CN108690165A - A kind of preparation method and applications of paper grade (stock) emulsion-type cationic dry strength agent - Google Patents
A kind of preparation method and applications of paper grade (stock) emulsion-type cationic dry strength agent Download PDFInfo
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- CN108690165A CN108690165A CN201810584362.8A CN201810584362A CN108690165A CN 108690165 A CN108690165 A CN 108690165A CN 201810584362 A CN201810584362 A CN 201810584362A CN 108690165 A CN108690165 A CN 108690165A
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- monomer
- emulsion
- dry strength
- strength agent
- acrylate
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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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
-
- 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
- D21H21/18—Reinforcing agents
Abstract
The present invention relates to a kind of preparation method and applications of paper grade (stock) emulsion-type cationic dry strength agent, including:(1) by cationic monomer, acrylate monomer is added reactor, is warming up to 80-85 DEG C, and causing polymerization with azodiisobutyronitrile is made the high molecular polymer with surface-active, and it is 5-6 to be dissolved in water and adjust pH;(2) acrylamide monomer, acrylate monomer, cross-linking monomer, cationic monomer and emulsifier are made into pre-emulsion, as dropping liquid A;Oxidant and deionized water are mixed and are made into dropping liquid B;(3) A, B are added drop-wise in reactor, reaction temperature is 80-85 DEG C, after completion of the reaction, cools down and supplements deionized water, blowing.The reaction product of the present invention is under the emulsification of the high molecular polymerization objects system with surface-active, effectively prevent local implode and gel phenomenon, stable emulsion system is formed, thus the gradually all moderate emulsion-type cationic dry strength agent of synthetic molecular weight, the degree of branching and viscosity.
Description
Technical field
The invention belongs to paper strengthening agent technical fields, and in particular to a kind of system of paper grade (stock) emulsion-type cationic dry strength agent
Preparation Method and its application.
Background technology
Drying strengthening agent be in paper industry enhance paper strength a kind of important chemical, commonly used in compensation addition filler or
The decline of paper intensity caused by the fiber (such as regenerated fiber) of inferior grade.It is many water-soluble, it can form hydrogen bond with fiber
High polymer can become drying strengthening agent.
Common drying strengthening agent has natural polymer such as starch and its modifier, and (cationic starch, anionic starch, crosslinking are formed sediment
Powder), other a kind of water-soluble natural product type drying strengthening agents such as synthetic polymer such as polyacrylamide, polyvinyl alcohol (such as melon and glue
And its derivative etc.).In most cases, only the substance of heating quality score 0.1-0.75% can reach effective
Do potent fruit.
In recent years, waste paper resources utilization rate in China's rises year by year, and development potentiality is huge.But the utilization rate of waste paper carries
Height means that waste paper recycles the increase of number, can cause declining to a great extent for paper intensity index, so needing to add drying strengthening agent
To increase paper strength.Continuous rising with consumption market to paper and cardboard demand, has pulled drying strengthening agent demand
It is swift and violent to increase.Study of Paper-Strengthening Agent Based has been widely used in the production process of all kinds of paper and paper, to dramatically increase paper and paper
The dry strength of plate reduces high-quality raw material consumption, reduces production cost;Or product specification is improved, it is constantly carried with meeting user
The higher and higher quality requirement gone out.
The best drying strengthening agent of application effect is polyacrylamide and its copolymer, including anionic polyacrylamide at present
Amine, cationic-type polyacrylamide and amphiprotic polyacrylamide.Wherein, amphiprotic polyacrylamide shows best application effect
Fruit.Polyacrylamide also divides straight chain type and branched chain type from structure.The high polyacrylamide of the degree of branching has preferably application
Effect.
The mainstream and trend of synthesized high-performance drying strengthening agent are synthetic molecular weight and the branched polymers of modest viscosity at present.
This drying strengthening agent can play good paper in the case where not adding aluminum sulfate and do humidification.Frequently with addition crosslinking agent
Method obtain branch type dry strength agent, but often there is a problem of one it is common, exactly there is reaction process control problem, institute
The viscosity for obtaining polymer often will appear excessive or too small problem, and control is improper also often to will appear local implode or gelation.
About the preparation of drying strengthening agent, also there are many patent documents to report.Such as:Chinese patent document CN107814875A is public
A kind of production method of liquid cationic drying strengthening agent has been opened, has been included the following steps:1) in a kettle, add ionized water, propylene
The oxidant of amide monomer, cationic monomer, acrylic acid, complexing agent and initiator mixes, and stirring is opened, with weak acid for adjusting pH
Value;2) oxidant that initiator is added after heating and heat preservation causes, then by repeatedly the oxidant of initiator being added to draw after heating and heat preservation
Hair, the reducing agent for being eventually adding initiator cause, and whole process is that the constant temperature tank polymerization of strict temperature control reacts.Example again
Such as:Chinese patent document CN103665258A discloses a kind of preparation method of dry strengthening agent used for making papers, including:(1) by alcohol and water
Reactor is added, is warming up to 80-85 DEG C;(2) acrylic monomers, acrylate monomer, comonomer X are made into dropping liquid A1;
Acrylamide monomer, remaining acrylic monomers, comonomer Y are made into dropping liquid A2;Respectively by initiator and deionized water
Mixing is made into dropping liquid B1, B2;(3) A1, B1 are added drop-wise in reactor, are cooled down after polymerization, adjusting pH is 4-6, is warming up to 80-
85 DEG C, then A2, B2 are added drop-wise in reactor, continue to polymerize;After completion of the reaction, heating distills out alcohol, finally cools down and supplements
Deionized water, blowing.
However, by reaction monomers, hybrid reaction not only needs stringent controlling reaction temperature simultaneously, but also is susceptible to reaction
Implode or gel phenomenon caused by object excessive concentration.It is diluted using alcohol solution, increases the process of subsequent evaporation alcohol,
Step is complicated to increase energy consumption simultaneously.
Invention content
In view of the deficiencies in the prior art, the present invention provides a kind of preparation of paper grade (stock) emulsion-type cationic dry strength agent
Method, this method is easy to operate, easily controllable, can effectively prevent implode and gelation, and molecular weight, the degree of branching and viscosity can be obtained
All moderate drying strengthening agent.
The technical solution adopted by the present invention is as follows:
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, includes the following steps:
(1) cationic monomer and acrylate monomer are mixed and is used as bottom material, 80-85 DEG C is warming up to, with two isobutyl of azo
Nitrile (AIBN) causes polymerization, and the high molecular polymer with surface-active is made, and is dissolved in water and is 5-6 with pH is adjusted;
(2) acrylamide monomer, acrylate monomer, cross-linking monomer, cationic monomer and emulsifier are made into pre- breast
Liquid, as dropping liquid A;Oxidant and deionized water are mixed and are made into initiation system, as dropping liquid B;
(3) dropping liquid A, B are at the uniform velocity added drop-wise in the material of step (1) simultaneously, reaction temperature is 80-85 DEG C;It has reacted
Bi Hou cools down and supplements deionized water to get emulsion-type cationic dry strength agent.
, according to the invention it is preferred to, cationic monomer accounts for the 50-60% of bottom material gross mass, acrylate list in step (1)
Body accounts for the 40-50% of bottom material gross mass, and the additive amount of initiator azodiisobutyronitrile (AIBN) is the 0.1- of bottom material total weight
0.2%;
Preferably, acrylamide monomer accounts for acrylamide monomer and acrylate monomer gross mass in step (2) dropping liquid A
43-54%, acrylate monomer accounts for the 46-67% of acrylamide monomer and acrylate monomer gross mass;Cross-linking monomer
Additive amount is the 2.5-3.6% of acrylamide monomer and acrylate monomer gross mass, and the additive amount of cationic monomer is propylene
The additive amount of the 14.5-16.5% of amide monomer and acrylate monomer gross mass, emulsifier are acrylamide monomer and propylene
The 0.8-1.2% of acid ester monomer gross mass;The usage amount of oxidant is acrylamide monomer and acrylate monomer in dropping liquid B
The 0.2~0.5% of gross mass.
Preferably, in step (3) bottom material gross mass:Acrylamide monomer and the total matter of acrylate monomer in dropping liquid A
Amount is than being 1.1:10-1.5:10.
, according to the invention it is preferred to, acrylate monomer described in step (1)-(2) is selected from hydroxy-ethyl acrylate, propylene
Sour hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methyl acrylate, methyl methacrylate, acrylic acid second
It is one or more in ester, ethyl methacrylate, butyl acrylate, butyl methacrylate.Third in bottom material and dropping material A
Olefin(e) acid ester monomer is identical or different.
Preferably, the cationic monomer is selected from methylacryoyloxyethyl ammonium chloride (DMC), methacrylic acid N, N- bis-
Methylamino ethyl ester (DM), diallyldimethylammonium chloride (DADMAC), methylacryloxyethyldimethyl benzyl ammonium chloride
One or more of (DMBC);
Preferably, the cross-linking monomer is selected from N,N-DMAA, N, N- methylene-bisacrylamides, N- hydroxyl first
One or more of base acrylamide, allyl methacrylate;
Preferably, the emulsifier is selected from OP-10 (polyoxethylene octylphenyl phenol ether -10), NP-10 (polyoxyethylene nonyl phenyls
Vinethene (10)), 1631 (hexadecyltrimethylammonium chlorides), one kind or several in 1831 (octadecyltrimethylammonium chloride)
Kind;
Preferably, the acrylamide monomer is selected from one or more of acrylamide, Methacrylamide;
Preferably, it is different to be selected from sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, azo two for the oxidant employed in dropping liquid B
One in Butyl Amidine HCl salt, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN
Kind.
, according to the invention it is preferred to, in step (1), initiator azodiisobutyronitrile is added by several times into bottom material monomer
(AIBN), polymerisation 1-1.5 hours;It is further preferred that 3-5 addition of average mark, per minor tick 5-10min;
Deionized water 20-25 times of bottom material total weight (weight be) is added after polymerisation, plays and dissolves and dilute
Then the effect released adjusts pH=5-6 with sulfuric acid or acetic acid.Adjust pH used in sulfuric acid or acetic acid be 10-20wt% dilution
Liquid.
, according to the invention it is preferred to, in step (2), when preparing dropping liquid A, a small amount of deionized water (weight can be added
It is 1.2-1.5 times of acrylamide monomer in dropping liquid A and acrylate monomer gross mass), play dissolving water-soluble monomer
Effect.
, according to the invention it is preferred to, in step (3), dropping liquid A, B polymerisation is added 1.5-2 hours;After being added dropwise to complete
Continue polymerisation to occur 0.5-1 hours, reaction total time is 2-3 hours.
, according to the invention it is preferred to, in step (3), it is 15-20% that supplement deionized water, which adjusts solid content,.
Application of the emulsion-type cationic dry strength agent that the present invention is obtained using above-mentioned preparation method in papermaking.
The main function of the principle of the present invention and each raw material is as follows:
The method of present invention combination emulsion polymerization, introduces ester groups in products molecule, makes it in fiber drying process
Middle film forming, with the bond strength of reinforcing fiber.Reduce the monomers such as acrylamide simultaneously to go out in process of production because of reaction density
Larger and appearance autoacceleration process, that is, avoid local implode or gelation.
In bottom material, cationic monomer provides cation and hydrophilic radical for high-molecular surface active polymer;Acrylic acid
Ester monomer provides hydrophobic grouping for high-molecular surface active polymer.
In dropping material A, acrylamide monomer, the backbone units that acrylate monomer is finally formed emulsion polymer.
Cationic monomer (such as methylacryoyloxyethyl ammonium chloride (DMC), methacrylic acid N, N- dimethylaminoethyl
(DM), diallyldimethylammonium chloride (DADMAC), methylacryloxyethyldimethyl benzyl ammonium chloride (DMBC) can make
Drying strengthening agent has better binding force with paper-making fibre.
Cross-linkable monomer (such as N,N-DMAA, N, N- methylene-bisacrylamides, N- methylol acryloyls
Amine, allyl methacrylate) polymer can be made to be easy to generate branched and be crosslinked and then form network structure.
Emulsifier is played water-soluble monomer and the emulsification of oiliness monomer, forms pre-emulsion, to ensure that stable reaction carries out simultaneously
Form stable lotion kenel.
Beneficial effects of the present invention:
1, according to method provided by the invention, in bottom material reaction, cationic monomer is raw first with acrylic ester monomer
At water-soluble high-molecular surface active polymer, make the emulsifier of subsequent reactions object, list containing main reaction is then added dropwise
The dropping liquid A and dropping liquid B of body acrylamide monomer and acrylate monomer, reactant under the stabilization of emulsifier with
And under the emulsification of aforementioned high-molecular surface active polymer, local implode and gel phenomenon, control production are effectively prevented
In relatively narrow range, final polymer is stable in the presence of with microgranular in lotion object molecular weight, to gradually synthetic molecular weight,
The degree of branching and all moderate emulsion-type cationic dry strength agent of viscosity.Avoiding being diluted using alcoholic solution causes step complicated and energy
Consumption increases.
2, the big disadvantage of method provided by the invention can overcome water solution polymerization process to bring product viscosity and
The problems such as environmental pollution that emulsion polymerization is brought using excessive surfactant and organic solvent.
3, the characteristics of present invention is by combining acrylic emulsion, while being combined with fiber, by dry in fibre
Fine and close glued membrane is formed between dimension, achievees the purpose that improve fibre strength, and the opposite use for reducing the monomers such as acrylamide
Amount, therefore avoid the autoacceleration phenomenon occurred by reaction density when the monomer polymerizations such as acrylamide.
Specific implementation mode
Below by specific embodiment, the invention will be further described, but not limited to this.
Raw materials used in embodiment is convenient source, commercial products." % " is mass percent.
Embodiment 1
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, includes the following steps:
(1) by 40kg methylacryoyloxyethyls ammonium chloride (DMC, effective content 78%, if without effective content if refering in particular to
100% meter, similarly hereinafter), reaction kettle is added in 8kg hydroxy-ethyl acrylates, 14kg butyl acrylates, stirs and is warming up to 70-75 DEG C, point
5 every minor tick 5-10min, are added the azodiisobutyronitrile (AIBN) that total amount is 0.1kg, controlling reaction temperature is in 80- later
85 DEG C, 1.5h is reacted, 1200kg deionized waters are then added, and pH is adjusted as 5.2 with 10% sulfuric acid solution;
(2) by 200kg acrylamides, 10kg N,N-DMAAs, 5kg N hydroxymethyl acrylamides, 50kg
Methylacryoyloxyethyl ammonium chloride (DMC, effective content 78%), (DM has 30kg methacrylic acids N, N- dimethylaminoethyl
Imitate content 90%), 2kg emulsifier op-10s, 3kg emulsifiers 1831 are dissolved in 600kg deionized waters, are then being vigorously stirred
Lower addition 120kg methyl acrylates, 100kg butyl acrylates form pre-emulsion, are dropping liquid A;Meanwhile by 2kg ammonium persulfates
It is dissolved in 200kg deionized waters, is dropping liquid B;
(3) at 80-85 DEG C, dropping liquid A, B are at the uniform velocity added drop-wise in step aforesaid reaction vessel simultaneously, it is anti-after being added dropwise to complete
It answers 1 hour, is cooled to 35-45 DEG C, and supplementing deionized water makes solid content be 15-20%, blowing.
The viscosity of obtained emulsion-type cationic dry strength agent is 2000-4000mpas.
Embodiment 2
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, includes the following steps:
(1) by 60kg methylacryloxyethyldimethyl benzyl ammonium chlorides (DMBC, effective content 60%), 12kg methyl
Reaction kettle is added in hydroxy-ethyl acrylate, 20kg butyl methacrylates, stirs and is warming up to 70-75 DEG C, point 5 every minor tick 5-
The azodiisobutyronitrile (AIBN) that total amount is 0.1kg is added in 10min, and controlling reaction temperature reacts 1h, so at 80-85 DEG C later
1200kg deionized waters are added afterwards, and pH is adjusted as 5.5 with 15% acetum;
(2) by 220kg acrylamides, 15kgN, N- dimethacrylamide, 80kg methylacryoyloxyethyl dimethyl
Benzyl ammonium chloride (DMBC, effective content 60%), 30kg methacrylic acids N, N- dimethylaminoethyl (DM, effective content
90%), 2kg emulsifiers NP-10,3kg emulsifier 1831, is dissolved in 600kg deionized waters, is then added with vigorous stirring
110kg ethyl acrylates, 150kg butyl methacrylates form pre-emulsion, are dropping liquid A;Meanwhile by 1.8kg sodium peroxydisulfates
It is dissolved in 200kg deionized waters, is dropping liquid B;
(3) at 80-85 DEG C, dropping liquid A, B are at the uniform velocity added drop-wise in step aforesaid reaction vessel simultaneously, it is anti-after being added dropwise to complete
It answers 0.5 hour, is cooled to 35-45 DEG C, and supplementing deionized water makes solid content be 15-20%, blowing.
The viscosity of obtained emulsion-type cationic dry strength agent is 3000-5000mpas.
Embodiment 3
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, includes the following steps:
(1) by 40kg methylacryoyloxyethyls ammonium chloride (DMC, effective content 78%), 8kg hydroxypropyl acrylates,
Reaction kettle is added in 14kg butyl acrylates, stirs and is warming up to 70-75 DEG C, point 5 every minor tick 5-10min, addition total amount is
The azodiisobutyronitrile (AIBN) of 0.1kg, controlling reaction temperature is at 80-85 DEG C later, reaction 1.5h, and 1200kg is then added and goes
Ionized water, and pH is adjusted as 5.4 with 12% sulfuric acid solution;
(2) by 250kg acrylamides, 12kgN, N- dimethacrylamide, 0.5kg N, N- methylene-bisacrylamides,
65kg methylacryloxyethyldimethyl benzyl ammonium chlorides (DMBC, effective content 60%), 40kg methacrylic acids N, N- bis-
Methylamino ethyl ester (DM, effective content 90%), 4kg emulsifiers 1831 are dissolved in 600kg deionized waters, are then acutely being stirred
Lower addition 80kg methyl methacrylates are mixed, 140kg butyl acrylates form pre-emulsion, are dropping liquid A;Meanwhile it is 1kg is even
Two isobutyl imidazoline hydrochloride of nitrogen is dissolved in 200kg deionized waters, is dropping liquid B;
(3) at 80-85 DEG C, dropping liquid A, B are at the uniform velocity added drop-wise in step aforesaid reaction vessel simultaneously, it is anti-after being added dropwise to complete
It answers 1 hour, is cooled to 35-45 DEG C, and supplementing deionized water makes solid content be 15-20%, blowing.
The viscosity of obtained emulsion-type cationic dry strength agent is 3000-5000mpas.
Embodiment 4
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, includes the following steps:
(1) by 30kg methacrylic acids N, N- dimethylaminoethyl (DM, effective content 90%), 10kg hydroxyethyl methacrylates
Reaction kettle is added in propyl ester, 14kg ethyl acrylates, stirs and is warming up to 70-75 DEG C, point 5 every minor tick 5-10min are added total
Amount is the azodiisobutyronitrile (AIBN) of 0.08kg, and controlling reaction temperature is reacted 1.2h, be then added at 80-85 DEG C later
1200kg deionized waters, and pH is adjusted as 5.8 with 18% acetum;
(2) by 210kg acrylamides, 14kgN- hydroxymethyl acrylamide, 0.5kg N, N- methylene-bisacrylamides,
55kg methylacryloxyethyldimethyl benzyl ammonium chlorides (DMBC, effective content 60%), 40kg methylacryoyloxyethyls
Ammonium chloride (DMC, effective content 78%), 4kg emulsifiers 1631 are dissolved in 600kg deionized waters, then with vigorous stirring
100kg methyl methacrylates, 100kg butyl acrylates is added, 20kg hydroxy-ethyl acrylates form pre-emulsion, are dropping liquid
A;Meanwhile 1.8kg potassium peroxydisulfates being dissolved in 200kg deionized waters, it is dropping liquid B;
(3) at 80-85 DEG C, dropping liquid A, B are at the uniform velocity added drop-wise in step aforesaid reaction vessel simultaneously, it is anti-after being added dropwise to complete
It answers 1 hour, is cooled to 35-45 DEG C, and supplementing deionized water makes solid content be 15-20%, blowing.
The viscosity of obtained emulsion-type cationic dry strength agent is 4000-5500mpas.
Comparative example 1
Implement according to the method for embodiment 1, unlike, azodiisobutyronitrile is disposably put into bottom material reaction process,
As a result,:Vigorous reaction, reaction heat can not be discharged in time, cause spray kettle, implode and gelatin phenomenon occur, can not carry out follow-up
Production.
Comparative example 2
Raw material proportioning with embodiment 1, unlike, be added without emulsifier in dropping liquid A, as a result,:Occur in reaction
There is water-oil separation in a large amount of gels, product, and have a large amount of oiliness monomer residues.
Comparative example 3
Raw material proportioning with embodiment 1, unlike, do not use the bottom material in step (1), directly dropping liquid A, B be added dropwise
Into deionized water.As a result:Because of the limited emulsifying capacity of conventional emulsifier, stable lotion cannot be formed, product occurs big
Gel and there are a large amount of oiliness monomer residues.
Application examples
It will be in emulsion-type cationic dry strength agent products application to paper technology made from embodiment 1-4.
In use, emulsion-type cationic dry strength agent is diluted with clear water, general 15-30 times of dilution is stirring evenly and then adding into
In paper making pulp, addition 10-20kg/t, point of addition selection can be sufficiently mixed place in paper manufacturing streams with slurry, generally
It is added in dosing chamber, header box or fan pump import.
The paper strength of emulsion-type cationic dry strength agent added with embodiment 1-4 is tested, the results are shown in Table 1.
Table 1
As shown in Table 1, the drying strengthening agent that prepared by addition the method for the present invention obtains the apparent increasing of paper strength than not adding drying strengthening agent
By force.
Above-described embodiment is to the present invention for example, the present invention can also be with other ad hoc fashions or others
Particular form is implemented, without departing from the gist of the invention or substantive characteristics.Therefore, from the point of view of the embodiment of description is in terms of any
It is regarded as illustrative and non-limiting.The scope of the present invention should illustrate by appended claims, any and claim
Intention and the equivalent variation of range should also be included in the scope of the present invention.
Claims (10)
1. a kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, includes the following steps:
(1) cationic monomer and acrylate monomer are mixed and is used as bottom material, be warming up to 80-85 DEG C, drawn with azodiisobutyronitrile
Hair polymerization, is made the high molecular polymer with surface-active, is dissolved in water and is 5-6 with pH is adjusted;
(2) acrylamide monomer, acrylate monomer, cross-linking monomer, cationic monomer and emulsifier are made into pre-emulsion, made
For dropping liquid A;Oxidant and deionized water are mixed and are made into initiation system, as dropping liquid B;
(3) dropping liquid A, B are at the uniform velocity added drop-wise in the material of step (1) simultaneously, reaction temperature is 80-85 DEG C;After completion of the reaction,
Cool down and supplements deionized water to get emulsion-type cationic dry strength agent.
2. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that step (1) middle-jiao yang, function of the spleen and stomach
Ion monomer accounts for the 50-60% of bottom material gross mass, and acrylate monomer accounts for the 40-50% of bottom material gross mass;
Preferably, the additive amount of initiator azodiisobutyronitrile is the 0.1-0.2% of bottom material total weight.
3. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that step (2) is added dropwise
Acrylamide monomer accounts for the 43-54% of acrylamide monomer and acrylate monomer gross mass in liquid A, and acrylate monomer accounts for third
The 46-67% of acrylamide monomer and acrylate monomer gross mass;The additive amount of cross-linking monomer is acrylamide monomer and propylene
The additive amount of the 2.5-3.6% of acid ester monomer gross mass, cationic monomer are acrylamide monomer and the total matter of acrylate monomer
The 14.5-16.5% of amount, the additive amount of emulsifier are the 0.8-1.2% of acrylamide monomer and acrylate monomer gross mass;
The usage amount of oxidant is the 0.2~0.5% of acrylamide monomer and acrylate monomer gross mass in dropping liquid B.
4. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that step (3) midsole
The gross mass of material:Acrylamide monomer and acrylate monomer total mass ratio are 1.1 in dropping liquid A:10-1.5:10.
5. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that step (1)-(2)
Described in acrylate monomer be selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate
Propyl ester, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, metering system
It is one or more in acid butyl ester;
The cationic monomer is selected from methylacryoyloxyethyl ammonium chloride, methacrylic acid N, N- dimethylaminoethyl, diene
One or more of diallyidimethylammonium chloride, methylacryloxyethyldimethyl benzyl ammonium chloride;
The cross-linking monomer be selected from N,N-DMAA, N, N- methylene-bisacrylamides, N hydroxymethyl acrylamide,
One or more of allyl methacrylate;
The emulsifier is selected from OP-10, NP-10,1631, one or more of 1831;
The acrylamide monomer is selected from one or more of acrylamide, Methacrylamide;
Oxidant employed in dropping liquid B is selected from sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, azo diisobutyl amidine hydrochloric acid
One kind in salt, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN.
6. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that in step (1), to
Initiator azodiisobutyronitrile, polymerisation 1-1.5 hours is added in bottom material monomer by several times;
Preferably, 3-5 addition of average mark, per minor tick 5-10min.
7. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that in step (2),
When preparing dropping liquid A, deionized water dissolving water-soluble monomer is added, the addition weight of deionized water is acryloyl in dropping liquid A
1.2-1.5 times of amine monomers and acrylate monomer gross mass.
8. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that in step (3), add
Enter dropping liquid A, B polymerisation 1.5-2 hours;Continue that polymerisation 0.5-1 hour occurs after being added dropwise to complete, reacting total time is
2-3 hours.
9. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that in step (3), mend
It is 15-20% to fill deionized water to adjust solid content.
10. application of the emulsion-type cationic dry strength agent being prepared described in claim 1-9 in papermaking.
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| CN115109196A (en) * | 2022-07-19 | 2022-09-27 | 浙江传化功能新材料有限公司 | Emulsion type polyacrylate-polyacrylamide copolymer and preparation method and application thereof |
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