CN108329421B - Emulsifier for emulsifying alkenyl succinic anhydride - Google Patents

Emulsifier for emulsifying alkenyl succinic anhydride Download PDF

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CN108329421B
CN108329421B CN201810001631.3A CN201810001631A CN108329421B CN 108329421 B CN108329421 B CN 108329421B CN 201810001631 A CN201810001631 A CN 201810001631A CN 108329421 B CN108329421 B CN 108329421B
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emulsifier
monomer
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sodium
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CN108329421A (en
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史亚鹏
何国锋
王勤
魏星光
陈炀
卫巧磊
郭志宇
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JIANGSU FEYMER TECHNOLOGY CO LTD
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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
    • C08F220/52—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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses an emulsifier for emulsifying alkenyl succinic anhydride, which is prepared by initiating a main functional monomer in a deionized water solution containing a chain transfer agent and a chelating agent through an initiator to form a polymer, reacting the polymer with polyaldehyde to prepare an intermediate product, and adding a stabilizer into the intermediate product; the main functional monomer consists of nonionic monomer, long-chain alkyl allyl ammonium chloride and cationic monomer. Long-chain alkyl is introduced into the emulsifier, so that the emulsification effect and the efficiency are obviously improved; through the reaction of the polybasic aldehyde and the amino, a cross-linked macromolecular structure is formed, the improvement on the emulsification is also obvious, and the storage stability can reach more than six months under the action of the stabilizer. When the ASA emulsifier is used as an ASA emulsifier, the hydrolysis resistance of ASA is obvious, and the stability of emulsion is improved after a stabilizer is used in the emulsifier; the emulsion has good emulsification effect on ASA with olefin chains of different lengths, and the emulsion has good particle size distribution and high stability.

Description

Emulsifier for emulsifying alkenyl succinic anhydride
Technical Field
The invention relates to the technical field of water-soluble polymers, and particularly relates to an emulsifier for emulsifying alkenyl succinic anhydride.
Background
Alkenyl succinic anhydride, ASA for short, is one of the reactive neutral sizing agents commonly used in the paper industry. Sizing is a very important process in the paper industry, by which good water resistance can be imparted to paper. At present, ASA is mainly used for gypsum mask paper, boxboard paper, liquid-bag paper and the like. The ASA has the advantages of strong anti-permeability, fast sizing and curing and the like.
The ASA structural formula (V) is shown below:
Figure BDA0001536948790000011
the acid anhydride in the ASA molecular structure is an active group with a reactive sizing effect, under the papermaking condition, the acid anhydride in the ASA molecules reacts with hydroxyl on a cellulose macromolecular chain to form ester bonds, the ASA molecules are fixed on cellulose, so that the ASA molecules are arranged in a directional manner, and the hydrophobic long-chain alkenyl in the ASA molecules points to the outside of a paper page, thereby achieving the purpose of water resistance. R in ASA molecular Structure1、R2In contrast, the ASA sizing properties are affected by the long chain olefins which are typically tetramers, pentamers and hexamers of the C3 fraction and trimers, tetramers of the C4 fraction. The long chain groups in the molecules have good hydrophobicity, the long chains are orderly arranged and cover the surface of the fiber, the longer the chain is, the better the hydrophobicity is, and the sizing effect is better.
ASA, however, is an oily liquid, insoluble in water, and requires on-site emulsification at the paper mill prior to wet end use in papermaking, the particle size range of the particles formed by emulsification being such as to have a greater impact on the use of ASA, which increases with decreasing emulsion particle size. However, the smaller the particle size, the faster the hydrolysis rate of ASA and the less effective it is on the fiber. The larger particle size results in an unstable emulsion, which lowers sizing efficiency, and the quality of the emulsion is closely related to the hydrophobic chain structure of ASA and the selection of emulsifier, while the longer the hydrophobic chain, the more difficult it is to emulsify, and therefore, both ASA and emulsifier have a very significant influence on the emulsification effect. The use of ASA emulsions and emulsifiers for sizing paper or board is described in patents CN100363555C, CN100415991C, CN104781471A, and although these sizing emulsions have been used in part in the paper industry, how to prepare a more efficient emulsifier suitable for emulsification of different long and short chain hydrophobic ASA is one of the more prominent industrial problems in current ASA emulsification.
Documents with patent numbers CN102174777B, CN101553508B, CN104093900B, CN104592441A, CN105531420A and CN104746388A disclose that ASA emulsification is performed by using polyacrylamide modified by glyoxal, and researches show that the products still have the problems of insufficient storage stability and insufficient emulsion stability. The researches of the researchers of the invention find that part of aldehyde groups are not reacted, and the unreacted aldehyde groups still react with amide groups during the storage process, so that the molecular weight of the system is increased, and even excessive crosslinking is generated to generate water-insoluble gel, which has great influence on the application effect and the shelf life of the polymer, and particularly has outstanding problems when being used as an emulsifier. Meanwhile, after the polymers emulsify ASA, micelle layers of colloidal particles formed by the emulsifier are thin in thickness and not compact enough in structure, so that water molecules easily enter latex particles, ASA is hydrolyzed, and the sizing effect is reduced.
Disclosure of Invention
The invention aims to provide an emulsifier for alkenyl succinic anhydride emulsification, long-chain alkyl is introduced into the emulsifier, and the emulsification effect and the efficiency are obviously improved; through the reaction of polyaldehyde and amido, a cross-linked macromolecular structure is formed, the promotion of emulsification is also obvious, and simultaneously, under the action of a stabilizer, the storage stability of the emulsion can reach more than six months.
In order to achieve the purpose, the invention adopts the technical scheme that:
an emulsifier for emulsifying alkenyl succinic anhydride is prepared by initiating a main functional monomer in a deionized water solution containing a chain transfer agent and a chelating agent by an initiator to form a polymer, reacting the polymer with a polyaldehyde to prepare an intermediate product, and adding a stabilizer into the intermediate product;
the main functional monomer consists of a nonionic monomer, long-chain alkyl allyl ammonium chloride and a cationic monomer;
the long-chain alkyl allyl ammonium chloride has a general structural formula (I):
Figure BDA0001536948790000031
wherein: r3Represents H or CH3；
R4Is represented by C1～C6The linear alkyl group of (1);
R5、R6is represented by C1～C6Alkyl or
Figure BDA0001536948790000032
R7Is represented by C14～C20A long-chain alkyl group of (a);
x represents one of fluorine, chlorine, bromine and iodine;
the long-chain alkyl allyl ammonium chloride accounts for 2-30 wt% of the mass of the main functional monomer.
Preferably, the nonionic monomer is composed of one or more of nonionic monomer A, nonionic monomer B and nonionic monomer C;
the nonionic monomer A is composed of one or more of acrylamide, methacrylamide, N-methyl (meth) acrylamide, N- (3, 3-dimethylpropyl) methacrylamide, N-hydroxypropylacrylamide, N-methylenebisacrylamide, N-tert-butylacrylamide, allylamine, diallylamine, and triallylamine;
the general structural formula (II) is as follows:
Figure BDA0001536948790000033
wherein: r8Represents H or CH3；
R9Is represented by C1～C6Straight chain alkyl of
Figure BDA0001536948790000034
R12、R13Is represented by C2～C4Straight chain alkane of (2)Base or
Figure BDA0001536948790000035
R10、R11Is represented by C1～C6Alkyl or
Figure BDA0001536948790000041
The nonionic monomer B is composed of one or more than one of substances described by a structural general formula (II);
the nonionic monomer C is composed of one or more of acrylonitrile, N-vinyl pyrrolidone, vinylpyridine, vinyl acetate, methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and vinyl alcohol;
the non-ionic monomer accounts for 15-93 wt% of the mass of the main functional monomer.
Preferably, the cationic monomer is quaternary ammonium salt formed by the structural general formula (III) and/or the structural general formula (IV) through the action of a quaternizing agent;
Figure BDA0001536948790000042
wherein: r14Represents H or CH3；
R15Is represented by C1～C6Straight chain alkyl of
Figure BDA0001536948790000043
R18、R19Is represented by C2～C4Straight chain alkyl of
Figure BDA0001536948790000044
R16、R17Is represented by C1～C6Alkyl or
Figure BDA0001536948790000045
Figure BDA0001536948790000046
Wherein: r20、R21Represents H or CH3；
R22、R23Is represented by C1～C6The linear alkyl group of (1);
R24represents H or C1～C6Straight chain alkyl of
Figure BDA0001536948790000051
R25Is represented by C1～C6The linear alkyl group of (1); r26Represents H or CH3；
The cationic monomer accounts for 5-80 wt% of the mass of the main functional monomer.
More preferably, the quaternizing agent is composed of one or more of methyl chloride, ethyl chloride, benzyl chloride, allyl chloride, dimethyl sulfate, and diethyl sulfate.
Preferably, the chelating agent is ethylene diamine tetraacetic acid disodium salt and/or diethylenetriamine pentaacetic acid sodium salt, and the mass of the chelating agent is 0.005-0.1 wt% of the total mass of all substances in the whole reaction system.
Preferably, the chain transfer agent is represented by C1-C4The low-grade fatty alcohol, benzyl alcohol, hypophosphite, formate, alkyl sulfonate, allyl sulfonate, methyl allyl sulfonate, mercaptoethanol and alkyl mercaptan, wherein the mass of the chain transfer agent is 0.01-1 wt% of the mass of the main functional monomer; the chain transfer agent is used for regulating and controlling the weight average molecular weight of the emulsifier to be between 5 and 200 ten thousand.
Preferably, the initiator is one of azo initiator, peroxide initiator and redox initiator consisting of oxidant and reducer, and the mass of the initiator is 0.001-0.1 wt% of the mass of the main functional monomer;
the azo initiator is composed of one or more of 2, 2-azobis (2-amidinopropane) dihydrochloride (V-50), 2-azobis (2-imidazolinylpropane) dihydrochloride (VA-044), 2-Azobisisobutyronitrile (AIBN) or 2, 2-azobis (2, 4-dimethylvaleronitrile) (ABVN);
the peroxide initiator is composed of one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and tert-butyl peroxypivalate;
among the redox initiators:
the oxidant is composed of one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and tert-butyl peroxypivalate; the reducing agent is composed of one or more of sodium bisulfite, sodium sulfite, sodium thiosulfate, sodium dithionite, ferrous sulfate, triethylamine, triethanolamine and tetramethylethylenediamine;
wherein the mass ratio of the oxidant to the reducing agent is 1:2-2: 1.
Preferably, the polyaldehyde is composed of one or more of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, paraformaldehyde, hydroxy-1, 4-succinaldehyde, furaldehyde, and 2-hydroxyadipaldehyde.
Preferably, the stabilizer is composed of one or more of urea, sodium bisulfite, sodium metabisulfite, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate; the amount of the stabilizer is 0.1 to 1 times of the amount of the polyaldehyde substance.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the emulsifier for emulsifying alkenyl succinic anhydride, the cationic polyacrylamide polymer with a long-chain alkyl structure is prepared, and the storage stability of the prepared polymer is greatly enhanced under the action of a stabilizer; when the polymer is used as an ASA emulsifier, the polymer has obvious hydrolysis resistance on ASA, and meanwhile, the stability of emulsion is improved after a stabilizer is used in the emulsifier; in addition, the prepared polymer has good emulsification effect on ASA with olefin chains of different lengths, and the emulsion has good particle size distribution and high stability.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
The emulsifier is prepared by initiating a main functional monomer in a deionized water solution containing a chain transfer agent and a chelating agent through an initiator to form a polymer, reacting the polymer with a polyaldehyde to prepare an intermediate product, and adding a stabilizer into the intermediate product.
The main functional monomer consists of nonionic monomer, long-chain alkyl allyl ammonium chloride and cationic monomer.
The long chain alkyl allyl ammonium chloride has the general structural formula (I):
Figure BDA0001536948790000061
wherein: r3Represents H or CH3；
R4Is represented by C1～C6The linear alkyl group of (1);
R5、R6is represented by C1～C6Alkyl or
Figure BDA0001536948790000071
R7Is represented by C14～C20A long-chain alkyl group of (a);
x represents one of fluorine, chlorine, bromine and iodine;
the long-chain alkyl allyl ammonium chloride accounts for 2-30 wt% of the mass of the main functional monomer.
The long-chain alkyl allyl ammonium chloride is introduced, the long-chain alkyl group of the long-chain alkyl allyl ammonium chloride greatly helps to improve the ASA emulsifying efficiency of the polymer and the stability of the emulsion, after ASA sizing, the ASA reacts with the fiber to provide a longer hydrophobic chain, and the long-chain alkyl group in the emulsifier molecule plays a role in hydrophobicity, so that the water resistance is further improved. When the polymer is used as an ASA emulsifier, the polymer has obvious hydrolysis resistance on ASA, and meanwhile, the stability of emulsion is improved after a stabilizer is used in the emulsifier; in addition, the prepared polymer has good emulsification effect on ASA with olefin chains of different lengths, and the emulsion has good particle size distribution and high stability.
The nonionic monomer is composed of one or more of nonionic monomer A, nonionic monomer B and nonionic monomer C.
The nonionic monomer A is composed of one or more of acrylamide, methacrylamide, N-methyl (meth) acrylamide, N- (3, 3-dimethylpropyl) methacrylamide, N-hydroxypropylacrylamide, N-methylenebisacrylamide, N-t-butylacrylamide, allylamine, diallylamine, and triallylamine.
The general structural formula (II) is as follows:
Figure BDA0001536948790000072
wherein: r8Represents H or CH3；
R9Is represented by C1～C6Straight chain alkyl of
Figure BDA0001536948790000073
R12、R13Is represented by C2～C4Straight chain alkyl of
Figure BDA0001536948790000074
R10、R11Is represented by C1～C6Alkyl or
Figure BDA0001536948790000081
The nonionic monomer B is composed of one or more than one of substances described by the general structural formula (II).
The nonionic monomer C is composed of one or more of acrylonitrile, N-vinyl pyrrolidone, vinylpyridine, vinyl acetate, methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and vinyl alcohol.
The non-ionic monomer accounts for 15-93 wt% of the main functional monomer.
The nonionic monomer is easy to form hydrogen bonds with the fibers, so that the binding force of the emulsifier macromolecules and the fibers is increased, and the emulsifying and attaching on the fibers are facilitated.
The cationic monomer is quaternary ammonium salt formed by the structural general formula (III) and/or the structural general formula (IV) through the action of a quaternizing agent.
Figure BDA0001536948790000082
Wherein: r14Represents H or CH3；
R15Is represented by C1～C6Straight chain alkyl of
Figure BDA0001536948790000083
R18、R19Is represented by C2～C4Straight chain alkyl of
Figure BDA0001536948790000084
R16、R17Is represented by C1～C6Alkyl or
Figure BDA0001536948790000085
Figure BDA0001536948790000086
Wherein: r20、R21Represents H or CH3；
R22、R23Is represented by C1～C6The linear alkyl group of (1);
R24represents H or C1～C6Straight chain alkyl of
Figure BDA0001536948790000091
R25Is represented by C1～C6The linear alkyl group of (1); r26Represents H or CH3；
The cationic monomer accounts for 5-80 wt% of the mass of the main functional monomer.
The quaternizing agent is one or more than one of chloromethane, chloroethane, benzyl chloride, allyl chloride, dimethyl sulfate and diethyl sulfate.
The structure of the introduced cationic monomer is easier to combine with the carboxyl with negative charge on the fiber, the reactivity with paper sheets is enhanced, and meanwhile, after the ASA is combined with the paper sheets, the long hydrophobic chain in the emulsifier extends to the outer side of the paper sheets together with the hydrophobic chain on the ASA, so that the improvement of the water resistance of the paper sheets is facilitated; the emulsifier macromolecule is introduced with a long hydrophobic chain, which has good combination effect on ASA with different carbon chain lengths and stronger applicability.
The chelating agent is ethylene diamine tetraacetic acid disodium salt and/or diethylenetriamine pentaacetic acid sodium salt, and the mass of the chelating agent is 0.005-0.1 wt% of the total mass of all substances in the whole reaction system.
Chain transfer agent from C1-C4The low-grade fatty alcohol, benzyl alcohol, hypophosphite, formate, alkyl sulfonate, allyl sulfonate, methyl allyl sulfonate, mercaptoethanol and alkyl mercaptan, wherein the mass of the chain transfer agent is 0.01-1 wt% of the mass of the main functional monomer; the chain transfer agent is used for regulating and controlling the weight average molecular weight (Mw) of the emulsifier to be between 5 and 200 ten thousand.
The initiator is one of azo initiator, peroxide initiator and redox initiator comprising oxidant and reductant, and has the mass of 0.001-0.1 wt% of the main functional monomer.
The azo initiator is composed of one or more of 2, 2-azobis (2-amidinopropane) dihydrochloride (V-50), 2-azobis (2-imidazolinylpropane) dihydrochloride (VA-044), 2-Azobisisobutyronitrile (AIBN), or 2, 2-azobis (2, 4-dimethylvaleronitrile) (ABVN).
The peroxide initiator is composed of one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and tert-butyl peroxypivalate.
Redox initiator:
the oxidant is one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and tert-butyl peroxypivalate; the reducing agent is composed of one or more of sodium bisulfite, sodium sulfite, sodium thiosulfate, sodium dithionite, ferrous sulfate, triethylamine, triethanolamine and tetramethylethylenediamine; wherein the mass ratio of the oxidant to the reducer is 1:2-2: 1.
The polyaldehyde is one or more of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, paraformaldehyde, hydroxy-1, 4-succinaldehyde, furaldehyde and 2-hydroxy adipaldehyde. A cross-linked macromolecular structure is formed by the reaction of a polybasic aldehyde and an amine group, the improvement of emulsification is obvious, a considerable part or a small amount of residual unreacted aldehyde groups exist in the polymer and have obvious effect on the improvement of the paper strength by the reaction of the aldehyde groups and active groups on cellulose macromolecules, but the researches of researchers of the invention find that the considerable part or the residual small amount of unreacted aldehyde groups have great hidden trouble on products in the storage process, which can cause water-insoluble gel substances to appear in the polymer, and the problem needs to be solved by adding a stabilizer.
The stabilizer is composed of one or more of urea, sodium bisulfite, sodium metabisulfite, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate; the amount of the stabilizer is 0.1 to 1 times of the amount of the polyaldehyde substance. Experiments show that the stabilizing agent or the compound has quite obvious effect on the storage stability of the emulsifier, and the storage stability of the product exceeds six months.
The emulsifying agent prepared by the invention can obviously improve the emulsifying effect and emulsion stability of the conventional polyacrylamide emulsifying agent to ASA with different lengths of olefin chains by introducing a long-chain alkyl structure, when the polymer is used as an ASA emulsifying agent, the polymer has obvious hydrolysis resistance to ASA, and simultaneously, under the action of a stabilizing agent, the storage stability of the emulsifying agent is also obviously improved. In addition, the prepared polymer has good emulsification effect on ASA with olefin chains of different lengths, and the emulsion has good particle size distribution and high stability.
The emulsifiers according to the invention are prepared by the following 5 examples:
example 1
Adding 220 parts of deionized water, 40 parts of acrylamide, 3 parts of hexadecyl dimethyl allyl ammonium chloride (65%), 20 parts of methacryloyloxyethyl trimethyl ammonium chloride (80%), 0.015 part of ethylene diamine tetraacetic acid disodium salt and 0.1 part of sodium hypophosphite into a four-neck flask provided with a thermometer, a condenser pipe, a nitrogen inlet and a stirrer, stirring to fully dissolve the deionized water, adjusting the pH value to the pH value required by an initiation system, regulating the rotation speed to 300 revolutions per minute, introducing nitrogen for 30 minutes to remove oxygen, adjusting the temperature of the system to the initiation temperature, adding 2 parts of 1% ammonium persulfate aqueous solution to initiate reaction, adding 1 part of 1% V50 aqueous solution again after 1-4 hours, continuing the reaction for 1-3 hours, cooling to 30-45 ℃, dropwise adding glyoxal aqueous solution, adjusting the pH value to 6.0-10.0 by using sodium hydroxide aqueous solution, and after reaching the viscosity, adding dilute sulfuric acid to terminate the reaction, adding sodium metabisulfite solution, stirring for 1 hr, and regulating pH to 2.5-4.0 with dilute sulfuric acid to obtain the emulsifier.
Example 2
Adding 225 parts of deionized water, 32 parts of acrylamide, 0.02 part of N, N-methylene bisacrylamide, 3 parts of octadecyl dimethyl allyl ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chloride (60%), 0.015 part of sodium diethylenetriamine pentaacetic acid and 0.5 part of isopropanol into a four-neck flask provided with a thermometer, a condenser pipe, a nitrogen inlet and a stirrer, stirring to fully dissolve the mixture, adjusting the pH to the pH required by an initiation system, regulating the rotation speed to 300 revolutions per minute, introducing nitrogen for 30 minutes to remove oxygen, adjusting the temperature of the system to the initiation temperature, adding 2 parts of 1% ammonium persulfate aqueous solution to initiate reaction, adding 1 part of 1% V50 aqueous solution again after 1-4 hours, continuing the reaction for 1-3 hours, cooling to 30-45 ℃, dropwise adding glutaraldehyde aqueous solution, and adjusting the pH to 6.0-10.0 by using sodium carbonate aqueous solution, after reaching the viscosity, adding dilute hydrochloric acid to stop the reaction, then adding sodium metabisulfite and urea solution, stirring for 1 hour, and then adjusting the pH value to 2.5-4.0 by using dilute hydrochloric acid to obtain the emulsifier.
Example 3
Adding 225 parts of deionized water, 32 parts of acrylamide, 0.02 part of N, N-methylene bisacrylamide, 3 parts of octadecyl dimethyl allyl ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chloride (60%), 0.015 part of ethylene diamine tetraacetic acid disodium salt and 0.5 part of isopropanol into a four-neck flask provided with a thermometer, a condenser pipe, a nitrogen inlet and a stirrer, stirring to fully dissolve the mixture, adjusting the pH to the pH required by an initiation system, regulating the rotation speed to 300 revolutions per minute, introducing nitrogen for 30 minutes to remove oxygen, adjusting the temperature of the system to the initiation temperature, adding 2 parts of 1% ammonium persulfate aqueous solution to initiate reaction, adding 1 part of 1% V50 aqueous solution again after 1-4 hours, continuing the reaction for 1-3 hours, cooling to 30-45 ℃, dropwise adding a succinic aldehyde aqueous solution, and adjusting the pH to 6.0-10.0 by using a potassium hydroxide aqueous solution, after the viscosity is reached, adding dilute sulfuric acid to stop the reaction, then adding sodium bisulfite and disodium hydrogen phosphate solution, stirring for 1 hour, and then adjusting the pH to 2.5-4.0 by using dilute sulfuric acid to obtain the emulsifier.
Example 4
Adding 225 parts of deionized water, 2 parts of sulfuric acid (50%), 32 parts of acrylamide, 0.02 part of N, N-methylene-bisacrylamide, 3 parts of octadecyl dimethyl allyl ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chloride (60%), 0.015 part of ethylene diamine tetraacetic acid disodium salt and 0.5 part of isopropanol into a four-neck flask provided with a thermometer, a condenser pipe, a nitrogen inlet and a stirrer, stirring to fully dissolve the mixture, adjusting the pH to the pH required by an initiation system, adjusting the rotation speed to 300 revolutions per minute, introducing nitrogen for 30 minutes to remove oxygen, adjusting the temperature of the system to the initiation temperature, adding 2 parts of 1% ammonium persulfate aqueous solution to initiate reaction, adding 1 part of 1% V50 aqueous solution again after 1-4 hours, continuing the reaction for 1-3 hours, cooling to 30-45 ℃, dropwise adding glyoxal and glutaraldehyde aqueous solution, simultaneously, adjusting the pH to 6.0-10.0 with sodium hydroxide aqueous solution, adding acetic acid to stop reaction after the viscosity is reached, then adding sodium metabisulfite and sodium dihydrogen phosphate solution, stirring for 1 hour, and adjusting the pH to 2.5-4.0 with acetic acid to obtain the emulsifier.
Example 5
Adding 225 parts of deionized water, 2 parts of sulfuric acid (50%), 32 parts of acrylamide, 0.02 part of N, N-methylene-bisacrylamide, 3 parts of octadecyl dimethyl allyl ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chloride (60%), 0.015 part of ethylene diamine tetraacetic acid disodium salt and 0.5 part of isopropanol into a four-neck flask provided with a thermometer, a condenser pipe, a nitrogen inlet and a stirrer, stirring to fully dissolve the mixture, adjusting the pH to the pH required by an initiation system, adjusting the rotation speed to 300 revolutions per minute, introducing nitrogen for 30 minutes to remove oxygen, adjusting the temperature of the system to the initiation temperature, adding 2 parts of 1% ammonium persulfate aqueous solution to initiate reaction, adding 1 part of 1% V50 aqueous solution again after 1-4 hours, continuing the reaction for 1-3 hours, cooling to 30-45 ℃, dropwise adding 2-hydroxyhexanal and glyoxal aqueous solution, simultaneously, regulating the pH to 6.0-10.0 by using a potassium hydroxide aqueous solution, adding dilute sulfuric acid to stop reaction after the viscosity is reached, then adding a sodium bisulfite solution, stirring for 1 hour, and regulating the pH to 2.5-4.0 by using dilute sulfuric acid to obtain the emulsifier.
Example 6
Adding 225 parts of deionized water, 2 parts of sulfuric acid (50%), 32 parts of acrylamide, 0.02 part of N, N-methylene-bisacrylamide, 3 parts of octadecyl dimethyl allyl ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chloride (60%), 0.015 part of ethylene diamine tetraacetic acid disodium salt and 0.5 part of isopropanol into a four-neck flask provided with a thermometer, a condenser pipe, a nitrogen inlet and a stirrer, stirring to fully dissolve the mixture, adjusting the pH to the pH required by an initiation system, adjusting the rotation speed to 300 revolutions per minute, introducing nitrogen for 30 minutes to remove oxygen, adjusting the temperature of the system to the initiation temperature, adding 2 parts of 1% ammonium persulfate aqueous solution to initiate reaction, adding 1 part of 1% V50 aqueous solution again after 1-4 hours, continuing the reaction for 1-3 hours, cooling to 30-45 ℃, dropwise adding glyoxal and hexanedial aqueous solution, simultaneously, adjusting the pH to 6.0-10.0 by using an aqueous solution of sodium hydroxide, adding dilute hydrochloric acid to stop reaction after the viscosity is reached, then adding a solution of sodium bisulfite and urea, stirring for 1 hour, and adjusting the pH to 2.5-4.0 by using dilute hydrochloric acid to obtain the emulsifier.
The ASA emulsifier prepared in the above 6 examples was prepared to a concentration of 10% with a control (prepared according to example 2 in the patent of document CN 104592441A), the pH of the emulsifier solution was adjusted to 4.0 with citric acid for use, 175.0g of the diluted emulsifier was added to an emulsifying machine, the temperature was maintained at 20 ℃ in a constant temperature water bath, 25.0g of an ASA (olefin having a long chain of 18 carbon atoms as a main component) stock solution was added, and the mixture was emulsified in the emulsifying machine for 2 min. The particle size distribution of the emulsified emulsion was measured using a HORIBA LA-300 particle size analyzer and the particle size results are shown in table 1.
TABLE 1
Figure BDA0001536948790000131
The experimental data in table 1 show that the emulsifier obtained in the example has excellent emulsifying property for ASA, the average particle size distribution is narrow, and the average particle size distribution does not change much after 2 hours.
ASA sizing performance detection adopts a method for testing water resistance (point penetration time). The water resistance refers to the water resistance of paper, and the testing principle is that the time required for water to permeate from one side of the paper to the other side is taken as the water resistance, and the water resistance is expressed in seconds, and the higher the seconds, the higher the water resistance is.
Preparing slurry: the OCC pulp obtained from paper mills for making gypsum board was prepared to a consistency of 0.8% and had a freeness of about 30 SR. The addition amount of the medicine is as follows: 10kg of aluminum sulfate per ton of pulp; ASA emulsion 2 kg/ton pulp; 0.3kg of retention and drainage aid per ton of pulp.
Stirring 500g (4g of oven dry pulp) of the prepared pulp in a stirrer (stirring rotation speed is adjusted to 800rpm), transferring 0.8ml of 5% (namely 10 kg/ton pulp) aluminum sulfate solution by using a liquid transfer gun for reaction for 30 seconds, transferring 0.16ml of freshly emulsified ASA emulsion (namely 2 kg/ton pulp) by using the liquid transfer gun for reaction for 10 seconds, transferring 1.2ml of 0.1% retention and filtration aid (namely 0.3 kg/ton pulp) by using the liquid transfer gun for reaction for 30 seconds, stopping stirring, and carrying out sheet making, wherein the quantitative amount is about 110g/m2, and carrying out parallel sheet making on three sheets. And (3) keeping the temperature and humidity constant for 24 hours, testing the water resistance by adopting a point infiltration method, timing 12 infiltration points of each group of samples, and taking the average value as the water resistance value of the final sample, wherein the experimental result is shown in table 2. The ASA addition amount is 1.5kg/t, the water resistance values of the emulsions of the test examples and the comparative examples are kept for different time, and the experimental results are shown in Table 3.
TABLE 2
Figure BDA0001536948790000141
TABLE 3
Figure BDA0001536948790000142
Figure BDA0001536948790000151
Tables 2 and 3 demonstrate that the emulsifiers prepared according to the invention contribute to the improvement of the water resistance and that the hydrolysis rate of the ASA emulsion is improved.
The ASA emulsifying agent prepared in example 1 was used, and the same emulsification and water resistance test methods were used to compare the particle size and water resistance of the emulsifying agent prepared in the present invention after emulsification of ASA with different chain lengths, and the experimental results are shown in tables 4 and 5.
TABLE 4
Figure BDA0001536948790000152
TABLE 5
Figure BDA0001536948790000153
Figure BDA0001536948790000161
The experimental data in tables 4 and 5 show that the ASA emulsifier prepared by the invention has good emulsifying effect on ASA with different chain lengths, narrow emulsion particle size distribution range and good emulsion stability.
The ASA emulsifier prepared in the examples was formulated with a control (prepared according to example 2 of the CN104592441A patent) to a concentration of 8.0%, adjusted to pH 3.0 with dilute sulfuric acid, and then placed in a constant temperature water bath to a constant temperature of 50 ℃ to measure the liquid viscosity every 20 days (25 ℃, DV-II + Pro Brookfield viscometer) and observe the flow conditions, the experimental results are shown in Table 6.
TABLE 6
Figure BDA0001536948790000162
Figure BDA0001536948790000171
The experimental data in table 6 show that, through the stability tracking observation, it can be seen that the emulsifier obtained by the present invention has better stability, which is very helpful for prolonging the storage period.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.

Claims (9)

1. An emulsifier for emulsification of alkenyl succinic anhydride, characterized by: the emulsifier is prepared by initiating a main functional monomer in a deionized water solution containing a chain transfer agent and a chelating agent through an initiator to form a polymer, reacting the polymer with polyaldehyde to prepare an intermediate product, and adding a stabilizer into the intermediate product;
the main functional monomer consists of a nonionic monomer, a monomer shown in a structural general formula (I), and a quaternary ammonium salt formed by a structural general formula (III) and/or a structural general formula (IV) through the action of a quaternizing agent;
general structural formula (I):
Figure FDA0002357716560000011
wherein: r3Represents H or CH3；
R4Is represented by C1～C6The linear alkyl group of (1);
R5、R6is represented by C1～C6Alkyl or
Figure FDA0002357716560000012
R7Is represented by C14～C20A long-chain alkyl group of (a);
x represents one of fluorine, chlorine, bromine and iodine;
the monomer shown in the structural general formula (I) accounts for 2-30 wt% of the mass of the main functional monomer;
Figure FDA0002357716560000013
wherein: r14Represents H or CH3；
R15Is represented by C1～C6Straight chain alkyl of
Figure FDA0002357716560000014
R18、R19Is represented by C2～C4Straight chain alkyl of
Figure FDA0002357716560000015
R16、R17Is represented by C1～C6Alkyl or
Figure FDA0002357716560000021
Figure FDA0002357716560000022
Wherein: r20、R21Represents H or CH3；
R22、R23Is represented by C1～C6The linear alkyl group of (1);
R24represents H or C1～C6Straight chain alkyl of
Figure FDA0002357716560000023
R25Is represented by C1～C6The linear alkyl group of (1); r26Represents H or CH3；
The quaternary ammonium salt formed by the structural general formula (III) and/or the structural general formula (IV) through the action of a quaternizing agent accounts for 5-80 wt% of the mass of the main functional monomer.
2. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the nonionic monomer is composed of one or more of nonionic monomer A, nonionic monomer B and nonionic monomer C;
the nonionic monomer A is composed of one or more of acrylamide, methacrylamide, N-methyl (meth) acrylamide, N- (3, 3-dimethylpropyl) methacrylamide, N-hydroxypropylacrylamide, N-methylenebisacrylamide, N-tert-butylacrylamide, allylamine, diallylamine, and triallylamine;
the general structural formula (II) is as follows:
Figure FDA0002357716560000024
wherein: r8Represents H or CH3；
R9Is represented by C1～C6Straight chain alkyl of
Figure FDA0002357716560000031
R12、R13Is represented by C2～C4Straight chain alkyl of
Figure FDA0002357716560000032
R10、R11Is represented by C1～C6Alkyl or
Figure FDA0002357716560000033
The nonionic monomer B is composed of one or more than one of substances described by a structural general formula (II);
the nonionic monomer C is composed of one or more of acrylonitrile, N-vinyl pyrrolidone, vinylpyridine, vinyl acetate, methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and vinyl alcohol;
the non-ionic monomer accounts for 15-93 wt% of the mass of the main functional monomer.
3. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the quaternizing agent is composed of one or more than one of chloromethane, chloroethane, benzyl chloride, allyl chloride, dimethyl sulfate and diethyl sulfate.
4. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the chelating agent is ethylene diamine tetraacetic acid disodium salt and/or diethylenetriamine pentaacetic acid sodium salt, and the mass of the chelating agent is 0.005-0.1 wt% of the total mass of all substances in the whole reaction system.
5. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the chain transfer agent is selected from C1-C4The chain transfer agent is composed of one or more of lower aliphatic alcohol, benzyl alcohol, hypophosphite, formate, alkyl sulfonate, allyl sulfonate, methyl allyl sulfonate, mercaptoethanol and alkyl mercaptan, and the mass of the chain transfer agent is the main function0.01-1 wt% of monomer mass.
6. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 5, wherein: the chain transfer agent is used for regulating and controlling the weight average molecular weight of the emulsifier to be between 5 and 200 ten thousand.
7. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the initiator is one of azo initiator, peroxide initiator and redox initiator consisting of oxidant and reducer, and the mass of the initiator is 0.001-0.1 wt% of that of the main functional monomer;
the azo initiator is composed of one or more of 2, 2-azobis (2-amidinopropane) dihydrochloride (V-50), 2-azobis (2-imidazolinylpropane) dihydrochloride (VA-044), 2-Azobisisobutyronitrile (AIBN) or 2, 2-azobis (2, 4-dimethylvaleronitrile) (ABVN);
the peroxide initiator is composed of one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and tert-butyl peroxypivalate;
among the redox initiators:
the oxidant is composed of one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and tert-butyl peroxypivalate; the reducing agent is composed of one or more of sodium bisulfite, sodium sulfite, sodium thiosulfate, sodium dithionite, ferrous sulfate, triethylamine, triethanolamine and tetramethylethylenediamine;
wherein the mass ratio of the oxidant to the reducing agent is 1:2-2: 1.
8. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the polybasic aldehyde is composed of one or more than one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, hexanedial, paraformaldehyde, hydroxy-1, 4-succinaldehyde, furan dialdehyde and 2-hydroxy hexanedial.
9. An emulsifier for emulsification of alkenyl succinic anhydride according to claim 1, wherein: the stabilizer is composed of one or more of urea, sodium bisulfite, sodium metabisulfite, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate; the amount of the stabilizer is 0.1 to 1 times of the amount of the polyaldehyde substance.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592441A (en) * 2013-10-31 2015-05-06 艺康美国股份有限公司 Dialdehyde-modified acrylamide polymer and preparation method thereof
CN104746388A (en) * 2013-12-25 2015-07-01 艺康美国股份有限公司 Method for improving sizing effect of ASA emulsion emulsified by macromolecular emulsifier
CN106928400A (en) * 2015-12-31 2017-07-07 埃科莱布美国股份有限公司 A kind of amphiphilic polymers and the alkenyl succinic anhydride emulsion comprising it

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592441A (en) * 2013-10-31 2015-05-06 艺康美国股份有限公司 Dialdehyde-modified acrylamide polymer and preparation method thereof
CN104746388A (en) * 2013-12-25 2015-07-01 艺康美国股份有限公司 Method for improving sizing effect of ASA emulsion emulsified by macromolecular emulsifier
WO2015100125A1 (en) * 2013-12-25 2015-07-02 Ecolab Usa Inc. Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier
CN106928400A (en) * 2015-12-31 2017-07-07 埃科莱布美国股份有限公司 A kind of amphiphilic polymers and the alkenyl succinic anhydride emulsion comprising it

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