CN107011501A - A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material - Google Patents
A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material Download PDFInfo
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- CN107011501A CN107011501A CN201710246645.7A CN201710246645A CN107011501A CN 107011501 A CN107011501 A CN 107011501A CN 201710246645 A CN201710246645 A CN 201710246645A CN 107011501 A CN107011501 A CN 107011501A
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- Prior art keywords
- epoxy resin
- composite material
- smoke
- resin composite
- phosphor
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 91
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 91
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000779 smoke Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003063 flame retardant Substances 0.000 title claims description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 25
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000013019 agitation Methods 0.000 claims abstract description 13
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000015778 magnesium gluconate Nutrition 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000001755 magnesium gluconate Substances 0.000 claims abstract description 9
- 229960003035 magnesium gluconate Drugs 0.000 claims abstract description 9
- IAKLPCRFBAZVRW-XRDLMGPZSA-L magnesium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate;hydrate Chemical compound O.[Mg+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IAKLPCRFBAZVRW-XRDLMGPZSA-L 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000007711 solidification Methods 0.000 claims abstract description 7
- 230000008023 solidification Effects 0.000 claims abstract description 7
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 5
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical group CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 claims description 7
- 230000009267 minimal disease activity Effects 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims 2
- 206010001497 Agitation Diseases 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims 1
- 235000019504 cigarettes Nutrition 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 3
- XLHUBROMZOAQMV-UHFFFAOYSA-N 1,4-benzosemiquinone Chemical group [O]C1=CC=C(O)C=C1 XLHUBROMZOAQMV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- -1 timber Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 150000002118 epoxides Chemical group 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- 239000000805 composite resin Substances 0.000 description 5
- 238000010980 drying distillation Methods 0.000 description 5
- 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
- 238000010792 warming Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Laminated Bodies (AREA)
Abstract
It is to mix the phosphorus phosphonitrile of precursor 6 (4 hydroxyphenoxy) ring three, cetyl trimethylammonium bromide, epoxychloropropane to stir 1 ~ 3h after 80 ~ 120 DEG C the invention provides a kind of preparation method of novel phosphorus-containing LSOH anti-flaming epoxy resin composite material；40 ~ 55 DEG C are cooled to, NaOH is added and neutralizes, filter, wash, dry, obtain water white transparency low-viscosity phosphorous epoxy resin；100 ~ 120 DEG C are heated to, mould is poured into after adding curing agent, curing accelerator, anti-flaming smoke-inhibiting agent, zinc hydroxide and magnesium gluconate, the h of constant temperature stirring and dissolving 1 ~ 3 under agitation, prior to the 120 DEG C h of isothermal curing 1 ~ 4 are produced then at 160 DEG C of 0.5 ~ 3 h of solidification.The LSOH anti-flaming epoxy resin composite material has good fire retardancy, while also there is the property of low cigarette, and satisfactory mechanical property, it can be widely used in electronic device, engineering building materials field.
Description
Technical field
The present invention relates to a kind of preparation of halogen-free smoke inhibition fire retardant, more particularly to a kind of phosphor-containing halogen-free low-smoke and flame retardant asphalt mixtures modified by epoxy resin
The preparation of resin composite material, belongs to fire proofing technical field and technical field of polymer materials.
Background technology
Epoxy resin is to refer to the organic compound containing two or more epoxide groups in molecule, it is characterized in that point
Contain active epoxide group in minor structure chain, epoxide group can be located at the end of strand, middle or circlewise structure.By
Contain active epoxide group in molecular structure, them is crosslinked reaction with polytype curing agent and is formed not
The molten high polymer with tridimensional network.Epoxy resin after solidification has good physics, chemical property, to metal and
The surface of nonmetallic materials has excellent adhesive strength, and dielectric properties are good, and deformation retract rate is small, product size stability
Good, hardness is high, and pliability preferably, to alkali and most of solvent-stable, thus is widely used in national defence, each department of national economy.
It is specifically most widely used in the following aspects：
1st, coating.Application of the epoxy resin in coating accounts for larger ratio, it can be made differ from one another, the product that purposes is different
Kind.
2nd, adhesive.Epoxy resin is in addition to bad to the non-polar plastic caking property such as polyolefin, for various metals
Material such as aluminium, steel, iron, copper；Nonmetallic materials such as glass, timber, concrete etc.；And thermosetting plastics such as phenolic aldehyde, amino, no
Saturated polyester etc. has excellent adhesive property, therefore has the title of all-purpose adhesive.Epoxy adhesive is the important product of sqtructural adhesive
Kind.
3rd, electronic apparatus material.Because the insulating properties of epoxy resin are high, structural strength is big and many such as good seal performance
Unique advantage, is used widely in the insulation and encapsulation of high and low voltage electrical equipment, motor and electronic component, and development is very
It hurry up.It is mainly used in：（1）The cast of electrical equipment, motor insulating envelope.Such as electromagnet, contactor coil, transformer, dry type transformation
The hermetically sealed insulating envelope of entirety of the high and low voltage electrical equipments such as device.（2）It is widely used in the device equipped with electronic component and circuit
Embedding is insulated.Turn into the indispensable important insulating materials of electronics industry.（3）Electron level epoxy molding plastic is used for semiconductor element
The plastic packaging of device.Development is exceedingly fast in recent years.Due to its superior performance, big substituted traditional metal, ceramics and glass-encapsulated
Trend.（4）Epoxy laminate plastics are very wide in electronics, appliance field application.The development of wherein epoxy copperplate is especially rapid,
One of basic material as electronics industry.Largely should in addition, epoxy insulation coating, dielectric adhesive and electric adhesive also have
With.
4th, engineering plastics and composite.Epoxy engineering plastics mainly include the epoxy molding plastic and ring for high-pressure molding
Oxygen layer compression molding material, and epoxy foam plastics.Epoxy engineering plastics can also regard a kind of epoxy composite material of broad sense as.Ring
O compoiste material mainly has fiber glass epoxy（Universal composite）With epoxy construction composite, the epoxy of such as pultrusion
Section bar, Wrapping formed hollow revolving body product and high-performance composite materials.Epoxy composite material be chemical industry and Aeronautics and Astronautics,
A kind of important structural material and functional material of the high-tech sectors such as military project.
5th, civil material.Be mainly used as anti-corrosion terrace, epoxy resin mortar and concrete product, high class pavement and airfield runway,
Fast repairing material, the grouting material of foundation, architecture adhesion agent and coating etc..
Although the physical property of epoxy resin is very good, also there is that fatal, common epoxy resin is very easy to
Burning, its oxygen index (OI) only has 19% or so, there is huge disaster hidden-trouble, especially in electronic products field and building materials field.By
The fire incident that epoxy resin triggers is very more, therefore, how to improve the anti-flammability of epoxy resin, can be safer
It is the problem of many scientific research personnel need solution to serve society.
At present, the fire-retardant research of epoxy resin is concentrated mainly on additive flame retardant, although currently solve epoxy resin
The problem of burning, but the mechanical performance of epoxy resin is sacrificed, limit its application field.In recent years, it is intrinsic fire-retardant to grind
It is a very popular problem to study carefully, and is also most to be hopeful to solve that high polymer material is fire-retardant and mechanical performance is conflicting arranges
Apply.But intrinsic fire-retardant shortcoming is to prepare cost height, and the suppression cigarette capability improving to material is not enough.Therefore, using it is intrinsic it is fire-retardant and
The advantage of additive flame retardant, the two is combined, and prepares a kind of LSOH anti-flaming epoxy resin composite material, can be effective
The combustion problem of epoxy resin is solved, can also retain the mechanical performance of epoxy resin, make it have wider purposes.
The content of the invention
The purpose of the present invention be for fire retarding epoxide resin is present in the prior art the problem of there is provided a kind of novel phosphorus-containing without
Halogen low-smoke and flame retardant epoxy resin composite material and preparation method thereof.
First, the preparation of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material
（1）The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three：Using tetrahydrofuran as solvent, anhydrous K2CO3
For catalyst, parahydroxyben-zaldehyde is with hexachlorocyclotriph,sphazene in 45 ~ 65 DEG C of h of back flow reaction 20 ~ 24；Filtering, washing, merge filter
Liquid is simultaneously concentrated into the 1/2 ~ 1/5 of original volume, is settled, washed with distilled water, and with re-crystallizing in ethyl acetate, vacuum drying obtains yellowish
The phosphonitrile (PN-CHO) of color solid 6 (4- aldehyde radicals phenoxy group) ring three；Again in THF- methanol mixed solvents, make sodium borohydride solids with
The phosphonitrile of 6 (4- aldehyde radicals phenoxy group) ring three h of reduction reaction 8 ~ 12 at room temperature, vacuum distillation goes out after solvent with distillation water sedimentation, takes out
Filter, is recrystallized after washing with absolute ethyl alcohol, is dried in vacuo, it is the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three to obtain white product
(PN-OH)。
The mass ratio of hexachlorocyclotriph,sphazene and parahydroxyben-zaldehyde is 1:3~1:6；Catalyst K2CO3Consumption be hydroxy benzenes
0.5 ~ 1 times of formaldehyde and hexachlorocyclotriph,sphazene gross mass.
In THF- methanol mixed solvents, the volume ratio of THF and methanol is 2:1~5:1；Sodium borohydride solids and 6 (4- aldehyde radicals
Phenoxy group) ring three phosphonitrile mass ratio be 0.5:1~1:1.
（2）The synthesis of phosphor-containing flame-proof resin：By the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three, cetyl trimethyl bromination
After ammonium, epoxychloropropane mixing, in being stirred vigorously 1 ~ 3 h at 80 ~ 120 DEG C；Then mixture is cooled to 40 ~ 55 DEG C, and
The NaOH aqueous solution is added, 8 ~ 12 h are reacted in 40 ~ 55 DEG C；Filtering separates out product after the completion of reaction, and is washed product with hot water
To neutrality, with anhydrous sodium sulfate drying, vacuum distillation removes unreacted epoxychloropropane, obtains water white transparency low-viscosity phosphorous
Epoxy resin；
The mass ratio of cetyl trimethylammonium bromide and the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three is 1:35~1:45；Six alkyl
Trimethylammonium bromide is 1 with epoxychloropropane mass ratio:2000~1:2500；NaOH effect is the byproduct salt of neutralization reaction
Acid, its addition is the 2% ~ 5% of three's gross mass.
（3）It is prepared by LSOH anti-flaming epoxy resin composite material：By step（2）Gained phosphorous epoxy resin is heated to
100 ~ 120 DEG C, curing agent, curing accelerator, anti-flaming smoke-inhibiting agent, zinc hydroxide and magnesium gluconate are separately added with agitation,
Mould is poured into after the h of constant temperature stirring and dissolving 1 ~ 3, prior to the 120 DEG C h of isothermal curing 1 ~ 4 solidify 0.5 ~ 3 h, i.e., then at 160 DEG C
Obtain LSOH anti-flaming epoxy resin composite material；
Curing agent is 4,4- MDAs（DDM）Or 4,4- diaminodiphenylsulfones（DDS）, the addition of curing agent be containing
0.01 ~ 0.1 times of phosphorus epoxy resin quality.
Curing accelerator is boron trifluoride ethylamine complex compound, and its addition is the 0.01 ~ 0.05 of phosphorous epoxy resin quality
Times.
Anti-flaming smoke-inhibiting agent is palygorskite, and its addition is 0.01 ~ 0.1 times of phosphorous epoxy resin quality.
The effect of zinc hydroxide is to provide zinc source, favourable into carbon during to burning, and its addition is phosphorous epoxy resin quality
0.05 ~ 0.1 times.
The effect of magnesium gluconate is to provide fire-retardant gas carbon dioxide and carbon forming agent magnesium elements, and its addition is phosphorous ring
0.005 ~ 0.05 times of oxygen resin quality.
The synthetic route of LSOH anti-flaming epoxy resin is as follows：
Epoxy resin prepared by the present invention1H NMR spectras are shown in Fig. 1.6.79 ~ 7.24ppm is mainly it can be seen from collection of illustrative plates
The formant of phenyl ring Hydrogen Proton in compound, the CH that 2.47 ~ 2.77ppm is belonged on epoxide ring2, 3.26ppm and 3.70ppm
Belong to the CH being joined directly together with epoxide ring2, 3.41ppm belongs to CH on epoxide ring, the compound structure with it is expected consistent.
Epoxy resin infrared spectrogram prepared by the present invention is shown in Fig. 2.Figure it is seen that 1208cm-1 For phosphonitrile structure
Middle P=N stretching vibration absworption peak, 609cm-1With 526cm-1For the P-Cl stretching vibration absworption peaks in phosphazene compound；
3390cm-1For PN-OH compound O-H stretching vibration peaks；In PN-CHO, 609cm-1With 526cm-1The P-Cl stretching vibration peaks at place
Disappear, it was demonstrated that Cl is fully substituted in HCCP；955cm-1And 833cm-1For C-O-C stretching vibration absworption peak, above analytical table
Bright, PNEP is the epoxy resin containing phosphonitrile, and structure is consistent with the expected structure of synthetic route.
Carbon-coating surface after Epoxy burns prepared by the present invention（a）And it is internal（b）Stereoscan photograph is shown in Fig. 3.From Fig. 3
As can be seen that a large amount of nanoscale little particles are accumulated on carbon-coating surface, it is fine and close, continuous, it may be possible to which that phosphorus-containing groups are fired in resin material
Burn after decomposing, is combined with carbon and be attached to material surface and form fine and close effectively carbon-coating.Carbon-coating inner surface is smooth, hard, continuous, interior
There are many depressions on surface, and this is mainly generation steam and other gases in combustion process and does not break through carbon-coating barrier, stays in material
Inside, forms a large amount of pits region.This shows that carbon-coating can give full play to heat-insulated, oxygen barrier, press down the effect of cigarette, has effectively carried height
The fire resistance of resin material.
2nd, phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material performance test
1st, fire resistance
Method of testing：Using GB/T2460-93 standard testings.
Test result：Oxygen index (OI) reaches more than 32, and horizontal vertical is burnt V-0 grades, and smoke density is less than 75.
2nd, mechanical performance
Method of testing：Using GB/T9341-88 and GB/T1843-80 standards.
Test result：Bending strength：28 ~ 31 MPa, impact strength：3.80~3.99 KJ/m2。
As can be seen here, the LSOH anti-flaming epoxy resin composite material that prepared by the present invention has good fire retardancy,
Also there is the property of low cigarette, and satisfactory mechanical property simultaneously, can be widely used in electronic device, engineering building materials field.
Brief description of the drawings
The epoxy resin that Fig. 1 is prepared for the present invention1H NMR spectras；
The infrared spectrogram for the epoxy resin that Fig. 2 is prepared for the present invention；
Carbon-coating surface and inner scanning electromicroscopic photograph after the Epoxy burns that Fig. 3 is prepared for the present invention.
Embodiment
Below by preparation method of the specific embodiment to phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material of the present invention
And performance is described further.
Embodiment 1
（1）The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
30 g parahydroxyben-zaldehydes and 250 mL THF are placed in 500 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution；20 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter（Time for adding is about 1 h）In the tetrahydrofuran solution of parahydroxyben-zaldehyde；65 DEG C are warming up to after 0.5 h, magnetic agitation is returned
24 h of stream reaction；Filtering, and with THF cyclic washings several times；Merging filtrate is simultaneously concentrated into after original volume about 1/5, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%；
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100 ml THF/ methanol solutions are added
(THF/ methanol=2/1v/v), 5 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.12 h are reacted at room temperature, are depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, yield
91%。
（2）The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 35g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2000 g epoxy chloropropionates
Alkane is added in 250mL three-necked flasks, and 3 h are stirred vigorously at 120 DEG C, mixture then is cooled into 55 DEG C, and add 90 g
The 50% NaOH aqueous solution, 12 h are reacted at 55 DEG C.After the completion of reaction by precipitate be filtered to remove and with hot water by product wash to
Neutrality, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains water white transparency low-viscosity
Phosphorous epoxy resin, yield is about 84%.
（3）It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 10g 4,4- MDAs is added（DDM）Or 4,
4- diaminodiphenylsulfones（DDS）With 10 g boron trifluoride ethylamine complex compounds, 10 g palygorskites, 50 g zinc hydroxides and 5 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 30, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
（4）The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy：Oxygen index (OI) reaches 32, and horizontal vertical is burnt V-0 grades, smoke density 73.
Mechanical performance：Bending strength：31 MPa, impact strength：3.99 KJ/m2。
Embodiment 2
（1）The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
60 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution；70 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter（Time for adding is about 1 h）In the tetrahydrofuran solution of parahydroxyben-zaldehyde；45 DEG C are warming up to after 0.5 h, magnetic agitation is returned
20 h of stream reaction；Filtering, and with THF cyclic washings several times；Merging filtrate is simultaneously concentrated into after original volume about 1/2, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%；
The phosphonitrile of 10g 6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100ml THF/ methanol solutions are added
(THF/ methanol=5/1 v/v), 10 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.8h is reacted at room temperature, is depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, produced
Rate 91%.
（2）The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 45g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2500 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 1 h is stirred vigorously at 80 DEG C, mixture then is cooled into 40 DEG C, and add
The 101.8 g 50% NaOH aqueous solution, 8 h are reacted at 40 DEG C.Precipitate is filtered to remove after the completion of reaction and will be produced with hot water
Thing is washed to neutrality, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains colourless
Bright low-viscosity phosphorous epoxy resin, yield is about 84%.
（3）It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 100 g4,4- MDAs are added（DDM）Or 4,
4- diaminodiphenylsulfones（DDS）With 50 g boron trifluoride ethylamine complex compounds, 100 g palygorskites, 100 g zinc hydroxides and
After 100 g magnesium gluconates, the min of constant temperature stirring and dissolving 50, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C
Solidify 3 h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming
Epoxy resin composite material sample.
（4）The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy：Oxygen index (OI) reaches 36, and horizontal vertical is burnt V-0 grades, smoke density 58.
Mechanical performance：Bending strength：28 MPa, impact strength： 3.80 KJ/m2。
Embodiment 3
（1）The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
40 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution；35 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter（Time for adding is about 1 h）In the tetrahydrofuran solution of parahydroxyben-zaldehyde；55 DEG C are warming up to after 0.5 h, magnetic agitation is returned
22 h of stream reaction；Filtering, and with THF cyclic washings several times；Merging filtrate is simultaneously concentrated into after original volume about 1/4, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%；
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100 ml THF/ methanol solutions are added
(THF/ methanol=4/1 v/v), 6 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.10h is reacted at room temperature, and decompression is steamed
Distillate it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with anhydrous
Ethyl alcohol recrystallization 2 times, 80 DEG C of 12 h of vacuum drying, obtains the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, yield
91%。
（2）The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 40g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2200 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 2 h are stirred vigorously at 100 DEG C, mixture then are cooled into 50 DEG C, and add
The 40.72 g 50% NaOH aqueous solution, 10 h are reacted at 50 DEG C.Precipitate is filtered to remove after the completion of reaction and will be produced with hot water
Thing is washed to neutrality, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains colourless
Bright low-viscosity phosphorous epoxy resin, yield is about 84%.
（3）It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 80 g4,4- MDAs are added（DDM）Or 4,
4- diaminodiphenylsulfones（DDS）With 40 g boron trifluoride ethylamine complex compounds, 60 g palygorskites, 60 g zinc hydroxides and 10 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 30, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
（4）The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy：Oxygen index (OI) reaches 35, and horizontal vertical is burnt V-0 grades, smoke density 65.
Mechanical performance：Bending strength：30 MPa, impact strength： 3.90 KJ/m2。
Embodiment 4
（1）The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
50 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution；60 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter（Time for adding is about 1 h）In the tetrahydrofuran solution of parahydroxyben-zaldehyde；65 DEG C are warming up to after 0.5 h, magnetic agitation is returned
24 h of stream reaction；Filtering, and with THF cyclic washings several times；Merging filtrate is simultaneously concentrated into after original volume about 1/4, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%；
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 200 ml THF/ methanol solutions are added
(THF/ methanol=3/1 v/v), 9 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.12 h are reacted at room temperature, are depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, produced
Rate 91%.
（2）The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 40g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2300 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 3 h are stirred vigorously at 120 DEG C, mixture then is cooled into 55 DEG C, and add 80
The g 50% NaOH aqueous solution, 12 h are reacted at 55 DEG C.Precipitate is filtered to remove after the completion of reaction and product is washed with hot water
To neutral, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains water white transparency low glutinous
Phosphorous epoxy resin is spent, yield is about 84%.
（3）It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 30 g4,4- MDAs are added（DDM）Or 4,
4- diaminodiphenylsulfones（DDS）With 20 g boron trifluoride ethylamine complex compounds, 50 g palygorskites, 40 g zinc hydroxides and 30 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 30, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
（4）The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy：Oxygen index (OI) reaches 34, and horizontal vertical is burnt V-0 grades, smoke density 70.
Mechanical performance：Bending strength：28.6 MPa, impact strength： 3.93 KJ/m2。
Embodiment 5
（1）The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
50 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution；30 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter（Time for adding is about 1 h）In the tetrahydrofuran solution of parahydroxyben-zaldehyde；65 DEG C are warming up to after 0.5 h, magnetic agitation is returned
24 h of stream reaction；Filtering, and with THF cyclic washings several times；Merging filtrate is simultaneously concentrated into after original volume about 1/4, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%；
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100ml THF/ methanol solutions are added
(THF/ methanol=2/1 v/v), 7g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.12 h are reacted at room temperature, are depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, produced
Rate 91%.
（2）The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 35g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2400 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 3 h are stirred vigorously at 120 DEG C, mixture then is cooled into 55 DEG C, and add 70
The g 50% NaOH aqueous solution, 12 h are reacted at 55 DEG C.Precipitate is filtered to remove after the completion of reaction and product is washed with hot water
To neutral, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains water white transparency low glutinous
Phosphorous epoxy resin is spent, yield is about 84%.
（3）It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 30 g4,4- MDAs are added（DDM）Or 4,
4- diaminodiphenylsulfones（DDS）With 45 g boron trifluoride ethylamine complex compounds, 70 g palygorskites, 45 g zinc hydroxides and 50 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 50, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
（4）The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy：Oxygen index (OI) reaches 35, and horizontal vertical is burnt V-0 grades, smoke density 72.
Mechanical performance：Bending strength：30 MPa, impact strength： 3.85 KJ/m2。
Claims (10)
1. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material, is comprised the following steps that：
（1）The synthesis of the phosphorus phosphonitrile of precursor 6 (4- hydroxyphenoxies) ring three：Using tetrahydrofuran as solvent, anhydrous K2CO3For catalyst,
Parahydroxyben-zaldehyde is with hexachlorocyclotriph,sphazene in 45 ~ 65 DEG C of h of back flow reaction 20 ~ 24；Filtering, washing, merging filtrate are simultaneously concentrated into
The 1/2 ~ 1/5 of original volume, is settled with distilled water, washed, and with re-crystallizing in ethyl acetate, vacuum drying obtains the (4- of faint yellow solid 6
Aldehyde radical phenoxy group) three phosphonitrile of ring；Again in THF- methanol mixed solvents, make sodium borohydride solids and 6 (4- aldehyde radicals phenoxy group) rings
The three phosphonitriles h of reduction reaction 8 ~ 12 at room temperature, vacuum distillation goes out after solvent with distillation water sedimentation, suction filtration, washing, absolute ethyl alcohol
Recrystallization, vacuum drying, it is the phosphorus phosphonitrile of precursor 6 (4- hydroxyphenoxies) ring three to obtain white product；
（2）The synthesis of phosphor-containing flame-proof resin：By the phosphorus phosphonitrile of precursor 6 (4- hydroxyphenoxies) ring three, cetyl trimethyl bromination
After ammonium, epoxychloropropane mixing, in being stirred vigorously 1 ~ 3 h at 80 ~ 120 DEG C；Then mixture is cooled to 40 ~ 55 DEG C, and
The NaOH aqueous solution is added, in 40 ~ 55 DEG C of h of neutralization reaction 8 ~ 12；Filtering separates out product after the completion of reaction, and with hot water by product
Washing is to neutrality, and with anhydrous sodium sulfate drying, vacuum distillation removes unreacted epoxychloropropane, obtains water white transparency low-viscosity
Phosphorous epoxy resin；
（3）It is prepared by LSOH anti-flaming epoxy resin composite material：By step（2）Gained phosphorous epoxy resin is heated to 100 ~
120 DEG C, it is separately added with agitation curing agent, curing accelerator, anti-flaming smoke-inhibiting agent, zinc hydroxide and magnesium gluconate, constant temperature
Mould is poured into after the h of stirring and dissolving 1 ~ 3, prior to the 120 DEG C h of isothermal curing 1 ~ 4, then at 160 DEG C of 0.5 ~ 3 h of solidification, produce nothing
Halogen low-smoke and flame retardant epoxy resin composite material.
2. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（1）In, the mass ratio of hexachlorocyclotriph,sphazene and parahydroxyben-zaldehyde is 1:3~1:6；Catalyst K2CO3Consumption be hydroxyl
0.5 ~ 1 times of benzaldehyde and hexachlorocyclotriph,sphazene gross mass.
3. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（1）In, in THF- methanol mixed solvents, the volume ratio of THF and methanol is 2:1~5:1.
4. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（1）In, the mass ratio of sodium borohydride solids and the phosphonitrile of 6 (4- aldehyde radicals phenoxy group) ring three is 0.5:1~1:1.
5. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（2）In, the mass ratio of cetyl trimethylammonium bromide and the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three is 1:35~1:
45；Six alkyl trimethyl ammonium bromides are 1 with epoxychloropropane mass ratio:2000~1:2500；NaOH addition is the total matter of three
The 2% ~ 5% of amount.
6. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（3）In, curing agent is 4,4- MDAs（DDM）Or 4,4- diaminodiphenylsulfones（DDS）, curing agent
Addition is 0.01 ~ 0.1 times of phosphorous epoxy resin quality.
7. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Curing accelerator is boron trifluoride ethylamine complex compound, and its addition is 0.01 ~ 0.05 times of phosphorous epoxy resin quality.
8. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（3）In, the addition of zinc hydroxide is 0.05 ~ 0.1 times of phosphorous epoxy resin quality.
9. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（3）In, anti-flaming smoke-inhibiting agent is palygorskite, and its addition is 0.01 ~ 0.1 times of phosphorous epoxy resin quality.
10. a kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material as claimed in claim 1, its feature exists
In：Step（3）In, the addition of magnesium gluconate is 0.005 ~ 0.05 times of phosphorous epoxy resin quality.
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| CN107216354A (en) * | 2017-07-04 | 2017-09-29 | 西北工业大学 | The preparation method of the six degree of functionality epoxy resin based on the phosphonitrile of ring three |
| CN107880252A (en) * | 2017-11-30 | 2018-04-06 | 西北师范大学 | A kind of preparation method of matrix immobilized dose of functionalization inorganic |
| CN112090413A (en) * | 2020-08-24 | 2020-12-18 | 四川大学 | Quasi-three-dimensional phosphazene covalent organic framework material and preparation method and application thereof |
| CN113621137A (en) * | 2021-08-02 | 2021-11-09 | 北京化工大学 | Preparation method of cyclophosphazenil polyimine vitrimer and application of cyclophosphazenil polyimine vitrimer in preparation of epoxy resin and polyurethane material |
| CN114015242A (en) * | 2021-11-18 | 2022-02-08 | 兰州石化职业技术学院 | Nano-attapulgite composite flame retardant and preparation method thereof |
| CN114032007A (en) * | 2021-12-15 | 2022-02-11 | 中国科学院兰州化学物理研究所 | Ultra-low-density environment-friendly flame-retardant abradable seal coating material and use method thereof |
| CN115286745A (en) * | 2022-08-26 | 2022-11-04 | 浙江浙创三维科技有限公司 | Flame-retardant SLA photosensitive resin for 3D printing and preparation method thereof |
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| CN107216354A (en) * | 2017-07-04 | 2017-09-29 | 西北工业大学 | The preparation method of the six degree of functionality epoxy resin based on the phosphonitrile of ring three |
| CN107880252A (en) * | 2017-11-30 | 2018-04-06 | 西北师范大学 | A kind of preparation method of matrix immobilized dose of functionalization inorganic |
| CN107880252B (en) * | 2017-11-30 | 2020-04-17 | 西北师范大学 | Preparation method of functionalized inorganic matrix curing agent |
| CN112090413A (en) * | 2020-08-24 | 2020-12-18 | 四川大学 | Quasi-three-dimensional phosphazene covalent organic framework material and preparation method and application thereof |
| CN112090413B (en) * | 2020-08-24 | 2021-09-07 | 四川大学 | Quasi-three-dimensional phosphazene covalent organic framework material and preparation method and application thereof |
| CN113621137A (en) * | 2021-08-02 | 2021-11-09 | 北京化工大学 | Preparation method of cyclophosphazenil polyimine vitrimer and application of cyclophosphazenil polyimine vitrimer in preparation of epoxy resin and polyurethane material |
| CN113621137B (en) * | 2021-08-02 | 2022-10-18 | 北京化工大学 | Preparation method of cyclophosphazenitrile polyimine vitrimer and application of same in preparation of epoxy resin and polyurethane material |
| CN114015242A (en) * | 2021-11-18 | 2022-02-08 | 兰州石化职业技术学院 | Nano-attapulgite composite flame retardant and preparation method thereof |
| CN114032007A (en) * | 2021-12-15 | 2022-02-11 | 中国科学院兰州化学物理研究所 | Ultra-low-density environment-friendly flame-retardant abradable seal coating material and use method thereof |
| CN115286745A (en) * | 2022-08-26 | 2022-11-04 | 浙江浙创三维科技有限公司 | Flame-retardant SLA photosensitive resin for 3D printing and preparation method thereof |
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