CN112430309A - Phosphorus-containing graphene-SiO2Preparation method and application of modified polyurethane elastomer - Google Patents
Phosphorus-containing graphene-SiO2Preparation method and application of modified polyurethane elastomer Download PDFInfo
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- CN112430309A CN112430309A CN202011322305.6A CN202011322305A CN112430309A CN 112430309 A CN112430309 A CN 112430309A CN 202011322305 A CN202011322305 A CN 202011322305A CN 112430309 A CN112430309 A CN 112430309A
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 65
- 239000011574 phosphorus Substances 0.000 title claims abstract description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 64
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 38
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 38
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 38
- 229910006124 SOCl2 Inorganic materials 0.000 claims abstract description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001263 acyl chlorides Chemical class 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims 1
- 239000000806 elastomer Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 17
- 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 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/36—Silica
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- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of flame retardance and discloses phosphorus-containing graphene-SiO2Modified polyurethane elastomer by SOCl2Reacting with carboxyl on the surface of graphene oxide, and reacting with 9, 10-dihydro-9-oxaReacting-10-phosphaphenanthrene-10-oxide to obtain phosphorus-containing graphene oxide serving as a composite flame retardant, so that the composite material is converted into stable lamellar SiO in the combustion process2The flame-retardant graphene oxide/nano SiO composite material has strong barrier property on heat and oxygen, has excellent flame-retardant effect, has the effect of promoting carbonization and carbon formation in the combustion process by taking the phosphaphenanthrene component as an organic flame-retardant component, forms a compact continuous carbon layer, inhibits the combustion process, and is doped with graphene oxide and nano SiO2Has excellent mechanical performance, and is nano SiO2The cross-linking degree between polyurethane molecules and nano particles can be deepened, the rigidity of the material is improved, and meanwhile, the phosphorus-containing graphene with good dispersibility interacts with a strong interface between the polyurethane elastomer, so that the mechanical strength of the material is further enhanced.
Description
Technical Field
The invention relates to the field of flame retardance, in particular to a flame-retardant flame-Phosphorus-containing graphene-SiO2A preparation method and application of a modified polyurethane elastomer.
Background
Polyurethane elastomer, usually take polymer polyol, diisocyanate, etc. as raw materials, add addition polymerization of auxiliaries such as chain extender, cross-linking agent, etc. to get block polymer, it is a kind of elastic and rigid macromolecule synthetic materials of plastics, it has high strength, toughness is good, wear-resisting, advantages such as the environment-friendly, the comprehensive properties are excellent, therefore have been applied widely, have almost applied to various trades, it is one of the fastest thermoplastic materials developed at present, but polyurethane elastomer material not modified usually has heat resistance, and the disadvantage such as being inferior in fire retardance, thus has limited its actual application effect in some fields, with the development of material, the expansion of application range, people's requirement on polyurethane elastomer is higher and higher, it is the important trend of material development to give the material multifunctionality.
The polyurethane elastic material is mainly composed of elements such as carbon, hydrogen and the like, so that the material does not have a flame retardant effect, toxic gases such as HCN, CO and the like can be released during combustion, the polyurethane elastomer can be endowed with good flame retardant performance through modes such as physical addition, surface grafting modification and the like, the polyurethane elastomer can exert excellent performance in more fields, the special structure of graphene has very good application potential as a flame retardant material, and the surface grafting introduces a phosphorus-containing flame retardant and nano SiO2Can further improve the flame retardant property, and simultaneously grafts the graphene and the nano SiO2Can solve the problem of mechanical property caused by introducing a flame retardant.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides phosphorus-containing graphene-SiO2The preparation method and the application of the modified polyurethane elastomer solve the problems that the polyurethane elastomer does not have flame retardant capability and the conventional flame retardant polyurethane elastomer has poor mechanical properties.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the phosphorus-containing graphene-SiO 2 modified polyurethane elastomer comprises the following steps:
(1) adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2Reacting for 10-15h at 55-75 ℃ in an oil bath kettle, centrifugally washing to obtain acylchlorinated graphene, adding a chlorobenzene solvent, ultrasonically dispersing, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, heating to 80-100 ℃, reacting for 10-15h, centrifugally washing, and vacuum drying to obtain phosphorus-containing graphene oxide;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to adjust the pH value of the agglomerated solution to 9-10, adding tetraethyl silicate, performing ultrasonic reaction for 20-30h at room temperature, washing and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol for 2-3h in vacuum at the temperature of 110 ℃ below zero, cooling, and adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 80-90 ℃ in a nitrogen atmosphere, pre-polymerizing for 2-3h, adding a chain extender 1, 4-butanediol, stirring for reacting for 1-2h, placing in a flat vulcanizing machine, and vulcanizing for 12-24h in an environment with the temperature of 100-120 ℃ to obtain the phosphorus-containing graphene-SiO 2 modified polyurethane elastomer.
Preferably, in the step (1), the mass ratio of the acylchlorinated graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1: 30-50.
Preferably, the oil bath kettle in the step (1) comprises a base, a digital display controller and a button are fixedly connected to the base, a heating device is fixedly connected to the base, a fixing device is fixedly connected to the heating device, the base is movably connected to a frame, a motor is fixedly connected to the frame, and a stirring rod is fixedly connected to the motor.
Preferably, the mass ratio of the phosphorus-containing graphene oxide to the tetraethyl silicate in the step (2) is 10: 80-120.
Preferably, in the step (3), the polyester diol, the diphenylmethylene diisocyanate and the nano SiO2The mass ratio of the loaded phosphorus-containing graphene oxide to the 1, 4-butanediol is 100:35-50:0.5-1.5: 6-10.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the phosphorus-containing graphene-SiO2Modified polyurethane elastomer by SOCl2Reacting with carboxyl on the surface of graphene oxide to obtain acylchlorinated graphene, reacting acyl chloride groups with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain phosphorus-containing graphene oxide, and generating a layer of nano SiO on the surface of the phosphorus-containing graphene oxide by an interfacial polymerization method2As composite fire retardant, added into the base body of polyurethane elastomer, nano SiO2The loaded phosphorus-containing graphene oxide is converted into lamellar SiO with high thermal oxidation stability in the high-temperature combustion process2The flame-retardant polyurethane elastomer has strong barrier property to heat and oxygen, reduces the conduction of heat and oxygen into the polyurethane elastomer, plays an excellent flame-retardant effect, has strong carbonization and carbonization promotion effects in the polyurethane combustion process as an organic flame-retardant component, forms a compact continuous carbon layer, and further inhibits the combustion process.
The phosphorus-containing graphene-SiO2The modified polyurethane elastomer is prepared by adding diphenyl methylene diisocyanate into polyester dihydric alcohol to obtain a polyurethane elastomer with good symmetry due to the existence of a methylene in two benzene rings, so that the influence of a hard-segment crystal region on a soft-segment crystal region is reduced, the mechanical property of the polyurethane elastomer is more outstanding, and simultaneously doped graphene oxide and nano SiO2Has excellent mechanical property, good reinforcing effect on the mechanical strength and the mechanical property of the polyurethane elastomer, and simultaneously the nano SiO2The cross-linking degree between polyurethane molecules and nano particles can be deepened, the rigidity of the material is improved, meanwhile, the phosphorus-containing graphene with good dispersibility interacts with the polyurethane elastomer molecules at a strong interface, the mechanical strength of the material is improved, and the mechanical property of the material is enhanced.
Drawings
FIG. 1 is a schematic plan view of an oil bath pan;
fig. 2 is a schematic side view of the motor.
1-a base; 2-a heater; 3-a digital display controller; 4-pressing a key; 5-a heating device; 6-oil bath cabin; 7-a frame; 8, a motor; 9-stirring rod.
Detailed Description
(1) Adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2In the oil bath pot, the oil bath pot comprises a base, a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, a fixing device is fixedly connected to the heating device, a frame is movably connected to the base, a motor is fixedly connected to the frame, a stirring rod is fixedly connected to the motor, the base is reacted for 10-15 hours at the temperature of 55-75 ℃, the mixture is centrifugally washed to obtain acylchlorinated graphene, the acylchlorinated graphene is added into a chlorobenzene solvent, the chlorobenzene solvent is ultrasonically dispersed, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, the mass ratio of the acylchlorinated graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:30-50, the temperature is increased to 80-100 ℃, the reaction is carried out, Vacuum drying to obtain phosphorus-containing graphene oxide;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to agglomerate the solution until the pH value is 9-10, adding tetraethyl silicate, performing ultrasonic reaction at room temperature for 20-30h at the mass ratio of 10:80-120, washing, and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol for 2-3h in vacuum at the temperature of 110 ℃ below zero, cooling, and adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 80-90 ℃ in a nitrogen atmosphere, pre-polymerizing for 2-3h, adding a chain extender 1, 4-butanediol with the mass ratio of 100:35-50:0.5-1.5:6-10, stirring for reacting for 1-2h, placing in a flat plate vulcanizing machine, and vulcanizing for 12-24h in an environment with the temperature of 100 ℃ and 120 ℃ to obtain the phosphorus-containing graphene-SiO 2 modified polyurethane elastomer.
Example 1
(1) Adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2In the oil bath pot, the oil bath pot comprises a base, a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, and a fixing device is fixedly connected to the heating devicePlacing a base, wherein the base is movably connected with a frame, the frame is fixedly connected with a motor, the motor is fixedly connected with a stirring rod, reacting for 10 hours at 55 ℃, centrifuging and washing to obtain acylchlorinated graphene, adding chlorobenzene solvent, performing ultrasonic dispersion, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, heating to 80 ℃, reacting for 10 hours, centrifuging and washing, and performing vacuum drying to obtain phosphorus-containing graphene oxide, wherein the mass ratio of the acylchlorinated graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1: 30;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to agglomerate the solution until the pH value is 9-10, adding tetraethyl silicate at the mass ratio of 10:80, performing ultrasonic reaction for 20 hours at room temperature, washing and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol at 100 deg.C under vacuum for 2-3h, cooling, adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 80 ℃ in a nitrogen atmosphere, pre-polymerizing for 2-3h, adding a chain extender 1, 4-butanediol with the mass ratio of 100:35:0.5:6, stirring for reaction for 1h, placing in a flat plate vulcanizing machine, vulcanizing for 12h in an environment at 100 ℃ to obtain the phosphorus-containing graphene-SiO2A modified polyurethane elastomer.
Example 2
(1) Adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2In the oil bath pot, the oil bath pot comprises a base, a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, a fixing device is fixedly connected to the heating device, a frame is movably connected to the base, a motor is fixedly connected to the frame, a stirring rod is fixedly connected to the motor, the base reacts for 12 hours at 65 ℃, is centrifugally washed to obtain acyl chloride graphene, is added into a chlorobenzene solvent, is ultrasonically dispersed, is added with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, has a mass ratio of the acyl chloride graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of 1:40, is heated to 90 ℃, reacts for 12 hours, is centrifugally washed and is dried in vacuum to obtain phosphorus-containing graphene oxide;
(2) oxidizing phosphorus-containing graphene oxideAdding into ethanol and distilled water solvent, ultrasonic dispersing, adding ammonia water to agglomerate the solution pH to 9, adding tetraethyl silicate with the mass ratio of 10:100, performing ultrasonic reaction at room temperature for 24h, washing and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol at 105 deg.C under vacuum for 2h, cooling, adding diphenylmethylene diisocyanate and nanometer SiO2Loading phosphorus-containing graphene oxide, heating to 85 ℃ in a nitrogen atmosphere, carrying out prepolymerization for 2h, adding a chain extender 1, 4-butanediol with the mass ratio of 100:40:1:8, stirring to react for 1.5h, placing the mixture in a flat-plate vulcanizing machine, and vulcanizing at 11 ℃ for 16h to obtain the phosphorus-containing graphene-SiO2A modified polyurethane elastomer.
Example 3
(1) Adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2In the oil bath pot, the oil bath pot comprises a base, a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, a fixing device is fixedly connected to the heating device, a frame is movably connected to the base, a motor is fixedly connected to the frame, a stirring rod is fixedly connected to the motor, the base reacts for 15 hours at 75 ℃, the mixture is centrifugally washed to obtain acyl chloride graphene, the acyl chloride graphene is added into a chlorobenzene solvent, ultrasonic dispersion is carried out, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, the mass ratio of the acyl chloride graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:50, the temperature is raised to 100 ℃, the reaction is carried out for 15 hours, the centrifugal washing and the vacuum drying are;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to agglomerate the pH value to 10, adding tetraethyl silicate, performing ultrasonic reaction for 30 hours at room temperature, washing and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol at 110 deg.C for 3 hr, cooling, adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 90 ℃ in nitrogen atmosphere, pre-polymerizing for 3h, and then adding chain extender 1, 4-butyleneStirring and reacting the alcohol and the solvent for 2 hours at the mass ratio of 100:50:1.5:10, putting the mixture into a flat-plate vulcanizing machine, and vulcanizing the mixture for 24 hours at the temperature of 120 ℃ to obtain the phosphorus-containing graphene-SiO2A modified polyurethane elastomer.
Comparative example 1
(1) Adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2In the oil bath pot, the oil bath pot comprises a base, a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, a fixing device is fixedly connected to the heating device, a frame is movably connected to the base, a motor is fixedly connected to the frame, a stirring rod is fixedly connected to the motor, the base reacts for 15 hours at 75 ℃, the mixture is centrifugally washed to obtain acyl chloride graphene, the acyl chloride graphene is added into a chlorobenzene solvent, ultrasonic dispersion is carried out, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, the mass ratio of the acyl chloride graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:70, the temperature is increased to 100 ℃, the reaction is carried out for 15 hours, the centrifugal washing and the vacuum drying are;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to adjust the pH value of an agglomerated solution to 10, adding tetraethyl silicate at a mass ratio of 10:150, performing ultrasonic reaction for 30 hours at room temperature, washing, and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol at 110 deg.C for 3 hr, cooling, adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 90 ℃ in a nitrogen atmosphere for prepolymerization for 3h, adding a chain extender 1, 4-butanediol with the mass ratio of 100:80:3:12, stirring for reaction for 2h, placing in a flat vulcanizing machine, vulcanizing for 24h at 120 ℃ to obtain the phosphorus-containing graphene-SiO2A modified polyurethane elastomer.
Comparative example 2
(1) Adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2In the oil bath pot, the oil bath pot comprises a base, a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, and the heating device is fixedly connected to the baseThe method comprises the following steps of reacting for 10 hours at 55 ℃, centrifugally washing to obtain acylchlorinated graphene, adding chlorobenzene solvent, performing ultrasonic dispersion, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, heating to 80 ℃ with the mass ratio of the acylchlorinated graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide being 1:20, reacting for 10 hours, centrifugally washing, and performing vacuum drying to obtain phosphorus-containing graphene oxide;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to agglomerate the solution until the pH value is 9, adding tetraethyl silicate, performing ultrasonic reaction at room temperature for 20 hours at the mass ratio of 10:80, washing and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol at 100 deg.C for 2 hr, cooling, adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 80 ℃ in a nitrogen atmosphere, carrying out prepolymerization for 2h, adding a chain extender 1, 4-butanediol with the mass ratio of 100:20:0.5:4, stirring for reaction for 1h, placing the mixture in a flat-plate vulcanizing machine, and vulcanizing for 12h in an environment at 100 ℃ to obtain the phosphorus-containing graphene-SiO2A modified polyurethane elastomer.
Phosphorus-containing graphene-SiO using YZS-8A oxygen index determinator2The limit oxygen index of the modified polyurethane elastomer is GB/T2406.2-2009.
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Limiting oxygen index (%) | 27.9 | 29.2 | 31.4 | 22.8 | 27.5 |
Testing of phosphorus-containing graphene-SiO Using ETM103B electronic Universal tester2The tensile strength of the modified polyurethane elastomer is tested according to GB/T34219-2017.
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Tensile Strength (MPa) | 30.6 | 44.4 | 32.3 | 35.8 | 28.4 |
Claims (5)
1. Phosphorus-containing graphene-SiO2The modified polyurethane elastomer is characterized in that: the phosphorus-containing graphene-SiO2The preparation method of the modified polyurethane elastomer comprises the following steps:
(1) adding graphene oxide into anhydrous tetrahydrofuran for ultrasonic dispersion, and then adding SOCl2Reacting for 10-15h at 55-75 ℃ in an oil bath kettle, centrifugally washing to obtain acylchlorinated graphene, adding a chlorobenzene solvent, ultrasonically dispersing, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, heating to 80-100 ℃, reacting for 10-15h, centrifugally washing, and vacuum drying to obtain phosphorus-containing graphene oxide;
(2) adding phosphorus-containing graphene oxide into ethanol and distilled water solvent, performing ultrasonic dispersion, adding ammonia water to adjust the pH value of the agglomerated solution to 9-10, adding tetraethyl silicate, performing ultrasonic reaction for 20-30h at room temperature, washing and drying to obtain nano SiO2Loading phosphorus-containing graphene oxide;
(3) dehydrating polyester diol for 2-3h in vacuum at the temperature of 110 ℃ below zero, cooling, and adding diphenyl methylene diisocyanate and nano SiO2Loading phosphorus-containing graphene oxide, heating to 80-90 ℃ in a nitrogen atmosphere for prepolymerization for 2-3h, adding a chain extender 1, 4-butanediol, stirring for reaction for 1-2h, placing in a flat-plate vulcanizing machine, vulcanizing at 100-120 ℃ for 12-24h to obtain phosphorus-containing graphene-SiO2A modified polyurethane elastomer.
2. The phosphorus-containing graphene-SiO of claim 12The modified polyurethane elastomer is characterized in that: in the step (1), the mass ratio of the acyl chloride graphene to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1: 30-50.
3. The phosphorus-containing graphene-SiO of claim 12Modified polyurethaneAn ester elastomer characterized by: the oil bath pot in the step (1) comprises a base, wherein a digital display controller and a key are fixedly connected to the base, a heating device is fixedly connected to the base, a fixing device is fixedly connected to the heating device, a frame is movably connected to the base, a motor is fixedly connected to the frame, and a stirring rod is fixedly connected to the motor.
4. The phosphorus-containing graphene-SiO of claim 12The modified polyurethane elastomer is characterized in that: the mass ratio of the phosphorus-containing graphene oxide to the tetraethyl silicate in the step (2) is 10: 80-120.
5. The phosphorus-containing graphene-SiO of claim 12The modified polyurethane elastomer is characterized in that: in the step (3), polyester diol, diphenyl methylene diisocyanate and nano SiO2The mass ratio of the loaded phosphorus-containing graphene oxide to the 1, 4-butanediol is 100:35-50:0.5-1.5: 6-10.
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