CN117442921B - Polymer gel fire-extinguishing flame retardant and preparation method thereof - Google Patents
Polymer gel fire-extinguishing flame retardant and preparation method thereof Download PDFInfo
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- CN117442921B CN117442921B CN202311432791.0A CN202311432791A CN117442921B CN 117442921 B CN117442921 B CN 117442921B CN 202311432791 A CN202311432791 A CN 202311432791A CN 117442921 B CN117442921 B CN 117442921B
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- 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 99
- 239000003063 flame retardant Substances 0.000 title claims abstract description 98
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 99
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 79
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011032 tourmaline Substances 0.000 claims abstract description 61
- 229940070527 tourmaline Drugs 0.000 claims abstract description 61
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 60
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000001913 cellulose Substances 0.000 claims abstract description 55
- 229920002678 cellulose Polymers 0.000 claims abstract description 55
- 239000002952 polymeric resin Substances 0.000 claims abstract description 52
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 52
- 239000000499 gel Substances 0.000 claims abstract description 47
- 239000000654 additive Substances 0.000 claims abstract description 44
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 239000000017 hydrogel Substances 0.000 claims abstract description 44
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 229920002472 Starch Polymers 0.000 claims abstract description 34
- 125000002091 cationic group Chemical group 0.000 claims abstract description 34
- 239000008107 starch Substances 0.000 claims abstract description 34
- 235000019698 starch Nutrition 0.000 claims abstract description 34
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 28
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 28
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 28
- 229960004853 betadex Drugs 0.000 claims abstract description 28
- -1 pentaerythritol diphosphate diphosphonic chloride Chemical compound 0.000 claims abstract description 27
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 26
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008117 stearic acid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 150
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 148
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 64
- 239000007864 aqueous solution Substances 0.000 claims description 59
- 238000005406 washing Methods 0.000 claims description 52
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 50
- 239000004202 carbamide Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 47
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 31
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 27
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 27
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- ZIOGVYRWWDCNEW-UHFFFAOYSA-N P(=O)(OP(=O)Cl)Cl.P(=O)(O)OP(=O)O.OCC(CO)(CO)CO Chemical compound P(=O)(OP(=O)Cl)Cl.P(=O)(O)OP(=O)O.OCC(CO)(CO)CO ZIOGVYRWWDCNEW-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 87
- 239000012043 crude product Substances 0.000 description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 22
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical class OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000000779 smoke Substances 0.000 description 14
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 13
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000001879 Curdlan Substances 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- GLPCWTYATLZOFQ-UHFFFAOYSA-N OCC(CO)(CO)COP(O)(OP(O)(O)=O)=O.Cl Chemical compound OCC(CO)(CO)COP(O)(OP(O)(O)=O)=O.Cl GLPCWTYATLZOFQ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000499828 Tristagma Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emergency Management (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Business, Economics & Management (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to the technical field of fire control, and discloses a novel polymer gel fire-extinguishing flame retardant and a preparation method thereof. The preparation method comprises the following steps: reacting beta-cyclodextrin with pentaerythritol diphosphate diphosphonic chloride to obtain modified beta-cyclodextrin; reacting the nano tourmaline with stearic acid to obtain modified nano tourmaline; mixing the modified beta-cyclodextrin with modified nano tourmaline to obtain a flame retardant additive; mixing cationic starch, acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid, a flame retardant additive, a cross-linking agent and an initiator to obtain modified high polymer resin; and mixing the modified polymer resin, the modified cellulose hydrogel and water to obtain the novel polymer gel fire-extinguishing flame retardant.
Description
Technical Field
The invention relates to the technical field of fire control, in particular to a novel polymer gel fire-extinguishing flame retardant and a preparation method thereof.
Background
The fire extinguishing agent mainly comprises water, foam, dry powder, haloalkane, carbon dioxide, nitrogen and some fire extinguishing agents with special purposes, wherein the water is the most common fire extinguishing agent and is widely used for extinguishing fire. However, the water has high fluidity, so that the utilization rate is low, the flow process not only loses the fire extinguishing effect, but also causes secondary loss, and even the penetration caused by water flow flushing can cause the re-spontaneous combustion after the fire extinguishing. In order to improve the fire extinguishing performance of water, the adhesion and flow performance of water can be changed by a chemical method, so that the fire extinguishing effect is improved.
The super absorbent resin is a three-dimensional network polymer with hydrophilic groups and slight crosslinking, can absorb a large amount of water to swell and keep the water from flowing out, and has the advantages of high water absorption rate, strong water retention performance and the like. The high molecular hydrogel fire extinguishing agent prepared by the water absorption of the high water absorption resin is a water-based fire extinguishing agent with burning resistance and strong adhesion performance, can effectively control the spread of fire, and has excellent fire extinguishing effect.
The polymer hydrogel fire extinguishing agent has been widely used in the field of fire extinguishment at present, and the polymer hydrogel fire extinguishing agent prepared from the polymer hydrogel fire extinguishing agent can consume a large amount of heat when losing water in fire due to the fact that the super absorbent resin has a quite large heat capacity under the high temperature condition, and can isolate a fire source from air and prevent the back fire from being re-burnt, so that the effect of instant fire extinguishment is achieved.
However, the prior art such as Chinese patent application CN109806535A discloses a polymer hydrogel fire extinguishing agent and a preparation method thereof, and the adhesive force and the fire extinguishing efficiency of gel are increased by adding curdlan, but the prepared polymer hydrogel has poor flame retardance and poor smoke suppression effect, so that the application of the polymer hydrogel fire extinguishing agent in the fire-fighting field is limited.
The prior art, such as Chinese patent application CN108992828A, discloses a polymer hydrogel fire extinguishing agent, which has a pH sensitive sol structure by adding sodium bicarbonate, modified gelatin powder and aluminum nitride whisker, so that the prepared polymer hydrogel fire extinguishing agent has flame retardance and excellent fire extinguishing effect. However, the fire extinguishing agent has poor smoke suppression effect, and limits the application of the fire extinguishing agent in the field of fire protection.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel polymer gel fire-extinguishing flame retardant and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the novel polymer gel fire-extinguishing flame retardant comprises the following steps:
Step (1), mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride, reacting, cooling, filtering, washing and drying after the reaction is finished to obtain pentaerythritol biphosphate diphosphonic chloride;
step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting, removing solvent dimethyl sulfoxide by rotary evaporation after the reaction is finished, washing, and drying to obtain modified beta-cyclodextrin;
Mixing the nano tourmaline, stearic acid and diethyl ether, stirring for reaction, filtering, washing and drying after the reaction is finished to obtain modified nano tourmaline;
mixing the modified beta-cyclodextrin with modified nano tourmaline to obtain a flame retardant additive;
mixing cationic starch with water for an activation reaction, adding an initiator after the reaction is finished, initiating the reaction, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, adding a cross-linking agent after the reaction is finished, continuing the reaction, washing, drying, crushing and sieving to obtain modified polymer resin;
step (4), mixing and dissolving lithium hydroxide/urea aqueous solution and cellulose, dropwise adding epichlorohydrin, reacting after the dropwise adding, defoaming after the reaction is finished, standing, and washing to be neutral to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water, and standing to obtain the novel polymer gel fire-extinguishing flame retardant.
Preferably, in the step (1): the mass ratio of pentaerythritol to phosphorus oxychloride to chlorobenzene to aluminum chloride is (14-16): (40-45): (90-110): (0.3-0.4); the reaction conditions are as follows: firstly, reacting for 1-2h at 50-60 ℃ in nitrogen atmosphere, then continuously reacting for 2-3h at 80-85 ℃ in nitrogen atmosphere, and finally continuously reacting for 8-12h at 100-110 ℃ in nitrogen atmosphere.
Preferably, the washing liquid used for washing comprises methylene chloride.
Preferably, in the step (2): the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1140-1200 (2400-2500) (10-20); the reaction conditions are as follows: in nitrogen atmosphere, reacting for 2-4h at 0-2 ℃.
Preferably, in the step (2): the mass ratio of the nano tourmaline to the stearic acid to the diethyl ether is (100-200): (1.5-3): (1000-1500); the conditions of the stirring reaction are as follows: the reaction is stirred at room temperature for 0.5-1h.
Preferably, in the step (2): the mass ratio of the modified beta-cyclodextrin to the modified nano tourmaline is 1 (3-5).
Preferably, in the step (3): the conditions of the activation reaction are as follows: activating reaction at 60-90 deg.c for 15-75min; the conditions for initiating the reaction are: the reaction is initiated at room temperature for 10-20min in an inert gas atmosphere.
Preferably, in the step (3): the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is (1-1.5): (10-18): (3-7): (3-5): (0.02-0.04): (0.15-0.2); the reaction conditions are as follows: reacting for 15-20min at room temperature in inert gas atmosphere; the conditions for continuing the reaction were: the reaction was continued at room temperature for 2-2.5h.
Preferably, the initiator comprises potassium persulfate; the cross-linking agent comprises N, N' -methylene bisacrylamide; the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% sodium hydroxide aqueous solution according to a mass ratio of 1:0.5-1, and carrying out neutralization reaction for 10-20min at the temperature of 0-2 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 80-90%.
Preferably, the number of sieves comprises 100-200 mesh.
Preferably, in the step (4): the mass ratio of the lithium hydroxide/urea aqueous solution to the cellulose is 99:1; the molar ratio of the cellulose to the epichlorohydrin is 1 (14-21).
Preferably, in the step (4): the dropping conditions are as follows: dripping at-15deg.C for 5-10min; the reaction conditions are as follows: reacting for 2h at the rotating speed of 150-200r/min and the temperature of minus 15-0 ℃; the defoaming conditions are as follows: centrifugal defoaming for 8-10min at the rotation speed of 1800-2000r/min and the temperature of 3-5 ℃.
Preferably, the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of the lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of the urea is 15%.
Preferably, in the step (4): the mass ratio of the modified polymer resin to the modified cellulose hydrogel to the water is (3-5) (5-7) (5000-8000).
Preferably, the novel polymer gel fire-extinguishing flame retardant is prepared by adopting the preparation method of the novel polymer gel fire-extinguishing flame retardant.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, phosphorus oxychloride and pentaerythritol react, and the obtained reaction product and beta-cyclodextrin undergo nucleophilic substitution reaction, so that the beta-cyclodextrin is grafted with a group with flame retardant function, and the obtained modified beta-cyclodextrin has better flame retardance, and the interface compatibility between the modified beta-cyclodextrin and resin is increased.
According to the invention, the tourmaline and the stearic acid are mixed and surface-modified, and the modified tourmaline is obtained through the interaction between the stearic acid and the functional groups on the surface of the tourmaline, so that the dispersibility of the tourmaline in a resin matrix is improved, and the agglomeration degree of the tourmaline is reduced; and mixing the modified tourmaline with the modified beta-cyclodextrin to obtain the flame retardant additive. As the tourmaline has the characteristics of porous structure, high stability and high adsorptivity, and can release anions in the air, the tourmaline can effectively adsorb the flue gas generated when the combustion object burns, and the effect of purifying the air is achieved.
In addition, tourmaline belongs to silicate inorganic matters and has a certain flame-retardant effect; the cavity structure of the beta-cyclodextrin has certain adsorption capacity, and the modified tourmaline and the modified beta-cyclodextrin are mixed, so that the flame retardant effect and adsorption capacity of the flame retardant additive can be effectively improved.
The cationic starch is pretreated, so that the water absorbability of the cationic starch is improved, the crystal structure of the cationic starch is damaged, and the grafting rate is improved; the active group of the cationic starch and the monomer rich in hydrophilic groups are subjected to graft copolymerization, and simultaneously, the flame retardant additive is added to serve as a physical crosslinking point, so that the thermal stability of the resin is increased through in-situ polymerization of the flame retardant additive and the resin, and the prepared modified polymer resin has excellent heat resistance, water absorption and flame retardance.
According to the invention, epichlorohydrin is used as a cross-linking agent, the modified cellulose hydrogel is prepared through chemical cross-linking of cellulose, and the novel polymer gel fire-extinguishing flame retardant prepared by mixing the hydrogel serving as a reinforcing material with modified polymer resin has excellent heat resistance and flame retardance, is less in smoke after fire extinguishment, is pollution-free to the environment, and has excellent fire extinguishing effect and smoke suppression and environmental friendliness.
Drawings
FIG. 1 is a process flow diagram of the preparation of the novel polymer gel fire-extinguishing flame retardant of the present invention;
FIG. 2 is a process flow diagram of the preparation of a modified cellulose hydrogel in accordance with the present invention;
FIG. 3 is a schematic representation of the reaction for preparing pentaerythritol diphosphonate chloride in accordance with the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Examples
The embodiment discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 14:40:90:0.3, reacting for 2 hours at 50 ℃, then continuing to react for 2 hours at 85 ℃, finally continuing to react for 12 hours at 100 ℃, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding methylene dichloride with the mass of 3 times of that of the reaction crude product for washing, and drying for 12 hours at 40 ℃ to obtain pentaerythritol diphosphonic chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to a mass ratio of 1:1, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 4 hours at a temperature of 0 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of a rotating speed of 200r/min, a vacuum degree of 0.03MPa and a temperature of 150 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass 3 times that of the modified beta-cyclodextrin crude product, washing for three times, and drying for 12 hours at a temperature of 50 ℃ to obtain the modified beta-cyclodextrin; mixing nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 100:1.5:1000, stirring at room temperature for reacting for 0.5h, filtering, adding 3 times of glacial ethanol with the mass of filter cake for washing for three times, and drying at 80 ℃ for 30h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:5 to obtain a flame retardant additive;
Wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1140:2400:10; the glacial ethanol is ethanol at the temperature of 0 ℃;
Mixing cationic starch and water according to a mass ratio of 1:20, carrying out an activation reaction at 90 ℃ for 15min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, carrying out an initiation reaction for 20min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, carrying out a reaction for 20min in the nitrogen atmosphere at room temperature, adding a cross-linking agent after the reaction is finished, continuously carrying out a reaction for 2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water with the mass 5 times of that of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 70 ℃, and sieving with a 200-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.5:18:7:5:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.5 and carrying out neutralization reaction for 20min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 90%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 5min, reacting for 2h at a temperature of minus 15 ℃ at a rotating speed of 200r/min after the dropwise adding, centrifugally defoaming for 8min at a temperature of 5 ℃ at a rotating speed of 1800r/min after the reacting is finished, standing for 18h at a temperature of 30 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 5:5:8000 for 20min, and standing for 18h to obtain a novel polymer gel fire-extinguishing flame retardant;
wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:14; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Examples
The embodiment discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 16:45:110:0.4, reacting at 60 ℃ for 1h, then continuously reacting at 80 ℃ for 3h, finally continuously reacting at 110 ℃ for 8h, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding dichloromethane with the mass of 5 times of the reaction crude product for washing, and drying at 50 ℃ for 10h to obtain pentaerythritol diphosphonic chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to the mass ratio of 1:1.5, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 2 hours at the temperature of 2 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of the rotating speed of 150r/min, the vacuum degree of 0.04MPa and the temperature of 130 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass which is 5 times that of the modified beta-cyclodextrin crude product, washing, and drying for 10 hours at the temperature of 60 ℃ to obtain the modified beta-cyclodextrin; mixing nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 200:3:1500, stirring at room temperature for reaction for 1h, filtering, adding 3 times of glacial ethanol with the mass of filter cake for three times, and drying at 100 ℃ for 24h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:4.5 to obtain a flame retardant additive;
Wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1200:2500:20; the glacial ethanol is ethanol at the temperature of 0 ℃;
mixing cationic starch and water according to a mass ratio of 1:30, performing an activation reaction at 60 ℃ for 75min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, performing an initiation reaction for 10min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, performing a reaction for 15min at room temperature in the nitrogen atmosphere, adding a cross-linking agent after the reaction is finished, continuously performing a reaction for 2.5h at room temperature to obtain a crude product of the modified polymer resin, adding ethanol and water with the mass 3 times that of the crude product of the modified polymer resin, respectively washing for three times, drying for 4h at 80 ℃, and sieving with a 100-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.4:16:6:4.5:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution in a mass ratio of 1:1, and carrying out neutralization reaction for 10min at the temperature of 2 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 80%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 10min, reacting for 2h at a rotating speed of 150r/min and a temperature of 0 ℃ after the dropwise adding is finished, centrifugally defoaming for 10min at a rotating speed of 2000r/min and a temperature of 3 ℃ after the reaction is finished, standing for 24h at a temperature of 25 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water in a mass ratio of 4.5:5.5:7000 for 15min, and standing for 24h to obtain a novel polymer gel fire-extinguishing flame retardant;
wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:21; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Examples
The embodiment discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to a mass ratio of 15:42:100:0.3, reacting at 55 ℃ for 1.5 hours, continuing to react at 82 ℃ for 2.5 hours, continuing to react at 105 ℃ for 10 hours, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding dichloromethane with the mass of 4 times of the reaction crude product for washing, and drying at 45 ℃ for 11 hours to obtain pentaerythritol diphosphate diphosphonic chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to the mass ratio of 1:1.2, respectively adding pentaerythritol biphosphate diphosphonic chloride and triethylamine, reacting for 3 hours at the temperature of 1 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of the rotating speed of 180r/min, the vacuum degree of 0.03MPa and the temperature of 140 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass of 4 times of that of the modified beta-cyclodextrin crude product, washing, and drying for 11 hours at the temperature of 55 ℃ to obtain the modified beta-cyclodextrin; mixing the nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 150:2:1200, stirring at room temperature for reaction for 0.8h, filtering, adding 3 times of glacial ethanol with the mass of the filter cake for washing for three times, and drying at 90 ℃ for 25h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:4 to obtain a flame retardant additive;
Wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol biphosphate to the triethylamine is 1170:2450:15; the glacial ethanol is ethanol at the temperature of 0 ℃;
Mixing cationic starch and water according to a mass ratio of 1:25, performing an activation reaction at 75 ℃ for 45min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, performing an initiation reaction for 15min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, performing a reaction for 18min at room temperature in the nitrogen atmosphere, adding a cross-linking agent after the reaction is finished, continuously performing a reaction for 2.3h at room temperature to obtain a crude product of the modified polymer resin, adding ethanol and water with the mass 4 times of that of the crude product of the modified polymer resin, respectively washing for three times, drying for 5h at 75 ℃, and sieving with a 150-mesh sieve after crushing to obtain the modified polymer resin;
wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.3:14:5:4:0.03:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.8, and carrying out neutralization reaction for 15min at the temperature of 1 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 85%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 7min, reacting for 2h at a temperature of minus 7 ℃ at a rotating speed of 180r/min after the dropwise adding, centrifugally defoaming for 9min at a temperature of 4 ℃ at a rotating speed of 1900r/min after the reacting is finished, standing for 20h at a temperature of 28 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 4:6:6000 for 18min, and standing for 20h to obtain a novel polymer gel fire-extinguishing flame retardant;
Wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:16; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Examples
The embodiment discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 14:41:95:0.4, reacting at 52 ℃ for 1.2 hours, continuing to react at 80 ℃ for 2.2 hours, continuing to react at 102 ℃ for 11 hours, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding dichloromethane with the mass 3 times of the reaction crude product for washing, and drying at 42 ℃ for 12 hours to obtain pentaerythritol diphosphate diphosphonic chloride;
step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to a mass ratio of 1:1, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 4 hours at a temperature of 0 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of 160r/min of rotating speed, 0.03MPa of vacuum degree and 135 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass 3 times of that of the modified beta-cyclodextrin crude product, washing, and drying for 12 hours at a temperature of 52 ℃ to obtain the modified beta-cyclodextrin; mixing the nano tourmaline, stearic acid and diethyl ether according to the mass ratio of 130:1.8:1000, stirring at room temperature for reacting for 0.8h, filtering, adding 3 times of glacial ethanol with the mass of filter cake for washing for three times, and drying at 85 ℃ for 28h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:3.5 to obtain a flame retardant additive;
wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1160:2400:12; the glacial ethanol is ethanol at the temperature of 0 ℃;
mixing cationic starch and water according to a mass ratio of 1:22, performing an activation reaction at 70 ℃ for 55min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, performing an initiation reaction for 12min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, performing a reaction for 16min at room temperature in the nitrogen atmosphere, adding a cross-linking agent after the reaction is finished, continuously performing a reaction for 2.2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water with the mass 3 times of that of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 72 ℃, and sieving with a 120-mesh sieve after crushing to obtain the modified polymer resin;
wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.2:12:4:3.5:0.02:0.15;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.6 and carrying out neutralization reaction for 18min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 82%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 5min, reacting for 2h at a temperature of minus 5 ℃ at a rotating speed of 200r/min after the dropwise adding, centrifugally defoaming for 10min at a temperature of 4 ℃ at a rotating speed of 1800r/min after the reacting is finished, standing for 18h at a temperature of 30 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 3.5:6.5:5000 for 15min, and standing for 18h to obtain a novel polymer gel fire-extinguishing flame retardant;
Wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:18; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Examples
The embodiment discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 16:44:105:0.3, reacting at 58 ℃ for 1.8 hours, continuing to react at 85 ℃ for 2 hours, continuing to react at 108 ℃ for 9 hours, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding dichloromethane with the mass of 5 times of the reaction crude product for washing, and drying at 48 ℃ for 10 hours to obtain pentaerythritol diphosphate chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to the mass ratio of 1:1.3, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 2 hours at the temperature of 2 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of the rotating speed of 180r/min, the vacuum degree of 0.04MPa and the temperature of 145 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass 5 times that of the modified beta-cyclodextrin crude product for washing, and drying for 11 hours at the temperature of 58 ℃ to obtain the modified beta-cyclodextrin; mixing nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 180:2.5:1400, stirring at room temperature for reaction for 1h, filtering, adding 3 times of glacial ethanol with the mass of filter cake for three times, and drying at 95 ℃ for 25h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:3 to obtain a flame retardant additive;
wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1190:2480:18; the glacial ethanol is ethanol at the temperature of 0 ℃;
Mixing cationic starch and water according to a mass ratio of 1:28, performing an activation reaction at 80 ℃ for 35min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, performing an initiation reaction for 18min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, performing a reaction for 20min at room temperature in the nitrogen atmosphere, adding a cross-linking agent after the reaction is finished, continuously performing a reaction for 2.4h at room temperature to obtain a crude product of the modified polymer resin, adding ethanol and water with the mass 5 times that of the crude product of the modified polymer resin, respectively washing for three times, drying for 5h at 78 ℃, and sieving with a 180-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1:10:3:3:0.02:0.15;
the initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.8, and carrying out neutralization reaction for 12min at the temperature of 2 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 88%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 10min, reacting for 2h at a temperature of minus 10 ℃ at a rotating speed of 160r/min after the dropwise adding, centrifugally defoaming for 10min at a temperature of 3 ℃ at a rotating speed of 2000r/min after the reacting is finished, standing for 24h at a temperature of 25 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 3:7:5000 for 20min, and standing for 24h to obtain a novel polymer gel fire-extinguishing flame retardant;
Wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:20; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Comparative example 1
The comparative example discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
Mixing cationic starch and water according to a mass ratio of 1:20, performing an activation reaction at 90 ℃ for 15min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished for initiating the reaction for 20min, adding an acrylic acid neutralization solution and 2-acrylamide-2-methylpropanesulfonic acid to react for 20min after the reaction is finished, adding a cross-linking agent after the reaction is finished, continuously reacting for 2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water which are 5 times of the mass of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 70 ℃, crushing, and sieving with a 200-mesh sieve to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the cross-linking agent to the initiator is 1.5:18:7:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.5 and carrying out neutralization reaction for 20min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 90%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 5min, reacting for 2h at a temperature of minus 15 ℃ at a rotating speed of 200r/min after the dropwise adding, centrifugally defoaming for 8min at a temperature of 5 ℃ at a rotating speed of 1800r/min after the reacting is finished, standing for 18h at a temperature of 30 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 5:5:8000 for 20min, and standing for 18h to obtain a novel polymer gel fire-extinguishing flame retardant;
wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:14; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Comparative example 2
The comparative example discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 14:40:90:0.3, reacting for 2 hours at 50 ℃, then continuing to react for 2 hours at 85 ℃, finally continuing to react for 12 hours at 100 ℃, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding methylene dichloride with the mass of 3 times of that of the reaction crude product for washing, and drying for 12 hours at 40 ℃ to obtain pentaerythritol diphosphonic chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to a mass ratio of 1:1, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 4 hours at a temperature of 0 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of a rotating speed of 200r/min, a vacuum degree of 0.03MPa and a temperature of 150 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass 3 times that of the modified beta-cyclodextrin crude product for washing, and drying for 12 hours at a temperature of 50 ℃ to obtain a flame retardant additive;
Wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1140:2400:10;
Mixing cationic starch and water according to a mass ratio of 1:20, carrying out an activation reaction at 90 ℃ for 15min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, carrying out an initiation reaction for 20min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, carrying out a reaction for 20min in the nitrogen atmosphere at room temperature, adding a cross-linking agent after the reaction is finished, continuously carrying out a reaction for 2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water with the mass 5 times of that of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 70 ℃, and sieving with a 200-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.5:18:7:5:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.5 and carrying out neutralization reaction for 20min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 90%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 5min, reacting for 2h at a temperature of minus 15 ℃ at a rotating speed of 200r/min after the dropwise adding, centrifugally defoaming for 8min at a temperature of 5 ℃ at a rotating speed of 1800r/min after the reacting is finished, standing for 18h at a temperature of 30 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 5:5:8000 for 20min, and standing for 18h to obtain a novel polymer gel fire-extinguishing flame retardant;
wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:14; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Comparative example 3
The comparative example discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
Step (1), mixing nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 100:1.5:1000, stirring at room temperature for reacting for 0.5h, filtering, adding 3 times of glacial ethanol with the mass of a filter cake for washing for three times, and drying at 80 ℃ for 30h to obtain a flame retardant additive;
wherein the glacial ethanol is ethanol at 0 ℃;
Mixing cationic starch and water according to a mass ratio of 1:20, carrying out an activation reaction at 90 ℃ for 15min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, carrying out an initiation reaction for 20min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, carrying out a reaction for 20min in the nitrogen atmosphere at room temperature, adding a cross-linking agent after the reaction is finished, continuously carrying out a reaction for 2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water with the mass 5 times of that of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 70 ℃, and sieving with a 200-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.5:18:7:5:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.5 and carrying out neutralization reaction for 20min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 90%;
Mixing lithium hydroxide/urea aqueous solution and cellulose according to a mass ratio of 99:1, dissolving at a temperature of minus 15 ℃, dropwise adding epichlorohydrin for 5min, reacting for 2h at a temperature of minus 15 ℃ at a rotating speed of 200r/min after the dropwise adding, centrifugally defoaming for 8min at a temperature of 5 ℃ at a rotating speed of 1800r/min after the reacting is finished, standing for 18h at a temperature of 30 ℃ in saturated humidity to obtain a modified cellulose gel crude product, and washing the modified cellulose gel crude product to be neutral by distilled water to obtain modified cellulose hydrogel; mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water according to a mass ratio of 5:5:8000 for 20min, and standing for 18h to obtain a novel polymer gel fire-extinguishing flame retardant;
wherein, the mol ratio of the cellulose to the epichlorohydrin is 1:14; the lithium hydroxide/urea aqueous solution is prepared by mixing a lithium hydroxide aqueous solution and a urea aqueous solution, wherein the mass percentage of lithium hydroxide in the lithium hydroxide/urea aqueous solution is 4.6%, and the mass percentage of urea is 15%.
Comparative example 4
The comparative example discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 14:40:90:0.3, reacting for 2 hours at 50 ℃, then continuing to react for 2 hours at 85 ℃, finally continuing to react for 12 hours at 100 ℃, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding methylene dichloride with the mass of 3 times of that of the reaction crude product for washing, and drying for 12 hours at 40 ℃ to obtain pentaerythritol diphosphonic chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to a mass ratio of 1:1, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 4 hours at a temperature of 0 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of a rotating speed of 200r/min, a vacuum degree of 0.03MPa and a temperature of 150 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass 3 times that of the modified beta-cyclodextrin crude product, washing for three times, and drying for 12 hours at a temperature of 50 ℃ to obtain the modified beta-cyclodextrin; mixing nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 100:1.5:1000, stirring at room temperature for reacting for 0.5h, filtering, adding 3 times of glacial ethanol with the mass of filter cake for washing for three times, and drying at 80 ℃ for 30h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:5 to obtain a flame retardant additive;
Wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1140:2400:10; the glacial ethanol is ethanol at the temperature of 0 ℃;
Mixing cationic starch and water according to a mass ratio of 1:20, carrying out an activation reaction at 90 ℃ for 15min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, carrying out an initiation reaction for 20min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, carrying out a reaction for 20min in the nitrogen atmosphere at room temperature, adding a cross-linking agent after the reaction is finished, continuously carrying out a reaction for 2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water with the mass 5 times of that of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 70 ℃, and sieving with a 200-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.5:18:7:5:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.5 and carrying out neutralization reaction for 20min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 90%;
And (4) mixing and stirring the modified polymer resin, the carboxymethyl cellulose and the water for 20min according to the mass ratio of 5:5:8000, and standing for 18h to obtain the novel polymer gel fire-extinguishing flame retardant.
Comparative example 5
The comparative example discloses a preparation method of a novel polymer gel fire-extinguishing flame retardant, which comprises the following steps:
In the nitrogen atmosphere, mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride according to the mass ratio of 14:40:90:0.3, reacting for 2 hours at 50 ℃, then continuing to react for 2 hours at 85 ℃, finally continuing to react for 12 hours at 100 ℃, cooling and filtering after the reaction is finished to obtain a reaction crude product, adding methylene dichloride with the mass of 3 times of that of the reaction crude product for washing, and drying for 12 hours at 40 ℃ to obtain pentaerythritol diphosphonic chloride;
Step (2), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide according to a mass ratio of 1:1, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting for 4 hours at a temperature of 0 ℃ in a nitrogen atmosphere, removing solvent dimethyl sulfoxide by rotary evaporation under the conditions of a rotating speed of 200r/min, a vacuum degree of 0.03MPa and a temperature of 150 ℃ after the reaction is finished, obtaining a modified beta-cyclodextrin crude product, adding ethanol with the mass 3 times that of the modified beta-cyclodextrin crude product, washing for three times, and drying for 12 hours at a temperature of 50 ℃ to obtain the modified beta-cyclodextrin; mixing nano tourmaline, stearic acid and diethyl ether according to a mass ratio of 100:1.5:1000, stirring at room temperature for reacting for 0.5h, filtering, adding 3 times of glacial ethanol with the mass of filter cake for washing for three times, and drying at 80 ℃ for 30h to obtain modified nano tourmaline; mixing modified beta-cyclodextrin and modified nano tourmaline according to a mass ratio of 1:5 to obtain a flame retardant additive;
Wherein the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1140:2400:10; the glacial ethanol is ethanol at the temperature of 0 ℃;
Mixing cationic starch and water according to a mass ratio of 1:20, carrying out an activation reaction at 90 ℃ for 15min, adding an initiator at room temperature in a nitrogen atmosphere after the reaction is finished, carrying out an initiation reaction for 20min, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, carrying out a reaction for 20min in the nitrogen atmosphere at room temperature, adding a cross-linking agent after the reaction is finished, continuously carrying out a reaction for 2h at room temperature to obtain a modified polymer resin crude product, adding ethanol and water with the mass 5 times of that of the modified polymer resin crude product, respectively washing for three times, drying for 6h at 70 ℃, and sieving with a 200-mesh sieve after crushing to obtain the modified polymer resin;
Wherein the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is 1.5:18:7:5:0.04:0.2;
The initiator is potassium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, the acrylic acid neutralization solution is prepared by mixing acrylic acid and 30wt% of sodium hydroxide aqueous solution according to the mass ratio of 1:0.5 and carrying out neutralization reaction for 20min at the temperature of 0 ℃, wherein the neutralization degree of the acrylic acid neutralization solution is 90%;
and (4) mixing and stirring the modified polymer resin and water in a mass ratio of 10:8000 for 20min, and standing for 18h to obtain the novel polymer gel fire-extinguishing flame retardant.
In the above examples and comparative examples: pentaerythritol was from sigma aldrich (Shanghai) trade limited, CAS number: 115-77-5; phosphorus oxychloride was from the Shandong quark chemical Co., ltd., CAS number: 10025-87-3; chlorobenzene was from the name of Mao city, male chemical Co., ltd., CAS number: 108-90-7; aluminum chloride was from atanan spring Star New Material Co., ltd., CAS number: 7446-70-0; methylene chloride from the company Jinan century to chemical industry Co., ltd., CAS number: 75-09-2; beta-cyclodextrin was from Guangdong chemical Co., ltd., model Analyzer, CAS number: 7585-39-9; dimethyl sulfoxide was from Jinan Jinbang environmental protection technology Co., ltd., CAS number: 67-68-5; triethylamine from Shanghai Ala Biochemical technologies Co., ltd., CAS number: 121-44-8; the nanometer tourmaline is from Hangzhou intelligent titanium purification technology Co., ltd, and has white powder appearance, model ZT-NF50 and particle size of 50nm; stearic acid from Hubei Xinyu macro biomedical technology Co., ltd., CAS number: 57-11-4; diethyl ether was obtained from the company, intel Bioengineering, inc., endocarpium, CAS number: 60-29-7; cationic starch was from the Taian mountain modified starch Co., ltd, with a degree of substitution of 0.03; 2-acrylamide-2-methylpropanesulfonic acid was obtained from Jinankai chemical Co., ltd., CAS number: 15214-89-8; acrylic acid from Shandong Chuang chemical Co., ltd., CAS number: 79-10-7; sodium hydroxide was obtained from san Jose chemical technology Co., hubei, CAS number: 1310-73-2; ethanol was obtained from guangdong chemical company, CAS number: 64-17-5; potassium persulfate is from Maoming, male university Co., ltd., CAS number: 7727-21-1; n, N' -methylenebisacrylamide from Guangdong Weng Jiang chemical Co., ltd., CAS number: 110-26-9; lithium hydroxide was obtained from Mao Ming, male university Co., ltd., CAS number: 1310-65-2; urea from lake Northern Wei Dynasty chemical company, CAS number: 57-13-6; cellulose from Hubei chemical fiber group Co., ltd, has a viscosity average molecular weight of 1.0X10 5 g/mol; epichlorohydrin comes from the company of MaoMing City, chemie, calif., CAS number: 106-89-8; carboxymethyl cellulose was obtained from lake Northern Wei Dynasty, chemical reagents, inc., CAS number: 9004-32-4.
Test examples
(1) Fire extinguishing performance test
The novel polymer gel fire-extinguishing flame retardants prepared in examples 1 to 5 and comparative examples 1 to 3 were tested for fire-extinguishing performance, and specific test results are shown in Table 1:
TABLE 1
| Fire extinguishing time(s) | Smoke outlet condition | Fire extinguishing time(s) | Smoke outlet condition | ||
| Example 1 | 35 | Without any means for | Comparative example 1 | 93 | Has the following components |
| Example 2 | 41 | Without any means for | Comparative example 2 | 40 | Has the following components |
| Example 3 | 46 | Without any means for | Comparative example 3 | 75 | Without any means for |
| Example 4 | 52 | Without any means for | Comparative example 4 | 82 | Has the following components |
| Example 5 | 58 | Without any means for | Comparative example 5 | 116 | Has the following components |
The detection of each index in table 1 is based on the following criteria: the extinguishing time is determined with reference to GB17835-2008 Water based extinguishing agent.
According to the test results of Table 1, it can be seen that the novel polymer gel fire-extinguishing flame retardant prepared by the invention has excellent fire-extinguishing performance.
According to the invention, phosphorus oxychloride and pentaerythritol react, and the obtained reaction product and beta-cyclodextrin undergo nucleophilic substitution reaction, so that the beta-cyclodextrin is grafted with a group with flame retardant function, and the obtained modified beta-cyclodextrin has better flame retardance, and the interface compatibility between the modified beta-cyclodextrin and resin is increased.
According to the invention, the tourmaline and the stearic acid are mixed and surface-modified, and the modified tourmaline is obtained through the interaction between the stearic acid and the functional groups on the surface of the tourmaline, so that the dispersibility of the tourmaline in a resin matrix is improved, and the agglomeration degree of the tourmaline is reduced; and mixing the modified tourmaline with the modified beta-cyclodextrin to obtain the flame retardant additive. As the tourmaline has the characteristics of porous structure, high stability and high adsorptivity, and can release anions in the air, the tourmaline can effectively adsorb the flue gas generated when the combustion object burns, and the effect of purifying the air is achieved.
In addition, tourmaline belongs to silicate inorganic matters and has a certain flame-retardant effect; the cavity structure of the beta-cyclodextrin has certain adsorption capacity, and the modified tourmaline and the modified beta-cyclodextrin are mixed, so that the flame retardant effect and adsorption capacity of the flame retardant additive can be effectively improved.
The cationic starch is pretreated, so that the water absorbability of the cationic starch is improved, the crystal structure of the cationic starch is damaged, and the grafting rate is improved; the active group of the cationic starch and the monomer rich in hydrophilic groups are subjected to graft copolymerization, and simultaneously, the flame retardant additive is added to serve as a physical crosslinking point, so that the thermal stability of the resin is increased through in-situ polymerization of the flame retardant additive and the resin, and the prepared modified polymer resin has excellent heat resistance, water absorption and flame retardance.
According to the invention, epichlorohydrin is used as a cross-linking agent, the modified cellulose hydrogel is prepared through chemical cross-linking of cellulose, and the hydrogel is used as a reinforcing material to be mixed with modified polymer resin, so that the prepared novel polymer gel fire-extinguishing flame retardant can better cover a combustion object, has excellent heat resistance and flame retardance, is less in smoke after fire extinguishment, is pollution-free to the environment, and has excellent fire extinguishing effect and smoke suppression and environmental friendliness.
In comparative example 1, no flame retardant additive is added, flame retardant effect and adsorption capacity of modified beta-cyclodextrin and nano tourmaline are lacking, and fire extinguishing time is longer than that of the examples, and smoke is generated, so that fire extinguishing performance is inferior to that of the examples;
In comparative example 2, modified tourmaline is not added, while modified beta-cyclodextrin has flame retardant effect, the adsorption capacity of nano tourmaline is lacking, the adsorption capacity is reduced, smoke cannot be adsorbed in time, and the fire extinguishing time is equivalent to that of the examples, but the smoke outlet condition exists;
In comparative example 3, modified beta-cyclodextrin is not added, and because the modified nano tourmaline has adsorption capacity, smoke is not generated, and although the modified nano tourmaline has certain flame retardant capacity, the flame retardant performance of the modified beta-cyclodextrin is lacking, so that the fire extinguishing time is longer than that of the example;
In comparative example 4, carboxymethyl cellulose is used as a reinforcing material of the hydrogel to replace modified cellulose hydrogel, and although the carboxymethyl cellulose has a certain tackifying effect on the hydrogel, the prepared hydrogel has poor coverage on combustibles, so the fire extinguishing time is higher than that of the embodiment, and smoke is generated, and the fire extinguishing performance is slightly lower than that of the embodiment;
In comparative example 5, modified cellulose hydrogel was not added, and the prepared gel lacked modified cellulose hydrogel as a reinforcing material, which could not well cover the combustibles during the fire extinguishing process, the fire extinguishing time was longer than that of the examples, and smoke was generated, so that the fire extinguishing performance was slightly lower than that of the examples.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the polymer gel fire-extinguishing flame retardant is characterized by comprising the following steps:
step (1), mixing and dissolving beta-cyclodextrin and dimethyl sulfoxide, respectively adding pentaerythritol diphosphate diphosphonic chloride and triethylamine, reacting, removing solvent dimethyl sulfoxide by rotary evaporation after the reaction is finished, washing and drying to obtain modified beta-cyclodextrin, mixing nano tourmaline, stearic acid and diethyl ether, stirring for reacting, filtering, washing and drying after the reaction is finished to obtain modified nano tourmaline, and mixing the modified beta-cyclodextrin and the modified nano tourmaline to obtain a flame retardant additive;
Step (2), mixing cationic starch with water for an activation reaction, adding an initiator after the reaction is finished, initiating the reaction, adding an acrylic acid neutralization solution, 2-acrylamide-2-methylpropanesulfonic acid and a flame retardant additive after the reaction is finished, adding a cross-linking agent after the reaction is finished, continuing the reaction, washing, drying, crushing and sieving to obtain modified polymer resin;
step (3), mixing and stirring the modified polymer resin, the modified cellulose hydrogel and water, and standing to obtain the polymer gel fire-extinguishing flame retardant;
the modified cellulose hydrogel in the step (3) is prepared by the following steps:
Mixing and dissolving lithium hydroxide/urea aqueous solution and cellulose, dropwise adding epichlorohydrin, reacting after the dropwise adding is finished, defoaming after the reaction is finished, standing, and washing to be neutral to obtain modified cellulose hydrogel;
Wherein the mass ratio of the lithium hydroxide/urea aqueous solution to the cellulose is 99:1; the mol ratio of the cellulose to the epichlorohydrin is 1 (14-21); the dropping conditions are as follows: dripping at-15deg.C for 5-10min; the reaction conditions are as follows: reacting for 2h at the rotating speed of 150-200r/min and the temperature of minus 15-0 ℃; the defoaming conditions are as follows: centrifugal defoaming for 8-10min at the rotation speed of 1800-2000r/min and the temperature of 3-5 ℃.
2. The preparation method of the polymer gel fire-extinguishing flame retardant according to claim 1, which is characterized in that the pentaerythritol diphosphonate diphosphonic chloride in the step (1) is prepared by the following steps:
Mixing pentaerythritol, phosphorus oxychloride, chlorobenzene and aluminum chloride, reacting, cooling, filtering, washing and drying after the reaction is finished to obtain pentaerythritol biphosphate diphosphonic chloride;
wherein the mass ratio of pentaerythritol to phosphorus oxychloride to chlorobenzene to aluminum chloride is (14-16) (40-45) (90-110) (0.3-0.4); the reaction conditions are as follows: firstly, reacting for 1-2h at 50-60 ℃ in nitrogen atmosphere, then continuously reacting for 2-3h at 80-85 ℃ in nitrogen atmosphere, and finally continuously reacting for 8-12h at 100-110 ℃ in nitrogen atmosphere.
3. The method for preparing the polymer gel fire-extinguishing flame retardant according to claim 1, wherein in the step (1): the mass ratio of the beta-cyclodextrin to the pentaerythritol diphosphate diphosphonic chloride to the triethylamine is 1140-1200 (2400-2500) (10-20); the reaction conditions are as follows: in nitrogen atmosphere, reacting for 2-4h at 0-2 ℃.
4. The method for preparing the polymer gel fire-extinguishing flame retardant according to claim 1, wherein in the step (1): the mass ratio of the nano tourmaline to the stearic acid to the diethyl ether is (100-200): (1.5-3): (1000-1500); the conditions of the stirring reaction are as follows: the reaction is stirred at room temperature for 0.5-1h.
5. The method for preparing the polymer gel fire-extinguishing flame retardant according to claim 1, wherein in the step (1): the mass ratio of the modified beta-cyclodextrin to the modified nano tourmaline is 1 (3-5).
6. The method for preparing a polymer gel fire-extinguishing flame retardant according to claim 1, wherein in the step (2): the conditions of the activation reaction are as follows: activating reaction at 60-90 deg.c for 15-75min; the conditions for initiating the reaction are: the reaction is initiated at room temperature for 10-20min in an inert gas atmosphere.
7. The method for preparing a polymer gel fire-extinguishing flame retardant according to claim 1, wherein in the step (2): the mass ratio of the cationic starch to the acrylic acid neutralization solution to the 2-acrylamide-2-methylpropanesulfonic acid to the flame retardant additive to the cross-linking agent to the initiator is (1-1.5): (10-18): (3-7): (3-5): (0.02-0.04): (0.15-0.2); the reaction conditions are as follows: reacting for 15-20min at room temperature in inert gas atmosphere; the conditions for continuing the reaction were: the reaction was continued at room temperature for 2-2.5h.
8. The method for preparing a polymer gel fire-extinguishing flame retardant according to claim 1, wherein in the step (3): the mass ratio of the modified polymer resin to the modified cellulose hydrogel to the water is (3-5) (5-7) (5000-8000).
9. A novel polymer gel fire-extinguishing flame retardant prepared by the preparation method of the polymer gel fire-extinguishing flame retardant according to any one of claims 1 to 8.
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