CN112813729B - Hydrolysis-resistant alkenyl succinic anhydride sizing agent and preparation method and application thereof - Google Patents
Hydrolysis-resistant alkenyl succinic anhydride sizing agent and preparation method and application thereof Download PDFInfo
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- CN112813729B CN112813729B CN202110034075.1A CN202110034075A CN112813729B CN 112813729 B CN112813729 B CN 112813729B CN 202110034075 A CN202110034075 A CN 202110034075A CN 112813729 B CN112813729 B CN 112813729B
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- succinic anhydride
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- 238000004513 sizing Methods 0.000 title claims abstract description 76
- 229940014800 succinic anhydride Drugs 0.000 title claims abstract description 36
- -1 alkenyl succinic anhydride Chemical compound 0.000 title claims abstract description 34
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000004945 emulsification Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 11
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 9
- 229960004624 perflexane Drugs 0.000 claims abstract description 9
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims abstract description 8
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 11
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002159 nanocrystal Substances 0.000 claims description 8
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003995 emulsifying agent Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LTMQZVLXCLQPCT-UHFFFAOYSA-N 1,1,6-trimethyltetralin Chemical compound C1CCC(C)(C)C=2C1=CC(C)=CC=2 LTMQZVLXCLQPCT-UHFFFAOYSA-N 0.000 description 2
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- RSPWVGZWUBNLQU-FOCLMDBBSA-N 3-[(e)-hexadec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O RSPWVGZWUBNLQU-FOCLMDBBSA-N 0.000 description 1
- GBBHWGRJHHNAGT-UHFFFAOYSA-N 3-hexadecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC1CC(=O)OC1=O GBBHWGRJHHNAGT-UHFFFAOYSA-N 0.000 description 1
- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 241000212749 Zesius chrysomallus Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention provides a preparation method of an anti-hydrolysis alkenyl succinic anhydride sizing agent, which comprises the following steps: mixing the CNC aqueous dispersion with acetone, ammonium monohydrate and hexadecyl trimethyl siloxane, and performing ultrasonic dispersion to obtain a mixed solution I; adding perfluorooctyl triethoxysilane into the mixed solution I, and performing ultrasonic dispersion to obtain a mixed solution II; drying the mixed solution II to obtain CNC-R powder; mixing CNC-R powder with perfluorohexane, performing ultrasonic dispersion, adding alkenyl succinic anhydride, mixing, and performing ultrasonic emulsification to obtain ASA-A emulsion; and mixing the ASA-A emulsion with a sodium dodecyl sulfate aqueous solution, and performing ultrasonic emulsification to obtain the hydrolysis-resistant alkenyl succinic anhydride sizing agent. The ASA emulsion prepared by the method has obviously improved surface sizing performance, and can greatly improve the hydrolysis resistance of ASA; the ASA sizing agent emulsion has the advantages of simple preparation process, small using amount of the emulsifying agent, low emulsifying cost and good sizing effect.
Description
Technical Field
The invention relates to the technical field of papermaking, in particular to an anti-hydrolysis alkenyl succinic anhydride sizing agent and a preparation method and application thereof.
Background
The emulsion is a dispersion system formed by dispersing a liquid in another liquid immiscible with the liquid, is mostly formed by mixing a water-insoluble oil phase and a water phase, and is widely applied to industries of papermaking, food, cosmetics, medicines and the like. Emulsions are thermodynamically unstable systems and in order to maintain the relative stability of the emulsion (kinetic stability) emulsifiers or stabilizers have to be added during the preparation of the emulsion. Most of the traditional emulsifiers or stabilizers are surfactants and high molecular polymers with surface activity, and the stability of the emulsion is maintained by reducing the interfacial tension between oil-water two-phase liquid, providing a stable interfacial film and improving the viscosity of a continuous phase. In recent years, solid particles have been receiving more and more attention because they can avoid adverse effects of surfactants on the environment, stabilize highly concentrated dispersed phase emulsions, and are less affected by changes in pH, salt concentration, temperature, and oil phase composition. For example, in the paper industry, water-insoluble sizing agents for papermaking need to be emulsified into an oil-in-water emulsion to be compatible with the papermaking system using water as a medium, and the purpose of sizing for papermaking is to increase the water resistance of paper, and the presence of surfactants generally reduces the water resistance of paper in addition to causing adverse effects on the environment, which can be avoided by using solid particle stabilized sizing agent emulsions.
The paper making industry in the twentieth century changes from an acid paper making system to medium-alkaline paper making, is an innovative change of a paper making process, greatly improves the paper quality, expands the filler range, reduces the pulp consumption and the energy consumption, lightens the environmental pollution and prolongs the service life of equipment. China adopts medium and alkaline sizing in production since 1989, and gradually popularizes in recent years, so that Alkyl Ketene Dimer (AKD) and Alkenyl Succinic Anhydride (ASA) are mainly used at present, and ASA is gradually adopted in large and medium-sized paper mills. In particular, in recent years, ASA sizing agents have been widely used for internal sizing of fine paper and board, particularly for large high-speed paper machines for internal coating, due to their high reactivity, low sizing cost, and high curing rate. However, ASA is a neutral sizing agent for papermaking with high reactivity, the hydrolysis speed is high, the sizing effect is reduced after the emulsion is stored for more than 1 hour at room temperature, the hydrolysate can cause paper making obstruction and the sizing efficiency is reduced, so when ASA is used, the ASA is required to be emulsified quickly, and the emulsified emulsion is required to be used as soon as possible. Alkenyl Succinic Anhydride (ASA) is very easy to hydrolyze, alcoholysis and aminolysis, so alcohol, carboxylic acid and ammonia compounds are not suitable for being used as an emulsifier for ASA. At present, cationic starch and low molecular surfactant are mainly utilized for on-site emulsification of the ASA sizing agent and are used immediately, the shelf life of the emulsified ASA emulsion is short, and most of the sizing activity can be lost in 2-6 hours; in addition, the starch used for emulsifying ASA needs to be gelatinized and cooled before use, so that the ASA emulsifying process is quite complex and difficult to control, and the problems of deposition, felt blockage and the like are often caused. In addition, the surfactant in the sizing agent has certain adverse effects on sizing and certain pollution on the environment.
At present, the research and the achievement of the emulsification preparation aspect of the ASA sizing agent are gradually enriched. US patent US6346554 discloses a method for stabilizing ASA emulsions using natural vegetable gums which purportedly increase ASA sizing efficiency by increasing ASA retention on the fibers, reducing ASA hydrolysis and consequent deposition problems, and forming a more uniform film on the fiber surface. US5962555 discloses a method for emulsifying ASA using a mixture of ionene polymers which not only increase sizing efficiency but also have a bactericidal effect and polyethyleneimine. These inventions avoid the inconvenience of starch gelatinization in handling, but still require the addition of about 2% surfactant to obtain a stable ASA emulsion. US6284099 discloses a method for stabilizing ASA emulsions using anionic microparticle retention aids such as bentonite, colloidal silica, organic microparticles, and small amounts of surfactants and chelating agents for papermaking, which combines the microparticle retention aid with a sizing agent, simplifies the operation, and reduces the amount of surfactant used; however, the adverse effects of surfactants cannot be completely avoided, and the addition of the particulate component is too large, resulting in ASA emulsions with very low concentrations, which are disadvantageous for the storage of the emulsions, and severe ASA hydrolysis. Chinese patent 201510417679.9 discloses a biodegradable solid particle emulsifier based on modified cellulose nanocrystal particles and an emulsified ASA sizing agent thereof, the emulsified emulsion has good stability and can meet the general production requirements, but the emulsion has general stability, the sizing activity can only be kept for about 3 hours, and the limitation of ASA used in field emulsification still can not be removed.
In conclusion, the ASA sizing agent emulsion needs to be prepared at present, the ASA sizing agent emulsion is poor in stability and extremely easy to hydrolyze, and the shelf life of the sizing agent emulsion for papermaking is short.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an anti-hydrolysis alkenyl succinic anhydride sizing agent, a preparation method and application thereof, and the prepared ASA sizing agent has high stability and strong hydrolysis resistance.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of an anti-hydrolysis alkenyl succinic anhydride sizing agent comprises the following steps:
(1) mixing Cellulose Nanocrystalline (CNC) water dispersion with acetone, ammonium monohydrate and hexadecyl trimethyl siloxane, and performing ultrasonic dispersion to obtain mixed solution I; adding perfluorooctyl triethoxysilane into the mixed solution I, and performing ultrasonic dispersion to obtain a mixed solution II; drying the mixed solution II to obtain CNC-R powder;
(2) mixing CNC-R powder with perfluorohexane, performing ultrasonic dispersion, adding Alkenyl Succinic Anhydride (ASA) for mixing, and performing ultrasonic emulsification to obtain ASA-A emulsion;
(3) mixing the ASA-A emulsion with a sodium dodecyl sulfate aqueous solution, and performing ultrasonic emulsification to obtain the ASA-B emulsion, namely the hydrolysis-resistant alkenyl succinic anhydride sizing agent.
The diameter of the Cellulose Nanocrystal (CNC) is 3-10nm, and the length is 100-500 nm.
The mass fraction of the cellulose nanocrystalline in the mixed solution I is 0.05-2%, the mass fraction of the acetone is 0.1-1%, and the mass fraction of the ammonium monohydrate is 0.5-2%.
The dosage of the hexadecyl trimethyl siloxane is 2-30% of the mass of the cellulose nanocrystal.
The consumption of the perfluorooctyl triethoxysilane accounts for 5-20% of the mass of the cellulose nanocrystal.
The alkenyl succinic anhydride is at least one of dodecyl to octadecyl alkenyl succinic anhydride monomers, and more preferably at least one of tetradecyl to hexadecyl alkenyl succinic anhydride monomers; when the alkenyl succinic anhydride is a mixture, the ratio of the dodecyl to octadecyl alkenyl succinic anhydride monomer is not particularly limited, and the dodecyl to octadecyl alkenyl succinic anhydride monomer can be mixed according to any ratio. The invention utilizes alkenyl succinic anhydride as a base stock for sizing agents.
The mass ratio of the CNC-R powder to the perfluorooctane is 1: 20-100.
The mass ratio of the alkenyl succinic anhydride to the perfluorooctane is 1: 0.1-2.
The mass ratio of the ASA-A emulsion to the sodium dodecyl sulfate aqueous solution is 1: 0.5-10.
The mass percentage of the sodium dodecyl sulfate aqueous solution is 0.1-2%, preferably 0.2-1%.
The power of the ultrasonic dispersion is 500-3000W.
An anti-hydrolysis alkenyl succinic anhydride sizing agent obtained by the preparation method.
An application of the anti-hydrolysis alkenyl succinic anhydride sizing agent in preparation of water-resistant paper.
The invention has the following advantages:
the oil-in-water-in-oil (W/O/O) type composite ASA emulsion emulsified and stabilized by CNC-R and sodium dodecyl sulfate has ultrahigh stability and strong hydrolysis resistance. The ASA sizing agent emulsion prepared by the invention does not generate particle aggregation and precipitation, does not have any phase body precipitation and demulsification phenomenon after being placed for 90 days, has good emulsion stability, almost does not attenuate the sizing degree of sized paper, can reach 455 seconds when the internal sizing amount of the paper pulp is 0.2% (relative to the mass percentage of absolute dry pulp), and has good sizing performance and hydrolysis resistance. The invention is expected to solve the problems of the on-site emulsification and on-site sizing process commonly adopted by the prior ASA papermaking sizing process and the sizing process limitation caused by ASA hydrolysis. Compared with ASA emulsions with stable emulsification of traditional surfactants (such as starch) and ASA emulsions with stable emulsification of solid particles (such as clay nanoparticles and modified particles thereof), the ASA emulsions prepared by the method have the advantages that the surface sizing performance is remarkably improved, and the hydrolysis resistance of ASA can be greatly improved; the ASA sizing agent emulsion has the advantages of simple preparation process, small using amount of the emulsifier, low emulsification cost and good sizing effect.
Drawings
FIG. 1 is a micrograph of an ASA-A emulsion prepared according to example 2;
FIG. 2 is a micrograph of an ASA-B emulsion prepared according to example 2.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Example 1 preparation of hydrolysis resistant dodecenyl succinic anhydride sizing agent
(1) Dispersing 1 part by weight of CNC (computerized numerical control) (with the diameter of 3nm and the length of 100 nm) in water to prepare a dispersion liquid with the mass fraction of 0.05%, adding 2 parts by weight of acetone, 10 parts by weight of ammonium monohydrate and 0.02 part by weight of hexadecyl trimethyl siloxane, mixing, and ultrasonically dispersing at the temperature of 25 ℃ for 1 hour at 500W to obtain a mixed solution I; adding 0.05 weight part of perfluorooctyl triethoxysilane into the mixed solution I, and continuing to perform ultrasonic dispersion for 1 hour to obtain mixed solution II; vacuum drying the mixed solution II at 65 ℃ to obtain CNC-R powder;
(2) mixing 1 part by weight of CNC-R powder with 20 parts by weight of perfluorohexane, ultrasonically dispersing the mixture at 25 ℃ for 1 hour by 500W, adding 200 parts by weight of dodecenyl succinic anhydride, mixing, and continuing to ultrasonically emulsify the mixture for 15 minutes to obtain ASA-A emulsion;
(3) mixing 2 parts by weight of ASA-A emulsion with 1 part by weight of sodium dodecyl sulfate aqueous solution with the mass concentration of 0.1%, and ultrasonically emulsifying for 15 minutes at 25 ℃ under 500W to obtain ASA-B emulsion, namely an anti-hydrolysis alkenyl succinic anhydride sizing agent.
Example 2 preparation of hydrolysis resistant hexadecylsuccinic anhydride sizing agent
(1) Dispersing 1 part by weight of CNC (computerized numerical control) (diameter 5nm and length 220 nm) in water to prepare a dispersion liquid with the mass fraction of 1%, adding 10 parts by weight of acetone, 20 parts by weight of ammonium monohydrate and 0.2 part by weight of hexadecyl trimethyl siloxane, mixing, and performing ultrasonic dispersion at 25 ℃ for 1 hour at 1000W to obtain a mixed solution I; adding 0.1 part by weight of perfluorooctyl triethoxysilane into the mixed solution I, and continuing to perform ultrasonic dispersion for 1 hour to obtain mixed solution II; vacuum drying the mixed solution II at 65 ℃ to obtain CNC-R powder;
(2) mixing 1 part by weight of CNC-R powder with 60 parts by weight of perfluorohexane, ultrasonically dispersing the mixture at the temperature of 25 ℃ for 1 hour by 1000W, adding 60 parts by weight of hexadecenyl succinic anhydride, mixing, and continuously ultrasonically emulsifying the mixture for 15 minutes to obtain ASA-A emulsion; the micrograph is shown in figure 1: wherein the continuous phase is perfluorohexane, the droplets are perfluorohexane-coated ASA emulsion (oil-in-oil) droplets, and the interface component of the droplets is composed of ASA emulsion (oil-in-oil) droplets with long-chain alkyl groups [ - (CH) grafted on the surface 2 ) x CH 3 ]And long-chain perfluoroalkane group [ - (CH) 2 ) x (CF 2 ) x CF 3 ]Modified CNC-R particles effective as interfacial particle stabilizers to stabilize perfluorohexane and ASA oil phases to form ASA-A emulsions having an average droplet diameter of about 1 μm.
(3) Mixing 1 part by weight of ASA-A emulsion with 5 parts by weight of sodium dodecyl sulfate aqueous solution with the mass concentration of 0.5%, and ultrasonically emulsifying for 15 minutes at the temperature of 25 ℃ under 1000W to obtain ASA-B emulsion, namely an anti-hydrolysis alkenyl succinic anhydride sizing agent, wherein a micrograph of the ASA-A emulsion is shown in figure 2:
the sizing agent emulsion takes sodium dodecyl sulfate aqueous solution as a continuous phase, and the ASA-perfluorooctane emulsion is uniformly dispersed in the sodium dodecyl sulfate aqueous solution in a spherical dispersion droplet form; wherein ASA is coated by perfluorooctane, and CNC-R is adsorbed at an oil-oil interface between ASA and perfluorooctane in the form of solid particles to form an oil-oil emulsion; the finally obtained ASA emulsion liquid drop is wrapped by the outer oil phase, so that the contact between ASA and a water phase is avoided, and the purpose of avoiding hydrolysis is achieved.
Example 3 preparation of hydrolysis resistant alkenyl succinic anhydride sizing agent
(1) Dispersing 2 parts by weight of CNC (computer numerical control) (with the diameter of 10nm and the length of 500 nm) in water to prepare a dispersion liquid with the mass fraction of 2%, adding 1 part by weight of acetone, 2 parts by weight of ammonium monohydrate and 0.6 part by weight of hexadecyl trimethyl siloxane, mixing, and ultrasonically dispersing at the temperature of 25 ℃ for 1 hour at 3000W to obtain a mixed solution I; adding 0.4 part by weight of perfluorooctyl triethoxysilane into the mixed solution I, and continuing to perform ultrasonic dispersion for 1 hour to obtain mixed solution II; vacuum drying the mixed solution II at 65 ℃ to obtain CNC-R powder;
(2) mixing 1 part by weight of CNC-R powder with 100 parts by weight of perfluorohexane, ultrasonically dispersing at 3000W for 1 hour at 25 ℃, adding 10 parts by weight of octadecenyl succinic anhydride, mixing, and continuing to ultrasonically emulsify for 15 minutes to obtain ASA-A emulsion;
(3) mixing 1 part by weight of ASA-A emulsion with 10 parts by weight of sodium dodecyl sulfate aqueous solution with the mass concentration of 1%, and ultrasonically emulsifying for 15 minutes at 3000W at 25 ℃ to obtain ASA-B emulsion, namely an anti-hydrolysis alkenyl succinic anhydride sizing agent.
Comparative example 1
The stable alkenyl succinic anhydride papermaking sizing agent emulsion (CN 200810017130.0) is prepared by using micro-floccules of anion and cation inorganic nano-particles as an emulsifying and stabilizing agent, and the specific method is the method adopted in example 4 in the patent. The method comprises the following specific steps: 2g of sodium fluoride modified sodium bentonite (crude soil is obtained from Liaoning), 0.02g of interlayer anion is Cl - Dispersing ionic hydrotalcite in 40mL of deionized water to prepare an ASA emulsifier, wherein the solid content of the emulsifier is 4.8%; weighing 20g of industrial ASA, mixing the prepared emulsifier with ASA, keeping the oil-water ratio at 1:2, and emulsifying for 3min at 10000r/min by using a shearing emulsifying machine. The ASA emulsion was obtained as a uniform milky white oil-in-water (O/W) emulsion.
Application example hydrolysis-resistant alkenyl succinic anhydride sizing agent performance measurement
(1) Paper making of sized paper
Sizing by an internal sizing method. Before sizing, the sizing agent prepared in the example or the comparative example is diluted to 0.2%, the pulp concentration is adjusted to 1%, 1% of aluminum sulfate (mass percent relative to the oven dry pulp) is added into the pulp at the stirring speed of 500rpm, then the pH value of the pulp is adjusted to 7.5-8.5 by using 1 mol/L of sodium hydroxide solution, then the sizing agent (the amount is 1%, the mass percent relative to the total mass of the oven dry pulp) and the cationic polyacrylamide (the amount is 0.03% (mass percent relative to the oven dry pulp) are sequentially added, then the pulp is stirred for 2 minutes at the shearing speed of 500rpm by using a stirrer and is kept still for 30 seconds, and then a PTI paper sheet maker (model: RK3 AKWT) is used for making handsheets, the handsheets have the quantitative of 60 g/m 2 (T205 om-88, TAPPI), the sheet making system selects a Kaiser method manual sheet making mode to make sheets according to the ISO5289/2 and DIN54358 standards. The handsheets produced were dried at 105 ℃ and then the moisture of the paper was equilibrated at room temperature for 24h with an ambient humidity of 50%.
(2) Sizing degree measuring method
Sizing performance was evaluated by measuring the degree of sizing of paper made (GB/T5405-2002). Before measurement, the paper was cut into square pieces of 30X 30mm and allowed to stand at 25 ℃ under a 50% humidity environment to equilibrate the moisture for 24 hours. Folding the four sides of the paper to form a boat-shaped structure with the bottom surface area of about 20 multiplied by 20mm, then floating the boat-shaped structure in dilute ammonium thiocyanate solution with the concentration of 2 percent, dripping 0.5 mu L of iron chloride solution with the mass concentration of 1 percent on the upper part of the boat-shaped paper by a rubber head dropper, simultaneously timing by a stopwatch, and ending the timing when red spots appear in the middle of the iron chloride solution drops, wherein the timing time is the sizing degree of the paper sample. The front and back sides of the test sample were measured 10 times each and the average was taken.
(3) Method for measuring average particle diameter of liquid drop
The diameters of 100 emulsion droplets observed under a microscope are counted by using particle size counting software carried by an optical microscope, and the average value is taken, namely the average particle size of the droplets.
TABLE 1 Properties of different sizing agents
According to the table 1, the average diameter of emulsion droplets of the anti-hydrolysis ASA sizing agent prepared by the invention is smaller, and the emulsion is not precipitated by any phase body or demulsified after being placed for 90 days, which shows that the stability of the emulsion is good; the paper sizing degree of the sized paper is 454-511 seconds, which shows that the sizing performance of the emulsion is good; the sizing degree of the sizing paper after the emulsion is placed for 90 days is 441-510 seconds, and the hydrolysis resistance of the emulsion is good.
Claims (7)
1. The preparation method of the hydrolysis-resistant alkenyl succinic anhydride sizing agent is characterized by comprising the following steps of:
(1) mixing the cellulose nanocrystalline water dispersion liquid with acetone, ammonium monohydrate and hexadecyl trimethyl siloxane, and performing ultrasonic dispersion to obtain a mixed liquid I; adding perfluorooctyl triethoxysilane into the mixed solution I, and performing ultrasonic dispersion to obtain a mixed solution II; drying the mixed solution II to obtain CNC-R powder;
(2) mixing CNC-R powder with perfluorohexane, performing ultrasonic dispersion, adding alkenyl succinic anhydride, mixing, and performing ultrasonic emulsification to obtain ASA-A emulsion;
(3) mixing the ASA-A emulsion with a sodium dodecyl sulfate aqueous solution, and performing ultrasonic emulsification to obtain an ASA-B emulsion, namely an anti-hydrolysis alkenyl succinic anhydride sizing agent;
the dosage of the hexadecyl trimethyl siloxane is 2-30% of the mass of the cellulose nanocrystal; the dosage of the perfluorooctyl triethoxysilane is 5-20% of the mass of the cellulose nanocrystal;
the mass ratio of the CNC-R powder to the perfluorooctane is 1: 20-100.
2. The method as claimed in claim 1, wherein the cellulose nanocrystals have a diameter of 3-10nm and a length of 100-500 nm;
the mass fraction of the cellulose nanocrystal in the mixed solution I is 0.05-2%, the mass fraction of the acetone is 0.1-1%, and the mass fraction of the ammonia monohydrate is 0.5-2%.
3. The method according to claim 1, wherein the alkenyl succinic anhydride is at least one of alkenyl succinic anhydride monomers of dodecyl to octadecyl;
the mass ratio of the alkenyl succinic anhydride to the perfluorooctane is 1: 0.1-2.
4. The method according to claim 1, wherein the mass ratio of the ASA-A emulsion to the aqueous solution of sodium dodecyl sulfate is 1: 0.5-10;
the mass percentage of the sodium dodecyl sulfate aqueous solution is 0.1-2%.
5. The method as claimed in claim 1, wherein the power of the ultrasonic dispersion is 500-3000W.
6. An hydrolysis-resistant alkenyl succinic anhydride sizing agent obtained by the production method according to any one of claims 1 to 5.
7. Use of the hydrolysis-resistant alkenyl succinic anhydride sizing agent of claim 6 in the preparation of water-resistant paper.
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