CN110409219A - A kind of method of soap-free emulsion method synthetic environment-friendly Cypres - Google Patents
A kind of method of soap-free emulsion method synthetic environment-friendly Cypres Download PDFInfo
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- CN110409219A CN110409219A CN201910674794.2A CN201910674794A CN110409219A CN 110409219 A CN110409219 A CN 110409219A CN 201910674794 A CN201910674794 A CN 201910674794A CN 110409219 A CN110409219 A CN 110409219A
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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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Abstract
The invention discloses a kind of methods of soap-free emulsion method synthetic environment-friendly Cypres, include the following steps: to mix polymeric dispersant, (methyl) styrene, (methyl) acrylic ester monomer, feature cation monomer with water, it is heated to 80-90 DEG C, then initiator for reaction is added, sufficiently obtain environment-friendly type Cypres after reaction, the polymeric dispersant be as maleic anhydride and polyvinyl alcohol after polycondensation reaction again and made of chlorosulfonic acid reaction.Environment-friendly type Cypres of the present invention are the products of a kind of high-performance for being able to satisfy paper for surface sizing, environmental protection.The product carries out top sizing to body paper together with starch, can significantly improve paper water resistance.The table that paper can also be improved simultaneously is strong.
Description
Technical field
It is strong the present invention relates to Cypres preparation field more particularly to a kind of water resistance and raising surface strength of paper
Cypres.
Background technique
The addition of Cypres can improve page characteristic or increase surface property, intensity and the water resistant of Paper or cardboard
Property.
Cypres are significant to the development of paper industry, and papermakers also extremely wish to apply by surface
Glue improves paper performance, improves product specification, to meet current papermaking, the needs of printing and related fields continue to develop.Table
The performance superiority and inferiority of surface sizing agent product directly influences the effect of top sizing.Surface Sizing Agent is used as to be occurred in recent years
New product rapidly developed in paper industry with its unique performance, it can satisfy various sheet paper products production need
It asks, the exploitation for high-grade paper and speciality paper provides a strong guarantee.
The R&D work of domestic Surface Sizing Agent is started late, the product developed at present and external several big chemicals
Products performance is compared to still there is certain gap, and the Cypres market of especially high-grade paper is almost by offshore company's product
Monopolization.Therefore, applied widely, efficient and cheap is researched and developed, environmentally friendly Surface Sizing Agent is very necessary
And it is urgent, for improving paper quality, reducing enterprise's production cost, replace external imported product, enhancing sheet paper products competing
It strives ability, the development of China's paper industry is pushed all to have far-reaching significance.
In the prior art, a kind of sizing agent disclosed in CN102140768A uses natural polymer as emulsifier
A cationic surface-sizing agent is synthesized, but because there is a large amount of hydrophilic radical, while day in itself in natural polymer
After right macromolecule modifier degrades natural polymer, emulsifier is easy to be enriched with to interfacial migration in film forming procedure, thus right
The water resistance and adhesive force of polymer film forming have a negative impact.
CN200710032539 has synthesized a anion SAE Cypres using emulsifier-free emulsion polymerization, but as table
The performance of surface sizing agent cationic is more stronger than anionic.
Summary of the invention
The present invention is intended to provide a kind of preparation method of efficient and environment-friendly type Cypres, to solve existing for background technique
Drawbacks described above.
The present invention realizes by the following technical solutions:
A kind of method of soap-free emulsion method synthetic environment-friendly Cypres, includes the following steps:
Polymeric dispersant, (methyl) styrene, (methyl) acrylic ester monomer, feature cation monomer and water is mixed
It closes, is heated to 80-90 DEG C, initiator for reaction is then added, environment-friendly type Cypres, the polymerization point are sufficiently obtained after reaction
Powder, be as maleic anhydride and polyvinyl alcohol after polycondensation reaction again and chlorosulfonic acid reaction made of.
The dosage of each component is distinguished as follows according to parts by weight as a preferred technical solution:
Wherein water is for dispersing each component, the need that those skilled in the art can easily actually use according to product
It wants, adjusts the dosage of water.It is preferred that 500-890 parts.Certainly, the needs actually used according to product, can also be in inventive formulation
Suitable quantity of water is added to adjust the solid content of final products, such as the water of 300-900 parts by weight can be added.
Preferably, the feature cation monomer is selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, metering system
At least one of monomethacryloxypropyl trimethoxy silane, dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate.
Preferably, the preparation method of the polymeric dispersant includes the following steps: maleic anhydride and polyvinyl alcohol,
Polycondensation reaction is carried out after being heated to melting；Cool down after the reaction was completed, chlorosulfonic acid is added, until obtaining the polymerization point after fully reacting
Powder.
Preferably, the dosage of each component is distinguished as follows according to parts by weight:
100 parts of maleic anhydride,
600-800 parts of polyvinyl alcohol,
120-150 parts of chlorosulfonic acid.
Preferably, the temperature of the polycondensation reaction is 80-120 DEG C, and reaction time 2-4hr is cooled to after the reaction was completed
40-60 DEG C, chlorosulfonic acid is added, the reaction was continued 1-3hr obtains the polymeric dispersant.
Preferably, described (methyl) acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, the positive fourth of acrylic acid
Ester, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, hydroxypropyl acrylate, metering system
Sour methyl esters, Tert-butyl Methacrylate, isooctyl methacrylate, n-propyl, cyclohexyl acrylate, lauryl
At least one of ester.
Preferably, the initiator is selected from dibenzoyl peroxide, peroxidized t-butyl perbenzoate, two laurel of peroxidating
Acid, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, sodium peroxydisulfate, hydrogen peroxide-sulfuric acid are sub-
At least one of iron, sodium peroxydisulfate-sodium sulfite, sodium peroxydisulfate-sodium hydrogensulfite, sodium peroxydisulfate-sodium hypophosphite.
As further preferred technical solution, initiator can be added at one time in step 1, can also be in step
A part is added in one, remaining part is then added in the polymerization reaction of step 2.If initiator is divided into two parts addition,
The initiator of the total dosage 75wt% of Zhan is then at least added in step 1.
The solid content for the environment-friendly type Cypres that the present invention is prepared is 25-30wt%, pH 2-3.
The present invention also provides application of the above-mentioned environment-friendly type Cypres in paper for surface sizing, specifically by the ring
Guarantor's type Cypres compound to obtain with the oxidized starch after gelatinization according to mass ratio 0.7-1.2:100 (the two is oven-dry weight)
Glue application solution is used for paper for surface sizing.
In the preparation method of efficient and environment-friendly type Cypres of the present invention, the inventors discovered that with the surface agent sizing agent
Coated on the Cobb value that paper can be greatly reduced after paper surface, while when detecting surface strength of paper, surface strength is found
Also there is enhancing, meet the requirement of high performance surface sizing agent.The sizing agent can also improve paper while reducing paper Cobb value
Open table is mainly (1) using self-control macromolecule dispersing agent by force, and when Cypres are coated on paper surface, dispersing agent will not be moved
Interface is moved to, so as to cause reduced performance.(2) self-control lotion is cationic surface-sizing agent, cation and paper fibre knot
It closes stronger, causes sizability outstanding.(3) it makes by oneself and uses maleic anhydride in polymeric dispersant, contain in maleic anhydride
There is double bond, in second step emulsion polymerization, double bond and monomer reaction in maleic anhydride make monomer graft on dispersant molecule
On, so that paper is had preferable water resistance, while the table that can also improve paper is strong.
Environment-friendly type Cypres of the present invention are the products of a kind of high-performance for being able to satisfy paper for surface sizing, environmental protection.
The product carries out top sizing to body paper together with starch, can significantly improve paper water resistance.Paper can also be improved simultaneously
Table is strong.
Specific embodiment
The present invention is illustrated below by specific embodiment, but is not intended to limit the present invention.
Embodiment 1
1, prepared by polymeric dispersant:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 100 grams of maleic acids are added
Acid anhydride, 600 grams of polyvinyl alcohol, heating melting, 80 DEG C of reaction 3hr.40 DEG C of addition 120g chlorosulfonic acids are cooled to, the reaction was continued 1hr.
2, the preparation of efficient and environment-friendly type Cypres:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 500 grams of deionizations are added
Water is heated to 50 DEG C, sequentially adds 10 grams of polymeric dispersants, 180 grams of mix monomers (100g styrene, 80g acrylic acid second
Ester), 1 gram of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is warming up to 80 DEG C, and 1g ammonium persulfate is added, and reacts 1.5hr.It is added
0.5 gram of ammonium persulfate the reaction was continued 1hr.Cypres are filtered to obtain through 325 mesh filter screens after cooling, pH=2.28, solid content=
27.2%.
Embodiment 2
1, prepared by polymeric dispersant:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 100 grams of maleic acids are added
Acid anhydride, 650 grams of polyvinyl alcohol dissolve by heating, 90 DEG C of reaction 3hr.50 DEG C of addition 125g chlorosulfonic acids are cooled to, the reaction was continued 1.5hr.
2, the preparation of efficient and environment-friendly type Cypres:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 600 grams of deionizations are added
Water is heated to 50 DEG C, sequentially adds 20 grams of polymeric dispersants, 200 grams of mix monomers (100g styrene, 100g acrylic acid second
Ester), 2 grams of dimethyl diallyl ammonium chlorides are warming up to 90 DEG C, and 1g potassium peroxydisulfate is added, and react 2.0hr.0.5 gram of over cure is added
Sour potassium the reaction was continued 1hr.Cypres, pH=2.35, solid content=26.1% are filtered to obtain through 325 mesh filter screens after cooling.
Embodiment 3
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 100 grams of maleic acids are added
Acid anhydride, 700 grams of polyvinyl alcohol dissolve by heating, 95 DEG C of reaction 3hr.50 DEG C of addition 130g chlorosulfonic acids are cooled to, the reaction was continued 2.5hr.
2, the preparation of efficient and environment-friendly type Cypres:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 530 grams of deionizations are added
Water is heated to 50 DEG C, sequentially adds 35 grams of polymeric dispersants, (100g styrene, 60g acrylic acid are different pungent for 160 grams of mix monomers
Ester), 1.5 grams of dimethyl diallyl ammonium chlorides are warming up to 90 DEG C, and 3g dibenzoyl peroxide is added, and react 2.0hr.It is added
2.0 grams of potassium peroxydisulfates the reaction was continued 1hr.Cypres are filtered to obtain through 325 mesh filter screens after cooling, pH=2.5, solid content=
25.9%.
Embodiment 4
1, prepared by polymeric dispersant:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 100 grams of maleic acids are added
Acid anhydride, 700 grams of polyvinyl alcohol dissolve by heating, 90 DEG C of reaction 2.5hr.45 DEG C of addition 130g chlorosulfonic acids are cooled to, the reaction was continued
2.0hr。
2, the preparation of efficient and environment-friendly type Cypres:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 530 grams of deionizations are added
Water is heated to 50 DEG C, sequentially adds 30 grams of polymeric dispersants, (100g styrene, 50g acrylic acid are different pungent for 150 grams of mix monomers
Ester), 1.5 grams of dimethylaminoethyl methacrylates are warming up to 85 DEG C, and 3g dibenzoyl peroxide is added, and react 2.5hr.Add
Enter 1.0 grams of potassium peroxydisulfates the reaction was continued 1hr.Cypres, pH=2.42, solid content are filtered to obtain through 325 mesh filter screens after cooling
=25.4%.
Embodiment 5
1, prepared by polymeric dispersant:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 100 grams of maleic acids are added
Acid anhydride, 750 grams of polyvinyl alcohol dissolve by heating, 100 DEG C of reaction 3hr.50 DEG C of addition 135g chlorosulfonic acids are cooled to, the reaction was continued
2.5hr。
2, the preparation of efficient and environment-friendly type Cypres:
In the 1000ml four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 510 grams of deionizations are added
Water is heated to 50 DEG C, sequentially adds 40 grams of polymeric dispersants, (100g styrene, 80g acrylic acid are different pungent for 180 grams of mix monomers
Ester), 3 grams of dimethylaminoethyl methacrylates are warming up to 90 DEG C, and 3g peroxidized t-butyl perbenzoate is added, and react 2.0hr.
It is added 5.0 grams of potassium peroxydisulfates the reaction was continued 1hr.Cypres, pH=2.39 are filtered to obtain through 325 mesh filter screens after cooling, admittedly contain
Amount=28.9%.
Comparative example
By sizing agent prepared by the method for Chinese patent CN106245431A embodiment 4, it is diluted to deionized water
15wt% is as a comparison case.
Application Example
Environment-friendly type Cypres prepared by embodiment 1-5, are diluted to 15wt% with deionized water.
The preparation of glue application solution: preparing 500 grams of 10wt% oxidized starch aqueous solutions, is warming up to 90 DEG C, is gelatinized 20 minutes, cooling
To 40 DEG C, add comparative example and Examples 1 to 5 formula preparation sizing agent (oxidized starch (dry): sizing agent (wet)=50:
3) it, adds water and is diluted to 8wt%.
The measurement of Cobb value:
Using can vigorous absorbability analyzer by GB/T 1540-1989 method detect pattern to be measured.
Surface strength test:
Pattern to be measured is detected using IGT printability instrument.
It is glued in speciality paper upper surface:
Above-mentioned sizing material is used on speciality paper using the glue application solution that comparative example and Examples 1 to 5 formula are prepared, in laboratory
On small-sized sizing applicator, with identical resin added (single side 1.3g/m2) single side sizing is carried out respectively, the pattern after sizing is with identical
Temperature, time (150 DEG C of * 20s) are dried on polisher, are measured after pattern curing 5min.Measurement result is shown in Table 1 institute
Show.
1 product performance index of table
From it is above-mentioned using result it can be seen that compared with comparative example, can not only be reduced using Cypres of the invention
The Cobb value of paper, while the surface strength of paper can be improved.
The above shows and describes the basic principle, main features and advantages of the invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The scope of protection of present invention by appended claims and
Its equivalent thereof.
Claims (10)
1. a kind of preparation method of soap-free emulsion method synthetic environment-friendly Cypres, which comprises the steps of: will
Polymeric dispersant, (methyl) styrene, (methyl) acrylic ester monomer, feature cation monomer are mixed with water, are heated to
80-90 DEG C, initiator for reaction is then added, sufficiently obtains environment-friendly type Cypres after reaction, the polymeric dispersant be by
Maleic anhydride and polyvinyl alcohol are after polycondensation reaction again and made of chlorosulfonic acid reaction.
2. the method as described in claim 1, which is characterized in that the dosage of each component is distinguished as follows according to parts by weight:
3. the method as described in claim 1, which is characterized in that the feature cation monomer is selected from methacryloxypropyl second
Base trimethyl ammonium chloride, methyl allyl acyloxypropyl trimethoxysilane, dimethyl diallyl ammonium chloride, methacrylic acid two
At least one of methylamino ethyl ester.
4. the method as described in claim 1, which is characterized in that the preparation method of the polymeric dispersant includes the following steps:
By maleic anhydride and polyvinyl alcohol, polycondensation reaction is carried out after being heated to melting；Cool down after the reaction was completed, chlorosulfonic acid be added,
The polymeric dispersant is obtained after to fully reacting.
5. method as claimed in claim 4, which is characterized in that the dosage of each component is distinguished as follows according to parts by weight:
100 parts of maleic anhydride,
600-800 parts of polyvinyl alcohol,
120-150 parts of chlorosulfonic acid.
6. method as claimed in claim 4, which is characterized in that the temperature of the polycondensation reaction is 80-120 DEG C, the reaction time
For 2-4hr, it is cooled to 40-60 DEG C after the reaction was completed, chlorosulfonic acid is added, the reaction was continued 1-3hr obtains the polymeric dispersant.
7. the method as described in claim 1, which is characterized in that (methyl) acrylic ester monomer is selected from acrylic acid first
Ester, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, acrylic acid hydroxyl second
Ester, hydroxypropyl acrylate, methyl methacrylate, Tert-butyl Methacrylate, isooctyl methacrylate, acrylic acid positive third
At least one of ester, cyclohexyl acrylate, lauryl acrylate.
8. the method as described in claim 1, which is characterized in that the initiator is selected from dibenzoyl peroxide, benzoyl peroxide
T-butyl formate, peroxidating tin dilaurate, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide,
Sodium peroxydisulfate, hydrogen peroxide-ferrous sulfate, sodium peroxydisulfate-sodium sulfite, sodium peroxydisulfate-sodium hydrogensulfite, the secondary Asia of sodium peroxydisulfate-
At least one of sodium phosphate.
9. the method as described in claim 1, which is characterized in that the initiator of the total dosage 75wt% of Zhan is added in step 1,
Then remaining initiator is added in the polymerization reaction of step 2.
10. the environment-friendly type Cypres of any one of -9 the method preparations are in paper for surface sizing according to claim 1
Using, which is characterized in that by the oxidized starch after the environment-friendly type Cypres and gelatinization according to mass ratio 0.7-1.2:100
Compounding obtains glue application solution, is used for paper for surface sizing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09195168A (en) * | 1996-01-22 | 1997-07-29 | Lion Corp | Sizing agent composition |
| CN101649579A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing cation high molecular base petroleum resin neutral sizing agent |
| CN109537358A (en) * | 2018-11-07 | 2019-03-29 | 上海东升新材料有限公司 | A kind of polymeric dispersant and the environment-friendly type Cypres using dispersing agent preparation |
| US20190263946A1 (en) * | 2016-12-30 | 2019-08-29 | Changzhou University | A Process for Preparing Branched Polymer Via Emulsion Polymerization at Room Temperature |
-
2019
- 2019-07-25 CN CN201910674794.2A patent/CN110409219A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09195168A (en) * | 1996-01-22 | 1997-07-29 | Lion Corp | Sizing agent composition |
| CN101649579A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing cation high molecular base petroleum resin neutral sizing agent |
| US20190263946A1 (en) * | 2016-12-30 | 2019-08-29 | Changzhou University | A Process for Preparing Branched Polymer Via Emulsion Polymerization at Room Temperature |
| CN109537358A (en) * | 2018-11-07 | 2019-03-29 | 上海东升新材料有限公司 | A kind of polymeric dispersant and the environment-friendly type Cypres using dispersing agent preparation |
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