CN108329421A - A kind of emulsifier for alkenyl succinic anhydride emulsification - Google Patents
A kind of emulsifier for alkenyl succinic anhydride emulsification Download PDFInfo
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- CN108329421A CN108329421A CN201810001631.3A CN201810001631A CN108329421A CN 108329421 A CN108329421 A CN 108329421A CN 201810001631 A CN201810001631 A CN 201810001631A CN 108329421 A CN108329421 A CN 108329421A
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- succinic anhydride
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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
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
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- 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
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- 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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- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a kind of emulsifiers for alkenyl succinic anhydride emulsification, it is to be caused to form polymer by initiator in the deionized water solution containing chain-transferring agent, chelating agent by function of tonic chord monomer, it is obtained after addition stabilizer by polymer and the obtained intermediate product of polynary aldehyde reaction, then into intermediate product；Function of tonic chord monomer is made of non-ionic monomer, chain alkyl allyl ammonium chloride, cationic monomer.Chain alkyl is introduced in emulsifier, it is obvious to the promotion of emulsification and efficiency；It is reacted with amido by polyaldehyde, forms cross-linked macromolecular structure, also more apparent for the promotion of emulsification, under the action of stabilizer, storage stability can reach six months or more.As ASA emulsifiers, in use, acting on ASA resistant to hydrolysis apparent, emulsion stability also gets a promotion after stabilizer has been used in emulsifier；There is good emulsification to the ASA of different length alkene chain, and the distribution of its emulsion particle diameter is good, stability is high.
Description
Technical field
The present invention relates to water soluble polymer technical field, more particularly to a kind of emulsifications for alkenyl succinic anhydride emulsification
Agent.
Background technology
Alkenyl succinic anhydride, abbreviation ASA are one of common response type neutral sizing agents in paper industry.Sizing is to make
One of very important process in paper industry can assign paper good water repelling property by sizing.Currently, ASA is mainly used
In gypsum mask paper, boxboard, liquid packet paper etc..ASA has many advantages, such as that impermeabilisation power is strong, and sizing curing is fast.
ASA structural formulas (V) are as follows：
Acid anhydrides in ASA molecular structures is its active group with reactive glue blending function, under the conditions of copy paper, ASA
Acid anhydrides in molecule forms ester bond with the hydroxyl reaction on cellulose macromolecule chain, on cellulose by the fixation of ASA molecules so that
ASA molecular orientations arrange, and the long alkenyl of hydrophobic is then directed toward outside paper page in ASA molecules, achievees the purpose that water resistant.ASA points
R in minor structure1、R2Difference will produce influence to ASA sizabilities, and general long-chain olefin is the tetramer of C3 fractions, five poly-
Body and the tripolymer of six aggressiveness and C 4 fraction, the tetramer.There is long-chain base in molecule good hydrophobicity, these long-chains to have
The arrangement of sequence is simultaneously covered in fiber surface, and chain is longer, then hydrophobicity is better, and sizing efficiency is also better.
But ASA is oil-based liquid, and it is not soluble in water, it needs to carry out live emulsification in paper plant before paper making wet part application,
The particle size range for emulsifying the particle formed is to be affected to the use of ASA, and ASA sizing efficiencies increase with the decline of Emulsion particle size
Add.But grain size is smaller, the hydrolysis rate of ASA is accelerated, and is not easy effectively to keep on fiber.Larger grain size can lead to lotion not
Stablize, reduces sizing efficiency, the selection of the quality of lotion and the hydrophobic chain structure of ASA and emulsifier is closely related, and hydrophobic chain
It is longer, it is more not easy to emulsify, therefore, ASA and emulsifier each other all have emulsifying effectiveness very great influence.In Patent No.
It is described in the patent of CN100363555C, CN100415991C, CN104781471A and page is used for ASA lotions and emulsifier
Or how the sizing of cardboard is prepared a kind of highly efficient although these sizing emulsions are partly used in paper industry
, be suitble to the emulsifier of different long short chain hydrophobic group ASA emulsifications, be in current ASA emulsifications industrial problem more outstanding it
One.
Patent No. CN102174777B, CN101553508B, CN104093900B, CN104592441A,
It is disclosed in the document of CN105531420A, CN104746388A and carries out ASA using the polyacrylamide being modified by glyoxal
Emulsification, the study found that there are still such as product storage stability deficiency, the problems of emulsion stability deficiency for such product.This
Researcher is invented the study found that may be that part aldehyde radical has neither part nor lot in reaction, these unreacted aldehyde radicals in storing process still
It can be reacted with amide group participation so that system molecular weight rises, or even excessive crosslinking occurs and generate jello not soluble in water,
This produces a very large impact polymer application effect and shelf-life, and especially when being used as emulsifier, these problems are particularly prominent
Go out.Meanwhile these polymer, after emulsifying ASA, the micella layer thickness for the micelle that emulsifier is formed is relatively thin, and structure is not tight enough
It is close, cause hydrone to be easier to enter in latex particle, ASA is caused to hydrolyze, sizing efficiency declines.
Invention content
The object of the present invention is to provide a kind of emulsifiers for alkenyl succinic anhydride emulsification, and length is introduced in emulsifier
Alkyl group, it is obvious to the promotion of emulsification and efficiency；It is reacted with amido by polyaldehyde, forms cross-linked macromolecular knot
Structure, it is also more apparent for the promotion of emulsification, meanwhile, under the action of stabilizer, storage stability can reach six
A month or more.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
A kind of emulsifier for alkenyl succinic anhydride emulsification, the emulsifier is to contain chain tra nsfer by function of tonic chord monomer
Agent, chelating agent deionized water solution in cause to form polymer by initiator, by the polymer and polynary aldehyde reaction system
Intermediate product, then be added into the intermediate product obtained after stabilizer；
The function of tonic chord monomer is made of non-ionic monomer, chain alkyl allyl ammonium chloride, cationic monomer；
The chain alkyl allyl ammonium chloride has general structure (I)：
Wherein：R3Indicate H or CH3；
R4Indicate C1~C6Straight chained alkyl；
R5、R6Indicate C1~C6Alkyl or
R7Indicate C14~C20Chain alkyl；
X indicates one kind in fluorine, chlorine, bromine, iodine；
The chain alkyl allyl ammonium chloride accounts for the 2-30wt% of the function of tonic chord monomer mass.
Preferably, the non-ionic monomer by non-ionic monomer A, non-ionic monomer B, non-ionic monomer C one kind or
More than one are constituted；
The non-ionic monomer A is by acrylamide, Methacrylamide, N- methyl (methyl) acrylamide, N- (3,3- bis-
Methyl-propyl) acrylamide, N- (3,3- dimethyl propyls) Methacrylamide, N- hydroxypropylacrylamides, N, N- methylene
One or more in bisacrylamide, N tert butyl acrylamide, allyl amine, diallylamine, triallylamine
It constitutes；
General structure (II) is：
Wherein：R8Indicate H or CH3；
R9Indicate C1~C6Straight chained alkyl orR12、R13
Indicate C2~C4Straight chained alkyl or
R10、R11Indicate C1~C6Alkyl or
One or more in non-ionic monomer B substances described in general structure (II) are constituted；
Non-ionic monomer C is by acrylonitrile, n-vinyl pyrrolidone, vinylpyridine, vinylacetate, methacrylic acid
One kind in ester, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, vinyl alcohol
Or more than one compositions；
The non-ionic monomer accounts for the 15-93wt% of the function of tonic chord monomer mass.
Preferably, the cationic monomer is to pass through quaternizing agent by general structure (III) and/or general structure (IV)
Act on the quaternary ammonium salt formed；
Wherein：R14Indicate H or CH3；
R15Indicate C1~C6Straight chained alkyl orR18、
R19Indicate C2~C4Straight chained alkyl or
R16、R17Indicate C1~C6Alkyl or
Wherein：R20、R21Indicate H or CH3；
R22、R23Indicate C1~C6Straight chained alkyl；
R24Indicate H or C1~C6Straight chained alkyl orR25Indicate C1~C6Straight chained alkyl；
R26Indicate H or CH3；
The cationic monomer accounts for the 5-80wt% of the function of tonic chord monomer mass.
It is highly preferred that the quaternizing agent is by chloromethanes, chloroethanes, benzyl chloride, allyl chloride, dimethyl suflfate, sulphur
One or more kinds of compositions in diethyl phthalate.
Preferably, the chelating agent is disodium EDTA and/or diethylene triamine pentacetic acid (DTPA) sodium salt, the chela
The quality of mixture is the 0.005-0.1wt% of all substances gross mass in entire reaction system.
Preferably, the chain-transferring agent is by C1-C4Lower aliphatic alcohols, benzyl alcohol, hypophosphites, formates, alkyl sulfonic acid
One or more kinds of compositions in salt, allylsulfonate, methallylsulfonic acid salt, mercaptoethanol, alkyl hydrosulfide, it is described
The quality of chain-transferring agent is the 0.01-1wt% of the function of tonic chord monomer mass；The chain-transferring agent, for regulating and controlling the emulsification
The weight average molecular weight of agent is between 5 ten thousand to 200 ten thousand.
Preferably, the initiator is azo-initiator, peroxide initiator, is made of Oxidizing and Reducing Agents
One kind in redox initiator, the quality of the initiator are the 0.001-0.1wt% of the function of tonic chord monomer mass；
The azo-initiator is by 2,2- azos two (2- amidine propanes) dihydrochloride (V-50), two (2- of 2,2- azos
Imidazolinyl propane) dihydrochloride (VA-044), 2,2- azodiisobutyronitriles (AIBN) or 2, (2, the 4- dimethyl-pentens of 2- azos two
Nitrile) one or more kinds of in (ABVN) constitute；
The peroxide initiator is by ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide
One or more kinds of compositions in hydrogen, dibenzoyl peroxide, the peroxidating trimethylacetic acid tert-butyl ester；
In the redox initiator：
The oxidant is by ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, peroxidating
One or more kinds of compositions in dibenzoyl, the peroxidating trimethylacetic acid tert-butyl ester；The reducing agent is by sodium hydrogensulfite, sulfurous
One kind in sour sodium, sodium thiosulfate, sodium dithionite, ferrous sulfate, triethylamine, triethanolamine, tetramethylethylenediamine or
More than one are constituted；
Wherein, the quality proportion of the oxidant and the reducing agent is 1:2-2:1.
Preferably, the polyaldehyde is by glyoxal, malonaldehyde, butanedial, glutaraldehyde, hexandial, paraformaldehyde, hydroxyl-
One or more kinds of compositions in 1,4- butanedial, furans dialdehyde, 2- hydroxyl hexandials.
Preferably, the stabilizer is by urea, sodium hydrogensulfite, sodium pyrosulfite, sodium phosphate, disodium hydrogen phosphate, phosphoric acid
One or more kinds of compositions in sodium dihydrogen；The amount of the substance of the stabilizer is the 0.1-1 of the amount of the polyaldehyde substance
Times.
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art：A kind of use of the present invention
In the emulsifier of alkenyl succinic anhydride emulsification, there is the cationic polyacrylamide polymer of chain alkyl structure by preparation,
Under the action of stabilizer, prepared polymer storage stability greatly enhances；This polymer is used as ASA emulsifiers
When, ASA resistant to hydrolysis is acted on obviously, meanwhile, emulsion stability also gets a promotion after stabilizer has been used in emulsifier；This
Outside, prepared polymer has good emulsification to the ASA of different length alkene chain, and the distribution of its emulsion particle diameter is good
Good, stability is high.
Specific implementation mode
Technical scheme of the present invention is further elaborated with reference to specific embodiment.
A kind of above-mentioned emulsifier for alkenyl succinic anhydride emulsification, emulsifier is to contain chain tra nsfer by function of tonic chord monomer
Agent, chelating agent deionized water solution in cause to form polymer by initiator, during polymer and polynary aldehyde reaction are made
Between product, then be added into intermediate product obtained after stabilizer.
Function of tonic chord monomer is made of non-ionic monomer, chain alkyl allyl ammonium chloride, cationic monomer.
Chain alkyl allyl ammonium chloride has general structure (I)：
Wherein：R3Indicate H or CH3；
R4Indicate C1~C6Straight chained alkyl；
R5、R6Indicate C1~C6Alkyl or
R7Indicate C14~C20Chain alkyl；
X indicates one kind in fluorine, chlorine, bromine, iodine；
Chain alkyl allyl ammonium chloride accounts for the 2-30wt% of the function of tonic chord monomer mass.
By introducing chain alkyl allyl ammonium chloride, the chain alkyl carried is to improving polymer emulsified ASA efficiency
Very useful with emulsion intercalation method, after ASA sizings, not only ASA provides longer hydrophobic chain, emulsifier point with fiber-reactive
Chain alkyl in son also plays hydrophobic effect so that water resistance is further promoted.Its polymer is emulsified as ASA
Agent in use, ASA resistant to hydrolysis is acted on it is apparent, meanwhile, emulsion stability also obtains after stabilizer has been used in emulsifier
It is promoted；In addition, prepared polymer has good emulsification, and its emulsion particle diameter to the ASA of different length alkene chain
Distribution is good, and stability is high.
Non-ionic monomer is by one or more kinds of structures in non-ionic monomer A, non-ionic monomer B, non-ionic monomer C
At.
Non-ionic monomer A is by acrylamide, Methacrylamide, N- methyl (methyl) acrylamide, N- (3,3- dimethyl
Propyl) acrylamide, N- (3,3- dimethyl propyls) Methacrylamide, N- hydroxypropylacrylamides, N, N- di-2-ethylhexylphosphine oxides third
One or more kinds of compositions in acrylamide, N tert butyl acrylamide, allyl amine, diallylamine, triallylamine.
General structure (II) is：
Wherein：R8Indicate H or CH3；
R9Indicate C1~C6Straight chained alkyl orR12、
R13Indicate C2~C4Straight chained alkyl or
R10、R11Indicate C1~C6Alkyl or
One or more in non-ionic monomer B substances described in general structure (II) are constituted.
Non-ionic monomer C is by acrylonitrile, n-vinyl pyrrolidone, vinylpyridine, vinylacetate, methacrylic acid
One kind in ester, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, vinyl alcohol
Or more than one compositions.
Non-ionic monomer accounts for the 15-93wt% of function of tonic chord monomer mass.
Non-ionic monomer is easy to form hydrogen bond between fiber, increases the binding force of emulsifier macromolecular and fiber, more sharp
It is attached on fiber in emulsification.
Cationic monomer is to act on the season formed by quaternizing agent by general structure (III) and/or general structure (IV)
Ammonium salt.
Wherein：R14Indicate H or CH3；
R15Indicate C1~C6Straight chained alkyl orR18、
R19Indicate C2~C4Straight chained alkyl or
R16、R17Indicate C1~C6Alkyl or
Wherein：R20、R21Indicate H or CH3；
R22、R23Indicate C1~C6Straight chained alkyl；
R24Indicate H or C1~C6Straight chained alkyl orR25Indicate C1~C6Straight chained alkyl；
R26Indicate H or CH3；
Cationic monomer accounts for the 5-80wt% of the function of tonic chord monomer mass.
Quaternizing agent is by one in chloromethanes, chloroethanes, benzyl chloride, allyl chloride, dimethyl suflfate, dithyl sulfate
Kind or more than one compositions.
It is more easy that the structure of the cationic monomer of introducing is combined with carboxyl negatively charged on fiber, with reacting for page
Property enhancing, meanwhile, after ASA is combined with page, in emulsifier grow hydrophobic chain and the hydrophobic chain on ASA together with stretch to outside page
Side improves the effect of page water resistant also helpful；Long hydrophobic chain is introduced in emulsifier macromolecular, to different carbon chain lengths
ASA has good combination, applicability stronger.
Chelating agent is disodium EDTA and/or diethylene triamine pentacetic acid (DTPA) sodium salt, the quality of the chelating agent
For the 0.005-0.1wt% of all substances gross mass in entire reaction system.
Chain-transferring agent is by C1-C4Lower aliphatic alcohols, benzyl alcohol, hypophosphites, formates, alkylsulfonate, allyl sulphur
One or more kinds of compositions in hydrochlorate, methallylsulfonic acid salt, mercaptoethanol, alkyl hydrosulfide, the chain-transferring agent
Quality is the 0.01-1wt% of the function of tonic chord monomer mass；The chain-transferring agent, for regulating and controlling dividing equally for the emulsifier again
Son amount (Mw) is between 5 ten thousand to 200 ten thousand.
Initiator is azo-initiator, peroxide initiator, is drawn by the redox that Oxidizing and Reducing Agents forms
One kind in agent is sent out, the quality of initiator is the 0.001-0.1wt% of main function monomer quality.
Azo-initiator is by 2,2- azos two (2- amidine propanes) dihydrochloride (V-50), (the 2- imidazoles of 2,2- azos two
Quinoline base propane) dihydrochloride (VA-044), 2,2- azodiisobutyronitriles (AIBN) or 2,2- azos two (2,4- methyl pentane nitrile)
(ABVN) one or more kinds of compositions in.
Peroxide initiator is by ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, mistake
Aoxidize one or more kinds of compositions in dibenzoyl, the peroxidating trimethylacetic acid tert-butyl ester.
In redox initiator：
Oxidant is by ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, diphenyl peroxide
One or more kinds of compositions in formyl, the peroxidating trimethylacetic acid tert-butyl ester；Reducing agent is by sodium hydrogensulfite, sodium sulfite, sulphur
One or more in sodium thiosulfate, sodium dithionite, ferrous sulfate, triethylamine, triethanolamine, tetramethylethylenediamine
It constitutes；Wherein, the quality proportion of oxidant and reducing agent is 1:2-2:1.
Polyaldehyde by glyoxal, malonaldehyde, butanedial, glutaraldehyde, hexandial, paraformaldehyde, hydroxyl -1,4- butanedial,
One or more kinds of compositions in furans dialdehyde, 2- hydroxyl hexandials.It is reacted with amido by polyaldehyde, it is big to form crosslinking
Molecular structure, it is obvious for the promotion of emulsification, there are quite a few or residual in the polymer described in document
A small amount of aldehyde radical for having neither part nor lot in reaction, these aldehyde radicals are reacted with the active group on cellulose macromolecule carries paper strength
Rising has an obvious effect, but researcher of the present invention the study found that these quite a few or it is remaining on a small quantity have neither part nor lot in reaction
Aldehyde radical very big hidden danger that product is brought in storing process, the gelling material for occurring not soluble in water in polymer may be caused
Matter, it is necessary to solve the problems, such as this by the way that stabilizer is added.
Stabilizer is by one in urea, sodium hydrogensulfite, sodium pyrosulfite, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate
Kind or more than one compositions；The amount of the substance of the stabilizer is 0.1-1 times of the amount of the polyaldehyde substance.By testing table
Bright, these stabilizers or compound are quite apparent for emulsifier stable storage function and effect, and the storage stability of product is super
Spend six months.
Emulsifier prepared by the present invention can significantly improve the emulsification of conventional polypropylene amides by introducing chain alkyl structure
Agent to the emulsifying effectiveness and stability of emulsion of the ASA of different length alkene chain, this polymer as ASA emulsifiers in use,
It is apparent to the effect of ASA resistant to hydrolysis, while under the action of stabilizer, the storage stability of emulsifier, which also obtains, to be obviously improved.
In addition, prepared polymer has good emulsification to the ASA of different length alkene chain, and the distribution of its emulsion particle diameter is good
Good, stability is high.
The emulsifier of the present invention is prepared below by 5 embodiments：
Embodiment 1
Equipped with thermometer, condenser pipe, nitrogen be passed through in the four-hole boiling flask of mouth and blender be added 220 parts of deionized waters,
40 parts of acrylamides, 3 parts of hexadecyldimethyl benzyl ammonium allyl ammonium chlorides (65%), 20 parts of methylacryoyloxyethyl trimethyl chlorine
Change ammonium (80%), 0.015 part of disodium EDTA, 0.1 part of sodium hypophosphite, stirring so that it is fully dissolved, adjust pH to
PH needed for initiation system turns speed to 300 revs/min, leads to nitrogen 30 minutes to remove oxygen, system temperature is adjusted to initiation
2 part 1% of ammonium persulfate aqueous solution initiation reaction is added after temperature, 1 part 1% of V50 aqueous solutions are added after 1-4 hours again simultaneously
The reaction was continued 1-3 hours, is cooled to 30-45 DEG C, is added dropwise glyoxal water solution, at the same with sodium hydrate aqueous solution adjust pH to
6.0-10.0 after reaching viscosity, after dilute sulfuric acid termination reaction is added, is then added sodium metabisulfite solution, stirs 1 hour, then
With dilute sulfuric acid tune pH to 2.5-4.0 to get emulsifier.
Embodiment 2
Equipped with thermometer, condenser pipe, nitrogen be passed through in the four-hole boiling flask of mouth and blender be added 225 parts of deionized waters,
32 parts of acrylamides, 0.02 part of N, N- methylene-bisacrylamides, 3 parts of solution properties (65%),
32 parts of dimethyl diallyl ammonium chlorides (60%), 0.015 part of diethylene triamine pentacetic acid (DTPA) sodium salt, 0.5 part of isopropanol, stirring make
It is fully dissolved, and adjusts pH needed for pH to initiation system, turns speed to 300 revs/min, leads to nitrogen 30 minutes to remove oxygen,
System temperature is adjusted to the ammonium persulfate aqueous solution initiation reaction of 2 part 1% of addition after initiation temperature, is added again after 1-4 hours
Enter 1 part 1% of V50 aqueous solutions and the reaction was continued 1-3 hours, be cooled to 30-45 DEG C, glutaraldehyde water solution is added dropwise, while using carbon
Acid sodium aqueous solution adjusts pH to 6.0-10.0, and after reaching viscosity, after dilute hydrochloric acid termination reaction is added, sodium pyrosulfite is then added
And urea liquid, it stirs 1 hour, then with dilute hydrochloric acid tune pH to 2.5-4.0 to get emulsifier.
Embodiment 3
Equipped with thermometer, condenser pipe, nitrogen be passed through in the four-hole boiling flask of mouth and blender be added 225 parts of deionized waters,
32 parts of acrylamides, 0.02 part of N, N- methylene-bisacrylamides, 3 parts of solution properties (65%),
32 parts of dimethyl diallyl ammonium chlorides (60%), 0.015 part of disodium EDTA, 0.5 part of isopropanol, stirring make it
Fully dissolving adjusts pH needed for pH to initiation system, turns speed to 300 revs/min, logical nitrogen 30 minutes will to remove oxygen
System temperature is adjusted to the ammonium persulfate aqueous solution initiation reaction of 2 part 1% of addition after initiation temperature, and 1 is added again after 1-4 hours
Simultaneously the reaction was continued 1-3 hours for the V50 aqueous solutions of part 1%, is cooled to 30-45 DEG C, butanedial aqueous solution is added dropwise, while using hydroxide
Aqueous solutions of potassium adjust pH to 6.0-10.0, after reaching viscosity, be added dilute sulfuric acid terminate reaction after, then be added sodium hydrogensulfite and
Disodium phosphate soln stirs 1 hour, then with dilute sulfuric acid tune pH to 2.5-4.0 to get emulsifier.
Embodiment 4
It is being passed through 225 parts of deionized waters, 2 of addition in the four-hole boiling flask of mouth and blender equipped with thermometer, condenser pipe, nitrogen
Part sulfuric acid (50%), 32 parts of acrylamides, 0.02 part of N, N- methylene-bisacrylamides, 3 parts of octadecyldimethyl allyls
Ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chlorides (60%), 0.015 part of disodium EDTA, 0.5 part it is different
Propyl alcohol, stirring make it fully dissolve, and adjust pH needed for pH to initiation system, turn speed to 300 revs/min, lead to nitrogen 30 minutes
To remove oxygen, system temperature is adjusted to the ammonium persulfate aqueous solution initiation reaction of 2 part 1% of addition after initiation temperature, 1-4 is small
When after 1 part 1% of V50 aqueous solutions are added again and the reaction was continued 1-3 hour, be cooled to 30-45 DEG C, dropwise addition glyoxal and penta 2
Aldehyde aqueous solution, while pH to 6.0-10.0 is adjusted with sodium hydrate aqueous solution, after reaching viscosity, after acetic acid termination reaction is added,
Then sodium pyrosulfite and sodium dihydrogen phosphate is added, stirs 1 hour, then with acetic acid tune pH to 2.5-4.0 to get emulsification
Agent.
Embodiment 5
It is being passed through 225 parts of deionized waters, 2 of addition in the four-hole boiling flask of mouth and blender equipped with thermometer, condenser pipe, nitrogen
Part sulfuric acid (50%), 32 parts of acrylamides, 0.02 part of N, N- methylene-bisacrylamides, 3 parts of octadecyldimethyl allyls
Ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chlorides (60%), 0.015 part of disodium EDTA, 0.5 part it is different
Propyl alcohol, stirring make it fully dissolve, and adjust pH needed for pH to initiation system, turn speed to 300 revs/min, lead to nitrogen 30 minutes
To remove oxygen, system temperature is adjusted to the ammonium persulfate aqueous solution initiation reaction of 2 part 1% of addition after initiation temperature, 1-4 is small
When after 1 part 1% of V50 aqueous solutions are added again and the reaction was continued 1-3 hour, be cooled to 30-45 DEG C, dropwise addition 2- hydroxyl hexandials
And glyoxal water solution, while pH to 6.0-10.0 is adjusted with potassium hydroxide aqueous solution, after reaching viscosity, dilute sulfuric acid is added and terminates
After reaction, solution of sodium bisulfite is then added, stirs 1 hour, then with dilute sulfuric acid tune pH to 2.5-4.0 to get emulsifier.
Embodiment 6
It is being passed through 225 parts of deionized waters, 2 of addition in the four-hole boiling flask of mouth and blender equipped with thermometer, condenser pipe, nitrogen
Part sulfuric acid (50%), 32 parts of acrylamides, 0.02 part of N, N- methylene-bisacrylamides, 3 parts of octadecyldimethyl allyls
Ammonium chloride (65%), 32 parts of dimethyl diallyl ammonium chlorides (60%), 0.015 part of disodium EDTA, 0.5 part it is different
Propyl alcohol, stirring make it fully dissolve, and adjust pH needed for pH to initiation system, turn speed to 300 revs/min, lead to nitrogen 30 minutes
To remove oxygen, system temperature is adjusted to the ammonium persulfate aqueous solution initiation reaction of 2 part 1% of addition after initiation temperature, 1-4 is small
When after 1 part 1% of V50 aqueous solutions are added again and the reaction was continued 1-3 hour, be cooled to 30-45 DEG C, be added dropwise glyoxal with oneself two
Aldehyde aqueous solution, while pH to 6.0-10.0 is adjusted with sodium hydrate aqueous solution, after reaching viscosity, dilute hydrochloric acid is added and terminates reaction
Afterwards, sodium hydrogensulfite and urea liquid is then added, stirs 1 hour, then with dilute hydrochloric acid tune pH to 2.5-4.0 to get emulsifier.
By ASA emulsifiers prepared in above-mentioned 6 embodiments with comparative sample (by document CN104592441A patents
It is prepared by embodiment 2) be configured to 10% concentration, emulsifier solution pH is adjusted to citric acid it is 4.0 spare, then by the breast after dilution
Agent 175.0g is added in mulser, and constant temperature is to 20 DEG C in constant temperature water bath, and ASA is added, and (long-chain is with the alkene of 18 carbon atoms
Based on hydrocarbon) stoste 25.0g, 2min is emulsified in mulser.Using lotion after the detection emulsification of HORIBA LA-300 particle size analyzers
Particle diameter distribution, particle size results are as shown in table 1.
Table 1
1 experimental data of table shows that the emulsifier that embodiment is obtained is excellent to ASA emulsifiabilities, and average particle size distribution is narrow,
And average particle size distribution variation is little after 2 hours.
ASA sizabilities detect, using the method for test water resistance (point oozes the time).Water resistance refers to paper water resistant power
Size, test philosophy are to be indicated with number of seconds, the second for its water resistance by the time of paper infiltrated on one side needed for another side with water
Number is higher, indicates that water resistance is higher.
It is prepared by slurry：By be derived from paper mill be used to prepare plasterboard paper OCC slurry be made into 0.8% concentration its mashing
Degree is 30 ° of SR or so.Adding amount of medicines：10kg/ tons of slurries of aluminum sulfate；2kg/ tons of slurries of ASA lotions；0.3kg/ tons of retention and drainage aid agent
Slurry.
500g (4g oven dry stocks) prepared slurry is stirred into (speed of agitator is adjusted to 800rpm) in blender, uses liquid relief
Rifle pipettes 0.8ml 5% (i.e. 10kg/ tons of slurry) aluminum sulfate solution and reacts 30 seconds, pipettes what 0.16ml had just been emulsified with liquid-transfering gun
It is anti-to pipette 1.2ml0.1% retention and drainage aid agents (i.e. 0.3kg/ tons of slurry) with liquid-transfering gun for ASA lotions (i.e. 2kg/ tons of slurry) reaction 10 seconds
It answers 30 seconds, stops stirring, handsheet is parallel to copy three pieces quantitatively in 110g/m2 or so.Constant temperature and humidity 24 hours oozes method using point
Water resistance is tested, every group of sample takes 12 to ooze a timing, and takes water resistant angle value of its average value as final sample, experimental result
It is shown in Table 2.ASA additive amounts are 1.5kg/t, and testing example and comparative example lotion place different time its water resistant angle value, experiment knot
Fruit is shown in Table 3.
Table 2
Table 3
Table 2 and table 3 description of test prepared emulsifier of the invention has certain help to water resistance raising, meanwhile, ASA
Lotion hydrolysis rate is also improved.
Using the ASA emulsifiers prepared by embodiment 1, and using identical emulsification and water resistance test method, compare this
The prepared emulsifier of invention is to the grain size and water resistance after different chain length ASA emulsifications, and experimental result is as shown in table 4, table 5.
Table 4
Table 5
It is good that table 4,5 experimental data of table show that the ASA emulsifiers prepared using the present invention all have the ASA of different chain length
Good emulsifying effectiveness, emulsion particle diameter narrow distribution range, stability of emulsion are good.
By ASA emulsifiers prepared in embodiment with comparative sample (by the embodiment 2 in document CN104592441A patents
Prepare) it is configured to 8.0% concentration, with dilute sulfuric acid tune pH to 3.0, then it is placed in constant temperature water bath that constant temperature is to 50 DEG C, every 20 days
Liquid viscosity (25 DEG C, DV-II+Pro type Brookfield viscosimeters) is detected, and observes flow regime, experimental result is shown in Table 6.
Table 6
6 experimental data of table illustrates, passes through stability Follow-up observation, it can be seen that the emulsifier that the present invention is obtained is stablized
Property it is preferable, this to store the period extension have very great help.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and be implemented, and it is not intended to limit the scope of the present invention, all according to the present invention
Equivalent change or modification made by Spirit Essence should all cover within the scope of the present invention.
Claims (10)
1. a kind of emulsifier for alkenyl succinic anhydride emulsification, it is characterised in that：The emulsifier is existed by function of tonic chord monomer
Containing chain-transferring agent, chelating agent deionized water solution in by initiator cause to form polymer, by the polymer with it is more
First aldehyde reaction is made intermediate product, then is added into the intermediate product obtained after stabilizer；
The function of tonic chord monomer is made of non-ionic monomer, chain alkyl allyl ammonium chloride, cationic monomer；
The chain alkyl allyl ammonium chloride has general structure (I)：
Wherein：R3Indicate H or CH3；
R4Indicate C1~C6Straight chained alkyl；
R5、R6Indicate C1~C6Alkyl or
R7Indicate C14~C20Chain alkyl；
X indicates one kind in fluorine, chlorine, bromine, iodine；
The chain alkyl allyl ammonium chloride accounts for the 2-30wt% of the function of tonic chord monomer mass.
2. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：It is described it is non-from
Sub- monomer is made of the one or more in non-ionic monomer A, non-ionic monomer B, non-ionic monomer C；
The non-ionic monomer A is by acrylamide, Methacrylamide, N- methyl (methyl) acrylamide, N- (3,3- dimethyl
Propyl) acrylamide, N- (3,3- dimethyl propyls) Methacrylamide, N- hydroxypropylacrylamides, N, N- di-2-ethylhexylphosphine oxides third
One or more kinds of compositions in acrylamide, N tert butyl acrylamide, allyl amine, diallylamine, triallylamine；
General structure (II) is：
Wherein：R8Indicate H or CH3；
R9Indicate C1~C6Straight chained alkyl orR12、R13It indicates
C2~C4Straight chained alkyl or
R10、R11Indicate C1~C6Alkyl or
One or more in non-ionic monomer B substances described in general structure (II) are constituted；
Non-ionic monomer C by acrylonitrile, n-vinyl pyrrolidone, vinylpyridine, vinylacetate, methacrylate,
One kind in hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, vinyl alcohol or
More than one are constituted；
The non-ionic monomer accounts for the 15-93wt% of the function of tonic chord monomer mass.
3. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：It is described sun from
Sub- monomer is to act on the quaternary ammonium salt formed by quaternizing agent by general structure (III) and/or general structure (IV)；
Wherein：R14Indicate H or CH3；
R15Indicate C1~C6Straight chained alkyl orR18、R19Table
Show C2~C4Straight chained alkyl or
R16、R17Indicate C1~C6Alkyl or
Wherein：R20、R21Indicate H or CH3；
R22、R23Indicate C1~C6Straight chained alkyl；
R24Indicate H or C1~C6Straight chained alkyl orR25Indicate C1~C6Straight chained alkyl；R26Table
Show H or CH3；
The cationic monomer accounts for the 5-80wt% of the function of tonic chord monomer mass.
4. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 3, it is characterised in that：The quaternary ammonium
Change reagent by the one or more in chloromethanes, chloroethanes, benzyl chloride, allyl chloride, dimethyl suflfate, dithyl sulfate
It constitutes.
5. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：The chelating
Agent is disodium EDTA and/or diethylene triamine pentacetic acid (DTPA) sodium salt, and the quality of the chelating agent is entire reactant
The 0.005-0.1wt% of all substances gross mass in system.
6. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：The chain turns
Agent is moved by C1-C4Lower aliphatic alcohols, benzyl alcohol, hypophosphites, formates, alkylsulfonate, allylsulfonate, methyl alkene
The quality of one or more kinds of compositions in propyl sulfonic acid salt, mercaptoethanol, alkyl hydrosulfide, the chain-transferring agent is the master
The 0.01-1wt% of function monomer quality.
7. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 6, it is characterised in that：The chain turns
Agent is moved, for regulating and controlling the weight average molecular weight of the emulsifier between 5 ten thousand to 200 ten thousand.
8. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：The initiation
Agent is one kind in azo-initiator, peroxide initiator, the redox initiator that is made of Oxidizing and Reducing Agents,
The quality of the initiator is the 0.001-0.1wt% of the function of tonic chord monomer mass；
The azo-initiator is by 2,2- azos two (2- amidine propanes) dihydrochloride (V-50), (the 2- imidazoles of 2,2- azos two
Quinoline base propane) dihydrochloride (VA-044), 2,2- azodiisobutyronitriles (AIBN) or 2,2- azos two (2,4- methyl pentane nitrile)
(ABVN) one or more kinds of compositions in；
The peroxide initiator is by ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, mistake
Aoxidize one or more kinds of compositions in dibenzoyl, the peroxidating trimethylacetic acid tert-butyl ester；
In the redox initiator：
The oxidant is by ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, diphenyl peroxide
One or more kinds of compositions in formyl, the peroxidating trimethylacetic acid tert-butyl ester；The reducing agent is by sodium hydrogensulfite, sulfurous acid
One kind in sodium, sodium thiosulfate, sodium dithionite, ferrous sulfate, triethylamine, triethanolamine, tetramethylethylenediamine or one
Kind or more constitute；
Wherein, the quality proportion of the oxidant and the reducing agent is 1:2-2:1.
9. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：It is described polynary
Aldehyde is by glyoxal, malonaldehyde, butanedial, glutaraldehyde, hexandial, paraformaldehyde, hydroxyl -1,4- butanedial, furans dialdehyde, 2- hydroxyls
One or more kinds of compositions in base hexandial.
10. a kind of emulsifier for alkenyl succinic anhydride emulsification according to claim 1, it is characterised in that：It is described steady
Determine agent by urea, sodium hydrogensulfite, sodium pyrosulfite, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate one kind or it is a kind of with
Upper composition；The amount of the substance of the stabilizer is 0.1-1 times of the amount of the polyaldehyde substance.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824807A (en) * | 2019-01-25 | 2019-05-31 | 南京理工大学 | The preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC |
| CN112358569A (en) * | 2020-11-10 | 2021-02-12 | 爱森（中国）絮凝剂有限公司 | Preparation method of dimethyl diallyl ammonium chloride and acrylamide copolymer product for daily chemicals |
| US20220064348A1 (en) * | 2018-12-20 | 2022-03-03 | Basf Se | Polyacrylate polymer |
Citations (3)
| 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 |
-
2018
- 2018-01-02 CN CN201810001631.3A patent/CN108329421B/en active Active
Patent Citations (4)
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220064348A1 (en) * | 2018-12-20 | 2022-03-03 | Basf Se | Polyacrylate polymer |
| CN109824807A (en) * | 2019-01-25 | 2019-05-31 | 南京理工大学 | The preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC |
| CN109824807B (en) * | 2019-01-25 | 2021-02-12 | 南京理工大学 | Preparation method of PDAC (polymer dispersed acrylate) with serialized relative molecular mass and high monomer conversion rate |
| CN112358569A (en) * | 2020-11-10 | 2021-02-12 | 爱森（中国）絮凝剂有限公司 | Preparation method of dimethyl diallyl ammonium chloride and acrylamide copolymer product for daily chemicals |
| CN112358569B (en) * | 2020-11-10 | 2022-03-22 | 爱森（中国）絮凝剂有限公司 | Preparation method of dimethyl diallyl ammonium chloride and acrylamide copolymer product for daily chemicals |
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