CN116040599A - Nitrogen-containing compound modified ammonium polyphosphate, and preparation method and application thereof - Google Patents
Nitrogen-containing compound modified ammonium polyphosphate, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116040599A CN116040599A CN202211574437.7A CN202211574437A CN116040599A CN 116040599 A CN116040599 A CN 116040599A CN 202211574437 A CN202211574437 A CN 202211574437A CN 116040599 A CN116040599 A CN 116040599A
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- Prior art keywords
- ammonium polyphosphate
- parts
- modified ammonium
- nitrogen
- smoke density
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- 229920001276 ammonium polyphosphate Polymers 0.000 title claims abstract description 197
- 235000019826 ammonium polyphosphate Nutrition 0.000 title claims abstract description 196
- 239000004114 Ammonium polyphosphate Substances 0.000 title claims abstract description 194
- -1 Nitrogen-containing compound modified ammonium Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract description 5
- 239000003733 fiber-reinforced composite Substances 0.000 claims abstract description 4
- 229920000098 polyolefin Polymers 0.000 claims abstract description 4
- 229920001587 Wood-plastic composite Polymers 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims abstract description 3
- 239000004753 textile Substances 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 239000011155 wood-plastic composite Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- 150000003863 ammonium salts Chemical class 0.000 claims description 90
- 239000002904 solvent Substances 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000003607 modifier Substances 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 125000003277 amino group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical class CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical class NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000002169 ethanolamines Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003940 butylamines Chemical class 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical class NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000000779 smoke Substances 0.000 description 159
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 79
- 239000001301 oxygen Substances 0.000 description 79
- 229910052760 oxygen Inorganic materials 0.000 description 79
- 239000003999 initiator Substances 0.000 description 42
- 229920006337 unsaturated polyester resin Polymers 0.000 description 41
- 239000003365 glass fiber Substances 0.000 description 39
- 239000002131 composite material Substances 0.000 description 28
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 238000009787 hand lay-up Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- KEYXFCXPVDEUKT-UHFFFAOYSA-N [O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])OP(=O)([O-])[O-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])OP(=O)([O-])[O-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] KEYXFCXPVDEUKT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/405—Polyphosphates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/09—Diamines
- C07C211/10—Diaminoethanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/14—Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nitrogen-containing compound modified ammonium polyphosphate, which has the following structural general formula:
Description
Technical Field
The invention belongs to the technical field of ammonium polyphosphate and preparation and application thereof, and particularly relates to a nitrogen-containing compound modified ammonium polyphosphate, and a preparation method and application thereof.
Background
The high molecular polymer is widely applied to various industries due to good electrical insulation property, mechanical property and machining property, but is further limited by the problems of flammability, large amount of smoke released during combustion and the like. Therefore, in recent decades, researchers have studied various flame retardants and added them to high molecular polymers to improve the flame retardant properties of materials, wherein in halogen-free flame retardant systems, intumescent flame retardants are a type of environment-friendly and efficient flame retardants with wider application.
The traditional intumescent flame retardant system mainly consists of three parts: an acid source, a gas source and a carbon source. For example, the traditional intumescent flame retardant formed by compounding ammonium polyphosphate and different char forming agents is widely used with excellent flame retardant performance. The carbon source-char forming agent in the intumescent flame retardant system can be dehydrated into carbon under the catalysis of an acid source, and the formed stable carbon layer covers the surface of the base material, so that the flame retardance of the material is realized. However, the synthesis process of the charcoal forming agent is mostly complex, and the solvent used may cause harm to the environment and human body. Ammonium polyphosphate (APP) is taken as another important component of the traditional intumescent flame retardant, and the high content of phosphorus (P) and nitrogen (N) makes the ammonium polyphosphate (APP) an ideal acid source in an intumescent flame retardant system and also plays a role of an air source. However, ammonium polyphosphate alone does not exhibit excellent flame retardant effect, and at the same time, has poor water resistance, thermal stability and substrate compatibility, and previous studies have focused on how to solve these problems, such as physical coating of ammonium polyphosphate with a char-forming agent, but these physical coatings tend to be unstable and fail to achieve the desired effect. Therefore, a new method for modifying ammonium polyphosphate is needed to be sought so as to endow high flame retardance and low smoke release of the high polymer material, and meanwhile, the thermal stability and mechanical property of the material are not seriously damaged.
Disclosure of Invention
The primary purpose of the invention is to provide a new nitrogen-containing compound modified ammonium polyphosphate which can be independently used as a flame retardant and has good smoke suppression effect.
The second object of the present invention is to provide a method for preparing the nitrogen-containing compound modified ammonium polyphosphate.
The invention also provides an application of the nitrogen-containing compound modified ammonium polyphosphate to flame retardance of high-molecular polymers.
The invention provides nitrogen-containing compound modified ammonium polyphosphate, which is characterized by having the following structural general formula:
wherein R is 1 And R is 1 ' as
Any one of R in the same structural general formula 1 And R is 1 ' not identical wherein X and Y are C or N atoms, Q 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); r is R 2 、R 2 ' as
Any one of R in the same structural general formula 2 And R is 2 'different' wherein A and B are C or N atoms, W 1 、W 2 、W 3 、W 4 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); r is R 3 、R 3 ' is aliphatic amine salt, aliphatic diamine salt, ethanolamine salt or has the structural formula +.>
Any one of R in the same structural general formula 3 And R is 3 ' different, n is greater than or equal to 1.
Q as described in the structural general formula of the nitrogen-containing compound modified ammonium polyphosphate 1 、Q 2 、Q 3 、Q 4 、Q 5 Preferably C 1 ～C 3 Straight-chain or branched alkyl groups, amino groups, hydrogen atoms or-R-NH 3 + R is preferably C 1 ～C 2 Straight chain alkyl of (a).
Above mentionedW in the structural general formula of nitrogen-containing compound modified ammonium polyphosphate 1 、W 2 、W 3 、W 4 Preferably C 1 A linear alkyl group, an amino group, a hydroxyl group or a hydrogen atom.
The aliphatic amine salt in the structural general formula of the nitrogen-containing compound modified ammonium polyphosphate is preferably ethylamine salt, butylamine salt, hexylamine salt or octylamine salt; the aliphatic diamine salt is preferably ethylenediamine, 1, 2-propyldiamine, 1, 3-propyldiamine or 1, 4-butyldiamine; the alcohol amine salt is preferably ethanolamine salt or diethanolamine salt;
preferably diethylenetriamine salt, triethylenetetramine salt or tetraethylenepentamine salt.
The preparation method of the nitrogen-containing compound modified ammonium polyphosphate is characterized in that the preparation method comprises the steps of firstly mixing any one of solvents with water according to a mass ratio of 100:1-20, then adding any one of ammonium polyphosphate and a modifier into a reaction vessel according to a molar ratio of 1:0.1-1, stirring and heating to 70-90 ℃, and reacting for 2-8 h to obtain the nitrogen-containing compound modified ammonium polyphosphate with a structural general formula of I, II, III, IV, V or VI, wherein the modifier is 
Aliphatic amine salts, aliphatic diamine salts, and alkanolamine salts, wherein X and Y are C or N atoms, Q 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); a and B are C or N atoms, W 1 、W 2 、W 3 、W 4 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); n is more than or equal to 1; the solvent used is a solvent which is miscible with both water and the modifier. Or (b)
Firstly, mixing any one of solvents with water according to the mass ratio of 100:1-20, then adding any one of ammonium polyphosphate and a first modifier into a reaction vessel according to the mass ratio of 1:0.1-1, stirring and heating to 70-90 ℃, reacting for 2-8 h, adding a mixture of any one of a second modifier and the solvent, stirring and heating to 70-90 ℃, reacting for 1-6 h, and obtaining the nitrogen-containing compound modified ammonium polyphosphate with the structural general formula VII, VIII or IX, wherein the molar ratio of the second modifier to the ammonium polyphosphate in the mixture is 0.1-0.6:1, and the mass ratio of the second modifier to the solvent is 1:1-15, and the first modifier and the second modifier are as follows 
Aliphatic amine salts, aliphatic diamine salts, alcohol amine salts, but not the same, wherein X and Y are C or N atoms, Q 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); a and B are C or N atoms, W 1 、W 2 、W 3 、W 4 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); n is more than or equal to 1; the solvent used is a solvent which is miscible with both water and the modifier.
The mass ratio of the solvent to water used in the above method is preferably 100:2-15.
The molar ratio of ammonium polyphosphate to modifier used in the above process is preferably 1:0.1 to 0.8.
The mass ratio of the second modifier to the solvent used in the above method is preferably 1:3-10; the molar ratio of the ammonium polyphosphate to the first modifier is preferably 1:0.1-0.8; the molar ratio of ammonium polyphosphate to the second modifier is preferably 1:0.1 to 0.5.
The ammonium polyphosphate used in the above method is any of form I ammonium polyphosphate, form II ammonium polyphosphate, ammonium tripolyphosphate or ammonium tetraphosphate, preferably form I ammonium polyphosphate, form II ammonium polyphosphate.
The solvent used in the above method is any one of water, methanol, ethanol, isopropanol, acetonitrile, acetic acid, acetone, dichloromethane, dioxane, tetrahydrofuran, N-dimethylformamide or dimethyl sulfoxide, preferably methanol, ethanol, acetone.
The application of the nitrogen-containing compound modified ammonium polyphosphate provided by the invention is characterized in that the nitrogen-containing compound modified ammonium polyphosphate can be used singly or in a mixed mode, and is used for flame retardance of unsaturated polyester, vinyl resin, epoxy resin or polyolefin or flame retardance of fiber reinforced composite materials, coatings, fiber textiles, wood and wood-plastic composite materials.
The mixed use described in the above application is a mixed use of at least two of the nitrogen-containing compound-modified ammonium polyphosphates, or a mixed use with at least one of pentaerythritol, dipentaerythritol, tetrol, mannitol, xylitol, sorbitol, arabitol, starch, cellulose, lignin, and sucrose char-forming agent.
When the flame retardant is applied to flame retardance of unsaturated polyester, epoxy resin or polyolefin, the additive amount of the flame retardant is 5-25 wt% in terms of mass percent.
1) When the preferable addition amount is 8 to 20wt%, the limiting oxygen index value of the obtained flame-retardant unsaturated polyester is 30.4 to 38.4 percent, the UL-94 is V-1 to V-0 grade, and the peak heat release rate p-HRR in the cone calorimeter test is 876 to 403kW/m 2 Maximum smoke density value D s (max) is 1123-537;
2) When the preferable addition amount is 8 to 20wt%, the limiting oxygen index value of the obtained flame-retardant epoxy resin is 35.0 to 43.7%, and UL-94 is V-Grade 0, p-HRR is 843-382 kW/m 2 ，D s (max) is 1068-513;
3) When the preferable addition amount is 10 to 22wt%, the limiting oxygen index value of the obtained flame retardant polyethylene is 28.0 to 33.8%, the UL-94 is V-1 to V-0 grade, and the p-HRR is 417 to 133kW/m 2 ，D s (max) is 502 to 294.
When the flame-retardant glass fiber reinforced unsaturated polyester composite material is applied to flame retardance of the fiber reinforced composite material, the addition amount is 5-25 wt% in percentage by mass, when the flame-retardant glass fiber reinforced unsaturated polyester composite material is applied to the fiber reinforced unsaturated polyester composite material, the addition amount is preferably 8-20 wt%, preferably the fiber is glass fiber cloth, the LOI of the obtained flame-retardant glass fiber reinforced unsaturated polyester composite material is 35.7-51.6%, the UL-94 is V-0 grade, and the p-HRR is 274-124 kW/m 2 ，D s (max) of 479-302, and the impact strength of 92.3-105.4 kJ/m 2 。
Compared with the prior art, the invention has the following advantages:
1. the modified ammonium polyphosphate provided by the invention is prepared by a chemical modification method, so that the original acid source and gas source functions of the modified ammonium polyphosphate serving as a traditional intumescent flame retardant are maintained, and the carbon source function of the modified ammonium polyphosphate is also endowed, and the modified ammonium polyphosphate can be independently used as a flame retardant to be applied to a high polymer material, so that the range of the modifier used by the modified ammonium polyphosphate is widened, and new choices are provided for the application field of the modified ammonium polyphosphate.
2. The modified ammonium polyphosphate provided by the invention is prepared by a chemical modification method, can be independently used as a flame retardant to be applied to flame-retardant high polymer materials, has small addition amount and good flame-retardant effect, and can reduce cost and reduce negative influence on the original mechanical properties of the high polymer materials.
3. The modified ammonium polyphosphate provided by the invention can play the flame retardant effect of the compound intumescent flame retardant when being singly used, so that the modified ammonium polyphosphate can be widely applied to various general plastics and engineering plastics, and when the addition amount is 5-25 wt%, the flame retardant property of the polymer material can be obviously improved, the release of smoke can be effectively inhibited, and meanwhile, the mechanical property of the material cannot be seriously damaged.
4. The preparation method provided by the invention is mature, is simple and convenient to operate, and is easy for industrial production.
Drawings
FIG. 1 shows an infrared spectrum (a) and an X-ray photoelectron spectrum N of the ammonium polyphosphate as a raw material used in the present invention 1s Spectrum (b).
FIG. 2 is an infrared spectrum (a) and an X-ray photoelectron spectrum N of an imidazole-modified ammonium polyphosphate prepared in example 6 of the present invention 1s Spectrum (b).
FIG. 3 is an infrared spectrum (a) and an X-ray photoelectron spectrum N of benzimidazole-modified ammonium polyphosphate prepared according to example 16 of the present invention 1s Spectrum (b).
As can be seen from the infrared spectra of figures 1, 2 and 3, the modified ammonium polyphosphate is 2800 cm to 3000cm -1 Characteristic absorption peaks of imidazole and benzimidazole=ch-appear on the left and right, whereas the infrared spectrum of the starting ammonium polyphosphate in fig. 1 does not have the characteristic peaks in this range, indicating that imidazole and benzimidazole have been successfully incorporated into the modified ammonium polyphosphate. X-ray photoelectron spectroscopy N through FIGS. 1, 2, and 3 1s The spectra can be seen that the binding energy of the raw material ammonium polyphosphate at 401.3eV and 399.1eV respectively corresponds to NH 4 + and-P-NH-P-, and imidazole and benzimidazole modified ammonium polyphosphates except NH 4 + (reduced, even disappeared) and-P-NH-P- (reduced) peaks also appear at 400.9eV and 400.6eV as-c=nh + The peak of C-demonstrates successful synthesis of imidazole and benzimidazole modified ammonium polyphosphate.
FIG. 4 is a graph showing heat release profiles of the pure unsaturated polyester UP prepared in comparative example 1 and the flame retardant unsaturated polyester prepared in application example 22 of the present invention. From the figure, the peak heat release rate p-HRR of the material is reduced by 67% due to the introduction of the modified ammonium polyphosphate, and the material shows extremely excellent heat inhibition performance.
FIG. 5 is a graph showing heat release profiles of the pure epoxy resin EP prepared in comparative example 2 and the flame retardant epoxy resin prepared in application example 44 of the present invention. From the figure, the peak heat release rate p-HRR of the material is reduced by 70% due to the introduction of the modified ammonium polyphosphate, and the material shows extremely excellent heat inhibition performance.
FIG. 6 is a graph (a) showing heat release and a graph (b) showing smoke density of the pure glass fiber-reinforced unsaturated polyester UP prepared in comparative example 3 according to the present invention and the flame retardant glass fiber-reinforced unsaturated polyester prepared in application example 58 according to the present invention. As can be seen from the graph, the peak heat release rate p-HRR of the material is reduced by 63% due to the introduction of the modified ammonium polyphosphate, and the maximum smoke density value D s (max) was reduced by 64%, and extremely excellent heat and smoke suppressing performance was exhibited.
FIG. 7 is a graph showing the impact strength of the pure glass fiber reinforced unsaturated polyester UP prepared in comparative example 3 of the present invention and the flame retardant glass fiber reinforced unsaturated polyester prepared in application examples 52, 54, 56, 58, 60 of the present invention. From the figure, it can be seen that the introduction of modified ammonium polyphosphate does not have serious negative effect on the impact strength of the composite material, and the material still maintains excellent mechanical properties.
Detailed Description
Examples are given below to further illustrate the invention. It is to be noted that the following examples are not to be construed as limiting the scope of the invention, and that if a person skilled in the art makes some insubstantial modifications and adaptations of the invention based on the above description, they still fall within the scope of the invention.
In addition, it is worth explaining that: 1) The limiting oxygen indices of the following application examples and comparative examples are each 120X 6.5X13.2 mm according to ASTM D2863-97 3 Is measured on an HC-2C type oxygen index meter; the vertical burning test was carried out according to UL-94 standard, and it was made 125X 12.7X 3.2mm 3 Is measured by a CZF-2 type vertical combustor; the cone calorimetric test is carried out according to ISO 5660-1, and 100X 3.2mm 3 Is irradiated on an FTT cone calorimeter at a power of 50kW/m 2 Or 35kW/m 2 Performing measurement; the smoke density test is carried out according to EN ISO 5659-2 standard, and the smoke density test is carried out by preparing 75X 3.2mm 3 On FTT smoke density box with irradiation power of 25kW/m 2 The measurement was performed. 2) The following fibrous composite application examples and comparative examples have impact strengthThe samples were prepared according to the GB/T1843-2008 standard and tested on a ZBC1400-2 type pendulum impact tester manufactured by Shenzhen Sansi Co., ltd. According to the ISO 2818:1994 method.
Example 1
700g of acetone and 14g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 6.8g of imidazole are added, the mixture is stirred and heated to 80 ℃ for 2 hours, and the product is obtained with the yield of 75 percent.
Example 2
700g of methanol and 14g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 6.8g of imidazole are added, the mixture is stirred and heated to 80 ℃ for 2 hours, and the product is obtained with the yield of 79 percent.
Example 3
700g of ethanol and 14g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 6.8g of imidazole are added, the temperature is raised to 80 ℃ by stirring, and the reaction is carried out for 2 hours, thus obtaining the product with the yield of 82 percent.
Example 4
800g of ethanol and 8g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, the mixture is stirred and heated to 90 ℃ for 4 hours, and the product is obtained with the yield of 80 percent.
Example 5
500g of ethanol and 50g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, the mixture is stirred and heated to 90 ℃ for 4 hours, and the product is obtained with the yield of 88 percent.
Example 6
800g of ethanol and 120g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, stirring and heating are carried out to 90 ℃, and reaction is carried out for 4 hours, thus obtaining the product with the yield of 94%.
Example 7
700g of ethanol and 140g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, the mixture is stirred and heated to 90 ℃ for 4 hours, and the product is obtained with the yield of 85 percent.
Example 8
600g of ethanol and 30g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 20.4g of imidazole are added, the mixture is stirred and heated to 70 ℃ for reaction for 6 hours, and the product is obtained with the yield of 87 percent.
Example 9
900g of ethanol and 45g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 54.4g of imidazole are added, the mixture is stirred and heated to 70 ℃ for reaction for 6 hours, and the product is obtained with the yield of 92 percent.
Example 10
600g of ethanol and 30g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, the mixture is stirred and heated to 70 ℃ for 6 hours, and the product is obtained with the yield of 90 percent.
Example 11
700g of ethanol and 35g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, stirring and heating are carried out to 83 ℃, and reaction is carried out for 8 hours, thus obtaining the product with the yield of 84%.
Example 12
800g of ethanol and 144g of water are mixed as a solvent, then 100g of I-type ammonium polyphosphate and 68.0g of imidazole are added, stirring and heating are carried out to 83 ℃, and reaction is carried out for 8 hours, thus obtaining the product with the yield of 81%.
Example 13
800g of acetone and 64g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 11.8g of benzimidazole are added, the mixture is stirred and heated to 80 ℃ for 5 hours, and the product is obtained with the yield of 70%.
Example 14
900g of methanol and 72g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 11.8g of benzimidazole are added, the mixture is stirred and heated to 80 ℃ for 5 hours, and the product is obtained, and the yield is 73%.
Example 15
700g of ethanol and 56g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 11.8g of benzimidazole are added, the temperature is raised to 80 ℃ by stirring, and the reaction is carried out for 5 hours, thus obtaining the product with the yield of 77%.
Example 16
800g of ethanol and 96g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 59.0g of benzimidazole are added, the mixture is stirred and heated to 75 ℃ for 7 hours, and the product is obtained with the yield of 85 percent.
Example 17
500g of ethanol and 60g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 94.4g of benzimidazole are added, the mixture is stirred and heated to 75 ℃ for 7 hours, and the product is obtained with the yield of 82 percent.
Example 18
700g of ethanol and 84g of water are mixed as a solvent, then 100g of I-type ammonium polyphosphate and 118.0g of benzimidazole are added, the temperature is raised to 75 ℃ by stirring, and the reaction is carried out for 7 hours, so that the product is obtained, and the yield is 76%.
Example 19
800g of ethanol and 120g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 103.2g of octylamine are added, stirring and heating are carried out to 86 ℃, and reaction is carried out for 3 hours, thus obtaining the product with the yield of 88%.
Example 20
800g of ethanol and 120g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 48.0g of ethylenediamine are added, stirring and heating are carried out to 86 ℃, and reaction is carried out for 3 hours, thus obtaining the product with the yield of 97%.
Example 21
800g of ethanol and 120g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 48.8g of ethanolamine are added, stirring and heating are carried out to 86 ℃, and reaction is carried out for 3 hours, thus obtaining the product with the yield of 92%.
Example 22
Mixing 800g of ethanol and 120g of water as a solvent, adding 100g of II-type ammonium polyphosphate and 116.8g of triethylene tetramine, stirring and heating to 86 ℃, and reacting for 3 hours to obtain the product with the yield of 85%.
Example 23
Mixing 800g of acetone and 16g of water as a solvent, adding 100g of II-type ammonium polyphosphate and 20.4g of imidazole, stirring and heating to 90 ℃, reacting for 2 hours, adding a mixed solution of 13.8g of 1,2, 4-triazole and 55.2g of acetone, stirring and heating to 80 ℃, and reacting for 6 hours to obtain the product with the yield of 73%.
Example 24
Mixing 500g of methanol and 10g of water as a solvent, adding 100g of II-type ammonium polyphosphate and 20.4g of imidazole, stirring and heating to 70 ℃, reacting for 8 hours, adding a mixed solution of 13.8g of 1,2, 4-triazole and 110.4g of methanol, stirring and heating to 90 ℃, and reacting for 1 hour to obtain the product with the yield of 78%.
Example 25
600g of ethanol and 6g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 20.4g of imidazole are added, stirring and heating are carried out to 80 ℃, reaction is carried out for 5 hours, then 13.8g of mixed solution of 1,2, 4-triazole and 165.6g of ethanol is added, stirring and heating are carried out to 76 ℃, reaction is carried out for 4 hours, and the product with the yield of 80% is obtained.
Example 26
600g of ethanol and 90g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 34.0g of imidazole are added, stirring and heating are carried out to 80 ℃, reaction is carried out for 5 hours, then 27.6g of mixed solution of 1,2, 4-triazole and 193.2g of ethanol is added, stirring and heating are carried out to 76 ℃, reaction is carried out for 4 hours, and the product with the yield of 90% is obtained.
Example 27
Mixing 500g of ethanol and 75g of water as a solvent, adding 100g of I-ammonium polyphosphate and 34.0g of imidazole, stirring and heating to 80 ℃, reacting for 5 hours, adding a mixed solution of 27.6g of 1,2, 4-triazole and 193.2g of ethanol, stirring and heating to 70 ℃, and reacting for 4 hours to obtain the product with the yield of 79%.
Example 28
600g of acetone and 24g of water are mixed to be used as a solvent, then 100g of II-type ammonium polyphosphate and 6.8g of imidazole are added, stirring and heating are carried out to 90 ℃, reaction is carried out for 2 hours, then 11.8g of benzimidazole and 35.4g of acetone are added, stirring and heating are carried out to 84 ℃, reaction is carried out for 6 hours, and the product is obtained, and the yield is 70%.
Example 29
900g of methanol and 36g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 6.8g of imidazole are added, stirring and heating are carried out to 70 ℃, reaction is carried out for 8 hours, then 11.8g of benzimidazole and 70.8g of methanol are added, stirring and heating are carried out to 90 ℃, reaction is carried out for 1 hour, and the product with the yield of 76% is obtained.
Example 30
700g of ethanol and 42g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 6.8g of imidazole are added, stirring and heating are carried out to 88 ℃, reaction is carried out for 6 hours, then 11.8g of benzimidazole and 106.2g of ethanol are added, stirring and heating are carried out to 70 ℃, reaction is carried out for 3 hours, and the product with the yield of 78% is obtained.
Example 31
600g of ethanol and 78g of water are mixed as a solvent, then 100g of II-type ammonium polyphosphate and 27.2g of imidazole are added, stirring and heating are carried out to 85 ℃, reaction is carried out for 6 hours, then 59.0g of benzimidazole and 118.0 g of ethanol are added, stirring and heating are carried out to 70 ℃, reaction is carried out for 3 hours, and the product with the yield of 88% is obtained.
Example 32
Mixing 800g of ethanol and 104g of ethanol as a solvent, adding 100g of I-type ammonium polyphosphate and 27.2g of imidazole, stirring and heating to 85 ℃, reacting for 4 hours, adding 59.0g of benzimidazole and 118.0 g of ethanol mixed solution, stirring and heating to 70 ℃, and reacting for 5 hours to obtain the product with the yield of 74%.
Example 33
600g of acetone and 48g of water are mixed to be used as a solvent, then 100g of II-type ammonium polyphosphate and 53.6g of pyrrole are added, stirring and heating are carried out to 90 ℃, reaction is carried out for 2 hours, then 35.1g of indole and 351.0g of acetone are added, stirring and heating are carried out to 84 ℃, reaction is carried out for 6 hours, and the product is obtained, and the yield is 77%.
Example 34
400g of methanol and 32g of water are mixed to be used as a solvent, then 100g of II-type ammonium polyphosphate and 53.6g of pyrrole are added, the temperature is raised to 70 ℃ by stirring, the reaction is carried out for 6 hours, then 35.1g of indole and 526.5g of methanol are added, the temperature is raised to 90 ℃ by stirring, the reaction is carried out for 2 hours, and the product with the yield of 81% is obtained.
Example 35
Mixing 900g of ethanol and 90g of water as a solvent, adding 100g of II-type ammonium polyphosphate and 53.6g of pyrrole, stirring and heating to 88 ℃, reacting for 5 hours, adding a mixed solution of 35.1g of indole and 35.1g of ethanol, stirring and heating to 70 ℃, and reacting for 5 hours to obtain the product with the yield of 84 percent.
Example 36
Mixing 500g of ethanol and 50g of water as a solvent, adding 100g of II-type ammonium polyphosphate and 67g of pyrrole, stirring and heating to 80 ℃, reacting for 5 hours, adding a mixed solution of 70.2g of indole and 351.0g of ethanol, stirring and heating to 73 ℃, and reacting for 3 hours to obtain the product with the yield of 91%.
Example 37
Mixing 800g of ethanol and 136g of ethanol as a solvent, adding 100g of I-type ammonium polyphosphate and 67g of pyrrole, stirring and heating to 80 ℃, reacting for 5 hours, adding a mixed solution of 70.2g of indole and 210.6g of ethanol, stirring and heating to 73 ℃, and reacting for 2 hours to obtain the product with the yield of 80%.
Example 38
Mixing 800g of ethanol and 160g of ethanol as a solvent, adding 100g of II-type ammonium polyphosphate and 27.2g of imidazole, stirring and heating to 80 ℃, reacting for 8 hours, adding a mixed solution of 30.0g of ethylenediamine and 240.0g of ethanol, stirring and heating to 75 ℃, and reacting for 3 hours to obtain the product with the yield of 90%.
Example 39
Mixing 800g of ethanol and 160g of ethanol as a solvent, adding 100g of II-type ammonium polyphosphate and 47.2g of benzimidazole, stirring and heating to 80 ℃, reacting for 8 hours, adding a mixed solution of 64.5g of octylamine and 516.0g of ethanol, stirring and heating to 75 ℃, and reacting for 3 hours to obtain the product with the yield of 85%.
Example 40
Mixing 800g of ethanol and 160g of ethanol as a solvent, adding 100g of II-type ammonium polyphosphate and 24.0g of ethylenediamine, stirring and heating to 80 ℃, reacting for 8 hours, adding a mixed solution of 64.5g of octylamine and 516.0g of ethanol, stirring and heating to 75 ℃, and reacting for 3 hours to obtain the product with the yield of 93%.
Application example 1
10 parts of the modified ammonium polyphosphate of example 6 of the present invention, 90 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and then cured at 160℃for 7 hours. The oxygen index of the obtained cured product was 31.7%, the vertical combustion rating V-1, conePeak heat release rate p-HRR in calorimetric test was 832kW/m 2 Maximum smoke density value D in smoke density test s (max) was 959.
Application example 2
14 parts of the modified ammonium polyphosphate according to example 6 of the present invention, 86 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 33.5%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 714kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 804.
Application example 3
18 parts of the modified ammonium polyphosphate according to example 6 of the present invention, 82 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 35.2%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 582kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 753.
Application example 4
After 22 parts of the modified ammonium polyphosphate of example 6 of the present invention, 78 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The oxygen index of the obtained cured product was 37.0%, the vertical burning grade V-0, and the peak heat release rate p-HRR in the cone calorimeter test was 479kW/m 2 Maximum smoke density value D in smoke density test s (max) is 615.
Application example 5
10 parts of the modified ammonium polyphosphate in example 12 of the present invention, 90 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 30.4%, a vertical burn rating of V-1, and a peak heat release rate p-HRR of 876kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 1123.
Application example 6
23 parts of the modified ammonium polyphosphate in example 12 of the present invention, 77 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. Oxygen finger of the obtained cured productThe number is 36.1%, the vertical combustion grade V-0, and the peak heat release rate p-HRR in the cone calorimetric test is 614kW/m 2 Maximum smoke density value D in smoke density test s (max) was 694.
Application example 7
9 parts of the modified ammonium polyphosphate in example 16 according to the invention, 91 parts of unsaturated polyester resin and 2 parts of initiator are mixed uniformly and cured for 7 hours at 160 ℃. The resulting cured product had an oxygen index of 31.1%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 805kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 911.
Application example 8
13 parts of the modified ammonium polyphosphate according to example 16 of the present invention, 87 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 33.7%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 680kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 785.
Application example 9
17 parts of the modified ammonium polyphosphate according to example 16 of the present invention, 83 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 34.5%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 573kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 734.
Application example 10
21 parts of the modified ammonium polyphosphate of example 16 of the present invention, 79 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 37.3%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 448kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 601.
Application example 11
After 9 parts of the modified ammonium polyphosphate in example 18 of the present invention, 91 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, Curing at 160℃for 7h. The resulting cured product had an oxygen index of 30.7%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 836kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 1016.
Application example 12
21 parts of the modified ammonium polyphosphate of example 18 of the present invention, 79 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 36.6%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 554kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 658.
Application example 13
After 7 parts of the modified ammonium polyphosphate in example 21 of the present invention, 93 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 31.4%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 792kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 903.
Application example 14
11 parts of the modified ammonium polyphosphate in example 21 of the present invention, 89 parts of the unsaturated polyester resin and 2 parts of the initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 34.0%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 643kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 741.
Application example 15
15 parts of the modified ammonium polyphosphate in example 21 of the present invention, 85 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 35.2%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 566kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 720.
Application example 16
19 parts of the modified ammonium polyphosphate according to example 21 of the present invention, 81 parts of the modified ammonium polyphosphate were notThe saturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The oxygen index of the resultant cured product was 37.6%, the vertical burning grade V-0, and the peak heat release rate p-HRR in the cone calorimeter test was 436kW/m 2 Maximum smoke density value D in smoke density test s (max) was 588.
Application example 17
After 7 parts of the modified ammonium polyphosphate in example 23 of the present invention, 93 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 30.9%, a vertical burn rating of V-1, and a peak heat release rate p-HRR of 816kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 973.
Application example 18
19 parts of the modified ammonium polyphosphate of example 23 of the present invention, 81 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The oxygen index of the obtained cured product was 37.1%, the vertical burning grade V-0, and the peak heat release rate p-HRR in the cone calorimeter test was 509kW/m 2 Maximum smoke density value D in smoke density test s (max) 627.
Application example 19
After 8 parts of the modified ammonium polyphosphate in example 26 of the present invention, 92 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 33.2%, a vertical burn rating of V-1, and a peak heat release rate p-HRR of 757kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 845.
Application example 20
After 12 parts of the modified ammonium polyphosphate in example 26 of the present invention, 88 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, they were cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 34.9%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 600kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 704.
Application example 21
16 parts of the invention The modified ammonium polyphosphate in example 26, 84 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and then cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 36.4%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 511kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 682.
Application example 22
After 20 parts of the modified ammonium polyphosphate in example 26 of the present invention, 80 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 38.4%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 403kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 537.
Application example 23
10 parts of the modified ammonium polyphosphate in example 28 of the present invention, 90 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 32.6%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 780kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 874.
Application example 24
25 parts of the modified ammonium polyphosphate of example 28 of the present invention, 75 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 37.7%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 452kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 561.
Application example 25
After 5 parts of the modified ammonium polyphosphate in example 30 of the present invention, 95 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 32.2%, a vertical burn rating of V-1, and a peak heat release rate p-HRR of 774kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 869.
Application example 26
After 12 parts of the modified ammonium polyphosphate in example 30 of the present invention, 88 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, they were cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 34.6%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 617kW/m in a cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 725.
Application example 27
16 parts of the modified ammonium polyphosphate according to example 33 of the present invention, 84 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 35.9%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 538kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 702.
Application example 28
After 20 parts of the modified ammonium polyphosphate in example 30 of the present invention, 80 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 37.8%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 420kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 565.
Application example 29
After 5 parts of the modified ammonium polyphosphate in example 33 of the present invention, 95 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed, it was cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 31.3%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 801kW/m in a cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 910.
Application example 30
25 parts of the modified ammonium polyphosphate of example 33 of the present invention, 75 parts of unsaturated polyester resin and 2 parts of initiator were uniformly mixed and cured at 160℃for 7 hours. The resulting cured product had an oxygen index of 37.3%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 488kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 596。
Application example 31
15 parts of the modified ammonium polyphosphate according to example 6 of the present invention, 75 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 35.4%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 812kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 931.
Application example 32
22 parts of the modified ammonium polyphosphate according to example 6 of the present invention, 68 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 38.0%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 452kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 596.
Application example 33
10 parts of the modified ammonium polyphosphate in example 12 of the present invention, 80 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 35.0%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 843kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 1068.
Application example 34
22 parts of the modified ammonium polyphosphate according to example 12 of the present invention, 68 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 37.4%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 614kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 660.
Application example 35
9 parts of the modified ammonium polyphosphate according to example 16 of the present invention, 81 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 36.6%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 793kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 917.
Application example 36
21 parts of the modified ammonium polyphosphate according to example 16 of the present invention, 69 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 38.7%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 435kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 574.
Application example 37
10 parts of the modified ammonium polyphosphate in example 18 of the present invention, 80 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 35.8%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 820kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 984.
Application example 38
After 20 parts of the modified ammonium polyphosphate in example 18 of the present invention, 70 parts of epoxy resin and 10 parts of curing agent were uniformly mixed, they were cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 37.8%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 588kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 629.
Application example 39
7 parts of the modified ammonium polyphosphate in example 21 of the present invention, 83 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 37.4%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 768kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 900.
Application example 40
17 parts of the modified ammonium polyphosphate according to example 21 of the present invention, 73 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 39.7%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 417kW/m in the cone calorimeter test 2 Maximum smoke in smoke density testDensity value D s (max) was 551.
Application example 41
7 parts of the modified ammonium polyphosphate of example 23 of the present invention, 83 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The oxygen index of the obtained cured product was 37.0%, the vertical burning grade V-0, and the peak heat release rate p-HRR in the cone calorimeter test was 794kW/m 2 Maximum smoke density value D in smoke density test s (max) was 966.
Application example 42
19 parts of the modified ammonium polyphosphate of example 23 of the present invention, 71 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 38.5%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 560kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 607.
Application example 43
After 8 parts of the modified ammonium polyphosphate in example 26 of the present invention, 82 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed, they were cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 40.6%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 720kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 861.
Application example 44
After 20 parts of the modified ammonium polyphosphate of example 26 of the present invention, 70 parts of epoxy resin and 10 parts of curing agent were uniformly mixed, they were cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 43.7%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 382kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 513.
Application example 45
13 parts of the modified ammonium polyphosphate according to example 28 of the present invention, 77 parts of epoxy resin and 10 parts of curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 39.3%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 746kW/m in the cone calorimeter test 2 Smoke density measurementMaximum smoke density value D in test s (max) was 894.
Application example 46
25 parts of the modified ammonium polyphosphate of example 28 of the present invention, 65 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 42.1%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 433kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 520.
Application example 47
After 5 parts of the modified ammonium polyphosphate in example 30 of the present invention, 85 parts of epoxy resin and 10 parts of curing agent were uniformly mixed, they were cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 39.3%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 741kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 886.
Application example 48
22 parts of the modified ammonium polyphosphate according to example 30 of the present invention, 68 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 41.3%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 400kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 537.
Application example 49
After 8 parts of the modified ammonium polyphosphate of example 33 of the present invention, 82 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed, they were cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 38.1%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 775kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 938.
Application example 50
17 parts of the modified ammonium polyphosphate according to example 33 of the present invention, 73 parts of epoxy resin and 10 parts of a curing agent were uniformly mixed and cured at 180℃for 10 hours. The resulting cured product had an oxygen index of 39.9%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 527kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 584.
Application example 51
After 5 parts of modified ammonium polyphosphate in the embodiment 6 of the invention and 95 parts of polyethylene are uniformly mixed, the mixture is put into a double-screw extruder, and the heating temperatures of all sections from a feed inlet to a discharge outlet are as follows: and (3) melt blending extrusion at 145 ℃, 150 ℃, 160 ℃, 155 ℃, 150 ℃ and 145 ℃. The oxygen index of the resultant cured product was 26.3%, the vertical burning grade V-2, and the peak heat release rate p-HRR in the cone calorimeter test was 541kW/m 2 Maximum smoke density value D in smoke density test s (max) is 602.
Application example 52
After 7 parts of the modified ammonium polyphosphate in example 12 of the present invention and 93 parts of polyethylene were uniformly mixed, the mixture was put into a twin-screw extruder and melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 26.7%, a vertical burning grade V-2, and a peak heat release rate p-HRR of 503kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 573.
Application example 53
After 8 parts of the modified ammonium polyphosphate in example 16 of the present invention and 92 parts of polyethylene were uniformly mixed, the mixture was put into a twin-screw extruder and melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 27.1%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 482kW/m in a cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 552.
Application example 54
10 parts of the modified ammonium polyphosphate in example 18 of the present invention and 90 parts of polyethylene were uniformly mixed and then put into a twin-screw extruder to be melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 28.0%, a vertical burning grade V-1, and a peak heat release rate p-HRR of 417kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 502.
Application example 55
15 parts of the modification according to example 21 of the present inventionAfter being uniformly mixed with 85 parts of polyethylene, the mixture is put into a double-screw extruder for melt blending extrusion (the temperature of each section is the same as that of application example 51). The resulting cured product had an oxygen index of 30.5%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 312kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 411.
Application example 56
After 20 parts of the modified ammonium polyphosphate in example 23 of the present invention and 80 parts of polyethylene were uniformly mixed, the mixture was put into a twin-screw extruder and melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 32.9%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 204kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 337.
Application example 57
After 19 parts of the modified ammonium polyphosphate in example 26 of the present invention and 81 parts of polyethylene were uniformly mixed, the mixture was put into a twin-screw extruder and melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 33.8%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 133kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 294.
Application example 58
25 parts of the modified ammonium polyphosphate in example 28 of the present invention and 75 parts of polyethylene were uniformly mixed and then put into a twin-screw extruder to be melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 33.4%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 156kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is 310.
Application example 59
22 parts of the modified ammonium polyphosphate in example 30 of the present invention and 78 parts of polyethylene were uniformly mixed and then put into a twin-screw extruder to be melt-blended and extruded (the temperatures of the respective sections were the same as in application example 51). The oxygen index of the resultant cured product was 32.6%, the vertical burning grade V-0, and the peak heat release rate p-HRR in the cone calorimeter test was 182kW/m 2 Smoke densityMaximum smoke density value D in test s (max) is 324.
Application example 60
17 parts of the modified ammonium polyphosphate in example 33 of the present invention and 83 parts of polyethylene were uniformly mixed and then put into a twin-screw extruder to be melt-blended and extruded (the temperature of each stage was the same as in application example 51). The resulting cured product had an oxygen index of 31.3%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 235kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 369.
Application example 61
After 8 parts of modified ammonium polyphosphate, 92 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 6 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 35.7%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 274kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 479, and the impact strength was 105.4kJ/m 2 。
Application example 62
15 parts of modified ammonium polyphosphate, 85 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 6 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 40.1%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 251kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 420, and the impact strength was 99.6kJ/m 2 。
Application example 63
After 7 parts of modified ammonium polyphosphate, 93 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 16 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 37.4%, a vertical burning rating of V-0, and a cone calorimetric test The medium peak heat release rate p-HRR was 264kW/m 2 Maximum smoke density value D in smoke density test s (max) 448, impact strength of 101.5kJ/m 2 。
Application example 64
After 25 parts of modified ammonium polyphosphate, 75 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 16 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 42.7%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 233kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 407, and the impact strength was 92.3kJ/m 2 。
Application example 65
After 5 parts of modified ammonium polyphosphate, 95 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 21 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 39.5%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 247kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 420, and the impact strength was 104.6kJ/m 2 。
Application example 66
After 22 parts of modified ammonium polyphosphate, 78 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 21 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 44.3%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 213kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 378, and the impact strength was 98.6kJ/m 2 。
Application example 67
13 parts of the modified ammonium polyphosphate of example 26 of the present invention, 87 parts of unsaturated polyester resin and 2 parts of initiator were mixedAfter being uniform, 60 parts of glass fiber cloth is added, the glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 42.8%, a vertical burn rating of V-0, and a peak heat release rate p-HRR of 218kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 382, impact strength of 102.1kJ/m 2 。
Application example 68
After 20 parts of modified ammonium polyphosphate, 80 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 26 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 51.6%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 124kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 302, and the impact strength was 93.9kJ/m 2 。
Application example 69
10 parts of modified ammonium polyphosphate, 90 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 30 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 41.8%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 225kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) 395, impact strength 102.7kJ/m 2 。
Application example 70
After 18 parts of modified ammonium polyphosphate, 82 parts of unsaturated polyester resin and 2 parts of initiator in the embodiment 30 of the invention are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 47.4%, a vertical burning grade V-0, and a peak heat release rate p-HRR of 176kW/m in the cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) is316, impact strength of 94.2kJ/m 2 。
Comparative example 1 was used
100 parts of unsaturated polyester resin and 2 parts of initiator are uniformly mixed and cured for 7 hours at 160 ℃. The resulting cured product had an oxygen index of 18.4%, a vertical burn rating of N.R. (stepless), and a peak heat release rate p-HRR of 1222kW/m in a cone calorimetric test 2 Maximum smoke density value D in smoke density test s (max) exceeds the maximum value 1320 of the instrument's range.
Comparative example 2 was used
80 parts of epoxy resin and 20 parts of curing agent are uniformly mixed and cured for 10 hours at 180 ℃. The resulting cured product had an oxygen index of 22.8%, a vertical burn rating of N.R. (stepless), and a peak heat release rate p-HRR of 1260kW/m in the cone calorimetric test 2 Maximum smoke density value D in smoke density test s (max) exceeds the maximum value 1320 of the instrument's range.
Comparative example 3 was used
100 parts of polyethylene were directly put into a twin-screw extruder and melt-blended and extruded (each stage temperature was the same as in application example 51). The resulting cured product had an oxygen index of 17.0%, a vertical burn rating of N.R. (stepless), and a peak heat release rate p-HRR of 582kW/m in the cone calorimetric test 2 Maximum smoke density value D in smoke density test s (max) 657.
Comparative example 4 was used
After 100 parts of unsaturated polyester resin and 2 parts of initiator are uniformly mixed, 60 parts of glass fiber cloth is added, a glass fiber reinforced unsaturated polyester composite material is prepared by adopting a hand lay-up molding method, and the glass fiber reinforced unsaturated polyester composite material is cured for 10 hours at 160 ℃. The resulting cured product had an oxygen index of 25.4%, a vertical burn rating of N.R. (stepless), and a peak heat release rate p-HRR of 335kW/m in a cone calorimeter test 2 Maximum smoke density value D in smoke density test s (max) was 849, and the impact strength was 100.5kJ/m 2 。
Claims (10)
1. The nitrogen-containing compound modified ammonium polyphosphate is characterized by having the following structural general formula:
wherein R is 1 And R is 1 ' as
Any one of R in the same structural general formula 1 And R is 1 ' not identical wherein X and Y are C or N atoms, Q 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); r is R 2 And R is 2 ' as
Any one of R in the same structural general formula 2 And R is 2 'different' wherein A and B are C or N atoms, W 1 、W 2 、W 3 、W 4 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight-chain or branched alkyl, R 3 、R 3 ' is aliphatic amine salt, aliphatic diamine salt, ethanolamine salt or has the structural formula +.>
Any one of R in the same structural general formula 3 And R is 3 ' different, n is greater than or equal to 1.
2. The nitrogen-containing compound-modified ammonium polyphosphate according to claim 1, wherein said Q in said modified ammonium polyphosphate 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 3 Straight chain alkanes of (2)Radicals or branched alkyl groups, amino groups, hydrogen atoms or-R-NH 3 + 。
3. The nitrogen-containing compound-modified ammonium polyphosphate according to claim 1, wherein said W is in the modified ammonium polyphosphate 1 、W 2 、W 3 、W 4 Is C 1 A linear alkyl group, an amino group, a hydroxyl group or a hydrogen atom.
4. A nitrogen-containing compound-modified ammonium polyphosphate according to claim 1,2 or 3, wherein the aliphatic amine salt in the modified ammonium polyphosphate is ethylamine salt, butylamine salt, hexylamine salt or octylamine salt; the aliphatic diamine salt is ethylenediamine, 1, 2-propyldiamine, 1, 3-propyldiamine or 1, 4-butyldiamine; the ethanolamine salt is ethanolamine salt or diethanolamine salt;
is diethylenetriamine salt, triethylenetetramine salt or tetraethylenepentamine salt.
5. A preparation method of nitrogen-containing compound modified ammonium polyphosphate as claimed in claim 1, which is characterized in that the preparation method comprises the steps of firstly mixing any one of solvents with water according to a mass ratio of 100:1-20, then adding any one of ammonium polyphosphate and a modifier into a reaction vessel according to a molar ratio of 1:0.1-1, stirring and heating to 70-90 ℃, reacting for 2-8 h, and obtaining the nitrogen-containing compound modified ammonium polyphosphate with a structural general formula of I, II, III, IV, V or VI, wherein the modifier is
Aliphatic amine salts, aliphatic diamine salts, and alkanolamine salts, wherein X and Y are C or N atoms, Q 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 4 Straight or branched chain alkane of (2)A group, an amino group, a hydroxyl group, a cyano group, a hydrogen atom or-R-NH 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); a and B are C or N atoms, W 1 、W 2 、W 3 、W 4 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); n is more than or equal to 1; the solvent is water and modifier miscible solvent, or
Firstly, mixing any one of solvents with water according to the mass ratio of 100:1-20, then adding any one of ammonium polyphosphate and a first modifier into a reaction vessel according to the mass ratio of 1:0.1-1, stirring and heating to 70-90 ℃, reacting for 2-8 h, adding a mixture of any one of a second modifier and the solvent, stirring and heating to 70-90 ℃, reacting for 1-6 h, and obtaining the nitrogen-containing compound modified ammonium polyphosphate with the structural general formula VII, VIII or IX, wherein the molar ratio of the second modifier to the ammonium polyphosphate in the mixture is 0.1-0.6:1, and the mass ratio of the second modifier to the solvent is 1:1-15, and the first modifier and the second modifier are as follows
Aliphatic amine salts, aliphatic diamine salts, alcohol amine salts, but not the same, wherein X and Y are C or N atoms, Q 1 、Q 2 、Q 3 、Q 4 、Q 5 Is C 1 ～C 4 Straight-chain or branched alkyl groups, amino groups, hydroxyl groups, cyano groups, hydrogen atoms or-R-NH groups 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); a and B are C or N atoms, W 1 、W 2 、W 3 、W 4 Is C 1 ～C 4 Straight-chain or branched alkyl, amino, hydroxy, cyano, hydrogenAtomic or-R-NH 3 + R is C, which may be the same or different 1 ～C 6 Straight or branched alkyl of (a); n is more than or equal to 1; the solvent used is a solvent which is miscible with both water and the modifier.
6. The process for producing a nitrogen-containing compound-modified ammonium polyphosphate according to claim 5, wherein the mass ratio of the solvent to water used in the process is 100:2 to 15; the molar ratio of the ammonium polyphosphate to the modifier is 1:0.1-0.8; the mass ratio of the second modifier to the solvent is 1:3-10, the molar ratio of the ammonium polyphosphate to the first modifier is 1:0.1-0.8, and the molar ratio of the ammonium polyphosphate to the second modifier is 1:0.1-0.5.
7. The process for producing a nitrogen-containing compound-modified ammonium polyphosphate as defined in claim 5 or 6, wherein the ammonium polyphosphate used in the process is any one of I-type ammonium polyphosphate, II-type ammonium polyphosphate, ammonium tripolyphosphate and ammonium tetrapolyphosphate.
8. The method for preparing nitrogen-containing compound-modified ammonium polyphosphate according to claim 5 or 6, wherein the solvent used in the method is any one of water, methanol, ethanol, isopropanol, acetonitrile, acetic acid, acetone, methylene chloride, dioxane, tetrahydrofuran, N-dimethylformamide or dimethyl sulfoxide.
9. Use of the nitrogen-containing compound-modified ammonium polyphosphate according to claim 1, characterized in that the nitrogen-containing compound-modified ammonium polyphosphate can be used alone or in combination for flame retardance of unsaturated polyesters, vinyl resins, epoxy resins or polyolefins, or for flame retardance of fiber-reinforced composites, coatings, fiber textiles, wood-plastic composites.
10. The use of the nitrogen-containing compound-modified ammonium polyphosphate according to claim 9, wherein the mixed use is a mixed use of at least two of the nitrogen-containing compound-modified ammonium polyphosphates or a mixed use with at least one of pentaerythritol, dipentaerythritol, tetrol, mannitol, xylitol, sorbitol, arabitol, starch, cellulose, lignin, and sucrose char-forming agent.
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