion obtained in the step (2) to obtain the compound thickener.
In some embodiments, step (1) comprises the sub-steps of:
(1-1) preparation of an aqueous phase: dissolving unsaturated cationic monomers and functional monomers in water under the condition of stirring, adding an initiator and deionized water, and mixing to obtain a water phase substance;
(1-2) Pre-emulsification: adding the water phase material into an oil phase consisting of an oil-soluble emulsifier, a cross-linking agent and a hydrocarbon solvent under high-speed stirring, stirring at a low speed, and controlling the mechanical stirring speed at 600-800rpm for 10-30 minutes to obtain a stable pre-emulsion;
(1-3) polymerization: the polymerization method comprises two polymerization modes, namely, the pre-emulsion is heated to 30-60 ℃ under the protection of nitrogen, the reaction starts to initiate gradually, the system temperature is gradually increased, the reaction temperature is controlled not to exceed 90 ℃, the temperature is gradually reduced after the reaction is finished, and the temperature is kept for 1-8 hours (preferably 1.5-2 hours) at 50-90 ℃ (preferably 65-75 ℃); controlling the temperature of the pre-emulsion at 18-20 ℃, dropwise adding a sodium bisulfite aqueous solution into the pre-emulsion, gradually starting the initiation of the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 50-90 ℃ for 1-8 hours;
(1-4) phase inversion: cooling to room temperature after heat preservation, adding a phase inversion emulsifier, and performing phase inversion emulsification for 10-20 minutes to obtain a finished product.
The step (2) comprises the following substeps:
(2-1) preparation of an aqueous phase: neutralizing an unsaturated acidic monomer with liquid alkali under the condition of stirring until the pH value is 5-7, adding an initiator and deionized water, and mixing to obtain an aqueous phase substance;
(2-2) Pre-emulsification: adding the water phase material into an oil phase consisting of an oil-soluble emulsifier, a cross-linking agent and a hydrocarbon solvent under high-speed stirring, and emulsifying for 30-50 minutes at the stirring speed of 1000-1500rpm to obtain a stable pre-emulsion;
(2-3) polymerization: the polymerization method comprises two polymerization modes, namely, heating the pre-emulsion to 30-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 65-75 ℃ for 1.5-2 hours; controlling the temperature of the pre-emulsion at 18-20 ℃, dropwise adding a sodium bisulfite aqueous solution into the pre-emulsion, gradually starting the initiation of the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 60-70 ℃ for 1.5-2 hours;
(2-4) phase inversion: cooling to room temperature after heat preservation, adding a phase inversion emulsifier, and performing phase inversion emulsification for 10-20 minutes to obtain a finished product.
According to the method for improving the thickening effect of the acrylic acid type thickening agent, the thickening effect of the thickening agent is improved by compounding the anionic polymer emulsion and the cationic polymer emulsion. The cross-linked ionic polymer can cause mutual repulsion among molecular chains in a polymer structure due to ionization in water, so that originally curled molecular chains are stretched out, the volume of particles is increased, the mutual extrusion friction among the particles is aggravated, the viscosity is increased, and the larger the volume of the particles after water absorption is, the higher the viscosity of a system is. The hydrophilic ability of the acrylic anionic polymer is generally stronger than that of the cationic polymer, and the acrylic anionic polymer has large charge density and high ionicity, so that the volume of the anionic polymer and the cationic polymer with the same particle size has larger difference after water absorption and expansion, and the volume of the anionic polymer particles is obviously smaller than that of the cationic polymer. In the case of the acrylic acid type thickener (i.e. the acrylic acid type anionic emulsion of the invention), because the surfaces of the polymer particles all have the same negative charge, electrostatic repulsion is generated between the particles, and the existence of the electrostatic repulsion causes certain 'gaps' between the particles, so that the particles in the whole system are in a dispersed independent state. The normal anion system is a fully extended system, the cross-linking degree is high, the pasting efficiency is high, but the de-pasting speed is slow due to the high cross-linking degree, the de-pasting speed is high due to the low cross-linking degree, the pasting efficiency is low, and the two contradict each other.
According to the invention, the cationic emulsion is compounded in the acrylic acid anionic emulsion, and the proper crosslinking degree of the anionic emulsion and the particle size of the cationic emulsion are controlled, so that the cationic emulsion and the anionic emulsion polymer have better crosslinking degree under a low-temperature condition, are decrosslinked under a high-temperature condition, have increased water solubility, and are easy to remove paste and wash. Meanwhile, after the cationic polymer with large particle size and high crosslinking degree is introduced, the cationic polymer absorbs water and expands and is distributed around the anionic polymer, when the stacking density and the particle size of the anionic and cationic particles exceed a certain range, the anionic and cationic particles are closely stacked and mutually contacted, positive charges on the surface of the cationic particles and negative charges on the surface of the surrounding adjacent thickener particles are bonded due to electrostatic attraction, molecular chains are mutually crossed, so that the adjacent anionic polymers are connected, the cationic polymer with large particle size plays a role similar to crosslinking association in the cationic polymer, the volume of the polymer particles is improved, the movement difficulty of the particles is increased, and the thickening effect of the thickener can be obviously improved. In the preferred embodiment of the invention, by synthesizing the cationic thickener with larger crosslinking degree, the particle size is about 2-5 μm, the volume is larger, and the cationic thickener is not easy to stretch, so the surface charge density of the emulsion is smaller, the cationic thickener has cationic property but weaker cationic property, and the destabilization demulsification phenomenon generated when the common cationic emulsion and the anionic emulsion are compounded is avoided. Although the cationic emulsion has poor effect when being used as a thickening agent alone, the cationic emulsion has unexpected thickening effect when being compounded with the traditional acrylic acid type anionic emulsion. Meanwhile, the invention controls the crosslinking degree of a proper anionic thickener to have better crosslinking association with the cationic emulsion; in the experiment, if the crosslinking degree is too high, the cation emulsion with large particle size can not enter into the network of the anion thickener system to form crosslinking association points; if the degree of crosslinking is too low, the cationic emulsion has a poor associative effect. The crosslinking degree of the anionic emulsion and the cationic emulsion can be controlled by controlling the dosage ratio of the monomer to the crosslinking agent, and the particle diameter of the cationic emulsion can be determined by controlling the stirring speed during the colostrum preparation of the cationic emulsion.
In the preferred embodiment of the invention, the thickening effect of the acrylic acid type anionic emulsion thickener can be obviously improved by synthesizing the cationic emulsion with a certain crosslinking degree and particle size and compounding the cationic emulsion with the acrylic acid type anionic emulsion thickener with a certain crosslinking degree. The preparation method comprises the following steps: (1) carrying out inverse suspension polymerization on an unsaturated cationic monomer, a crosslinking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier, and then carrying out phase inversion to obtain a cationic emulsion with high crosslinking degree; (2) unsaturated acid monomer, cross-linking agent and functional monomer are subjected to reversed phase suspension polymerization in a hydrocarbon solvent under the action of an initiator and an emulsifier and then phase inversion is carried out to generate acrylic acid series thickener emulsion with a certain cross-linking degree; (3) and compounding the cationic emulsion and an acrylic acid type thickening agent to obtain the compound emulsion. The method disclosed by the invention can avoid the phenomenon of emulsion breaking and instability generated in the conventional anion/cation compounding process, and the thickener emulsion obtained by compounding has good thickening and paste removing effects.
The following are specific examples:
example 1:
preparation of cationic emulsion: 14g of dimethyldiallylammonium chloride, 2g of potassium persulfate, 34g of acrylamide and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 2g diallyl phthalate, 5g sorbitan monooleate and 35g kerosene were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring and emulsifying at 700rpm for 10min to obtain stable emulsion. Heating the emulsion in the flask to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 3.5 um.
Preparation of anionic emulsion: 50g of acrylic acid is neutralized by 70g of liquid alkali under the condition of stirring at room temperature, 0.5g of potassium persulfate, 5g of acrylamide and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 2g of diallyl phthalate, 5g of sorbitan monooleate and 35g of kerosene are mixed uniformly to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 15g of cationic emulsion and 85g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 2:
preparation of cationic emulsion: 10g of methacryloyloxyethyl trimethyl ammonium chloride, 3g of ammonium persulfate and 30g of deionized water were uniformly mixed at room temperature with stirring to prepare an aqueous phase. 3g of divinylbenzene, 34g of ethyl acrylate, 5g of sorbitan monostearate and 35g of kerosene are uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 600rpm for 15min to obtain stable emulsion. Heating the emulsion in the flask to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal A-25, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.8 um.
Preparation of anionic emulsion: 60g of methacrylic acid is neutralized by 70g of liquid alkali under the condition of stirring at room temperature, 0.7g of ammonium persulfate, 6g of ethyl acrylate and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 0.3g of divinylbenzene, 5g of sorbitan monostearate and 35g of kerosene are mixed uniformly to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal A-25, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 10g of cationic emulsion and 90g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 3:
preparation of cationic emulsion: 10g of acryloyloxyethyltrimethylammonium chloride, 3g of azobisisobutyramidine hydrochloride and 30g of deionized water were mixed uniformly with stirring at room temperature to prepare an aqueous phase. 4g of ethylene glycol diacrylate, 34g of styrene, 5g of sorbitan monopalmitate and 45g of white oil are uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 600rpm for 15min to obtain stable emulsion. Heating the emulsion in the flask to 40-50 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal A-20, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.7 um.
Preparation of anionic emulsion: 30g of acrylic acid and 30g of maleic acid are neutralized by 85g of liquid alkali under the condition of stirring at room temperature, 0.7g of azobisisobutyramidine hydrochloride and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 0.4g of ethylene glycol diacrylate, 7g of styrene, 5g of sorbitan monopalmitate and 45g of white oil are mixed uniformly to prepare an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 40-50 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal A-20, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 3g of cationic emulsion and 97g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 4:
preparation of cationic emulsion: under the condition of stirring at room temperature, 11g of acryloyloxyethyl dimethyl benzyl ammonium chloride, 3g of azodiisobutylaminazoline hydrochloride and 30g of deionized water are uniformly mixed to prepare a water phase substance. 3g of triethylene glycol diacrylate, 33g of ethyl methacrylate, 6g of propylene glycol monostearate and 45g of white oil are uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 600rpm for 15min to obtain stable emulsion. Heating the emulsion in the flask to 30-40 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O-35, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.6 um.
Preparation of anionic emulsion: 30g of acrylic acid and 30g of itaconic acid are neutralized by 80g of liquid alkali under the condition of stirring at room temperature, 0.7g of azodiisobutyronidazoline hydrochloride and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 0.3g of triethylene glycol diacrylate, 8g of ethyl methacrylate, 6g of propylene glycol monostearate and 45g of white oil are mixed uniformly to prepare an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 30-40 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O-35, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 5g of cationic emulsion and 95g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 5:
preparation of cationic emulsion: 5g of dimethyldiallylammonium chloride, 10g of methacryloyloxyethyl trimethylammonium chloride, 2g of potassium persulfate and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 5g of polyvinyl alcohol (400) diacrylate, 35.5g of butyl acrylate, 5g of sorbitan sesquioleate and 55g of gasoline are uniformly mixed to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 600rpm for 15min to obtain stable emulsion. Dropwise adding 0.1g of sodium bisulfite into the reactor under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO8, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.7 um.
Preparation of anionic emulsion: 30g of acrylic acid and 30g of fumaric acid were neutralized with 70g of liquid alkali under stirring at room temperature, and 0.5g of potassium persulfate and 30g of deionized water were added and mixed uniformly to prepare an aqueous phase. 0.5g of polyvinyl alcohol (400) diacrylate, 5.5g of butyl acrylate, 5g of sorbitan sesquioleate and 55g of gasoline are uniformly mixed to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Dropwise adding 0.1g of sodium bisulfite into the reactor under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO8, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 8g of cationic emulsion and 92g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 6:
preparation of cationic emulsion: 5g of dimethyldiallylammonium chloride, 10g of acryloyloxyethyltrimethylammonium chloride, 1.2g of potassium persulfate, 1.2g of azobisisobutyramidine oxazoline hydrochloride and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. An oil phase was prepared by uniformly mixing 5g of tripropylene glycol diacrylate, 30g of butyl methacrylate, 8g of diethylene glycol monolaurate and 55g of gasoline. Adding the water phase into the oil phase, and stirring at 700rpm for 15min to obtain stable emulsion. Heating the emulsion in the reactor to 30-40 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO9, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 3.8 um.
Preparation of anionic emulsion: 50g of acrylic acid and 30g of methacrylic acid were neutralized with 95g of liquid alkali under stirring at room temperature, and 0.3g of potassium persulfate, 0.3g of azobisisobutyramidine hydrochloride and 30g of deionized water were added and mixed uniformly to prepare an aqueous phase. 0.5g of tripropylene glycol diacrylate, 8g of butyl methacrylate, 8g of diethylene glycol monolaurate and 55g of gasoline were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 30-40 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO9, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 7g of cationic emulsion and 93g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 7:
preparation of cationic emulsion: 5g of dimethyldiallylammonium chloride, 5g of acryloyloxyethyltrimethylammonium chloride, 2.5g of potassium persulfate and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 2.1g of trimethylolpropane triacrylate, 40g of methacrylamide, 10g of tetraethyleneglycol monostearate and 40g of kerosene were uniformly mixed to prepare an oil phase composition. Adding the water phase into the oil phase, and stirring at 700rpm for 15min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually increasing the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually decreasing the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of LAE-9, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 3.8 um.
Preparation of anionic emulsion: 50g of acrylic acid and 10g of maleic acid were neutralized with 70g of liquid caustic soda under stirring at room temperature, and 0.6g of potassium persulfate and 30g of deionized water were added and mixed uniformly to prepare an aqueous phase. 0.7g of trimethylolpropane triacrylate, 6g of methacrylamide, 10g of tetraethyleneglycol monostearate and 40g of kerosene were uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 1500rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of LAE-9, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 10g of cationic emulsion and 90g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 8:
preparation of cationic emulsion: 2.5g of dimethyldiallylammonium chloride, 5g of acryloyloxyethyltrimethylammonium chloride, 4g of potassium persulfate and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 5g of butylene dimethacrylate, 42g of acrylamide, 8g of sorbitan monostearate and 50g of kerosene are uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 700rpm for 15min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually increasing the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually decreasing the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of LAE-9, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 3.6 um.
Preparation of anionic emulsion: 50g of acrylic acid and 10g of itaconic acid are neutralized by 80g of liquid caustic soda under stirring at room temperature, and 0.8g of potassium persulfate and 30g of deionized water are added and mixed uniformly to prepare an aqueous phase. 0.5g of butylene dimethacrylate, 6g of acrylamide, 8g of sorbitan monostearate and 50g of kerosene are uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 1000rpm for 40min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of LAE-9, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 4g of cationic emulsion and 96g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 9:
preparation of cationic emulsion: 5g of dimethyldiallylammonium chloride, 5g of acryloyloxyethyldimethylbenzylammonium chloride, 2.5g of azobisisobutyramidine oxazoline hydrochloride and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 2.4g N' N-methylene bisacrylamide, 30g ethyl acrylate, 8g sorbitan monooleate and 40g kerosene were uniformly mixed to prepare an oil phase composition. Adding the water phase into the oil phase, and stirring at 600rpm for 15min to obtain stable emulsion. Heating the emulsion in the reactor to 30-40 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO8, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.5 um.
Preparation of anionic emulsion: 50g of acrylic acid and 10g of fumaric acid were neutralized with 75g of liquid base at room temperature with stirring, and 0.6g of azobisisobutyramidine oxazoline hydrochloride and 30g of deionized water were added and mixed uniformly to prepare an aqueous phase. 0.8g of N' -N-methylene bisacrylamide, 5g of ethyl acrylate, 8g of sorbitan sesquioleate and 40g of kerosene were uniformly mixed to form an oil phase composition. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 30-40 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO8, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 5g of cationic emulsion and 95g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
Example 10:
preparation of cationic emulsion: 5g of acryloyloxyethyltrimethylammonium chloride, 10g of acryloyloxyethyldimethylbenzylammonium chloride, 4g of azobisisobutyramidine hydrochloride and 30g of deionized water were mixed uniformly with stirring at room temperature to prepare an aqueous phase. 4g of pentaerythritol trivinyl ester, 35g of styrene, 10g of diethylene glycol monolaurate and 40g of kerosene were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring at 600rpm for 15min to obtain stable emulsion. Heating the emulsion in the reactor to 40-50 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO8, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.8 um.
Preparation of anionic emulsion: 70g of acrylic acid was neutralized with 90g of liquid base under stirring at room temperature, and 0.8g of azobisisobutyramidine hydrochloride and 30g of deionized water were added and mixed uniformly to prepare an aqueous phase. 0.8g of pentaerythritol trivinyl ester, 5g of styrene, 10g of diethylene glycol monolaurate and 40g of kerosene were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 40-50 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of AEO8, and stirring for 10 min. The particle size of the anionic emulsion is less than 1 μm.
Respectively taking 10g of cationic emulsion and 90g of anionic emulsion, and uniformly mixing the two to obtain a finished product. Comparative example 1:
an anionic polymer emulsion was prepared as in example 1 and removed for use.
Comparative example 2:
an anionic polymer emulsion was prepared as in example 4 and removed for use.
Comparative example 3:
an anionic polymer emulsion was prepared as in example 7 and removed for use.
Comparative example 4:
the resulting cationic polymer emulsion was prepared as in example 1 and removed for use.
Comparative example 5:
the resulting cationic polymer emulsion was prepared as in example 4 and removed for use.
Comparative example 6:
the resulting cationic polymer emulsion was prepared as in example 7 and removed for use.
Comparative example 7:
a cationic polymer was prepared according to the method of patent document CN107690494A, wherein 9g of acrylamide solution (mass fraction 50%), 71g of methyl chloride quaternized dimethylaminoethyl methacrylate (mass fraction 75%), 20g of deionized water, 0.04g of methylene bisacrylamide, 0.45g of sodium formate, and pH was adjusted to 3.4-4.8 with phosphoric acid, and the polymer composition was 92.0% by weight of quaternized dimethylaminoethyl methacrylate and 8.0% by weight of acrylamide; after stirring for 30 minutes, the monomer solution was cooled to 10 ℃, transferred to a dewar flask, purged with nitrogen for 15 minutes to remove oxygen, and polymerized by adding adiabatically: 0.02g of sodium persulfate and 0.01g of the molar salt, 0.08g of azobisisobutyronitrile, the temperature of the solution spontaneously rose to 75 ℃ within 2 hours and was then maintained at 75 ℃ for a further 2 hours. Drying for 4 hours at 150 ℃ to obtain the finished product.
Comparative example 8:
a cationic polymer prepared according to the method of patent document CN102482619A, wherein 47g of dimethylamino ethyl methacrylate methyl chloride quaternary ammonium salt, 6g of acrylamide, 0.03g of diethylenetriamine pentaacetic acid pentasodium salt, 14g of water, 0.03g of methylene bisacrylamide and 0.4g of sodium formate are mixed together to obtain an aqueous phase, and the pH value is adjusted to 4.0-6.0 by using citric acid; mixing 2g of sorbitan monooleate, 5.5g of a polymer stabilizer, 19g of white mineral oil and 6g of a dearomatized hydrocarbon solvent together to obtain an oil phase; the oil phase and the water phase are mixed together in a reactor under high shear rate to prepare a water-in-oil emulsion, then the water-in-oil emulsion is sprayed with nitrogen to remove oxygen, and an aqueous solution of sodium metabisulfite and tert-butyl peroxide is added to start the polymerization. After the emulsion reaches the highest temperature, the emulsion is kept for 60 minutes at the temperature of 65 ℃, and finally the finished product is obtained. Comparative example 9:
preparation of cationic emulsion: 14g of dimethyldiallylammonium chloride, 2g of potassium persulfate, 34g of acrylamide and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 2g diallyl phthalate, 5g sorbitan monooleate and 35g kerosene were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring and emulsifying at 1000rpm for 15min to obtain stable emulsion. Heating the emulsion in the flask to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 1.2 um.
Preparation of anionic emulsion: 50g of acrylic acid is neutralized by 70g of liquid alkali under the condition of stirring at room temperature, 0.5g of potassium persulfate, 5g of acrylamide and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 2g of diallyl phthalate, 5g of sorbitan monooleate and 35g of kerosene are mixed uniformly to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min.
Respectively taking 15g of cationic emulsion and 85g of anionic emulsion, and uniformly mixing the two to obtain a finished product. Comparative example 10:
cationic, anionic polymer emulsions were prepared as in example 1.
Respectively taking 30g of cationic emulsion and 70g of anionic emulsion, and uniformly mixing the two to obtain a finished product. Comparative example 11:
preparation of cationic emulsion: 14g of dimethyldiallylammonium chloride, 2g of potassium persulfate, 34g of acrylamide and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 2g diallyl phthalate, 5g sorbitan monooleate and 35g kerosene were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring and emulsifying at 700rpm for 10min to obtain stable emulsion. Heating the emulsion in the flask to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 3.6 um.
Preparation of anionic emulsion: 50g of acrylic acid is neutralized by 70g of liquid alkali under the condition of stirring at room temperature, 0.5g of potassium persulfate, 5g of acrylamide and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 8g of diallyl phthalate, 5g of sorbitan monooleate and 35g of kerosene are mixed uniformly to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min.
Respectively taking 15g of cationic emulsion and 85g of anionic emulsion, and uniformly mixing the two to obtain a finished product. Comparative example 12:
preparation of cationic emulsion: 14g of dimethyldiallylammonium chloride, 2g of potassium persulfate, 34g of acrylamide and 30g of deionized water were mixed uniformly at room temperature with stirring to obtain an aqueous phase. 2g diallyl phthalate, 5g sorbitan monooleate and 35g kerosene were uniformly mixed to form an oil phase. Adding the water phase into the oil phase, and stirring and emulsifying at 700rpm for 10min to obtain stable emulsion. Heating the emulsion in the flask to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after 15min of reaction, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min. The average particle diameter Z-average of the cationic emulsion was measured to be 4.0 um.
Preparation of anionic emulsion: 50g of acrylic acid is neutralized by 70g of liquid alkali under the condition of stirring at room temperature, 0.5g of potassium persulfate, 5g of acrylamide and 30g of deionized water are added and mixed uniformly to prepare a water phase substance, and 0.5g of diallyl phthalate, 5g of sorbitan monooleate and 35g of kerosene are mixed uniformly to form an oil phase substance. Adding the water phase into the oil phase, and stirring at 1000rpm for 30min to obtain stable emulsion. Heating the emulsion in the reactor to 50-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after reacting for 15min, preserving the temperature for 2h at 65 ℃, cooling to room temperature, adding 3g of peregal O, and stirring for 10 min.
Respectively taking 15g of cationic emulsion and 85g of anionic emulsion, and uniformly mixing the two to obtain a finished product.
The products obtained in the above examples were subjected to the following performance tests:
1. white paste viscosity (i.e. pasting rate) test:
testing equipment: brookfield DV-II + Pro viscometer
Test conditions No. 6 rotor 20rpm
A5% strength thickener base paste was prepared with deionized water and the viscosity of the white slurry was measured at room temperature at a constant speed of 20 rpm.
Viscosity of acrylic acid type thickener: 21650 mPas
The viscosity of the cationic emulsion is less than 1500 mPas, and the partial emulsion has almost no viscosity.
2. And (3) testing salt resistance:
testing equipment: BrookFIELD viscometer, DV-2T
Test conditions No. 6 rotor 20rpm
The test method comprises the following steps: weighing 2g of sodium hexametaphosphate, 2g of anti-staining salt and 20g of urea in a 200mL beaker, adding 76g of deionized water to prepare a base solution, adding 12g of thickening agent, adding water to 84g, stirring for 10min at the rotation speed of 1500rpm by using a multifunctional dispersion machine until the slurry is fine, adding 100g of the prepared base solution until the slurry is fine, finally adding 6g of baking soda and 10g of 32% sodium acetate solution salt, stirring for 5min at the rotation speed of 1500rpm by using the multifunctional dispersion machine until the slurry is fine, taking down and placing for 30 min. The viscosity was measured.
3. Evaluation of the efficiency of removal of paste:
the test method comprises the following steps: and (3) sizing and drying the cloth, then rinsing until the cloth surface is not sticky any more, and recording the rinsing times at the moment, wherein the smaller the rinsing times, the higher the paste removal efficiency is.
Comparison of thickener effects:
Figure BDA0003371421630000241
Figure BDA0003371421630000251
as can be seen from the table above, the viscosity of the white slurry of the compounded thickener in the embodiment of the invention is increased by 46-130% compared with the viscosity of the anionic emulsion in the comparative example 1, and the thickening effect is obviously improved.
Comparative example 7 and comparative example 8, directly utilize cationic monomer and anionic monomer to polymerize simultaneously and prepare the thickening agent, the comparison of comparative example and example shows, directly utilize the thickening agent that cationic monomer and anionic monomer polymerized and obtained under the same amount, also can not reach the white thick liquid viscosity of the thickening agent after compounding, have proved that the direct synthesis method has certain limitation to the promotion of viscosity. Meanwhile, the comparison between examples 1 to 10 and comparative examples 7 and 8 shows that the paste removal speed of the examples is better than that of the comparative examples, and the probable reason is that the molecules obtained by polymerization of anions and cations are larger, the acting force on fibers is stronger, and the paste removal efficiency is lower. According to the invention, the anionic emulsion and the cationic emulsion are respectively prepared, and the anionic emulsion and the cationic emulsion are compounded to obtain the compound thickener, wherein the thickening effect of the compound thickener is superior to that of the emulsion obtained by anionic and cationic polymerization.
The comparison between examples 1, 4 and 7 and comparative examples 1 to 6 shows that the effect of single use of the cationic emulsion can not achieve the effect of compound use no matter the anionic emulsion or the cationic emulsion, and the effect of single use of the cationic emulsion even has almost no viscosity, which indicates that the effect of 1+1>2 can be obtained by compounding the cationic emulsion with high crosslinking degree and large particle size with the traditional anionic emulsion, and the performance of the traditional anionic thickener is greatly improved.
Comparative example 9 compared with the experimental conditions of example 1, there was no difference except that the stirring speed was increased at the time of the preliminary emulsification of the cationic emulsion, and it was confirmed that the cationic emulsion could function as a crosslinking site only when the particle size was large to a certain extent.
As can be seen from comparative example 10, the cationic emulsion should not be added in too much amount, and too much cation may cause charge destabilization, resulting in demulsification of the compounded emulsion.
Comparative examples 11 and 12 are the same as example 1 in other conditions, and the only difference is the addition amount of diallyl phthalate as a crosslinking agent, the more the amount of the crosslinking agent is, the larger the crosslinking degree of the corresponding anionic emulsion is, and the comparison shows that the anionic emulsion needs to meet a certain crosslinking degree range, the too high crosslinking degree (comparative example 11) or too low crosslinking degree (comparative example 12) and the synergistic effect with the cationic emulsion is worse, and the thickening effect of the prepared thickener is not obviously improved.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A complex thickener comprising an acrylic anionic emulsion and a cationic emulsion; the mass ratio of the cationic emulsion in the compound thickener is less than or equal to 20 percent;
when the thickening agent is used, the acrylic acid series anionic emulsion and the cationic emulsion are mutually attracted through the electrostatic action of anions and cations, the volume of an aggregate after the anionic emulsion is swelled is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickening agent is improved.
2. The compound thickener of claim 1, wherein the cationic emulsion is present in the compound thickener in a mass ratio of 3% to 15%;
the cationic emulsion is prepared from the following components in parts by weight: 1-40 parts of unsaturated cationic monomer, 5-70 parts of functional monomer, 1-10 parts of initiator, 0.1-5 parts of cross-linking agent, 2-5 parts of emulsifier, 15-30 parts of hydrocarbon solvent and 1-10 parts of phase inversion emulsifier.
3. The complex thickener according to claim 2, wherein said cationic emulsion is prepared from components comprising the following ranges of parts by weight: 5-20 parts of unsaturated cationic monomer, 15-30 parts of functional monomer, 2-4 parts of initiator, 1-5 parts of cross-linking agent, 2-5 parts of emulsifier, 15-30 parts of hydrocarbon solvent and 3-5 parts of phase inversion emulsifier.
4. The compound thickener according to claim 2 or 3, wherein the cationic emulsion is obtained by performing inverse suspension polymerization on the unsaturated cationic monomer, the crosslinking agent and the functional monomer in a hydrocarbon solvent under the action of the initiator and the emulsifier, and then performing phase inversion; wherein the unsaturated cationic monomer is selected from one or more of dimethyl diallyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and acryloyloxyethyl dimethyl benzyl ammonium chloride.
5. The complex thickener of claim 1 wherein said cationic emulsion has a particle size of 1-10 μm and said acrylic anionic emulsion has a particle size of less than 1 μm.
6. The compound thickener according to claim 1, wherein the acrylic acid-based anionic emulsion is obtained by performing inverse suspension polymerization on an unsaturated acidic monomer, a crosslinking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier and then performing phase inversion; the composition is prepared from the following components in parts by weight: 25-35 parts of unsaturated acidic monomer, 35-60 parts of liquid alkali, 0.2-0.5 part of initiator, 10-30 parts of deionized water, 0.01-0.1 part of cross-linking agent, 10-30 parts of functional monomer, 5-15 parts of emulsifier, 35-55 parts of hydrocarbon solvent and 3-5 parts of phase inversion emulsifier;
preferably, the functional monomer is one or more of acrylamide, methacrylamide, styrene, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.
7. The process for preparing a complex thickener according to any of claims 1 to 6, comprising the steps of:
(1) carrying out inverse suspension polymerization on an unsaturated cationic monomer, a cross-linking agent and a functional monomer in a hydrocarbon solvent under the action of an initiator and an emulsifier, and then carrying out phase inversion to obtain a cationic emulsion;
(2) unsaturated acidic monomers, cross-linking agents and functional monomers are subjected to reversed-phase suspension polymerization in a hydrocarbon solvent under the action of an initiator and an emulsifier and then phase inversion is carried out to generate acrylic acid series anionic emulsion;
(3) and (3) compounding the cationic emulsion obtained in the step (1) and the acrylic acid series anionic emulsion obtained in the step (2) to obtain the compound thickener.
8. The method of claim 7, wherein the method of preparing the cationic emulsion comprises the substeps of:
(1-1) dissolving unsaturated cationic monomers and functional monomers in water under the condition of stirring, adding an initiator and deionized water, and mixing to obtain a water phase substance;
(1-2) mixing the water phase substance prepared in the step (1) with an oil phase consisting of an emulsifier, a cross-linking agent and a hydrocarbon solvent under the stirring condition, and controlling the mechanical stirring speed at 600-800rpm for 10-30 minutes to obtain a stable pre-emulsion;
(1-3) heating the pre-emulsion obtained in the step (2) to 30-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after the reaction is finished, and preserving the temperature for 1-8 hours at 50-90 ℃ to obtain the polymerized emulsion, or
Controlling the temperature of the pre-emulsion in the step (2) to be 18-20 ℃, dropwise adding a sodium bisulfite aqueous solution into the pre-emulsion, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after the reaction is finished, and preserving the temperature at 50-90 ℃ for 1-8 hours to obtain a polymerized emulsion;
(1-4) cooling the polymerized emulsion to room temperature, adding a phase inversion emulsifier, and performing reverse emulsification for 10-20 minutes to obtain the cationic emulsion.
9. The method of claim 7, wherein the acrylic anionic emulsion is prepared by a method comprising the steps of:
(2-1) neutralizing an unsaturated acidic monomer with liquid alkali under stirring to pH 5-7, adding an initiator and deionized water, and mixing to obtain an aqueous phase;
(2-2) mixing the water phase substance prepared in the step (2-1) with an oil phase consisting of an emulsifier, a cross-linking agent and a hydrocarbon solvent under the stirring condition, and emulsifying for 30-50 minutes at the stirring speed of 1000-1500rpm to obtain a stable pre-emulsion;
(2-3) heating the pre-emulsion obtained in the step (2-2) to 30-60 ℃ under the protection of nitrogen, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 90 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 65-75 ℃ for 1.5-2 hours to obtain polymerized emulsion; or
Controlling the temperature of the pre-emulsion in the step (2-2) to be 18-20 ℃, dropwise adding a sodium bisulfite aqueous solution into the pre-emulsion, gradually starting the reaction, gradually raising the temperature of the system, controlling the reaction temperature not to exceed 80 ℃, gradually lowering the temperature after the reaction is finished, and preserving the heat at 60-70 ℃ for 1.5-2 hours; obtaining polymerized emulsion;
and (2-4) cooling the polymerized emulsion to room temperature, adding a phase inversion emulsifier, and performing reverse emulsification for 10-20 minutes to obtain the acrylic acid series anionic emulsion.
10. A method for improving the thickening effect of an acrylic acid type thickener is characterized in that a cationic emulsion is introduced into an acrylic acid type anionic emulsion thickener to form a complex thickener, so that the mass ratio of the cationic emulsion in the complex thickener is less than or equal to 20 percent;
when the thickening agent is used, the acrylic acid series anionic emulsion and the cationic emulsion are mutually attracted through the electrostatic action of anions and cations, the volume of an aggregate after the anionic emulsion is swelled is increased, the movement difficulty of polymer particles is increased, and the thickening effect of the thickening agent is improved.
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