CN116622190A - Organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, and preparation method and application thereof - Google Patents
Organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, and preparation method and application thereof Download PDFInfo
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- CN116622190A CN116622190A CN202310708668.0A CN202310708668A CN116622190A CN 116622190 A CN116622190 A CN 116622190A CN 202310708668 A CN202310708668 A CN 202310708668A CN 116622190 A CN116622190 A CN 116622190A
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- flame retardant
- epoxy resin
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- nitrogen flame
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- 239000002071 nanotube Substances 0.000 title claims abstract description 133
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 104
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 97
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000003063 flame retardant Substances 0.000 claims abstract description 72
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 71
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 25
- 229920000877 Melamine resin Polymers 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- -1 heterocyclic amine Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 229940116254 phosphonic acid Drugs 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229920013822 aminosilicone Polymers 0.000 claims description 5
- 230000033444 hydroxylation Effects 0.000 claims description 5
- 238000005805 hydroxylation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229940120146 EDTMP Drugs 0.000 claims description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- DLXBSPPKDRUFHL-UHFFFAOYSA-N P1(OC(CCO1)N)=O.N1=C(N)N=C(N)N=C1N Chemical compound P1(OC(CCO1)N)=O.N1=C(N)N=C(N)N=C1N DLXBSPPKDRUFHL-UHFFFAOYSA-N 0.000 description 35
- 238000012360 testing method Methods 0.000 description 19
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- CMQAMENQCKNUPB-UHFFFAOYSA-N NC1CCOP(=O)O1 Chemical compound NC1CCOP(=O)O1 CMQAMENQCKNUPB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZVCNBVJYXBEKTC-UHFFFAOYSA-L azanium;zinc;phosphate Chemical compound [NH4+].[Zn+2].[O-]P([O-])([O-])=O ZVCNBVJYXBEKTC-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, and a preparation method and application thereof, wherein the composite material comprises the following components in percentage by weight: 0.5 to 10 percent of organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid; 18% -22% of curing agent; 68 to 81.5 percent of bisphenol A epoxy resin. Compared with the prior art, the invention utilizes the synergistic effect between the organophosphorus-nitrogen flame retardant and the halloysite nanotube to obtain the epoxy resin composite material with high mechanical property and high flame retardant property; the epoxy resin/organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid composite material prepared by the method has the advantages of rich raw material sources, simple process, high yield and low addition amount of the composite flame retardant, has excellent flame retardant property and mechanical property, and can be applied to the industrial fields of advanced equipment, automobiles, electronic appliances and the like.
Description
Technical Field
The invention relates to the technical field of materials, in particular to an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, and a preparation method and application thereof.
Background
Epoxy resins (EP) are used as a typical thermosetting resin, and are widely used in the fields of communications, electronics, aerospace, engineering composite materials, etc., because of their excellent mechanical properties, electrical insulation properties, corrosion resistance, adhesion properties, and processability. However, EP's have low Limiting Oxygen Index (LOI), and their flammability by themselves limits their development and use. Thus, flame retardance of EP's is becoming increasingly important. The halogen flame retardant has high-efficiency flame retardant effect, but releases a large amount of smoke and toxic and harmful corrosive gas during combustion, and can bring great damage to personnel and compact instruments in a fire scene. The common phosphorus flame retardant has the advantages of good compatibility, flame retardance, plasticization and the like, but also has the defects of poor thermal stability, easiness in hydrolysis, reduced mechanical property and the like.
Halloysite Nanotubes (HNTs) are natural mineral materials with hollow nanotube structures and have a molecular formula of Al 2 SiO 5 (OH) 4 ·nH 2 O (n=0 or 2). The outer surface of HNTs mainly comprises Si-O-Si bonds, the inner wall is mainly aluminum hydroxyl, and a small amount of silicon/aluminum hydroxyl exists on the surface and the end face of the nanotube. Because of the advantages of high specific surface area, large length-diameter ratio, high strength, high modulus, low cost and the like, the polymer material is commonly used for improving the mechanical properties of the polymer material. However, HNTs also suffer from the disadvantage of low flame retardant efficiency.
According to the report of the literature [ Lv Jiashuai male, academic paper, influence of phosphorus flame retardant compound halloysite nanotube on the performance of epoxy resin, 2021], compared with blank epoxy resin, the epoxy resin composite material added with 10 parts of HNTs can reach the UL 94V-1 level. Dong Yanmao et al [ science and engineering of Polymer materials, 2020, 36 (1): 75-82] and adopting an adsorption-chemical precipitation method to synthesize ammonium zinc phosphate/halloysite nanotube (ZAP/HNT), the epoxy resin composite material added with 15% of ZAP/HNT still has no grade in UL 94 test, and the epoxy resin composite material containing 20% of ZAP/HNT can reach UL 94V-2 grade.
According to patent CN10997103A (phosphorus-containing nano flame retardant and preparation method thereof), the surface of halloysite nanotube is modified by amino high polymer and then reacts with phosphoric acid, and ammonium phosphate is loaded on the surface of the nanotube to improve the flame retardance of the halloysite nanotube, but the patent does not report the influence of the ammonium phosphate loaded halloysite nanotube on the flame retardance and mechanical property of the polymer (including epoxy resin). Along with the progress of scientific technology, the requirements on the material performance are higher and higher, and besides meeting the requirements on flame retardant performance, excellent mechanical properties and low addition amount of flame retardant are required.
Therefore, there is a need to realize low addition of flame retardant and excellent mechanical properties of epoxy resin composite materials under the condition of solving the problem that the epoxy resin meets the flame retardant requirement.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, a preparation method and application thereof, and the epoxy resin composite material prepared by adding the composite flame retardant into epoxy resin has excellent flame retardant property and excellent mechanical property.
The applicant considers in conception history that: it is necessary to modify halloysite nanotubes with flame retardants to enhance their flame retardant properties. The organic phosphorus-nitrogen flame retardant does not contain halogen elements and does not need to be added with organic solvents in the synthesis process, so that the organic phosphorus-nitrogen flame retardant is a safe and environment-friendly flame retardant with excellent flame retardant property. The organic phosphorus-nitrogen flame retardant loaded halloysite nanotube can improve poor flame retardance of the halloysite nanotube, can exert excellent mechanical properties of high length-diameter ratio of the surface of the halloysite nanotube, and has rich hydroxyl groups on the surface, so that organic groups are easy to modify on the surface to improve compatibility of resin. The invention has the advantages of abundant and low raw material sources, simple preparation process and environmental protection. The prepared epoxy composite material has excellent flame retardant property, high mechanical property and small addition amount of flame retardant.
The aim of the invention can be achieved by the following technical scheme:
the invention provides an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, which comprises the following components in percentage by weight:
0.5 to 10 percent of organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid;
18% -22% of curing agent;
68 to 81.5 percent of bisphenol A epoxy resin.
Further, the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid is prepared by sequentially carrying out hydroxylation modification and amination modification on halloysite nanotubes, and then respectively reacting with an organic phosphonic acid aqueous solution and a melamine aqueous solution.
Further, the curing agent is one or more selected from heterocyclic amine curing agents, aromatic amine curing agents, anhydride curing agents and alicyclic amine curing agents.
The second aspect of the invention provides a preparation method of the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, which comprises the following steps:
s1: carrying out hydroxylation modification on halloysite nanotubes by adopting alcohol alkali solution to obtain a material A;
s2: amino siloxane is used for carrying out amino modification on the material A to obtain a material B;
s3: adding the material B into an organic phosphonic acid aqueous solution, heating for reaction, slowly dropwise adding a melamine aqueous solution, continuously stirring for reaction, and then filtering, washing and drying the obtained product to prepare an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid;
s4: mixing and curing to obtain the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material.
Further, in S3, the organic phosphonic acid is selected from one or more of aminotrimethylene phosphonic acid, phenyl phosphonic acid, phytic acid, diethylenetriamine penta-methylene phosphonic acid, hexamethylenediamine tetra-methylene phosphonic acid, ethylenediamine tetra-methylene phosphonic acid;
in S3, the molar ratio of the organic phosphonic acid to the melamine is 1:3-3:1;
in S3, the temperature of the temperature-rising reaction is 80-120 ℃ and the reaction time is 1-24 h.
Further, in S1, the alcohol in the alcohol lye is a saturated fatty alcohol, specifically at least one selected from methanol, ethanol, n-propanol and isopropanol;
the alkali in the alcohol alkali is at least one selected from sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
Further, in S2, the aminosilicone is selected from one or more of γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl triethoxysilane, N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl methyldimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl methyldiethoxysilane, γ -aminopropyl methyldimethoxysilane, γ -aminopropyl ethoxydimethylsilane.
Further, in S4, bisphenol A epoxy resin, organic phosphonic acid metal salt@halloysite nanotube hybrid and curing agent are weighed according to the proportion, uniformly stirred and then put into a polytetrafluoroethylene mold, and cured in different temperature ranges and time ranges, wherein the curing temperature is 100-150 ℃ and the curing time is 2-8 hours.
The third aspect of the invention provides an application of the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material in special epoxy resin materials.
Further, when the organic phosphorus-nitrogen flame retardant in the organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid/epoxy resin composite material is heated, the organic phosphorus-nitrogen flame retardant can promote the carbonization of a matrix material to generate a carbon layer, meanwhile, the generated non-combustible gas has the concentration of dilution air and combustible gas, the halloysite nanotubes play a physical shielding effect, the flame retardant performance of the epoxy resin is jointly improved, and meanwhile, the organic phosphorus-nitrogen flame retardant loaded on the surface promotes the compatibility between the halloysite nanotubes and the epoxy resin, so that the mechanical performance of the epoxy resin is improved.
Compared with the prior art, the invention has the following technical advantages:
1) According to the invention, the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid is added into the epoxy resin, and the mass ratio of the organic phosphorus-nitrogen flame retardant to the halloysite nanotube is regulated by controlling the reaction conditions, so that the prepared epoxy resin composite material has excellent flame retardant property and mechanical property. The organic phosphorus-nitrogen flame retardant is prepared from organic polyphosphonic acid and melamine, and can promote the carbonization of a matrix material to generate a carbon layer when heated, and meanwhile, the generated non-combustible gas has the concentration of diluted air and combustible gas to generate a flame retardant effect.
2) The halloysite nanotube adopted in the invention is a hollow nanotube with a multi-wall structure, has higher length-diameter ratio and high temperature resistance, can play a certain physical shielding effect, and can play a certain flame-retardant effect in an epoxy resin system. The surface-loaded organophosphorus-nitrogen flame retardant can improve the compatibility between halloysite nanotubes and epoxy resin, thereby improving the mechanical properties of the epoxy resin.
Drawings
FIG. 1 is a transmission electron microscope image of an unmodified halloysite nanotube;
FIG. 2 is a transmission electron microscopy image of melamine aminotrimethylene phosphonate loaded halloysite nanotubes (mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes 1:1);
FIG. 3 is an infrared spectrum of a melamine-supported halloysite nanotube (melamine aminotrimethylene phosphonate to halloysite nanotube mass ratio of 1:1);
FIG. 4 is a graph of thermal weight loss of epoxy and melamine aminotrimethylene phosphonate loaded halloysite nanotubes (mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes 1:1)/epoxy composite (nitrogen atmosphere, heating rate 10 ℃/min).
Detailed Description
In general, the invention relates to an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material and a preparation method thereof. The method specifically comprises the following steps: the preparation method comprises the steps of carrying out amination on the surface of a halloysite nanotube, reacting the aminated halloysite nanotube with amino trimethylene phosphonic acid, then slowly dropwise adding melamine aqueous solution, synthesizing an organic phosphorus-nitrogen flame retardant loaded halloysite nanotube, applying the organic phosphorus-nitrogen flame retardant loaded halloysite nanotube to epoxy resin, preparing an epoxy resin/organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid composite material, and obtaining the epoxy resin composite material with high mechanical property and high flame retardant property by utilizing the synergistic effect between the organic phosphorus-nitrogen flame retardant and the halloysite nanotube. The epoxy resin/organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid composite material prepared by the method has the advantages of rich raw material sources, simple process, high yield and low addition amount of the composite flame retardant, has excellent flame retardant property and good mechanical property, and can be applied to the industrial fields of advanced equipment, automobiles, electronic appliances and the like.
Specifically, the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material comprises the following raw materials in percentage by weight: 0.5 to 10 percent of organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid, 18 to 22 percent of curing agent and 68 to 81.5 percent of bisphenol A epoxy resin. Preferably, the mass ratio of the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid is 1% -2%.
The organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid is prepared by firstly carrying out hydroxylation modification on a halloysite nanotube by using an alcohol alkali solution, then carrying out amination modification by using aminosilicone, adding the modified halloysite nanotube into an organic phosphonic acid aqueous solution, raising the temperature to a specified temperature for reacting for a certain time, slowly dropwise adding a melamine aqueous solution, reacting under continuous stirring, and filtering, washing and drying the obtained product to prepare the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid.
The organic phosphonic acid is selected from one or more of amino trimethylene phosphonic acid, phenyl phosphonic acid, phytic acid, diethylenetriamine pentamethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid and ethylenediamine tetramethylene phosphonic acid. The molar ratio of the organic phosphonic acid to the melamine is 1:3-3:1. The mass ratio of the organic phosphorus-nitrogen flame retardant to the halloysite nanotube is 1:3-3:1.
The curing agent is one or more of heterocyclic amine curing agent, aromatic amine curing agent, anhydride curing agent or alicyclic amine curing agent.
The halloysite nanotube is treated by an alcohol alkali solution, wherein the alcohol of the alcohol alkali solution refers to at least one of methanol, ethanol, n-propanol and isopropanol, and preferably ethanol; the alkali of the alcohol alkali is at least one of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
The specified temperature of the reaction is 80-120 ℃, and the reaction time is 1-24 h.
The aminosilicone is one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldiethoxysilane, gamma-aminopropyl methyldimethoxysilane and gamma-aminopropyl ethoxydimethylsilane, preferably gamma-aminopropyl triethoxysilane.
Finally, weighing bisphenol A epoxy resin, organic phosphonic acid metal salt@halloysite nanotube hybrid and curing agent according to the proportion, uniformly stirring, and then placing into a polytetrafluoroethylene mold for curing at different temperature and time periods, wherein the curing temperature is 100-150 ℃ and the curing time is 2-8 h.
The invention will now be described in detail with reference to the drawings and specific examples. In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
Example 1
Preparing 250mL of aqueous solution with the pH value of 10 by using 0.1mol/L NaOH solution, and mixing 250mL of alkaline solution with 250mL of ethanol solution; adding 50g of halloysite nanotubes into the alcohol-alkali solution, mixing and carrying out ultrasonic treatment for 5min, stirring for 2-5h in a room temperature environment, and carrying out centrifugal separation or suction filtration, and washing with deionized water until the solution is neutral to obtain the hydroxylated halloysite nanotubes. Adding 50g of hydroxylated halloysite nanotubes into an aminosilicone solution system, and refluxing the mixed system at 80 ℃ for 4-6 hours; and after the reaction is finished, washing the mixture to be neutral by deionized water, and drying the mixture at 80 ℃ for 24 hours to obtain the aminated halloysite nanotube.
11.94g of 50% aminotrimethylene phosphonic acid aqueous solution, 10g of aminated halloysite nanotubes and 200mL of deionized water are weighed, added into a reaction vessel with a stirrer, heated to 100 ℃ and reacted for 2 hours under the stirring action, then 4.57g of melamine and 100mL of deionized water are added into the reactor, the reaction is continued under the stirring action for 2 hours at 100 ℃, and then the product is filtered and dried to obtain the melamine aminotrimethylene phosphonate loaded halloysite nanotubes (ATMP-MEL@HNTs, wherein the mole ratio of ATMP to MEL is 1.1:2 and the mass ratio of ATMP-MEL to HNTs is 1:1).
FIG. 1 is a transmission electron microscope image of an unmodified halloysite nanotube; FIG. 2 is a transmission electron microscopy image of melamine aminotrimethylene phosphonate loaded halloysite nanotubes (mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes 1:1). As can be seen from the transmission electron microscope, granular substances are attached to the inner cavity and the outer surface of the halloysite nanotube.
FIG. 3 is an infrared spectrum of melamine aminotrimethylene phosphonate loaded halloysite nanotubes (mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes 1:1). From the infrared spectrum, successful synthesis of melamine aminotrimethylene phosphonate was seen.
FIG. 4 is a graph of thermal weight loss of epoxy and melamine aminotrimethylene phosphonate loaded halloysite nanotubes (mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes 1:1)/epoxy composite (nitrogen atmosphere, heating rate 10 ℃/min). From the TGA curve, the addition of the flame retardant improves the carbon residue of the composite material, and the initial decomposition temperature (5% of sample mass loss) of the composite material added with 2% of the flame retardant @ halloysite nanotube hybrid is reduced by 15.8 ℃ compared with that of the pure epoxy resin.
47.4g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 0.3g of melamine aminotrimethylene phosphonate loaded halloysite nanotube powder is weighed into a 50mL container, stirred for 10min, then 12.3g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally a corresponding polytetrafluoroethylene mould is poured, and curing is carried out for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material is obtained (the addition amount of the melamine amino trimethylene phosphonate loaded modified halloysite nanotube is 0.5 weight percent). The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1,2 and 3.
Example 2
The procedure for the preparation of melamine aminotrimethylene phosphonate loaded halloysite nanotubes (ATMP-MEL@HNTs) was consistent with example 1.
47.2g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 0.6g of melamine aminotrimethylene phosphonate loaded modified halloysite nanotube powder is weighed into a 50mL container, stirred for 10min, then 12.2g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally the mixture is poured into a corresponding polytetrafluoroethylene mould, and cured for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material is obtained (the addition amount of the melamine amino trimethylene phosphonate loaded modified halloysite nanotube is 1 wt%). The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1,2 and 3.
Example 3
The preparation of melamine aminotrimethylene phosphonate loaded modified halloysite nanotubes (ATMP-MEL@HNTs) was consistent with example 1.
46.7g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 1.2g of melamine aminotrimethylene phosphonate loaded modified halloysite nanotube powder is weighed into a 50mL container, stirred for 10min, then 12.1g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally the mixture is poured into a corresponding polytetrafluoroethylene mould, and cured for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material (the added mass ratio of the melamine amino trimethylene phosphonate loaded modified halloysite nanotube is 2 wt%) is obtained. The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1,2 and 3.
Example 4
11.94g of 50% aminotrimethylene phosphonic acid aqueous solution, 20g of aminated halloysite nanotubes and 200mL of deionized water are weighed, added into a reaction vessel with a stirrer, heated to 100 ℃ and reacted for 2 hours under the stirring action, then 4.57g of melamine and 100mL of deionized water are added into the reactor, the reaction is continued under the stirring action for 2 hours at 100 ℃, and then the product is filtered, washed with boiling water and dried to obtain melamine aminotrimethylene phosphonate loaded modified halloysite nanotubes (ATMP-MEL@HNTs, wherein the mole ratio of ATMP to MEL is 1.1:2 and the mass ratio of ATMP-MEL to HNTs is 1:2).
47.4g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 0.3g of melamine aminotrimethylene phosphonate loaded modified halloysite nanotube powder is weighed into a 50mL container, stirred for 10min, then 12.3g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally the mixture is poured into a corresponding polytetrafluoroethylene mould, and cured for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material is obtained (the addition amount of the melamine amino trimethylene phosphonate loaded modified halloysite nanotube is 0.5 weight percent). The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1,2 and 3.
Example 5
The preparation of melamine aminotrimethylene phosphonate loaded modified halloysite nanotubes (ATMP-MEL@HNTs) was consistent with example 4.
47.2g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 0.6g of melamine aminotrimethylene phosphonate loaded modified halloysite nanotube powder is weighed into a 50mL container, stirred for 10min, then 12.2g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally the mixture is poured into a corresponding polytetrafluoroethylene mould, and cured for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material is obtained (the addition amount of the melamine amino trimethylene phosphonate loaded modified halloysite nanotube is 1 wt%). The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1-3.
Example 6
The preparation of melamine aminotrimethylene phosphonate loaded modified halloysite nanotubes (ATMP-MEL@HNTs) was consistent with example 4.
46.7g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 1.2g of melamine aminotrimethylene phosphonate loaded modified halloysite nanotube powder is weighed into a 50mL container, stirred for 10min, then 12.1g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally the mixture is poured into a corresponding polytetrafluoroethylene mould, and cured for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material is obtained (the addition amount of the melamine amino trimethylene phosphonate loaded modified halloysite nanotube is 2 wt%). The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1,2 and 3.
Comparative example 1
47.6g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, stirred for 10min, then added with 12.4g of 4,4' -diaminodiphenyl methane curing agent, stirred for 3min, vacuumized for 5min at 90 ℃, finally poured into a corresponding polytetrafluoroethylene mould, cured for 2h at 120 ℃ and cured for 2h at 140 ℃. Finally, the epoxy resin composite material is obtained. Epoxy resin material composition, flame retardant test results, and mechanical test results are shown in tables 1-3.
Comparative example 2
47.2g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 0.6g of aminated halloysite nanotube (the preparation method is referred to in example 1) powder is weighed into a 50mL container, stirred for 10min, then 12.3g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuum pumping is carried out for 5min at 90 ℃, finally a corresponding polytetrafluoroethylene mould is poured, and curing is carried out for 2h at 120 ℃ and 2h at 140 ℃. Finally, the epoxy resin composite material (halloysite addition amount is 1 wt%) is obtained. The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1-3.
Comparative example 3
Preparation of melamine powder an aminotrimethylene phosphonate flame retardant (preparation method referred to CN 104497041a.
47.2g of epoxy resin is weighed into a 200mL stainless steel container, placed on a heating magnetic stirrer, stirred at a proper speed and heated to 90 ℃, 0.6g of melamine powder aminotrimethylene phosphonate flame retardant is weighed into a 50mL container, stirred for 10min, then 12.3g of 4,4' -diaminodiphenyl methane curing agent is added and stirring is continued for 3min, then vacuumized for 5min at 90 ℃, finally poured into a corresponding polytetrafluoroethylene mould, cured for 2h at 120 ℃ and cured for 2h at 140 ℃. Finally, the epoxy resin composite material is obtained (the addition amount of the melamine powder amino trimethylene phosphonate flame retardant is 1 wt%). The epoxy resin composite material consists of flame retardant test results and mechanical test results are shown in tables 1,2 and 3.
From Table 2, it can be seen that the melamine aminotrimethylene phosphonate @ halloysite nanotube hybrid is added into the epoxy resin, and the flame retardant effect is improved obviously, which proves that the melamine aminotrimethylene phosphonate and the halloysite nanotube can be used for synergistic flame retardance. When the addition amount is 1 weight percent and 2 weight percent, the melamine aminotrimethylene phosphonate@halloysite nanotube loaded in the mass ratio of 1:2 and 1:1 can improve the flame retardant property of the epoxy composite material to the greatest extent, and the LOI and the flame retardant grade are obviously improved, wherein the melamine aminotrimethylene phosphonate loaded halloysite nanotube with the mass ratio of 1:1 has the best flame retardant property.
As can be seen from Table 3, the same for the 2 different load ratios testedSamples of melamine aminotrimethylene phosphonate @ halloysite nanotube hybrid/epoxy resin composite at equal 1wt% add-on levels were example 2, example 5, with a loading ratio of 1:1, 1:2, respectively. It can be seen that the impact property of the material increases progressively with the decrease of the load ratio of melamine aminotrimethylene phosphonate to halloysite nanotube, i.e. the increase of the halloysite nanotube content, between 34 and 37kJ/m 2 Between them. The melamine amino trimethylene phosphonate @ halloysite nanotube hybrid/epoxy resin composite material sample can obviously improve the mechanical properties under the condition of ensuring the optimal UL-94 grade V-0, and compared with pure epoxy resin, the tensile strength of the composite material sample can be improved by 17.1% at most, and the impact strength of the composite material sample is improved by 42.3%. The epoxy resin flame retardant can improve the mechanical property of epoxy resin, has high flame retardant efficiency, and is expected to be applied to the industrial fields of advanced equipment, automobiles, electronic appliances and the like.
Table 1A list of the compositions of the epoxy resin composites prepared in the examples and comparative examples
Note that: ATMP-mel@hnts=1:1 represents melamine aminotrimethylene phosphonate loaded halloysite nanotubes, wherein the molar ratio of aminotrimethylene phosphonic acid to melamine is 1.1:2, and the mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes is 1:1; ATMP-mel@hnts=1:2 represents melamine aminotrimethylene phosphonate loaded halloysite nanotubes, wherein the molar ratio of aminotrimethylene phosphonic acid to melamine is 1.1:2, and the mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes is 1:2; ATMP-mel@hnts=1:3 represents melamine aminotrimethylene phosphonate loaded halloysite nanotubes, wherein the molar ratio of aminotrimethylene phosphonic acid to melamine is 1.1:2, and the mass ratio of melamine aminotrimethylene phosphonate to halloysite nanotubes is 1:3; N-HNTs represent aminated halloysite nanotubes; ATMP-MEL represents melamine aminotrimethylene phosphonate wherein the molar ratio of aminotrimethylene phosphonic acid to melamine is 1:2; EP represents bisphenol A type epoxy resin; DDM represents 4,4' -diaminodiphenylmethane.
Table 2A list of flame retardant properties of epoxy resin composites prepared in examples and comparative examples
Table 3 mechanical Properties Table of the epoxy resin composite materials prepared in examples and comparative examples
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material is characterized by comprising the following components in percentage by weight:
0.5 to 10 percent of organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid;
18% -22% of curing agent;
68 to 81.5 percent of bisphenol A epoxy resin.
2. The organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid/epoxy resin composite material according to claim 1 is characterized in that the organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid is prepared by sequentially carrying out hydroxylation modification and amination modification on halloysite nanotubes, and then respectively reacting with an organic phosphonic acid aqueous solution and a melamine aqueous solution.
3. The organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material according to claim 1, wherein the curing agent is one or more selected from heterocyclic amine curing agents, aromatic amine curing agents, acid anhydride curing agents and alicyclic amine curing agents.
4. A method for preparing the organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material according to any one of claims 1 to 3, comprising the following steps:
s1: carrying out hydroxylation modification on halloysite nanotubes by adopting alcohol alkali solution to obtain a material A;
s2: amino siloxane is used for carrying out amino modification on the material A to obtain a material B;
s3: adding the material B into an organic phosphonic acid aqueous solution, heating for reaction, slowly dropwise adding a melamine aqueous solution, continuously stirring for reaction, and then filtering, washing and drying the obtained product to prepare an organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid;
s4: mixing and curing to obtain the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material.
5. The preparation method of the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material according to claim 4, wherein in S3, the organic phosphonic acid is selected from one or more of amino trimethylene phosphonic acid, phenyl phosphonic acid, phytic acid, diethylenetriamine pentamethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid and ethylenediamine tetramethylene phosphonic acid;
in S3, the molar ratio of the organic phosphonic acid to the melamine is 1:3-3:1;
in S3, the temperature of the temperature-rising reaction is 80-120 ℃ and the reaction time is 1-24 h.
6. The preparation method of the organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material according to claim 4, wherein in S1, the alcohol in the alcohol alkali solution is saturated fatty alcohol, and specifically at least one selected from methanol, ethanol, n-propanol and isopropanol;
the alkali in the alcohol alkali is at least one selected from sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
7. The method for preparing the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material according to claim 4, wherein in S2, the aminosilicone is one or more selected from gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldiethoxysilane, gamma-aminopropyl methyldimethoxysilane and gamma-aminopropyl ethoxydimethylsilane.
8. The preparation method of the organic phosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, which is disclosed in claim 4, is characterized in that in S4, bisphenol A type epoxy resin, organic phosphonic acid metal salt @ halloysite nanotube hybrid and curing agent are weighed according to the proportion, uniformly stirred and then put into a polytetrafluoroethylene mold for curing in different temperature ranges and time ranges, wherein the curing temperature is 100-150 ℃ and the curing time is 2-8 hours.
9. Use of the organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material according to any one of claims 1 to 3 in special epoxy resin materials.
10. The application of the organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid/epoxy resin composite material according to claim 9 is characterized in that the organic phosphorus-nitrogen flame retardant in the organic phosphorus-nitrogen flame retardant@halloysite nanotube hybrid/epoxy resin composite material can promote carbonization of a matrix material to generate a carbon layer when heated, and meanwhile, generated non-combustible gas has dilution air and combustible gas concentration, and the halloysite nanotubes play a physical shielding effect to jointly promote the flame retardant property of epoxy resin, and meanwhile, the surface-loaded organic phosphorus-nitrogen flame retardant promotes the compatibility between the halloysite nanotubes and the epoxy resin, so that the mechanical property of the epoxy resin is improved.
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