CN108690165B - 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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- CN108690165B CN108690165B CN201810584362.8A CN201810584362A CN108690165B CN 108690165 B CN108690165 B CN 108690165B CN 201810584362 A CN201810584362 A CN 201810584362A CN 108690165 B CN108690165 B CN 108690165B
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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
- C08F2/12—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
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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
- D21H21/18—Reinforcing agents
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Paper (AREA)
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Abstract
The present invention relates to a kind of preparation method and applications of paper grade (stock) emulsion-type cationic dry strength agent, it include: (1) by cationic monomer, acrylate monomer, reactor is added, it is warming up to 80-85 DEG C, cause polymerization with azodiisobutyronitrile and the high molecular polymer with surface-active is made, being dissolved in water and adjusting pH is 5-6；(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.Reaction product of the 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 technique
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, hydrogen bond can be formed 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 mentions
Height means that the increase of number is recycled in waste paper, will 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 mentioned with meeting user
Higher and higher quality requirement 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 the branched polymers of synthetic molecular weight and 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 is opened, comprising 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, comprising: (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 strict control reaction temperature simultaneously, but also is easy to appear reaction
Implode caused by object excessive concentration or gel phenomenon.It is diluted using alcohol solution, increases the process of subsequent evaporation alcohol,
Step is complicated to increase energy consumption simultaneously.
Summary of the invention
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 invention is as follows:
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, comprising 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- cream
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 14.5-16.5% of amide monomer and acrylate monomer gross mass, the additive amount of 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
One of ester, ethyl methacrylate, butyl acrylate, butyl methacrylate are a variety of.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-bisacrylamide, 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 phenyl
Vinethene (10)), 1631 (hexadecyltrimethylammonium chlorides), one of 1831 (octadecyltrimethylammonium chloride) or several
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 oxidant employed in dropping liquid B
Butyl Amidine HCl salt, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, one in 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), polymerization reaction 1-1.5 hours；It is further preferred that average mark 3-5 times addition, every minor tick 5-10min；
It is added after polymerization reaction deionized water 20-25 times of bottom material total weight (weight be), plays and dissolve and dilute
Then the effect released adjusts pH=5-6 with sulfuric acid or acetic acid.Sulfuric acid used in pH or acetic acid are adjusted as the dilution of 10-20wt%
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 dissolution water-soluble monomer
Effect.
, according to the invention it is preferred to, in step (3), it is added dropping liquid A, B polymerization reaction 1.5-2 hours；After being added dropwise to complete
Continue to occur polymerization reaction 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 because of reaction density in process of production
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 and paper-making fibre have better binding force.
Cross-linkable monomer (such as N,N-DMAA, N, N- methylene-bisacrylamide, N- methylol acryloyl
Amine, allyl methacrylate) polymer can be made to be easy to generate branching 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, the method provided according to the present invention, in bottom material reaction, cationic monomer and acrylic ester monomer are raw first
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 are effectively prevented, control produces
In relatively narrow range, final polymer is stable in the presence of in lotion object molecular weight with microgranular, thus 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, method provided by the invention can overcome water solution polymerization process bring product viscosity big disadvantage and
Emulsion polymerization uses the problems such as excessive surfactant and organic solvent bring environmental pollution.
3, the characteristics of present invention is by combining acrylic emulsion, while in conjunction with fiber, by dry in fibre
Fine and close glue film 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 when the monomer polymerizations such as acrylamide by reaction density.
Specific embodiment
Below by specific embodiment, the invention will be further described, but not limited to this.
Raw materials used in embodiment is conventional raw material, commercial products." % " is mass percent.
Embodiment 1
A kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, comprising the following steps:
(1) by 40kg methylacryoyloxyethyl 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 acrylate, 14kg butyl acrylate, and it 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, control reaction temperature later in 80-
85 DEG C, 1.5h is reacted, 1200kg deionized water is then added, and pH is adjusted as 5.2 with 10% sulfuric acid solution；
(2) by 200kg acrylamide, 10kg N,N-DMAA, 5kg N hydroxymethyl acrylamide, 50kg
Methylacryoyloxyethyl ammonium chloride (DMC, effective content 78%), (DM has 30kg methacrylic acid N, N- dimethylaminoethyl
Imitate content 90%), 2kg emulsifier op-10,3kg emulsifier 1831 is dissolved in 600kg deionized water, is then being vigorously stirred
Lower addition 120kg methyl acrylate, 100kg butyl acrylate form pre-emulsion, are dropping liquid A；Meanwhile by 2kg ammonium persulfate
It is dissolved in 200kg deionized water, 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 supplement deionized water to make solid content 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, comprising the following steps:
(1) by 60kg methylacryloxyethyldimethyl benzyl ammonium chloride (DMBC, effective content 60%), 12kg methyl
Reaction kettle is added in hydroxy-ethyl acrylate, 20kg butyl methacrylate, stirs and is warming up to 70-75 DEG C, point 5 every minor tick 5-
10min, is added the azodiisobutyronitrile (AIBN) that total amount is 0.1kg, controls reaction temperature later at 80-85 DEG C, reacts 1h, so
1200kg deionized water is added afterwards, and pH is adjusted as 5.5 with 15% acetum；
(2) by 220kg acrylamide, 15kgN, N- dimethylacrylamide, 80kg methylacryoyloxyethyl dimethyl
Benzyl ammonium chloride (DMBC, effective content 60%), 30kg methacrylic acid N, N- dimethylaminoethyl (DM, effective content
90%), 2kg emulsifier NP-10,3kg emulsifier 1831, is dissolved in 600kg deionized water, is then added with vigorous stirring
110kg ethyl acrylate, 150kg butyl methacrylate form pre-emulsion, are dropping liquid A；Meanwhile by 1.8kg sodium peroxydisulfate
It is dissolved in 200kg deionized water, 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 supplement deionized water to make solid content 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, comprising the following steps:
(1) by 40kg methylacryoyloxyethyl ammonium chloride (DMC, effective content 78%), 8kg hydroxypropyl acrylate,
Reaction kettle is added in 14kg butyl acrylate, 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 controls reaction temperature at 80-85 DEG C later, reacts 1.5h, 1200kg is then added and goes
Ionized water, and pH is adjusted as 5.4 with 12% sulfuric acid solution；
(2) by 250kg acrylamide, 12kgN, N- dimethylacrylamide, 0.5kg N, N- methylene-bisacrylamide,
65kg methylacryloxyethyldimethyl benzyl ammonium chloride (DMBC, effective content 60%), 40kg methacrylic acid N, N- bis-
Methylamino ethyl ester (DM, effective content 90%), 4kg emulsifier 1831 are dissolved in 600kg deionized water, are then acutely being stirred
Lower addition 80kg methyl methacrylate is mixed, 140kg butyl acrylate forms pre-emulsion, is dropping liquid A；Meanwhile it is 1kg is even
Two isobutyl imidazoline hydrochloride of nitrogen is dissolved in 200kg deionized water, 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 supplement deionized water to make solid content 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, comprising the following steps:
(1) by 30kg methacrylic acid N, N- dimethylaminoethyl (DM, effective content 90%), 10kg hydroxyethyl methacrylate
Reaction kettle is added in propyl ester, 14kg ethyl acrylate, stirs and is warming up to 70-75 DEG C, point 5 every minor tick 5-10min are added always
Amount is the azodiisobutyronitrile (AIBN) of 0.08kg, controls reaction temperature later at 80-85 DEG C, reacts 1.2h, be then added
1200kg deionized water, and pH is adjusted as 5.8 with 18% acetum；
(2) by 210kg acrylamide, 14kgN- hydroxymethyl acrylamide, 0.5kg N, N- methylene-bisacrylamide,
55kg methylacryloxyethyldimethyl benzyl ammonium chloride (DMBC, effective content 60%), 40kg methylacryoyloxyethyl
Ammonium chloride (DMC, effective content 78%), 4kg emulsifier 1631 are dissolved in 600kg deionized water, then with vigorous stirring
100kg methyl methacrylate, 100kg butyl acrylate is added, 20kg hydroxy-ethyl acrylate forms pre-emulsion, is dropping liquid
A；Meanwhile 1.8kg potassium peroxydisulfate being dissolved in 200kg deionized water, 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 supplement deionized water to make solid content 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 subsequent
Production.
Comparative example 2
Raw material proportioning with embodiment 1, unlike, emulsifier is added without in dropping liquid A, as a result, occurring 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
By emulsion-type cationic dry strength agent products application made from embodiment 1-4 into paper technology.
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, additional amount 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 of addition the method for the present invention preparation, obtains paper strength than not adding drying strengthening agent and obviously increases
By force.
Above-described embodiment is only to of the 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, the embodiment of description is in any way
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 (8)
1. a kind of preparation method of paper grade (stock) emulsion-type cationic dry strength agent, comprising 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；
It is added initiator azodiisobutyronitrile by several times into bottom material monomer, polymerization reaction 1-1.5 hours；Average mark 3-5 times addition,
Every minor tick 5-10min；
(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；
Acrylate monomer described in step (1)-(2) is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate second
Ester, hydroxy propyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propylene
One of acid butyl ester, butyl methacrylate are a variety of；
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-bisacrylamide, N hydroxymethyl acrylamide,
One or more of allyl methacrylate；
The emulsifier is selected from one or more of OP-10, NP-10,1631,1831；
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 of salt, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN.
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；Initiator azo two is different
The additive amount of butyronitrile 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 acrylic acid
The 2.5-3.6% of ester monomer gross mass, the additive amount of cationic monomer are acrylamide monomer and acrylate monomer gross mass
14.5-16.5%, the additive amount of emulsifier are the 0.8-1.2% of acrylamide monomer and acrylate monomer gross mass；Dropping liquid B
The usage amount of middle oxidant is the 0.2~0.5% of acrylamide monomer and acrylate monomer gross mass.
4. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that step (3) indsole
The gross mass of material: acrylamide monomer and acrylate monomer total mass ratio are 1.1:10-1.5:10 in dropping liquid A.
5. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that in step (2), In
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.
6. 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 polymerization reaction 1.5-2 hours；Continue after being added dropwise to complete occur polymerization reaction 0.5-1 hour, react total time be
2-3 hours.
7. the preparation method of emulsion-type cationic dry strength agent according to claim 1, which is characterized in that in step (3), mend
Filling deionized water to adjust solid content is 15-20%.
8. application of the emulsion-type cationic dry strength agent being prepared described in claim any one of 1-7 in papermaking.
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| CN103059216A (en) * | 2012-11-27 | 2013-04-24 | 江苏博特新材料有限公司 | Dispersant and preparation method thereof, and application of dispersant in anionic polyacrylamide water-dispersible emulsion polymerization |
| CN103194933A (en) * | 2013-03-14 | 2013-07-10 | 徐朝华 | Preparation method of cationic controllable styrene-acrylate micro-emulsion papermaking surface sizing agent |
| CN103665258A (en) * | 2013-11-25 | 2014-03-26 | 康吉诺（北京）科技有限公司 | Preparation method and application for papermaking dry strength agent |
| CN104672377A (en) * | 2015-03-12 | 2015-06-03 | 苏州飞翔新材料研究院有限公司 | Preparation method for high-solid-content cationic polyacrylamide inverse emulsion |
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| CN103059216A (en) * | 2012-11-27 | 2013-04-24 | 江苏博特新材料有限公司 | Dispersant and preparation method thereof, and application of dispersant in anionic polyacrylamide water-dispersible emulsion polymerization |
| CN103194933A (en) * | 2013-03-14 | 2013-07-10 | 徐朝华 | Preparation method of cationic controllable styrene-acrylate micro-emulsion papermaking surface sizing agent |
| CN103665258A (en) * | 2013-11-25 | 2014-03-26 | 康吉诺（北京）科技有限公司 | Preparation method and application for papermaking dry strength agent |
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