CN109056411B - Core-shell-structured paper flame retardant and preparation method and application thereof - Google Patents
Core-shell-structured paper flame retardant and preparation method and application thereof Download PDFInfo
- Publication number
- CN109056411B CN109056411B CN201810807060.2A CN201810807060A CN109056411B CN 109056411 B CN109056411 B CN 109056411B CN 201810807060 A CN201810807060 A CN 201810807060A CN 109056411 B CN109056411 B CN 109056411B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- parts
- paper
- core
- shell structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 124
- 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 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000011258 core-shell material Substances 0.000 claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 28
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 18
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 18
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 18
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 9
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 9
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 abstract description 66
- 239000011087 paperboard Substances 0.000 abstract description 12
- 230000002411 adverse Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 239000011111 cardboard Substances 0.000 description 5
- 238000012552 review Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- D21H21/34—Ignifugeants
-
- 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
-
- 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
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- 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
-
- 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
- D21H17/10—Phosphorus-containing 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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/26—Ethers thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- 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
- D21H21/18—Reinforcing agents
-
- 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
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The invention discloses a paper flame retardant with a core-shell structure, which can be used for adding in pulp and solves the problem that the performance of a paperboard is adversely affected by adding a flame retardant in the pulp in the prior art. The paper flame retardant with the core-shell structure is prepared from the following raw materials in parts by weight: 0.1-1 part of hydroxypropyl methyl cellulose, 5-10 parts of emulsifier and 20-50 parts of flame retardant particles with a core-shell structure; the flame retardant particles with the core-shell structure take a polyethyleneimine crosslinking substance as a shell and a nano molecular sieve coated with ammonium polyphosphate as an inner core. The invention also discloses a preparation method and application of the paper flame retardant with the core-shell structure. The paper flame retardant with the core-shell structure can be uniformly dispersed in paper, and various performances of the paper are not influenced.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a paper flame retardant with a core-shell structure, and a preparation method and application thereof.
Background
The cardboard is formed by interweaving fibers, so that the cardboard is flammable, has high burning speed and forms a fire which develops rapidly. The flame retardancy of paperboard is a requirement in some particular industries. The following considerations are generally considered for the production of a paperboard having a flame-retardant effect: firstly, if the raw materials are prepared by adopting the flame-retardant fibers, the burning of the paperboard can be stopped from the source, but the cost of the paperboard prepared by the method is very high; secondly, to isolate the board from the flame, or to reduce the oxygen content and burning temperature, this method generally employs the addition of flame retardants.
There are 3 methods for preparing flame-retardant paperboard by using flame retardant: the first is a coating method, wherein the flame retardant is coated on the surface of a paperboard; the second is a dipping method, the paper board is dipped in the solution containing the flame retardant; and thirdly, adding the flame retardant into the pulp during pulping. When the coating method is adopted, the problems of uneven distribution of the flame retardant, poor film-forming performance and easy occurrence of aging and fracture exist. The paperboard prepared by the impregnation method has the defect of strong moisture absorption. The cardboard is prepared by adopting the in-pulp addition method, the flame retardant is uniformly distributed in the cardboard, the flame retardant effect is good, but the performance of the cardboard is adversely affected by adding the flame retardant in the pulp.
Therefore, the flame retardant for adding into the pulp is provided, which has good flame retardant effect and does not affect various performances of the paperboard, so that the problem to be solved by the technical personnel in the field is urgently needed.
Disclosure of Invention
One of the purposes of the invention is to provide a paper flame retardant with a core-shell structure, which can be used for adding in pulp and solves the problem that the performance of a paperboard is adversely affected by adding the flame retardant in the pulp in the prior art.
The second purpose of the invention is to provide a preparation method of the paper flame retardant with the core-shell structure.
The invention also aims to provide application of the paper flame retardant with the core-shell structure.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a paper flame retardant with a core-shell structure, which is prepared from the following raw materials in parts by weight: 0.1-1 part of hydroxypropyl methyl cellulose, 5-10 parts of emulsifier and 20-50 parts of flame retardant particles with a core-shell structure; the flame retardant particles with the core-shell structure take a polyethyleneimine crosslinking substance as a shell and a nano molecular sieve coated with ammonium polyphosphate as an inner core.
Further, the flame retardant particles are prepared from the following components in parts by weight:
80-120 parts of phosphoric acid;
90-140 parts of urea;
60-90 parts of a nano molecular sieve;
30-120 parts of polyethyleneimine;
1-15 parts of glutaraldehyde.
Further, the flame retardant particles are prepared from the following components in parts by weight:
100 parts of phosphoric acid;
100 parts of urea;
70 parts of a nano molecular sieve;
60 parts of polyethyleneimine;
and 10 parts of glutaraldehyde.
Further, the nano molecular sieve is a nano ZSM-5 zeolite molecular sieve.
The preparation method of the paper flame retardant with the core-shell structure is characterized by comprising the following steps of:
step 1, weighing raw materials in parts by weight;
step 2, preparation of prepolymer solution: adding a glutaraldehyde solution into a polyethyleneimine solution, fully stirring, heating to 70-90 ℃, and preserving heat to obtain a prepolymer solution;
step 3, heating phosphoric acid to 60-80 ℃, adding urea, slowly heating to 120-140 ℃, adding a nano molecular sieve, dispersing under high-speed stirring, preserving heat for 30-50min, cooling to 70-90 ℃, dropwise adding the prepolymer solution prepared in the step 2, fully stirring at 70-90 ℃, carrying out polymerization reaction, ensuring the pH value of the reaction system to be 3-5, after the reaction is finished, adjusting the pH value to be alkalescent, standing, carrying out centrifugal separation, washing with water and absolute ethyl alcohol in sequence, and drying to obtain flame retardant particles with a core-shell structure;
and 4, adding water into the hydroxypropyl methyl cellulose for dispersion, adding the emulsifier and the flame retardant particles, uniformly mixing, and discharging.
Further, the concentration of the polyethyleneimine solution in the step 2 is 5-10 wt%; the concentration of the glutaraldehyde solution is 3-7wt%, and in the step 4, the hydroxypropyl methyl cellulose is dispersed in 5-10 times of water.
Further, the high-speed stirring in the step 3 is 3000-4000 rpm.
Further, in the step 4, adding an emulsifier and the flame retardant particles, uniformly mixing, adjusting the pH value of the system to 7.5-8.5, and discharging.
The application of the paper flame retardant is to prepare the flame retardant paper after mixing the paper flame retardant with paper pulp.
Further, the amount of the flame retardant for paper is 10-20wt% of the absolute dry fiber amount of the paper.
Compared with the prior art, the invention has the following beneficial effects:
the paper flame retardant with the core-shell structure can be uniformly dispersed in paper, and various performances of the paper are not influenced.
The flame retardant particle with the core-shell structure takes a polyethyleneimine crosslinking substance as a shell and takes a nano molecular sieve coated with ammonium polyphosphate as an inner core. The surface of the molecular sieve is provided with a large number of micropores, the molecular sieve is added in the synthesis process of the ammonium polyphosphate, and the phosphoric acid and the urea are subjected to in-situ polymerization reaction on the surface of the molecular sieve and in the micropores by utilizing the porosity and high adsorbability of the molecular sieve, so that the large number of ammonium polyphosphate and the molecular sieve are tightly combined, and the ammonium polyphosphate has better thermal stability and improves the flame retardant effect.
The polyethyleneimine can effectively increase the wet strength of paper, the crosslinking substances of the polyethyleneimine are coated on the surface of the nano molecular sieve, and the polyethyleneimine is used for combining the flame retardant particles with paper fibers, so that the problem that the traditional flame retardant particles exist in the paper in a physical dispersion manner to influence the performance such as the paper strength is solved.
The hydroxypropyl methyl cellulose can be used as a protective colloid, so that the flame retardant particles are uniformly dispersed in the paper pulp, and meanwhile, the hydroxypropyl methyl cellulose has hydrogen bonds and can be combined with the paper pulp fibers and the flame retardant particles to strengthen the strength of the paper.
The paper flame retardant is alkalescent, can effectively neutralize free acid in paper, and meets the requirements of paper for archives.
The method of the invention adopts the method that the nano molecular sieve is added in the process of synthesizing the ammonium polyphosphate, so that the generated ammonium polyphosphate with small particle size directly enters the molecular sieve pore canal, thereby reducing the dosage of the emulsifier and lowering the production cost.
Detailed Description
The following embodiments are intended to explain the present invention in more detail, but the scope of the subject matter of the present invention is not limited to the following embodiments, and all the techniques and processes realized based on the present invention are within the scope of the present invention.
The burning test of the paper in the embodiment of the invention is carried out according to GB/T14656-:
the paper was cut into 21cm × 7cm, and after 12 seconds of ignition with a flame adjusted to a length of 4cm, the flame was removed, and the ember time and the length of the carbonized paper strip were measured. Each set of burning tests was performed for 2 times.
The tensile property test of the paperboard in the embodiment of the invention is carried out according to GB/T12914-2008, and the following concrete steps are carried out:
the specimen size was 21cm by 1.5cm, the measuring range was set to 200mm, the drawing rate was 20mm/min, and the nip pitch was set to 180 mm. Tensile properties tests were performed in parallel for 2 experiments.
Example 1
The embodiment provides a preparation method of the flame retardant particle with the core-shell structure, which specifically comprises the following steps:
step 1, weighing the following raw materials in parts by weight:
100 parts of phosphoric acid;
100 parts of urea;
70 parts of a nano molecular sieve;
60 parts of polyethyleneimine;
and 10 parts of glutaraldehyde.
Step 2, preparation of prepolymer solution: adding water into polyethyleneimine to prepare a solution with the concentration of 8 wt%; adding water into glutaraldehyde to prepare a solution with the concentration of 5wt%, adding the glutaraldehyde solution into a polyethyleneimine solution, fully stirring, heating to 80 ℃, and preserving heat to obtain a prepolymer solution;
and 3, heating phosphoric acid to 70 ℃, adding urea, slowly heating to 130 ℃, controlling the heating rate to be 2 ℃/min, then adding a nano molecular sieve, stirring and dispersing at the rotating speed of 3500 rpm, keeping the temperature for 40min, cooling to 80 ℃, dropwise adding the prepolymer solution prepared in the step 2, stirring at the rotating speed of 200 rpm at the temperature of 80 ℃, carrying out polymerization reaction, ensuring the pH value of the reaction system to be 4, regulating the pH value to be 7.5 after the reaction is finished, standing, carrying out centrifugal separation, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the flame retardant particles with the core-shell structure.
Example 2
The embodiment provides a preparation method of the flame retardant particle with the core-shell structure, which specifically comprises the following steps:
step 1, weighing the following raw materials in parts by weight:
80 parts of phosphoric acid;
140 parts of urea;
90 parts of a nano molecular sieve;
30 parts of polyethyleneimine;
and 15 parts of glutaraldehyde.
Step 2, preparation of prepolymer solution: adding water into polyethyleneimine to prepare a solution with the concentration of 5 wt%; adding water into glutaraldehyde to prepare a solution with the concentration of 7wt%, adding the glutaraldehyde solution into a polyethyleneimine solution, fully stirring, heating to 90 ℃, and preserving heat to obtain a prepolymer solution;
and 3, heating phosphoric acid to 80 ℃, adding urea, slowly heating to 120 ℃, controlling the heating rate to be 2 ℃/min, then adding a nano molecular sieve, stirring and dispersing at the rotating speed of 3000 r/min, keeping the temperature for 50min, cooling to 70 ℃, dropwise adding the prepolymer solution prepared in the step 2, stirring at the rotating speed of 100 r/min at the temperature of 70 ℃, carrying out polymerization reaction, ensuring the pH value of a reaction system to be 3, regulating the pH value to be 7.5 after the reaction is finished, standing, carrying out centrifugal separation, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the flame retardant particles with the core-shell structure.
Example 3
The embodiment provides a preparation method of the flame retardant particle with the core-shell structure, which specifically comprises the following steps:
step 1, weighing the following raw materials in parts by weight:
120 parts of phosphoric acid;
90 parts of urea;
60 parts of a nano molecular sieve;
120 parts of polyethyleneimine;
1 part of glutaraldehyde.
Step 2, preparation of prepolymer solution: adding water into polyethyleneimine to prepare a solution with the concentration of 10 wt%; adding water into glutaraldehyde to prepare a solution with the concentration of 3wt%, adding the glutaraldehyde solution into a polyethyleneimine solution, fully stirring, heating to 70 ℃, and preserving heat to obtain a prepolymer solution;
and 3, heating phosphoric acid to 60 ℃, adding urea, slowly heating to 140 ℃, controlling the heating rate to be 2 ℃/min, then adding a nano molecular sieve, stirring and dispersing at the rotating speed of 4000 rpm, keeping the temperature for 30min, cooling to 90 ℃, dropwise adding the prepolymer solution prepared in the step 2, stirring at the rotating speed of 300 rpm at the temperature of 90 ℃, carrying out polymerization reaction, ensuring the pH value of a reaction system to be 5, regulating the pH value to be 7.4 after the reaction is finished, standing, carrying out centrifugal separation, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the flame retardant particles with the core-shell structure.
Example 4
The embodiment provides a preparation method of the core-shell structure paper flame retardant, which specifically comprises the following steps:
step 1, weighing the following raw materials in parts by weight: 0.5 part of hydroxypropyl methyl cellulose, 7 parts of an emulsifier and 35 parts of flame retardant particles with a core-shell structure. The flame retardant particles having a core-shell structure according to the present example were the flame retardant particles prepared by the method of example 1.
And 2, adding water into the hydroxypropyl methyl cellulose for dispersion, adding the emulsifier and the flame retardant particles, uniformly mixing, adjusting the pH value of the system to 7.5, and discharging.
Example 5
The embodiment provides a preparation method of the core-shell structure paper flame retardant, which specifically comprises the following steps:
step 1, weighing the following raw materials in parts by weight: 0.1 part of hydroxypropyl methyl cellulose, 5 parts of an emulsifier and 50 parts of flame retardant particles with a core-shell structure. The flame retardant particles having a core-shell structure according to the present example were the flame retardant particles prepared by the method of example 2.
And 2, adding water into the hydroxypropyl methyl cellulose for dispersion, adding the emulsifier and the flame retardant particles, uniformly mixing, adjusting the pH value of the system to 8.5, and discharging.
Example 6
The embodiment provides a preparation method of the core-shell structure paper flame retardant, which specifically comprises the following steps:
step 1, weighing the following raw materials in parts by weight: 1 part of hydroxypropyl methyl cellulose, 10 parts of an emulsifier and 20 parts of flame retardant particles with a core-shell structure. The flame retardant particles having a core-shell structure according to the present example were the flame retardant particles prepared by the method of example 3.
And 2, adding water into the hydroxypropyl methyl cellulose for dispersion, adding the emulsifier and the flame retardant particles, and discharging.
Example 7
This example provides a review of the amount of different molecular sieves used.
In this example, the amount of the molecular sieve used was different for each paper flame retardant than in example 4, and the other conditions were the same. The flame retardant for each paper prepared in this example was used to prepare flame retardant paper, and the obtained flame retardant paper was tested for each property, and the results are shown in table 1.
The preparation method of the flame retardant paper comprises the following steps: dispersing paper pulp into 2wt% pulp suspension, adding paper flame retardant into the pulp, and making flame retardant paper in a rapid paper sheet former, wherein the basis weight of the paper is 120 g.m-2. The amount of flame retardant added was 15wt% of the absolute dry fiber amount of the paper.
TABLE 1
Meanwhile, paper without the flame retardant is prepared, the tensile property of the paper is tested, and the tensile strength of the paper without the flame retardant is 7.056kN.m-1. The result shows that the tensile strength of the paper can be effectively increased by adopting the flame retardant disclosed by the invention, and the flame retardant has a good flame retardant effect.
Example 8
This example provides a review of the amount of different polyethyleneimines used.
In this example, the amount of polyethyleneimine used was different for each paper flame retardant compared with example 4, and the other conditions were the same. The flame retardant for each paper prepared in this example was used to prepare flame retardant paper, and the obtained flame retardant paper was tested for each property, and the results are shown in table 2.
Flame retardant paper was prepared as in example 7.
TABLE 2
The result shows that the tensile strength of the paper can be effectively increased by adopting the flame retardant disclosed by the invention, and the flame retardant has a good flame retardant effect. The tensile strength of the flame-retardant paper without the polyethyleneimine is reduced.
Example 9
This example provides a review of the amount of hydroxypropyl methylcellulose used.
In this example, the amount of the hydroxypropyl methylcellulose used was different for each paper flame retardant than in example 4, and the other conditions were the same. The flame retardant for each paper prepared in this example was used to prepare flame retardant paper, and the obtained flame retardant paper was tested for each property, and the results are shown in table 3.
Flame retardant paper was prepared as in example 7.
TABLE 3
The results show that the addition of hydroxypropyl methylcellulose can increase the tensile strength and flame retardant effect of paper.
Example 10
This example provides a review of the amount of different paper flame retardants used.
A flame retardant was prepared by using the flame retardant for paper obtained in example 4, and flame retardant paper was prepared in the same manner as in example 7 except that the amount of the flame retardant was different and the other conditions were the same. The obtained flame retardant paper was tested for various properties and the results are shown in table 4.
TABLE 4
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (8)
1. The flame retardant for the paper with the core-shell structure is characterized by being prepared from the following raw materials in parts by weight: 0.1-1 part of hydroxypropyl methyl cellulose, 5-10 parts of emulsifier and 20-50 parts of flame retardant particles with a core-shell structure; the flame retardant particles with the core-shell structure take a polyethyleneimine crosslinking substance as a shell and a nano molecular sieve coated with ammonium polyphosphate as an inner core; the flame retardant particles are prepared from the following components in parts by weight:
80-120 parts of phosphoric acid;
90-140 parts of urea;
60-90 parts of a nano molecular sieve;
30-120 parts of polyethyleneimine;
1-15 parts of glutaraldehyde;
the preparation method of the flame retardant particles comprises the following steps:
step 1, weighing raw materials in parts by weight;
step 2, preparation of prepolymer solution: adding a glutaraldehyde solution into a polyethyleneimine solution, fully stirring, heating to 70-90 ℃, and preserving heat to obtain a prepolymer solution;
and 3, heating phosphoric acid to 60-80 ℃, adding urea, slowly heating to 120-140 ℃, adding a nano molecular sieve, dispersing under a high-speed stirring condition, keeping the temperature for 30-50min, cooling to 70-90 ℃, dropwise adding the prepolymer solution prepared in the step 2, fully stirring at 70-90 ℃, carrying out polymerization reaction, ensuring the pH value of the reaction system to be 3-5, after the reaction is finished, adjusting the pH value to be alkalescent, standing, carrying out centrifugal separation, washing with water and absolute ethyl alcohol in sequence, and drying to obtain the flame retardant particles with the core-shell structure.
2. The core-shell-structured paper flame retardant according to claim 1, wherein the flame retardant particles are prepared from the following components in parts by weight:
100 parts of phosphoric acid;
100 parts of urea;
70 parts of a nano molecular sieve;
60 parts of polyethyleneimine;
and 10 parts of glutaraldehyde.
3. The core-shell structure paper flame retardant according to claim 1 or 2, wherein the nano molecular sieve is a nano ZSM-5 zeolite molecular sieve.
4. The preparation method of the core-shell structure paper flame retardant according to any one of claims 1 to 3, characterized by comprising the following steps:
step 1, weighing raw materials in parts by weight;
step 2, preparation of prepolymer solution: adding a glutaraldehyde solution into a polyethyleneimine solution, fully stirring, heating to 70-90 ℃, and preserving heat to obtain a prepolymer solution;
step 3, heating phosphoric acid to 60-80 ℃, adding urea, slowly heating to 120-140 ℃, adding a nano molecular sieve, dispersing under high-speed stirring, preserving heat for 30-50min, cooling to 70-90 ℃, dropwise adding the prepolymer solution prepared in the step 2, fully stirring at 70-90 ℃, carrying out polymerization reaction, ensuring the pH value of the reaction system to be 3-5, after the reaction is finished, adjusting the pH value to be alkalescent, standing, carrying out centrifugal separation, washing with water and absolute ethyl alcohol in sequence, and drying to obtain flame retardant particles with a core-shell structure;
step 4, adding water into the hydroxypropyl methyl cellulose for dispersion, adding the emulsifier and the flame retardant particles, uniformly mixing, and discharging;
the high-speed stirring in the step 3 is 3000-.
5. The preparation method of the core-shell structure paper flame retardant according to claim 4, wherein the concentration of the polyethyleneimine solution in the step 2 is 5-10 wt%; the concentration of the glutaraldehyde solution is 3-7wt%, and in the step 4, the hydroxypropyl methyl cellulose is dispersed in 5-10 times of water.
6. The preparation method of the core-shell structure paper flame retardant according to claim 5, characterized in that in step 4, the emulsifier and the flame retardant particles are added, mixed uniformly, the pH value of the system is adjusted to 7.5-8.5, and the product is discharged.
7. Use of the paper flame retardant according to any one of claims 1 to 3, characterized in that the flame retardant is mixed with paper pulp to prepare flame retardant paper.
8. Use according to claim 7, characterised in that the paper flame retardant is used in an amount of 10-20 wt.% based on the absolute dry fibre content of the paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810807060.2A CN109056411B (en) | 2018-07-18 | 2018-07-18 | Core-shell-structured paper flame retardant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810807060.2A CN109056411B (en) | 2018-07-18 | 2018-07-18 | Core-shell-structured paper flame retardant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109056411A CN109056411A (en) | 2018-12-21 |
| CN109056411B true CN109056411B (en) | 2021-04-06 |
Family
ID=64834900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810807060.2A Expired - Fee Related CN109056411B (en) | 2018-07-18 | 2018-07-18 | Core-shell-structured paper flame retardant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109056411B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330662A (en) * | 2019-07-02 | 2019-10-15 | 北京理工大学 | A kind of polyethyleneimine and polyphosphoric acid polyelectrolyte complex compound and preparation method thereof |
| CN111662561B (en) * | 2020-07-13 | 2021-10-01 | 南京林业大学 | Preparation method of flame-retardant and repeatedly-processable wood-plastic composite material |
| CN112850740B (en) * | 2021-02-23 | 2022-03-08 | 浙江浙能技术研究院有限公司 | Synthesis method of sheet MFI topological structure molecular sieve |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087360B (en) * | 2013-01-17 | 2015-07-29 | 沈阳化工大学 | Micro encapsulation expandable flame retardant natural rubber and preparation method thereof is covered in double-contracting |
| CN105566683B (en) * | 2015-12-25 | 2018-12-25 | 中国科学院宁波材料技术与工程研究所 | A kind of supermolecule fire retardant and preparation method thereof based on ionic bond |
| CN105949476B (en) * | 2016-06-23 | 2018-11-30 | 浙江大学宁波理工学院 | The preparation method of core-shell structure organic inorganic hybridization object |
| CN108084333B (en) * | 2017-12-30 | 2020-02-07 | 扬州大学 | Low-pollution flame-retardant thermal expansion microsphere and preparation method thereof |
-
2018
- 2018-07-18 CN CN201810807060.2A patent/CN109056411B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN109056411A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109056411B (en) | Core-shell-structured paper flame retardant and preparation method and application thereof | |
| CN103541279B (en) | A kind of high dust containing capacity glass fibre air filter paper and production technology | |
| JP6636501B2 (en) | Continuous coating method for cellulosic fibrous substrate web using fatty acid chloride | |
| CN111805678B (en) | Preparation method of flame-retardant shaving board | |
| CN103556544B (en) | A kind of high flame retardant glass fibre air filter paper and preparation method thereof | |
| CN103590281A (en) | Surface sizing solution, and surface sizing solution used sized paper | |
| JP2012527544A (en) | Improving the strength of paper and paperboard products | |
| JP2021509416A (en) | Film of microfibrillated cellulose | |
| WO2022148295A1 (en) | High-quality central heating tobacco cigarette core material and preparation method therefor | |
| Su et al. | A novel biomass vitamin B6-based flame retardant for lyocell fibers | |
| CN112021634B (en) | Preparation method of special sheet for heating cigarettes by papermaking method | |
| Egamberdiyev et al. | Obtaining wrapping paper used in furniture wrapping and quality delivery and determining its quality indicators | |
| CN108130808A (en) | A kind of faced deorative paper with fire retardation and the fire-retardant overlaid wood based panel using the facing paper | |
| JP2023544541A (en) | bio-based carbon foam | |
| Yang et al. | In Situ Polymerization and Flame Retardant Mechanism of Bio‐Based Nitrogen and Phosphorus Macromolecular Flame Retardant in Plywood | |
| Yang et al. | Hydrophobic microcapsule modification of nitrogen–phosphorus flame retardant and its application in lignocellulosic materials | |
| CN103510429A (en) | Compound flame-retardant paper-based material and preparation method thereof | |
| CN109629320B (en) | Preparation method of plant fiber/glass fiber-based special tissue base material | |
| CN110318287A (en) | A kind of preparation method of sound-absorbing and flame-retardant fiber type composite material | |
| CN110318286A (en) | A kind of preparation method of Halogen sound-absorbing and flame-retardant paper | |
| JPS6233360B2 (en) | ||
| WO2014148207A1 (en) | Wrapping paper for cigarette | |
| CN113439867B (en) | Method for preparing reconstituted tobacco for heating non-combustible cigarettes by combining dry method and rolling method | |
| CN108532015A (en) | A kind of method and flame retardant viscose fiber preparing flame retardant viscose fiber based on self-assembling technique | |
| US3779861A (en) | Fireproofing cellulose-containing materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210406 |