CN110886130A - Modified nano-cellulose emulsifier and AKD emulsion prepared by adopting same - Google Patents
Modified nano-cellulose emulsifier and AKD emulsion prepared by adopting same Download PDFInfo
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- CN110886130A CN110886130A CN201811055778.7A CN201811055778A CN110886130A CN 110886130 A CN110886130 A CN 110886130A CN 201811055778 A CN201811055778 A CN 201811055778A CN 110886130 A CN110886130 A CN 110886130A
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- cellulose
- akd
- emulsifier
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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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The invention discloses a modified nano-cellulose emulsifier, which is prepared by dispersing nano-cellulose in a proper amount of water, adding molten AKD wax, then adding styrene, acrylic monomers and an initiator, and polymerizing and emulsifying under high-speed shearing. The invention also provides an AKD emulsion, which is prepared by emulsifying the AKD wax by adopting the modified nano-cellulose emulsifier. The invention carries out chemical modification on the nano-cellulose, successfully prepares a modified nano-cellulose emulsifier and further obtains a novel AKD emulsion with excellent performance. The AKD emulsion has the characteristics of high curing rate and high sizing degree, and has wide application value in the field of papermaking.
Description
Technical Field
The invention relates to the technical field of preparation of AKD sizing agents, in particular to a modified nano-cellulose emulsifier and AKD emulsion prepared by adopting the emulsifier.
Background
The purpose of sizing is to provide the paper or paperboard with resistance to liquid diffusion and penetration, to be suitable for writing and to resist moisture and humidity. In this process, the neutral sizing agent AKD is of great interest due to its good properties.
AKD is a waxy solid, does not have a charge per se, and therefore cannot be applied to fibersOn the other hand, cationic emulsifier is needed to make it have positive charge, and the cationic emulsifier is adsorbed on the fiber to react with the fiber to produce sizing effect. Earlier, cationic starches were generally used as emulsifiers. Because the starch has low charge quantity, the starch has low retention rate on fiber and is easy to mildew, and the stability of the emulsion and the later-stage sizing effect are influenced. The nano microcrystalline cellulose has the advantages of high purity, high crystallinity, high elastic modulus, high strength and the like, has the characteristics of light weight, degradability, good biocompatibility, renewability and the like of biological materials, and shows great application prospect in high-performance composite materials. However, pure nanocrystalline cellulose has a large specific surface area (higher than 100 m)2/g), agglomeration and flocculation are easy to occur; high hydrophilicity, strong binding force with water and poor compatibility with hydrophobic materials, thereby limiting the application range of the hydrophobic materials.
Disclosure of Invention
The invention aims to provide a modified nano-cellulose emulsifier and AKD emulsion prepared by adopting the emulsifier, so as to solve the defects in the background technology.
The invention is realized by the following technical scheme:
a modified nano-cellulose emulsifier is prepared by adding nano-cellulose and AKD wax into a reaction system for preparing styrene-acrylic emulsion for modification. The preparation method comprises the following steps: ultrasonically dispersing nano-cellulose in a proper amount of water, adding molten AKD wax, then adding styrene, acrylic monomers and an initiator, and polymerizing and emulsifying under high-speed shearing to obtain the modified nano-cellulose emulsifier.
Further, the following components are used in parts by weight:
preferably, the diameter of the nano-cellulose is 5-20 nanometers, and the length of the nano-cellulose is 50-1000 nanometers.
Preferably, the acrylic monomer is at least one selected from acrylic acid, acrylate, methacrylic acid and methacrylate;
the initiator is at least one selected from sodium persulfate, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide, azobisisobutyronitrile, azobisisobutylamidine hydrochloride, N-dimethylaniline, N-dimethyl-p-toluidine, azobisisoheptonitrile and dimethyl azobisisobutyrate.
As a preferable technical scheme, the preparation method of the modified nano-cellulose emulsifier comprises the following steps: ultrasonically dispersing nano-cellulose in a proper amount of water to prepare a dispersion liquid with the concentration of 10 wt%, adding molten AKD wax, then adding styrene, acrylic monomers and an initiator, and polymerizing and emulsifying at the rotation speed of 8000-.
The invention further provides AKD emulsion, which is prepared by emulsifying AKD wax by adopting the modified nano-cellulose emulsifier.
As a further preferable technical scheme, the AKD emulsion comprises the following components in parts by weight:
preferably, the stabilizing auxiliary agent is selected from at least one of high-purity polyaluminium chloride, polyamide polyamine epichlorohydrin resin, sodium dodecyl sulfate and cetyl alcohol.
The AKD emulsion emulsified by the modified nano-cellulose emulsifier can be prepared by adopting a conventional method in the field, for example, the following method is adopted:
and melting AKD wax in a water bath, slowly adding the modified nano-cellulose emulsifier, shearing and emulsifying for 2-3 minutes at 8000r/min of 5000-. Wherein the amount of the added water is adjusted according to the actual use requirement of the AKD emulsion product, and the preferable amount of the water is 200-500 parts by weight.
The invention makes full use of a large amount of active hydroxyl groups on the surface of the nano microcrystalline cellulose to carry out chemical modification, successfully prepares a modified nano cellulose emulsifier and further obtains a novel AKD emulsion with excellent performance. The AKD emulsion has the characteristics of high curing rate and high sizing degree, and has wide application value in the field of papermaking.
Detailed Description
The invention is illustrated below by means of specific examples, without being restricted thereto.
Example 1
The technical scheme of the embodiment is as follows:
1. by mass, 100 parts of nano-cellulose is ultrasonically dispersed in a proper amount of water, 70 parts of molten AKD is added, the temperature is heated to 65 ℃, and the AKD is heated for 10-20 minutes to be fully melted.
2. Then adding 10 parts of styrene, 20 parts of methyl methacrylate, 0.1 part of sodium persulfate and 10 parts of butyl acrylate into the system, uniformly mixing, and carrying out high-speed shearing emulsification at the rotating speed of 10500r/min to obtain the modified nanofiber emulsifier.
3. Melting 250 parts of AKD wax in a water bath, slowly adding the modified nano-cellulose emulsifier solution, shearing and emulsifying for 3 minutes at 8000r/min, adding 5 parts of sodium dodecyl sulfate and 300 parts of water, continuously shearing and stirring at a high speed for a certain time, rapidly cooling, and discharging.
Example 2
The technical scheme of the embodiment is as follows:
1. by mass, 100 parts of nano-cellulose is ultrasonically dispersed in a proper amount of water, 75 parts of molten AKD is added, the temperature is heated to 65 ℃, and the AKD is heated for 10-20 minutes to be fully melted.
2. Then adding 8 parts of styrene, 20 parts of methyl methacrylate, 0.1 part of ammonium persulfate and 10 parts of butyl acrylate into the system, uniformly mixing, and carrying out high-speed shearing emulsification at the rotating speed of 10000r/min to obtain the modified nanofiber emulsifier.
3. And (2) melting 200 parts of AKD wax in a water bath, slowly adding the modified nano-cellulose emulsifier solution, shearing and emulsifying for 2 minutes at the speed of 5000r/min, adding 3 parts of polyaluminum chloride and 200 parts of water, continuously shearing and stirring at a high speed for a certain time, rapidly cooling, and discharging.
Example 3
The technical scheme of the embodiment is as follows:
1. by mass, 100 parts of nano-cellulose is ultrasonically dispersed in a proper amount of water, 70 parts of molten AKD is added, the temperature is heated to 65 ℃, and the AKD is heated for 10-20 minutes to be fully melted.
2. Then adding 8 parts of styrene, 20 parts of methyl methacrylate, 0.1 part of dibenzoyl peroxide and 10 parts of butyl acrylate into the system, uniformly mixing, and carrying out high-speed shearing emulsification at the rotating speed of 9500r/min to obtain the modified nanofiber emulsifier.
3. And (2) melting 400 parts of AKD wax in a water bath, slowly adding the modified nano-cellulose emulsifier solution, shearing and emulsifying at 7000r/min for 2 minutes, adding 4 parts of sodium bicarbonate and 400 parts of water, continuously shearing and stirring at a high speed for a certain time, rapidly cooling, and discharging.
Example 4
The technical scheme of the embodiment is as follows:
1. by mass, 100 parts of nano-cellulose is ultrasonically dispersed in a proper amount of water, 80 parts of molten AKD is added, the temperature is heated to 65 ℃, and the AKD is heated for 10-20 minutes to be fully melted.
2. Then adding 8 parts of styrene, 20 parts of methyl methacrylate and 0.1 part of azobisisobutyronitrile and 10 parts of butyl acrylate into the system, uniformly mixing, and carrying out high-speed shearing emulsification at the rotating speed of 8500r/min to obtain the modified nanofiber emulsifier.
3. And (2) melting 350 parts of AKD wax in a water bath, slowly adding the modified nano-cellulose emulsifier solution, shearing and emulsifying for 3 minutes at 8000r/min, adding 5 parts of polyamide polyamine epoxy chloropropane resin and 500 parts of water, continuously shearing and stirring at a high speed for a certain time, rapidly cooling, and discharging.
Application examples
Taking the gelatinized starch AKD emulsion as a comparative example, papermaking:
selecting 0.5% softwood pulp by mass, sequentially adding 0.2% AKD and 0.02% cationic polyacrylamide by mass of oven-dried pulp, stirring for 1min, finally adding 20% GCC (ground calcium carbonate), stirring uniformly, making paper, and making quantitative 60 g.m.-2About, squeezing with oil press under 0.4MPa for 1min, and drying with vacuum drier (about 92 deg.C) for 4 min. And (5) taking the rubber coating off the machine to measure the sizing degree. The sizing degree is determined according to GB/T5405-1985.
Further, the aging rate was calculated according to the following formula:
the measurement results are shown in table 1:
TABLE 1
| Degree of sizing (%) | Maturation Rate (%) | |
| Comparative example | 51 | 59 |
| Example one | 76 | 85 |
| Example two | 69 | 80 |
| EXAMPLE III | 71 | 82 |
| Example four | 74 | 87 |
The result shows that the AKD emulsion prepared by the invention has higher sizing degree and curing rate, and generates unexpected technical effect.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A modified nano-cellulose emulsifier is characterized in that nano-cellulose and AKD wax are added into a reaction system for preparing styrene-acrylic emulsion for modification.
2. The preparation method of the modified nano-cellulose emulsifier is characterized by comprising the following steps: ultrasonically dispersing nano-cellulose in a proper amount of water, adding molten AKD wax, then adding styrene, acrylic monomers and an initiator, and polymerizing and emulsifying under high-speed shearing to obtain the modified nano-cellulose emulsifier.
3. The method of claim 2, wherein the components are used in the following amounts in parts by weight:
4. the method of claim 2, wherein the nanocellulose has a diameter of 5-20 nm and a length of 50-1000 nm.
5. The method of claim 2, wherein the acrylic monomer is selected from at least one of acrylic acid, acrylate, methacrylic acid, and methacrylate.
6. The method of claim 2, wherein said initiator is selected from at least one of sodium persulfate, ammonium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, azobisisobutyronitrile, azobisisobutylamidine hydrochloride, N-dimethylaniline, N-dimethyl-p-toluidine, azobisisoheptonitrile, and dimethyl azobisisobutyrate.
7. The method of any one of claims 2 to 6, wherein the modified nanocellulose emulsifier is prepared by a process comprising the steps of: ultrasonically dispersing nano-cellulose in a proper amount of water to prepare a dispersion liquid with the concentration of 10 wt%, adding molten AKD wax, then adding styrene, acrylic monomers and an initiator, and polymerizing and emulsifying at the rotation speed of 8000-.
8. An AKD emulsion, characterized in that it is prepared by emulsifying AKD wax with the modified nanocellulose emulsifier prepared by the method of any one of claims 2 to 7.
9. The AKD emulsion according to claim 8, comprising the following components in parts by weight:
10. the AKD emulsion according to claim 9, wherein the stabilizing additive is at least one selected from the group consisting of high purity polyaluminum chloride, polyamide polyamine epichlorohydrin resins, sodium lauryl sulfate, and cetyl alcohol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811055778.7A CN110886130B (en) | 2018-09-11 | 2018-09-11 | Modified nano-cellulose emulsifier and AKD emulsion prepared by adopting same |
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| CN201811055778.7A CN110886130B (en) | 2018-09-11 | 2018-09-11 | Modified nano-cellulose emulsifier and AKD emulsion prepared by adopting same |
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| CN110886130B CN110886130B (en) | 2022-07-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745451A (en) * | 2020-12-29 | 2021-05-04 | 华南理工大学 | Styrene-acrylic emulsion stabilized by CNF (styrene-butadiene-styrene) and preparation method and application thereof |
| CN113136194A (en) * | 2021-04-26 | 2021-07-20 | 中国石油大学(华东) | Emulsion based on nanocellulose and preparation method and application thereof |
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Cited By (3)
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| CN112745451B (en) * | 2020-12-29 | 2021-11-23 | 华南理工大学 | Styrene-acrylic emulsion stabilized by CNF (styrene-butadiene-styrene) and preparation method and application thereof |
| CN113136194A (en) * | 2021-04-26 | 2021-07-20 | 中国石油大学(华东) | Emulsion based on nanocellulose and preparation method and application thereof |
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