CN116791403A - Preparation method of starch-based intumescent flame retardant - Google Patents
Preparation method of starch-based intumescent flame retardant Download PDFInfo
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- CN116791403A CN116791403A CN202310627164.6A CN202310627164A CN116791403A CN 116791403 A CN116791403 A CN 116791403A CN 202310627164 A CN202310627164 A CN 202310627164A CN 116791403 A CN116791403 A CN 116791403A
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- starch
- flame retardant
- intumescent flame
- based intumescent
- acid
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- 229920002472 Starch Polymers 0.000 title claims abstract description 110
- 239000008107 starch Substances 0.000 title claims abstract description 107
- 235000019698 starch Nutrition 0.000 title claims abstract description 107
- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 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 69
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 230000000865 phosphorylative effect Effects 0.000 claims abstract description 7
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 11
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000467 phytic acid Substances 0.000 claims description 10
- 229940068041 phytic acid Drugs 0.000 claims description 10
- 235000002949 phytic acid Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 8
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 7
- 240000003183 Manihot esculenta Species 0.000 claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 7
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002261 Corn starch Polymers 0.000 claims description 6
- 239000008120 corn starch Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 240000004922 Vigna radiata Species 0.000 claims description 3
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 3
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 229940100486 rice starch Drugs 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- 239000002655 kraft paper Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 238000006366 phosphorylation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002023 wood Substances 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
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
-
- 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
- D21H17/65—Acid 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The invention relates to a method for preparing a flame retardant from starch, and the prepared starch-based flame retardant belongs to the technical field of environment-friendly flame retardants. Starch is used as a carbon source, a phosphorylating reagent is used as an acid source, amine substances are used as an air source, and boron substances are introduced into a flame-retardant system to construct the starch-based intumescent flame retardant. The prepared starch-based intumescent flame retardant is an aqueous solution, can be applied to flame retardant treatment of paper by an impregnation method, a spraying method and the like, and has excellent flame retardant property.
Description
Technical Field
The invention relates to a method for preparing a flame retardant from starch, and the prepared starch-based flame retardant belongs to the technical field of environment-friendly flame retardants.
Background
The paper-based functional material is generally manufactured by plant fibers, and has wide application in the fields of packaging, construction, decoration, electronic equipment, even aerospace and the like. But it is composed of cellulose, hemicellulose and lignin, is highly flammable and burns at a high rate, and fire hazards caused by paper-based materials in life are not a few, and flame retardant treatment of paper-based materials is becoming increasingly important. With the continuous research of flame retardant paper, halogens (organic chlorides and organic bromides), inorganic substances (metal oxides, metal hydroxides, boron compounds, silicon compounds, and the like), and the like are applied to flame retardant treatment of paper-based materials. Intumescent flame retardants have been extensively studied for their good flame retardant properties. The intumescent flame retardant is a composite flame retardant mainly composed of nitrogen and phosphorus, and generally consists of an acid source (inorganic acid, phosphoric acid and ammonium polyphosphate in general), a carbon source (polyhydroxy compound with high carbon content) and a gas source (foaming agent). The acid source decomposes when heated to produce phosphoric acid, pyrophosphates, and other compounds that can form esters with the carbon source, which dehydrate and crosslink to form carbon, while the gas source releases a large amount of gas to help form an expanded carbon layer. The thick carbon layer improves the temperature gradient between the surface of the polymer and the surface of the carbon layer, so that the surface temperature of the polymer is much lower than the flame temperature, the possibility that the polymer is further degraded to release combustible gas is reduced, and meanwhile, the entry of external oxygen is isolated, so that the flame retardant effect on the polymer is realized.
With the development of biology-based material science, biomass such as cellulose, starch, tannin, lignin, chitosan and the like has high carbon content, polyhydroxy structure and excellent char formation performance, and can replace the traditional petroleum-based carbon source (pentaerythritol). The biomacromolecules can be obtained from byproducts of wood industry, agriculture or food industry through a biomass refining technology, so that the resource utilization rate is improved, and meanwhile, economic benefits are brought, and the intumescent flame retardant constructed by the bio-based carbon source gradually becomes the key point and research direction of flame retardant modification of paper. How to utilize biomass resources with abundant reserves and develop an environment-friendly and efficient biomass intumescent flame retardant is one of the development directions of flame retardant technology.
Disclosure of Invention
In order to solve the defects of insufficient flame retardant efficiency and poor compatibility with paper of the existing flame retardant for paper, the invention aims to provide a preparation process of a starch-based intumescent flame retardant, which takes starch as a raw material and adopts a phosphorylating reagent to carry out grafting modification on the starch so as to construct the starch-based intumescent flame retardant.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a preparation method of a starch-based intumescent flame retardant comprises the following specific preparation steps:
s1, mixing 20-40 parts of starch and 100 parts of deionized water, and performing ultrasonic dispersion at 25-30 ℃ for 10-20 min to enable the starch to be fully dispersed;
s2, adding a phosphorylation reagent and boron substances into a starch system, and stirring and reacting for 2-4 hours at 100-140 ℃, wherein the molar ratio of the starch to the phosphorylation reagent to the boron substances=1 (3-6) to (2-5), wherein the starch is calculated as a glucose unit to obtain an intermediate product A;
s3, adding amine substances into the A, wherein the molar ratio of the starch to the amine substances is 1 (2-6), and obtaining the starch-based intumescent flame retardant after cooling and filtering after reacting for 1-3 hours by taking the starch as a glucose unit.
The starch is one or a combination of more of corn starch, mung bean starch, rice starch, tapioca starch, pea starch and wheat starch;
the phosphorylating reagent is one or a mixture of more of phytic acid, phosphoric acid, hydroxyethylidene diphosphonic acid or amino trimethylene phosphonic acid; the boron substance is one or a mixture of boric acid and borax;
the amine substance is one or a mixture of urea, dicyandiamide or melamine;
the invention has the following characteristics
(1) The prepared flame retardant adopts starch as a main raw material, and has the advantages of low cost, environmental protection and the like.
(2) The prepared flame retardant is an aqueous solution, has low viscosity and good fluidity, and has higher flame retardant efficiency and better expansibility. The paper can be subjected to flame retardant treatment by dipping, spraying and the like, the process is simple, the obtained flame retardant paper can self-extinguish during a combustion test, and the flame retardant performance is excellent;
(3) The prepared flame retardant takes starch as a carbon source, the carbon chain framework structure of the starch is similar to that of cellulose, the compatibility of the starch-based flame retardant and paper fibers is good, and the flame retardant has obvious effect on solving the problem of poor compatibility of the traditional flame retardant and paper. Therefore, the prepared starch-based flame retardant has good compatibility with paper.
Preferably, the starch in S1 is one or more of corn starch, mung bean starch, rice starch, tapioca starch, pea starch and wheat starch;
preferably, the phosphorylating agent of S2 is one or more of phytic acid, phosphoric acid, hydroxyethylidene diphosphonic acid or aminotrimethylene phosphonic acid; the boron substance is one or a mixture of boric acid and borax;
preferably, the amine substance in S3 is one or more of urea, dicyandiamide or melamine;
description of the embodiments
The present invention is further illustrated in detail below by means of specific examples, which are given solely for the purpose of illustration and are not intended to limit the scope of the invention. The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
Example 1
S1, weighing 30 parts of corn starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 30 ℃ for 15min to enable the starch to be fully dispersed;
s2, adding phytic acid and boric acid into a starch system, and stirring at 130 ℃ for reaction for 3 hours, wherein the molar ratio of the phytic acid to the boric acid=1:3:3, wherein the starch is calculated by glucose units to obtain an intermediate product A;
s3, dicyandiamide is added into the A, the molar ratio of starch to dicyandiamide is 1:3, wherein the starch is calculated by glucose units, and after 2 hours of reaction, the starch-based intumescent flame retardant is obtained after cooling and filtering.
Example 2
S1, weighing 30 parts of corn starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 30 ℃ for 15min to enable the starch to be fully dispersed;
s2, adding phytic acid and boric acid into a starch system, and stirring at 130 ℃ for reaction for 3 hours, wherein the molar ratio of the phytic acid to the boric acid=1:4:3.5, wherein the starch is calculated by a glucose unit to obtain an intermediate product A;
s3, dicyandiamide is added into the A, the molar ratio of starch to dicyandiamide is 1:3.5, wherein the starch is calculated by glucose units, and after 2 hours of reaction, the starch-based intumescent flame retardant is obtained after cooling and filtering.
Example 3
S1, weighing 30 parts of tapioca starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 30 ℃ for 20min to enable the starch to be fully dispersed;
s2, adding hydroxyethylidene diphosphonic acid and boric acid into a starch system, and stirring at 130 ℃ to react for 3 hours, wherein the molar ratio of the starch to the hydroxyethylidene diphosphonic acid to the boric acid=1:5:4, wherein the starch is calculated by a glucose unit to obtain an intermediate product A;
s3, adding melamine into the A, wherein the molar ratio of starch to the melamine is 1:4, taking glucose units as starch, reacting for 2 hours, cooling, and filtering to obtain the starch-based intumescent flame retardant.
Example 4
S1, weighing 30 parts of tapioca starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 30 ℃ for 20min to enable the starch to be fully dispersed;
s2, adding hydroxyethylidene diphosphonic acid and boric acid into a starch system, and stirring at 130 ℃ for reaction for 3 hours, wherein the molar ratio of the starch to the hydroxyethylidene diphosphonic acid to the boric acid=1:5.5:4.5, wherein the starch is calculated by glucose units to obtain an intermediate product A;
s3, dicyandiamide is added into the A, the molar ratio of starch to dicyandiamide is 1:5, wherein the starch is calculated by glucose units, and after 2 hours of reaction, the starch-based intumescent flame retardant is obtained after cooling and filtering.
Example 5
S1, weighing 30 parts of tapioca starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 25 ℃ for 15min to enable the starch to be fully dispersed;
s2, adding amino trimethylene phosphonic acid and boric acid into a starch system, and stirring at 130 ℃ for reaction for 3 hours, wherein the molar ratio of the amino trimethylene phosphonic acid to the boric acid is 1:6:5, and the starch is calculated by glucose units to obtain an intermediate product A;
s3, adding urea into the A, wherein the molar ratio of the starch to the urea is 1:6, and obtaining the starch-based intumescent flame retardant after cooling and filtering after reacting for 2 hours by taking the starch as a glucose unit.
Comparative example 1
S1, weighing 30 parts of corn starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 30 ℃ for 20min to enable the starch to be fully dispersed;
s2, adding phytic acid into a starch system, and stirring at 130 ℃ for reaction for 3 hours, wherein the molar ratio of the phytic acid to the phytic acid is 1:4, wherein the starch is calculated by a glucose unit to obtain an intermediate product A;
s3, dicyandiamide is added into the A, the molar ratio of starch to dicyandiamide is 1:3.5, wherein the starch is calculated by glucose units, and after 2 hours of reaction, the starch-based intumescent flame retardant is obtained after cooling and filtering.
Comparative example 2
S1, weighing 30 parts of tapioca starch, adding 100 parts of deionized water, and performing ultrasonic dispersion at 30 ℃ for 20min to enable the starch to be fully dispersed;
s2, adding amino trimethylene phosphonic acid and boric acid into a starch system, stirring and reacting for 3 hours at 130 ℃, wherein the molar ratio of the amino trimethylene phosphonic acid to the boric acid is 1:4:3.5, wherein the starch is calculated by a glucose unit, cooling and filtering to obtain the starch-based intumescent flame retardant;
the above examples 1 to 5 and comparative examples 1 to 2 were applied to flame retardant treatment of paper using an impregnation method, and the obtained flame retardant paper was subjected to flame retardant property test according to UL-94-2018 standard method. The limiting oxygen index test was performed on the flame retardant paper according to the GB/T2406-93 standard method.
TABLE 1 vertical Combustion test results
As shown in the data of Table 1, the starch-based intumescent flame retardant of the invention has excellent flame retardant property, and the prepared flame retardant paper can reach UL-94V-0 grade. Starch is used as a carbon source, a starch-based intumescent flame retardant is constructed, the obtained starch-based flame retardant is an aqueous solution, the fluidity is good, the viscosity is low, the flame retardant treatment can be carried out on paper by an impregnation method or a spraying method, and the obtained flame retardant paper has excellent flame retardant property.
Finally, it should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and that other various changes and modifications can be made by one skilled in the art based on the above description and the idea, and it is not necessary or exhaustive of all the embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (8)
1. The preparation method of the starch-based intumescent flame retardant is characterized by comprising the following steps:
s1, mixing starch and deionized water, and performing ultrasonic dispersion to fully disperse the starch;
s2, adding a phosphorylating reagent and boron substances into a starch system, and stirring at a high temperature for reaction to obtain an intermediate product A;
s3, adding amine substances into the A, continuously reacting, cooling, and filtering to obtain the starch-based intumescent flame retardant.
2. A process for the production of a starch-based intumescent flame retardant as claimed in claim 1, characterized in that,
the starch is one or a combination of more of corn starch, mung bean starch, rice starch, tapioca starch, pea starch and wheat starch;
the phosphorylating reagent is one or a mixture of more of phytic acid, phosphoric acid, hydroxyethylidene diphosphonic acid or amino trimethylene phosphonic acid; the boron substance is one or a mixture of boric acid and borax;
the amine substance is one or a mixture of urea, dicyandiamide or melamine.
3. The method for preparing a starch-based intumescent flame retardant as claimed in claim 1, characterized in that,
in the step S1, the mass ratio of the starch to the deionized water is 1 (2.5-5);
in the step S2, the molar ratio of the substances is starch, a phosphorylating agent and boron substances=1 (3-6): 2-5, wherein the starch is calculated by glucose units;
in the step S3, the molar ratio of the starch to the amine substances is 1 (2-6), wherein the starch is calculated by glucose units.
4. The method for preparing a starch-based intumescent flame retardant as claimed in claim 1, wherein the reaction temperature of S2 is 100-150 ℃.
5. The method for preparing a starch-based intumescent flame retardant as claimed in claim 1, wherein the reaction time of S2 is 2-4 hours.
6. The method for preparing a starch-based intumescent flame retardant as claimed in claim 1, wherein the reaction time of S3 is 1-3 hours.
7. The method for preparing a starch-based intumescent flame retardant as claimed in claim 1, wherein the reaction temperature of S3 is 100-150 ℃.
8. The starch-based intumescent flame retardant prepared by the method of claim 1 can be used for flame retardant treatment of cardboard paper, white cardboard, kraft paper and the like to prepare high-performance flame retardant paper.
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