CN116289322A - Preparation method of cationized hydrophobic microcapsule flame-retardant paper - Google Patents
Preparation method of cationized hydrophobic microcapsule flame-retardant paper Download PDFInfo
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- CN116289322A CN116289322A CN202310235388.2A CN202310235388A CN116289322A CN 116289322 A CN116289322 A CN 116289322A CN 202310235388 A CN202310235388 A CN 202310235388A CN 116289322 A CN116289322 A CN 116289322A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 83
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 61
- 239000003094 microcapsule Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920001661 Chitosan Polymers 0.000 claims abstract description 116
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 98
- 239000000835 fiber Substances 0.000 claims abstract description 53
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 40
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 175
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 23
- 238000007873 sieving Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 239000012948 isocyanate Substances 0.000 claims description 20
- 150000002513 isocyanates Chemical class 0.000 claims description 20
- 230000014759 maintenance of location Effects 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000011122 softwood Substances 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004472 Lysine Substances 0.000 claims description 9
- 150000001413 amino acids Chemical class 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011121 hardwood Substances 0.000 claims description 4
- 239000004475 Arginine Substances 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 3
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 239000010902 straw Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000012986 modification Methods 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 12
- 125000002091 cationic group Chemical group 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011162 core material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 61
- 238000012360 testing method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- 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
-
- 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
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- 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
- D21H17/07—Nitrogen-containing compounds
- D21H17/08—Isocyanates
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
-
- 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
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
- 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
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- 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
- D21H21/34—Ignifugeants
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a method for preparing cationic hydrophobic microcapsule flame retardant paper. The invention takes plant fiber as a carrier, comprises the steps of preparation of chitosan and cross-linked prepolymer, preparation of hydrophobic microcapsule shell layer, preparation of cationic hydrophobic microcapsule flame-retardant paper and the like, takes ammonium polyphosphate as a core material, takes chitosan and cross-linking agent as a hydrophobic shell layer and a flame-retardant synergist, carries out further cationic modification on the hydrophobic shell layer, and adds the cationic hydrophobic microcapsule flame retardant into the plant fiber by adopting an intra-pulp adding method to prepare the flame-retardant paper with high flame retardant property and certain moisture resistance. The preparation method of the cationized hydrophobic microcapsule flame retardant and the flame retardant paper can be widely applied to materials which mainly take plant fibers or contain the plant fibers, can accelerate the char formation of the materials, slow down and prevent the spread of flame, and improve the flame retardant property of the materials.
Description
Technical Field
The invention belongs to the field of flame-retardant materials, and relates to a method for preparing cationic hydrophobic microcapsule flame-retardant paper.
Background
Ammonium polyphosphate is currently widely used as a common phosphorus-nitrogen flame retardant in various flame retardant materials and fields. Because of the molecular structure characteristics, the material has the defects of high hygroscopicity, poor compatibility with materials and the like. And because the ammonium polyphosphate belongs to a polyanionic electrolyte, the electronegativity of the particles is stronger. However, the main reasons for affecting filler retention in the intrapulking process are to adjust the charge balance of the wet end chemistry and to reduce the solubility of the filler. Therefore, when ammonium polyphosphate is used as a flame retardant filler and flame retardant paper is prepared by an in-pulp addition method, modification treatment of ammonium polyphosphate is required. At present, the modification method of ammonium polyphosphate comprises the methods of surfactant modification, silane coupling agent modification, microcapsule coating modification and the like, wherein microcapsule coating modification is mainly performed, and microcapsule coating is mainly performed by melamine and melamine formaldehyde resin. However, although melamine coated modified ammonium polyphosphate can improve the flame retardant performance of ammonium polyphosphate and reduce the water solubility of ammonium polyphosphate, a large amount of formaldehyde gas is released in the combustion process, which is harmful to human health.
Chitosan belongs to natural biological high molecular polymer, contains amino and hydroxyl groups, and is the only cationic basic polysaccharide found at present. The amino groups in the chitosan can lead the chitosan to have positive charges, and can generate flame-retardant synergistic effect, thereby improving the flame-retardant effect of the material. The hydroxyl in the chitosan can be combined with the hydroxyl in the plant fiber, and the retention rate of ammonium polyphosphate in the plant fiber is improved by utilizing a similar compatibility principle. In addition, the existence of N-acetyl in chitosan makes chitosan not dissolved in water, ethanol and acetone, but dissolved in a certain dilute acid, and the degree of deacetylation also affects the solubility of chitosan in an acidic solution, which also indicates that the chitosan is coated on the surface of ammonium polyphosphate, so that the formation of a hydrophobic layer on the surface of ammonium polyphosphate is possible.
Amino acids are amphiphilic organic compounds containing basic amino groups and acidic carboxyl groups, and amino acids that are positively charged at neutral pH have lysine, histidine and arginine. After the surface of ammonium polyphosphate is cationized and modified by positively charged amino acid, the coated ammonium polyphosphate is positively charged in water, and the amino group in the amino acid can further improve the flame retardant effect of the material. Meanwhile, the amino acid belongs to biomass materials, and has good environmental friendliness compared with positively charged substances such as polyethyleneimine with positive charges, polymethyl methacrylate-N, N-dimethylaminoethyl ester and the like.
The paper belongs to a good environment-friendly material, and is mainly formed by interweaving plant fibers after paper making, and the traditional paper material has extremely strong inflammability, so that the application field of the paper-based material is limited. Therefore, in order to solve the above problems, ammonium polyphosphate is used as a core material, chitosan and a cross-linking agent are used as a hydrophobic shell layer and a flame retardant synergist, and the hydrophobic shell layer is further cationized and modified, so that a hydrophobic shell layer with cations is formed on the surface of the ammonium polyphosphate, and the influence of electronegativity of ammonium polyphosphate particles on chemical charges of wet ends is reduced. And adding the cationic hydrophobic microcapsule flame retardant into the plant fiber by adopting an in-pulp adding method to prepare the flame-retardant paper with high flame-retardant property and moisture-resistant property.
Disclosure of Invention
The invention aims to provide a preparation method of cationized hydrophobic microcapsule flame-retardant paper.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing cationized hydrophobic microcapsule fire retardant paper, comprising the following steps:
(1) Preparation of chitosan prepolymer: dispersing 2-10g chitosan in 100ml acetic acid solution with 1-5 wt.% and stirring at 20-40deg.C for 0.5-2hr to obtain chitosan prepolymer solution.
(2) Preparation of crosslinked prepolymer: 4-8g of isocyanate is dispersed in 30ml of solvent and stirred for 10min to be fully dissolved, so as to prepare the cross-linked prepolymer solution.
(3) Preparation of hydrophobic microcapsule shell: dispersing 100g of ammonium polyphosphate in 200ml of solvent, adding 1g of emulsifier, uniformly mixing, adding the chitosan prepolymer solution prepared in the step (1), reacting for 15min at 60-90 ℃, dripping the crosslinker prepolymer solution prepared in the step (2) into a reaction system for 30min, reacting the whole reaction system for 4-8hr at 60-90 ℃, filtering and washing 3 times by using the solvent and water respectively, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Preparation of a cationized hydrophobic microcapsule shell: dispersing 2-6g of amino acid in a mixed solvent of water (10 ml) and ethanol (200 ml), then adding 8g of APP@chitosan, reacting for 4-6 hours at 60-80 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain the amino acid- (APP@chitosan).
(5) Preparation of cationized hydrophobic microcapsule flame retardant paper: pulping the fiber slurry to 25-40 DEG SR for standby. 2-6g pulped pulp fibers are weighed by a wet papermaking process and dispersed in water to form pulp with the concentration of 0.2-0.6 wt.%, amino acid- (APP@chitosan) flame retardant accounting for 20-50% of absolute dry fibers is weighed and added into the dispersed pulp, a binary retention and filter aid is added, the mixed pulp is poured into a sheet making machine for molding, squeezing and drying, and the cationized hydrophobic microcapsule flame-retardant paper is prepared.
Preferably, in the preparation of the chitosan prepolymer in the step (1), the deacetylation degree of chitosan is more than 55%.
Preferably, the isocyanate in the step (2) is toluene diisocyanate.
Preferably, the solvent in the step (2) is one of organic solvents such as ethyl acetate, ethanol, and isopropanol.
Preferably, the emulsifier in the step (3) is selected from one of emulsifiers such as octyl phenol polyoxyethylene ether-10 (OP-10) and Tween-80.
Preferably, in the preparation of the hydrophobic microcapsule shell layer in the step (3), the solvent is one of organic solvents such as ethyl acetate, ethanol, isopropanol and the like.
Preferably, in the preparation of the shell layer of the cationized hydrophobic microcapsule in the step (4), the amino acid is one of lysine, histidine and arginine.
Preferably, in the preparation of the cationized hydrophobic microcapsule flame retardant paper in the step (5), the fiber pulp is one or more of various plant fiber pulps, such as unbleached softwood pulp, bleached softwood pulp, unbleached hardwood pulp, bleached hardwood pulp, grass pulp and the like.
Preferably, in the preparation of the cationized hydrophobic microcapsule flame retardant paper in the step (5), the binary retention and drainage aid system is CPAM/bentonite. CPAM is added in an amount of 0.05% -0.2% relative to the absolute dry fiber content, and bentonite is added in an amount of 0.1% -0.4% relative to the absolute dry fiber content.
Preferably, in the preparation of the cationized hydrophobic microcapsule flame retardant paper in the step (5), the pressing pressure is 0.2-0.4Mpa.
Preferably, in the preparation of the cationized hydrophobic microcapsule flame retardant paper in the step (5), the drying temperature is 80-130 ℃.
The invention has the beneficial effects that: according to the invention, plant fibers are used as a carrier, the cationic chitosan hydrophobic shell layer with cations is formed on the surface of ammonium polyphosphate, and the prepared cationic hydrophobic flame retardant is added into plant fiber raw materials by adopting an internal slurry adding method, so that the flame retardant paper is finally prepared.
Drawings
FIG. 1 is a graph showing the effect of coated modified ammonium polyphosphate on water contact angle.
FIG. 2 shows the Zeta potential of the coated modified ammonium polyphosphate.
FIG. 3 is a graph showing the effect of coated modified ammonium polyphosphate on LOI values of flame retardant paper.
Detailed Description
The invention will be described in further detail with reference to specific examples.
1. Examples 1 to 3 below illustrate the effect of isocyanate coating modification on the hydrophobic effect of ammonium polyphosphate
Example 1:
(1) 4g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(2) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system for 6hr at 60 ℃, respectively carrying out suction filtration and washing for 3 times by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain the APP@isocyanate.
(3) And (3) testing: the test example shows that the APP water contact angle after coating modification is 43.2 degrees, and the Zeta potential is-58.4 mv.
Example 2:
(1) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(2) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system for 6hr at 60 ℃, respectively carrying out suction filtration and washing for 3 times by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain the APP@isocyanate.
(3) And (3) testing: the test example shows that the APP water contact angle after coating modification is 63.5 degrees, and the Zeta potential is-56.3 mv.
Example 3:
(1) 8g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(2) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system for 6hr at 60 ℃, respectively carrying out suction filtration and washing for 3 times by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain the APP@isocyanate.
(3) And (3) testing: the test example shows that the APP water contact angle after coating modification is 65.7 degrees, and the Zeta potential is-57.5 mv.
Conclusion 1:
based on examples 1 to 3, the water contact angle of the isocyanate coated modified ammonium polyphosphate can reach 65.7 degrees, zeta potential-56.3 mv, see FIGS. 1 and 2..
2. The following examples 4 to 7 illustrate the effect of chitosan coating modification on the hydrophobic effect of ammonium polyphosphate and the effect of APP@chitosan flame retardant on the flame retardant effect of flame retardant paper
Example 4:
(1) 2g of chitosan was dispersed in 100ml of 1wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. 2g of pulped fiber is weighed and dispersed in water by adopting a wet papermaking process to form slurry with the concentration of 0.2 wt%, 30% of APP@chitosan flame retardant relative to absolute dry fiber is weighed and added into the dispersed slurry, a binary retention and drainage aid is added, the mixed slurry is poured into a sheet making machine to be molded, squeezed and dried, and the chitosan hydrophobic microcapsule flame retardant paper is prepared.
(5) And (3) testing: the test APP@chitosan water contact angle is 70.8 degrees, zeta potential is-53.3 mv, and LOI value of the chitosan hydrophobic microcapsule flame-retardant paper is 26.8%.
Example 5:
(1) 6g of chitosan was dispersed in 100ml of 1wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. And (3) adopting a wet papermaking process, weighing 2g of pulped pulp fibers, dispersing in water to form slurry with the concentration of 0.2wt.%, weighing 30% of APP@chitosan flame retardant relative to absolute dry fibers, adding the APP@chitosan flame retardant to the dispersed slurry, adding a binary retention and drainage aid, pouring the mixed slurry into a sheet machine for molding, squeezing and drying to obtain the chitosan hydrophobic microcapsule flame retardant paper.
(5) And (3) testing: the test APP@chitosan water contact angle is 91.2 degrees, zeta potential is-52.7 mv, and LOI value of the chitosan hydrophobic microcapsule flame-retardant paper is 28.4%.
Example 6:
(1) 10g of chitosan was dispersed in 100ml of 1wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. 2g of pulped fiber is weighed and dispersed in water by adopting a wet papermaking process to form slurry with the concentration of 0.2 wt%, 30% of APP@chitosan flame retardant relative to absolute dry fiber is weighed and added into the dispersed slurry, a binary retention and drainage aid is added, the mixed slurry is poured into a sheet making machine to be molded, squeezed and dried, and the chitosan hydrophobic microcapsule flame retardant paper is prepared.
(5) And (3) testing: the test APP@chitosan water contact angle is 91.2 degrees, zeta potential is-51.9 mv, and LOI value of the chitosan hydrophobic microcapsule flame-retardant paper is 31.4%.
Example 7:
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. 2g of pulped fiber is weighed and dispersed in water by adopting a wet papermaking process to form slurry with the concentration of 0.2 wt%, 30% of APP@chitosan flame retardant relative to absolute dry fiber is weighed and added into the dispersed slurry, a binary retention and drainage aid is added, the mixed slurry is poured into a sheet making machine to be molded, squeezed and dried, and the chitosan hydrophobic microcapsule flame retardant paper is prepared.
(5) And (3) testing: the test APP@chitosan water contact angle is 94.6 degrees, zeta potential is-51.6 mv, and LOI value of the chitosan hydrophobic microcapsule flame-retardant paper is 30.8%. See fig. 1, 2 and 3.
Conclusion II:
based on the results of examples 4 to 7, the contact angle of APP@chitosan water can reach 94.6 degrees, the Zeta potential is-51.6 mv, and the LOI value of the chitosan hydrophobic microcapsule flame retardant paper is more than 30%.
3. Examples 8 to 10 illustrate the effect of cationization coating modification on the hydrophobic effect of ammonium polyphosphate and the effect of lysine- (app@chitosan) on the flame retardant effect of flame retardant paper.
Example 8:
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Dispersing 2g of lysine in a mixed solvent of water (10 ml) and ethanol (200 ml), adding 8g of APP@chitosan, reacting for 4hr at 60 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain lysine- (APP@chitosan).
(5) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. And (3) adopting a wet papermaking process, weighing 2g of pulped fibers, dispersing in water to form slurry with the concentration of 0.2wt.%, weighing 30% of arginine- (APP@chitosan) flame retardant relative to absolute dry fibers, adding the slurry into the dispersed slurry, adding a binary retention and drainage aid, pouring the mixed slurry into a sheet machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
(6) And (3) testing: the test example shows that the water contact angle of arginine- (APP@chitosan) is 101.3 degrees, the Zeta potential is-35.8 mv, and the LOI value of the cationized hydrophobic microcapsule flame retardant paper is 32.3%.
Example 9:
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Dispersing 4g of lysine in a mixed solvent of water (10 ml) and ethanol (200 ml), adding 8g of APP@chitosan, reacting for 4hr at 60 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain lysine- (APP@chitosan).
(5) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. And (3) adopting a wet papermaking process, weighing 2g of pulped fibers, dispersing in water to form slurry with the concentration of 0.2wt.%, weighing 30% of arginine- (APP@chitosan) flame retardant relative to absolute dry fibers, adding the slurry into the dispersed slurry, adding a binary retention and drainage aid, pouring the mixed slurry into a sheet machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
(6) And (3) testing: the test example shows that the water contact angle of arginine- (APP@chitosan) is 103.6 degrees, the Zeta potential is 33.6mv, and the LOI value of the cationized hydrophobic microcapsule flame retardant paper is 33.1%.
Example 10:
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Dispersing 6g of lysine in a mixed solvent of water (10 ml) and ethanol (200 ml), adding 8g of APP@chitosan, reacting for 4hr at 60 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain lysine- (APP@chitosan).
(5) Pulping bleached softwood fiber slurry to 30 DEG SR for later use. And (3) adopting a wet papermaking process, weighing 2g of pulped fibers, dispersing in water to form slurry with the concentration of 0.2wt.%, weighing 30% of arginine- (APP@chitosan) flame retardant relative to absolute dry fibers, adding the slurry into the dispersed slurry, adding a binary retention and drainage aid, pouring the mixed slurry into a sheet machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
(6) And (3) testing: the test example shows that the water contact angle of arginine- (APP@chitosan) is 108.2 degrees, the Zeta potential is-30.4 mv, and the LOI value of the cationized hydrophobic microcapsule flame retardant paper is 34.7%.
Conclusion III:
based on the results of examples 8 to 10, the contact angle of arginine- (APP@chitosan) water can reach 108.2 degrees, zeta potential-30.4 mv, and LOI value of the cationized hydrophobic microcapsule flame retardant paper is more than 34%.
4. Examples 11 to 13 illustrate the effect of the properties of the fiber slurry on the flame retarding effect of the flame retardant paper.
Example 11
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Dispersing 6g of lysine in a mixed solvent of water (10 ml) and ethanol (200 ml), adding 8g of APP@chitosan, reacting for 4hr at 60 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain lysine- (APP@chitosan).
(5) The fiber slurry was beaten to 25 ° SR for use. And (3) adopting a wet papermaking process, weighing 2g of pulped pulp fibers, dispersing in water to form pulp with the concentration of 0.2wt.%, weighing 30% of amino acid- (APP@chitosan) flame retardant relative to the absolute dry fibers, adding the pulp into the dispersed pulp, adding a binary retention and drainage aid, pouring the mixed pulp into a sheet machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
(6) And (3) testing: the LOI value of the cationized hydrophobic microcapsule flame retardant paper tested in this example is 33.6%.
Example 12
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Dispersing 6g of lysine in a mixed solvent of water (10 ml) and ethanol (200 ml), adding 8g of APP@chitosan, reacting for 4hr at 60 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain lysine- (APP@chitosan).
(5) The fiber slurry was beaten to 40 ° SR for use. And (3) adopting a wet papermaking process, weighing 2g of pulped pulp fibers, dispersing in water to form pulp with the concentration of 0.6wt.%, weighing 30% of amino acid- (APP@chitosan) flame retardant relative to the absolute dry fibers, adding the pulp into the dispersed pulp, adding a binary retention and drainage aid, pouring the mixed pulp into a sheet machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
(6) And (3) testing: the LOI value of the cationized hydrophobic microcapsule flame retardant paper tested in this example is 35.4%.
Example 13
(1) 6g of chitosan was dispersed in 100ml of 3wt.% acetic acid solution, and reacted at 20℃for 0.5hr with stirring to prepare a chitosan prepolymer solution.
(2) 6g of isocyanate was dispersed in 30ml of ethanol and stirred for 10 minutes to be sufficiently dissolved, to prepare a crosslinked prepolymer solution.
(3) Dispersing 100g of ammonium polyphosphate in 200ml of ethanol, adding 1g of OP-10, adding the prepared chitosan prepolymer solution, reacting for 15min at 60 ℃, dripping the prepared cross-linking agent prepolymer solution into a reaction system within 30min, reacting the whole reaction system at 60 ℃ for 6hr, filtering and washing for 3 times respectively by using ethanol and water, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan.
(4) Dispersing 6g of lysine in a mixed solvent of water (10 ml) and ethanol (200 ml), adding 8g of APP@chitosan, reacting for 4hr at 60 ℃ under nitrogen atmosphere, respectively carrying out suction filtration and washing on the ethanol and the water for 3 times, drying in an oven at 80 ℃, grinding and sieving to obtain lysine- (APP@chitosan).
(5) The fiber slurry was beaten to 30 ° SR for use. And (3) adopting a wet papermaking process, weighing 4g of pulped pulp fibers, dispersing in water to form pulp with the concentration of 0.2wt.%, weighing 30% of amino acid- (APP@chitosan) flame retardant relative to the absolute dry fibers, adding the pulp into the dispersed pulp, adding a binary retention and drainage aid, pouring the mixed pulp into a sheet machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
(6) And (3) testing: the LOI value of the cationized hydrophobic microcapsule flame retardant paper tested in this example is 38.7%.
Conclusion IV:
based on the results of examples 11 to 13, the LOI of the cationized hydrophobic microcapsule flame retardant paper was > 38%, see FIG. 3.
Claims (9)
1. The preparation method of the cationized hydrophobic microcapsule flame retardant paper is characterized by comprising the following steps of:
step 1, preparation of chitosan prepolymer: dispersing 2-10g chitosan in 100ml acetic acid solution with 1-5 wt.% and stirring at 20-40deg.C for 0.5-2hr to obtain chitosan prepolymer solution;
step 2, preparation of a crosslinked prepolymer: dispersing 4-8g of isocyanate in 30ml of solvent, stirring for 10min to fully dissolve the isocyanate, and preparing a crosslinked prepolymer solution;
step 3, preparation of a hydrophobic microcapsule shell: dispersing 100g of ammonium polyphosphate in 200ml of solvent, adding 1g of emulsifying agent, and uniformly mixing;
adding the chitosan prepolymer solution prepared in the step (1), reacting for 15min at 60-90 ℃, dripping the crosslinking agent prepolymer solution prepared in the step (2) into a reaction system within 30min, reacting the whole reaction system for 4-8hr at 60-90 ℃, filtering and washing 3 times by using a solvent and water respectively, drying in an oven at 80 ℃, grinding and sieving to obtain APP@chitosan;
step 4, preparing a shell layer of the cationized hydrophobic microcapsule: dispersing 2-6g of amino acid in a mixed solvent of water and ethanol, and then adding 8g of APP@chitosan; reacting at 60-80deg.C under nitrogen atmosphere for 4-6hr, filtering and washing with ethanol and water respectively for 3 times, oven drying at 80deg.C, grinding, and sieving to obtain amino acid- (APP@chitosan);
step 5, preparing the cationized hydrophobic microcapsule flame retardant paper: pulping the fiber slurry to 25-40 DEG SR for standby; 2-6g of pulped pulp fibers are weighed by adopting a wet papermaking process and dispersed in water to form pulp with the concentration of 0.2-0.6 wt%; and (3) weighing 20% -50% of amino acid- (APP@chitosan) flame retardant relative to the absolute dry fiber, adding the amino acid- (APP@chitosan) flame retardant into the well-dispersed slurry, adding a binary retention and drainage aid, pouring the mixed slurry into a sheet making machine for molding, squeezing and drying to obtain the cationized hydrophobic microcapsule flame retardant paper.
2. The method of claim 1, wherein the chitosan has a degree of deacetylation greater than 55%.
3. The method according to claim 1, wherein the isocyanate is toluene diisocyanate.
4. The method according to claim 1, wherein the solvent is ethyl acetate, ethanol or isopropanol.
5. The method of claim 1, wherein the emulsifier is octyl phenol polyoxyethylene ether-10 (OP-10) or Tween-80.
6. The method of claim 1, wherein the amino acid is one of lysine, histidine, arginine.
7. The method of claim 1, wherein the fibrous pulp is one or more of unbleached softwood pulp, bleached softwood pulp, unbleached hardwood pulp, bleached hardwood pulp, and straw pulp.
8. The method of claim 1, wherein the binary retention and drainage aid system is CPAM/bentonite; wherein the CPAM addition amount is 0.05% -0.2% relative to the absolute dry fiber content, and the bentonite addition amount is 0.1% -0.4% relative to the absolute dry fiber content.
9. The method according to claim 1, wherein in the preparation of the cationized hydrophobic microcapsule flame retardant paper, the pressing pressure is 0.2-0.4Mpa and the drying temperature is 80-130 ℃.
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