CN115287938B - Food grade AKD sizing agent emulsion and preparation method thereof - Google Patents
Food grade AKD sizing agent emulsion and preparation method thereof Download PDFInfo
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- 238000004513 sizing Methods 0.000 title claims abstract description 66
- 239000000839 emulsion Substances 0.000 title claims abstract description 50
- 235000013305 food Nutrition 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000004945 emulsification Methods 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000013119 CD-MOF Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 241001122767 Theaceae Species 0.000 claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 1-octadecenyl Chemical group 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 12
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims abstract description 9
- 238000010008 shearing Methods 0.000 claims abstract description 8
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000005457 ice water Substances 0.000 claims abstract description 3
- 229940014800 succinic anhydride Drugs 0.000 claims abstract 2
- 239000012071 phase Substances 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 229920000858 Cyclodextrin Polymers 0.000 claims description 17
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 17
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012459 cleaning agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 239000001116 FEMA 4028 Substances 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 2
- 229960004853 betadex Drugs 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 28
- 235000013616 tea Nutrition 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000013146 β-CD-MOF Substances 0.000 description 4
- 235000019224 Camellia sinensis var Qingmao Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000020339 pu-erh tea Nutrition 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000212749 Zesius chrysomallus Species 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013145 α-CD-MOF Substances 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- D21H17/02—Material of vegetable origin
-
- 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
-
- 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
- D21H17/17—Ketenes, e.g. ketene dimers
-
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/64—Alkaline compounds
-
- 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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- 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
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention belongs to the technical field of papermaking, and provides food grade AKD sizing agent emulsion and a preparation method thereof. The preparation method of the AKD sizing agent emulsion comprises the following steps: (1) Dispersing CD in deionized water, regulating the pH to 8.5, dropwise adding 1-octadecenyl succinic anhydride until the pH is constant, and regulating the pH to 6.5 to obtain modified CD; (2) Dissolving the modified CD and KOH in water, adding methanol and CTAB for reaction to obtain modified CD-MOFs; (3) using the molten AKD as an oil phase; uniformly dispersing the modified CD-MOFs in tea juice to serve as a water phase; and shearing and emulsifying the water phase and the oil phase under the heat preservation condition, and then carrying out ice water bath to obtain the food grade AKD sizing agent. The CD-MOFs synthesized by using the food-grade raw materials has good biocompatibility and good application prospect in the food industry.
Description
Technical Field
The invention belongs to the technical field of papermaking, and particularly relates to food grade AKD sizing agent emulsion and a preparation method thereof.
Background
China has started to use neutral and alkaline sizing in production since 1989, and has become popular in recent years, and sizing agents using Alkyl Ketene Dimer (AKD) as a raw material are particularly popular. Alkyl ketene dimer is an unsaturated lactone, is a water insoluble waxy solid at normal temperature, can be used as a sizing agent for paper making, but must be prepared into emulsion before being used, and is one of sizing agents commonly used for alkaline sizing in the paper industry at present. The existing emulsification process of alkyl ketene dimer generally comprises the steps of heating the alkyl ketene dimer to be molten, adding dispersing agent, surfactant, gelatinized cationic starch and the like, homogenizing and emulsifying after premixing, cooling and canning after homogenizing is finished, wherein the process is complex, and the production period is long. The surfactant added in the emulsification process can reduce sizing efficiency, is easy to generate bubbles, brings foam problems to a papermaking system, and even generates paper diseases. Therefore, developing a high-efficiency alkyl ketene dimer emulsifying system, reducing the dosage of surfactant and even not using surfactant is beneficial to improving the sizing efficiency of alkyl ketene dimer, and meets the production requirements of paper-making enterprises and the current green production requirements.
Emulsions are dispersions of a liquid dispersed in another liquid immiscible with it, a thermodynamically unstable system, and in order to maintain the relative stability of the emulsion, an emulsifier or stabilizer must be added during the emulsion preparation process. Conventional emulsifiers or stabilizers are mostly surfactants and high-molecular polymers with surface activity, and in recent years, solid particles are attracting more and more attention because adverse effects of the surfactants on the environment can be avoided, high-concentration dispersed phase emulsions are stabilized, and the emulsions are less affected by changes in pH value, salt concentration, temperature and oil phase composition. For example, in the paper industry, water-insoluble paper sizing agents require emulsification into oil-in-water emulsions to be compatible with water-based paper systems, and paper sizing is aimed at improving the water resistance of the paper, and the presence of surfactants generally reduces the water resistance of the paper in addition to the adverse environmental effects that can be avoided by stabilizing the sizing agent emulsion with solid particles. The stable emulsion of solid (granule), usually called Pickering emulsion, is an emulsion which can be emulsified and stabilized only by solid particles without adding traditional polymer organic surfactant, the solid particles adsorbed at the oil-water interface have extremely high adsorption energy, so that the solid particles are difficult to separate from the oil-water interface, the way of emulsifying and stabilizing the emulsion by the solid particles can be considered to be irreversible, and the Pickering emulsion has extremely strong stability, and the emulsifying technology and research are widely used in various industries and fields at present.
MOFs have good biocompatibility and no reactivity with the host, and have become very promising materials for applications in the food industry. The cyclodextrin-metal organic frameworks CD-MOFs prepared from food-grade Cyclodextrin (CD) and metal ions have the characteristics of being non-toxic, edible, renewable and biodegradable. In addition, CD-MOFs contain K, which is critical to the human body + CD-MOFs are reported to be used as potash fertilizers to promote plant growth, which provides a good indication of CD-MOFs as a nutritional supplement in the food industry in the future.
Disclosure of Invention
Aiming at the problem that the current Alkyl Ketene Dimer (AKD) sizing agent is not suitable for being used in the production of food paper, the invention provides a preparation method of the food grade AKD paper sizing agent, no other surfactant is needed to be added, and the obtained sizing agent has good storage stability and can be used for sizing hydrophobic food grade packaging paper.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A method for preparing food grade AKD sizing agent emulsion, comprising the steps of:
(1) Dispersing Cyclodextrin (CD) in deionized water, heating and stirring uniformly, adjusting the pH of the suspension to 8.5, then dropwise adding 1-octadecenylsuccinic anhydride (ODSA), adjusting the pH to 6.5, freeze-drying the obtained product, washing with a cleaning agent, and drying to obtain modified CD;
(2) Dissolving the modified CD and KOH in water, adding methanol and Cetyl Trimethyl Ammonium Bromide (CTAB), reacting at room temperature, separating solid from liquid of a reaction system, washing and drying the solid to obtain modified CD-MOFs;
(3) Taking Alkyl Ketene Dimer (AKD) in a molten state as an oil phase; soaking tea in 100deg.C water to obtain tea juice, and uniformly dispersing modified CD-MOFs in tea juice to obtain water phase; and shearing and emulsifying the water phase and the oil phase under the heat preservation condition, and then carrying out ice water bath to obtain the food grade AKD sizing agent.
In step (1), the cyclodextrin may be β -cyclodextrin or γ -cyclodextrin; preferred is gamma-cyclodextrin. The concentration of cyclodextrin is 0.09-0.13wt%.
In the step (1), the mass ratio of the octadecenyl succinic anhydride to the cyclodextrin is (1-11): 100.
In step (1), the heating temperature was 50 ℃.
In the step (1), the cleaning agent is a solution of hexane/isopropanol mixed in equal volume; the mass ratio of the cleaning agent to the octadecenyl succinic anhydride is 10-30:1.
In the step (2), the mass ratio of the modified CD to the KOH is 2.5:1-3.5:1; the mass ratio of the modified CD to the CTAB is 1:1-1.5:1; the concentration of modified CD in water is 3% -3.5% wt.
In the step (2), the volume ratio of the methanol to the water is 1.5:1-2.5:1.
In step (2), the solvent for washing is isopropyl alcohol.
In step (3), the molten alkyl ketene dimer refers to an alkyl ketene dimer at 65-80 ℃.
In the step (3), the mass ratio of the tea to the deionized water is 1:10-2:10.
In step (3), the modified CD-MOFs are present in the aqueous phase at a concentration of 0.1% to 4% wt.
In the step (3), the volume ratio of the oil phase to the water phase is 1:3-1:20.
In the step (3), the temperature of heat preservation is 65-80 ℃.
In the step (3), the soaking time is 5-20min.
A food grade AKD sizing agent emulsion obtained by the above preparation method. The average particle size of the droplets in the emulsion is 2-5 μm.
The food grade AKD sizing agent emulsion can be used for sizing hydrophobic food grade packaging paper.
The invention has the following advantages:
the food grade AKD sizing agent with light tea flavor is prepared by taking food grade modified CD-MOFs as an emulsifying agent and tea juice as a water phase. The CD-MOFs synthesized by using the food-grade raw materials have good biocompatibility, so that the CD-MOFs have good application prospects in the food industry. The emulsifier is a green, environment-friendly, edible and renewable resource material, and has simple production process, no environmental pollution and low production cost. According to the invention, the CD of the raw material is modified by the octadecenyl succinic anhydride (ODSA), so that the water stability of the CD-MOFs is enhanced, and the amphipathy of the CD-MOFs is increased; the modified CD-MOFs particles and tea polyphenol in the tea juice can form a network crosslinked compact particle film, so that the emulsion stabilizing AKD has a very strong promoting effect on the AKD, and the AKD emulsion is endowed with the characteristics of bacteriostasis, tea fragrance and the like; in addition, the tea juice provides weak acidity for the AKD emulsification environment, so that the emulsion has stronger hydrolytic stability.
Drawings
FIG. 1 is a modified gamma-CD-MOFs scanning electron microscope image;
FIG. 2 is an appearance (left) and micrograph (right) of an AKD sizing agent emulsion with modified gamma-CD-MOFs as stabilizer;
fig. 3 is the lyophobic effect of AKD sizing emulsion surface coated sizing paper with modified gamma-CD-MOFs as stabilizer.
Detailed Description
The present invention will be further described with reference to examples and drawings, but the present invention is not limited to the examples.
Example 1 preparation of food grade AKD sizing agent
(1) Modification of gamma-CD: dissolving 100 parts by weight of gamma-CD into deionized water to make the mass fraction of the gamma-CD be 1.11%, magnetically stirring the mixture for 1h at 50 ℃, and adjusting the pH value of the suspension to 8.5 by using NaOH solution; then 5 parts by weight of 1-octadecenylsuccinic anhydride (ODSA) were slowly added, and when the pH reached a constant value, it was neutralized to pH 6.5 with hydrochloric acid, and then freeze-dried; using 50 parts by weight of hexane/isopropanol equal volume mixed solution as a cleaning agent, oscillating and washing for 15min on a 160rpm table, centrifuging for 20min at 8000rpm, collecting precipitate, washing for 2 times under the same conditions, and drying the precipitate to obtain modified gamma-CD;
(2) Preparation of modified gamma-CD-MOFs particles: 29 parts by weight of modified gamma-CD and 10 parts by weight of KOH are dissolved in deionized water, so that the mass fraction of the gamma-CD is 3.25%, 1.5 times of volume of methanol and 22 parts by weight of CTAB are added according to the water quantity, after CTAB is completely dissolved, the mixture is left to react for 24 hours at room temperature, then isopropanol is used for washing, centrifugation is carried out at 8000rpm for 20 minutes, sediment is collected, washing is carried out for 2 times under the same conditions, and the sediment is dried in vacuum at 60 ℃ for 12 hours to obtain modified gamma-CD-MOFs; the appearance of the modified gamma-CD-MOFs particles is shown in figure 1, the appearance of the modified gamma-CD-MOFs particles is regular hexahedron, and the vast majority of the modified gamma-CD-MOFs particles have the particle size of 400-500nm; the contact angle with water is 77 DEG, and the three-phase contact angle (water-solid-oil) is 98 DEG;
(3) Preparation of food grade AKD sizing agent: alkyl Ketene Dimer (AKD) in a molten state at 70 ℃ is taken as an oil phase; 2 parts by weight of Pu' er tea pieces are soaked in 20 parts by weight of deionized water at 100 ℃ for 10min and filtered to obtain tea, and the modified gamma-CD-MOFs are dispersed in the tea to serve as a water phase, so that the mass fraction of the modified gamma-CD-MOFs is 1.0%; mixing the oil phase and the water phase according to the volume ratio of 1:10, shearing and stirring for 5min at 12000rpm under the heating condition of 70 ℃, and rapidly cooling in an ice bath to obtain the oil-in-water Pickering emulsion, namely the food grade AKD sizing agent. The appearance and emulsion micrograph of the obtained food grade AKD sizing agent is shown in figure 2: the emulsion takes tea water as water phase, has a gray brown appearance, is uniform, and has tea fragrance. The average particle diameter of emulsion droplets is 2.2 mu m, and the emulsion droplets are uniformly distributed. The emulsion is diluted by 10 times and then the surface coating sizing of paper is carried out, the coating weight is 6g/m 2 The sizing effect is shown in figure 3: the water contact angle of the sized paper reaches 133 degrees.
Example 2 preparation of food grade AKD sizing agent
(1) Modification of gamma-CD: dissolving 100 parts by weight of gamma-CD into deionized water to make the mass fraction of the gamma-CD be 1.11%, magnetically stirring the mixture for 1h at 50 ℃, and adjusting the pH value of the suspension to 8.5 by using NaOH solution; then 5 parts by weight of 1-octadecenylsuccinic anhydride (ODSA) were slowly added, and when the pH reached a constant value, it was neutralized to pH 6.5 with hydrochloric acid, and then freeze-dried; using 150 parts by weight of hexane/isopropanol equal volume mixed solution as a cleaning agent, oscillating and washing for 15min on a 160rpm table, centrifuging for 20min at 8000rpm, collecting precipitate, washing for 2 times under the same conditions, and drying the precipitate to obtain modified gamma-CD;
(2) Preparation of modified gamma-CD-MOFs particles: dissolving 25 parts by weight of modified gamma-CD and 10 parts by weight of KOH in deionized water to enable the mass fraction of the gamma-CD to be 3.25%, adding 2 times of volume of methanol and 25 parts by weight of CTAB according to the water quantity, standing for 24 hours at room temperature for reaction after CTAB is completely dissolved, washing by using isopropanol, centrifuging at 8000rpm for 20 minutes, collecting precipitate, washing for 2 times under the same conditions, and vacuum drying the precipitate at 60 ℃ for 12 hours to obtain modified gamma-CD-MOFs; the appearance of the modified gamma-CD-MOFs particles is cube, and the particle size range is 60-300nm; the contact angle with water is 67 degrees, and the three-phase contact angle (water-solid-oil) is 91 degrees;
(3) Preparation of food grade AKD sizing agent: taking Alkyl Ketene Dimer (AKD) in a molten state at 65 ℃ as an oil phase; 2 parts by weight of Pu' er tea pieces are soaked in 20 parts by weight of deionized water at 100 ℃ for 10min and filtered to obtain tea, and the modified gamma-CD-MOFs are dispersed in the tea to serve as a water phase, so that the mass fraction of the modified gamma-CD-MOFs is 1.0%; mixing the oil phase and the water phase according to the volume ratio of 1:3, shearing and stirring for 5min at 12000rpm under the heating condition of 65 ℃, and rapidly cooling in an ice bath to obtain the oil-in-water Pickering emulsion, namely the food grade AKD sizing agent, wherein the average particle size of the emulsion liquid drops is 3.7 mu m. The emulsion is diluted by 10 times and then the surface coating sizing of paper is carried out, the coating weight is 4g/m 2 The water contact angle of the sized paper reaches 109 degrees.
Example 3 preparation of food grade AKD sizing agent
(1) Modification of beta-CD: dissolving 100 parts by weight of beta-CD into deionized water to make the mass fraction of the beta-CD be 1.11%, magnetically stirring the solution for 1h at 50 ℃, and adjusting the pH value of the suspension to 8.5 by using NaOH solution; then, 11 parts by weight of 1-octadecenylsuccinic anhydride (ODSA) was slowly added, and when the pH reached a constant value, it was neutralized to pH 6.5 with hydrochloric acid, and then freeze-dried; using 150 parts by weight of hexane/isopropanol equal volume mixed solution as a cleaning agent, oscillating and washing for 15min on a 160rpm table, centrifuging for 20min at 8000rpm, collecting precipitate, washing for 2 times under the same conditions, and drying the precipitate to obtain modified beta-CD;
(2) Preparation of modified beta-CD-MOFs particles: dissolving 35 parts by weight of modified beta-CD and 10 parts by weight of KOH in deionized water to enable the mass fraction of the beta-CD to be 3.25%, adding 2.5 times of volume of methanol and 23 parts by weight of CTAB according to the water quantity, standing for 24 hours at room temperature for reaction after CTAB is completely dissolved, washing by using isopropanol, centrifuging at 8000rpm for 20 minutes, collecting precipitate, washing for 2 times under the same conditions, and vacuum drying the precipitate at 60 ℃ for 12 hours to obtain modified alpha-CD-MOFs; the appearance of the modified beta-CD-MOFs particles is that the obtained particles are in a cube shape, and the particle size range is 80-250nm; the contact angle with water is 55 DEG, and the three-phase contact angle (water-solid-oil) is 83 DEG;
(3) Preparation of food grade AKD sizing agent: alkyl Ketene Dimer (AKD) in a molten state at 85 ℃ is used as an oil phase; 3 parts by weight of broken tea is soaked in 20 parts by weight of deionized water at 100 ℃ for 10min and filtered to obtain tea, and the modified beta-CD-MOFs are dispersed in the tea to serve as a water phase, so that the mass fraction of the modified beta-CD-MOFs is 4.0%; mixing the oil phase and the water phase according to the volume ratio of 1:20, shearing and stirring for 5min at 12000rpm under the heating condition of 85 ℃, and rapidly cooling in an ice bath to obtain the oil-in-water Pickering emulsion, namely the food grade AKD sizing agent, wherein the average particle size of liquid drops of the emulsion is 4.8 mu m. The emulsion is diluted by 10 times and then the surface coating sizing of paper is carried out, the coating weight is 8g/m 2 The water contact angle of the sized paper reaches 125 degrees.
Comparative example 1 preparation of food grade AKD sizing agent
Alkyl Ketene Dimer (AKD) in a molten state at 70 ℃ is taken as an oil phase; 2 parts by weight of Pu' er tea pieces are soaked in 20 parts by weight of deionized water at 100 ℃ for 10min to obtain tea water as a water phase; mixing the oil phase and the water phase according to the volume ratio of 1:10, shearing and stirring for 5min at 12000rpm under the heating condition of 70 ℃ to obtain the food grade AKD sizing agent.
Comparative example 2 preparation of food grade AKD sizing agent
Modified gamma-CD-MOFs were prepared as in example 1, then food grade AKD sizing agents were prepared as follows:
alkyl Ketene Dimer (AKD) in a molten state at 70 ℃ is taken as an oil phase; dispersing the modified gamma-CD-MOFs into deionized water to be used as a water phase, so that the mass fraction of the modified gamma-CD-MOFs is 1.0%; mixing the oil phase and the water phase according to the volume ratio of 1:10, shearing and stirring for 5min at 12000rpm under the heating condition of 70 ℃, and rapidly cooling in an ice bath to obtain the oil-in-water Pickering emulsion, namely the food grade AKD sizing agent.
Application example 1 sizing Effect of AKD sizing agent
After 10-fold dilution of the AKD sizing agents in examples 1-3 and comparative examples 1-2, the surface coating sizing of the paper was performed and the sizing degree was determined as follows:
the paper to be sized is placed on a nanocellulose film/coater (CUF 5-200 model, sumet, germany), the diluted AKD sizing emulsion is added into a coating material box, the coating speed is regulated to be 1.5cm/s, the coating pressure is 10N/m, the coating drying temperature is 105 ℃, and the drying time is 30min.
Sizing performance was evaluated by measuring sizing of the manufactured paper (GB/T5405-2002). Before measurement, the paper was cut into 30X 30mm square paper pieces, and the paper pieces were placed in an environment of 25℃and 50% humidity to equilibrate the water for 24 hours. The paper sheet is folded at four sides to form a ship-shaped structure with the bottom surface area of about 20 multiplied by 20mm, then the ship-shaped structure floats in an ammonium thiocyanate dilute solution with the concentration of 2%, a drop of 0.5 mu L of ferric chloride solution with the mass concentration of 1% is dripped on the upper part of the ship-shaped paper sheet by using a rubber head dropper, and meanwhile, a stopwatch is used for timing, and when red spots appear in the middle part of the ferric chloride liquid drop, the timing is finished, and the sizing degree of the paper sample is obtained. The front and back sides of the test sample were each measured 10 times and averaged.
TABLE 1 influence of different time periods on the emulsion properties and sizing degree of different AKD sizing agents
As can be seen from the data in table 1, AKD emulsions obtained with either tea alone or modified CD-MOFs particles alone failed to form stable emulsions and had substantially no sizing effect. When AKD is emulsified by the modified CD-MOFs particles and tea juice together, AKD surface sizing agent emulsion with good stability (no phase separation) and good sizing performance can be obtained; and the AKD emulsion stabilized by the modified gamma-CD-MOFs particles has the lowest emulsion particle size and the best sizing performance and stability.
Claims (10)
1. A method for preparing food grade AKD sizing agent emulsion, comprising the steps of:
(1) Dispersing cyclodextrin in deionized water, heating and stirring uniformly, adjusting the pH of the suspension to 8.5, then dropwise adding 1-octadecenyl succinic anhydride, adjusting the pH to 6.5, and washing and drying the obtained product after freeze-drying by using a cleaning agent to obtain modified CD;
(2) Dissolving the modified CD and KOH in water, adding methanol and hexadecyl trimethyl ammonium bromide, reacting at room temperature, separating solid from liquid of a reaction system, washing and drying the solid to obtain modified CD-MOFs;
(3) Taking the melted alkyl ketene dimer as an oil phase; soaking tea in 100deg.C water to obtain tea juice, and uniformly dispersing modified CD-MOFs in tea juice to obtain water phase; and shearing and emulsifying the water phase and the oil phase under the heat preservation condition, and then carrying out ice water bath to obtain the food grade AKD sizing agent.
2. The method of claim 1, wherein in step (1), the cyclodextrin is β -cyclodextrin or γ -cyclodextrin; the concentration of cyclodextrin is 0.09-0.13wt%; the mass ratio of the octadecenyl succinic anhydride to the cyclodextrin is (1-11): 100.
3. The method according to claim 1, wherein in the step (2), the mass ratio of modified CD to KOH is 2.5:1 to 3.5:1; the mass ratio of the modified CD to the hexadecyl trimethyl ammonium bromide is 1:1-1.5:1; the concentration of modified CD in water is 3% -3.5% wt.
4. The method according to claim 1, wherein in the step (1), the heating temperature is 50 ℃; the cleaning agent is a hexane/isopropanol equal volume mixed solution; the mass ratio of the cleaning agent to the octadecenyl succinic anhydride is 10-30:1.
5. The method of claim 1, wherein in step (2), the volume ratio of methanol to water is 1.5:1-2.5:1; the solvent for washing was isopropanol.
6. The method of claim 1, wherein in step (3), the concentration of the modified CD-MOFs in the aqueous phase is 0.1% -4% wt; the volume ratio of the oil phase to the water phase is 1:3-1:20.
7. The process according to claim 1, wherein in the step (3), the molten alkyl ketene dimer is 65-80 ℃ alkyl ketene dimer; the temperature of the heat preservation is 65-80 ℃.
8. The method according to claim 1, wherein in the step (3), the mass ratio of the tea leaves to the deionized water is 1:10-2:10; the soaking time is 5-20min.
9. A food grade AKD size emulsion obtainable by the process of any one of claims 1 to 8.
10. Use of the food grade AKD sizing emulsion of claim 9 in the production of a hydrophobic food grade wrapper.
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| JPH1136184A (en) * | 1997-07-16 | 1999-02-09 | Mitsubishi Paper Mills Ltd | Sizing agent composition for papermaking and sized paper |
| CN108425275A (en) * | 2018-04-25 | 2018-08-21 | 齐鲁工业大学 | A kind of preparation method and products thereof of AKD paper sizings agent |
| AU2020102641A4 (en) * | 2020-10-08 | 2020-11-26 | Qilu University Of Technology | Alkenyl succinic anhydride paper sizing agent emulsion and preparation method and application thereof |
| CN112813729A (en) * | 2021-01-12 | 2021-05-18 | 齐鲁工业大学 | Hydrolysis-resistant alkenyl succinic anhydride sizing agent and preparation method and application thereof |
| CN112878097A (en) * | 2021-01-12 | 2021-06-01 | 齐鲁工业大学 | Preparation method of alkyl ketene dimer papermaking sizing agent and product |
| CN113186752A (en) * | 2021-05-14 | 2021-07-30 | 齐鲁工业大学 | Boron crosslinked organic compound gel emulsifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1136184A (en) * | 1997-07-16 | 1999-02-09 | Mitsubishi Paper Mills Ltd | Sizing agent composition for papermaking and sized paper |
| CN108425275A (en) * | 2018-04-25 | 2018-08-21 | 齐鲁工业大学 | A kind of preparation method and products thereof of AKD paper sizings agent |
| AU2020102641A4 (en) * | 2020-10-08 | 2020-11-26 | Qilu University Of Technology | Alkenyl succinic anhydride paper sizing agent emulsion and preparation method and application thereof |
| CN112813729A (en) * | 2021-01-12 | 2021-05-18 | 齐鲁工业大学 | Hydrolysis-resistant alkenyl succinic anhydride sizing agent and preparation method and application thereof |
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