CN106674905A - Application of pyridine functional group-containing cyclotriphosphazene derivative - Google Patents
Application of pyridine functional group-containing cyclotriphosphazene derivative Download PDFInfo
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- CN106674905A CN106674905A CN201710006315.0A CN201710006315A CN106674905A CN 106674905 A CN106674905 A CN 106674905A CN 201710006315 A CN201710006315 A CN 201710006315A CN 106674905 A CN106674905 A CN 106674905A
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- ring
- functional groups
- pyridine functional
- phosphazene derivative
- containing pyridine
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical class N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 title abstract 7
- -1 polypropylene Polymers 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- 239000004743 Polypropylene Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 150000003222 pyridines Chemical class 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000000979 retarding effect Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 241001597008 Nomeidae Species 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000003385 sodium Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 27
- 239000001301 oxygen Substances 0.000 abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 abstract description 27
- 229920001276 ammonium polyphosphate Polymers 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 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 6
- 238000001125 extrusion Methods 0.000 abstract description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 abstract description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000001746 injection moulding Methods 0.000 abstract 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical group [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/659—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having three phosphorus atoms as ring hetero atoms in the same ring
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention relates to application of a pyridine functional group-containing cyclotriphosphazene derivative, and belongs to the technical field of processing aids. According to the structural characteristics, the pyridine functional group-containing cyclotriphosphazene derivative can also be applied to biological, pharmaceutical and pesticide fields. The pyrithione functional group-containing cyclotriphosphazene derivative is compounded with epoxy resin and a curing agent to obtain flame-retardant epoxy resin; the heat resistance and flame retardance of epoxy resin are improved by the pyridine functional group-containing cyclotriphosphazene derivative to a certain extent. The pyridine functional group-containing cyclotriphosphazene derivative is compounded with ammonium polyphosphate, polypropylene and an antioxidant to obtain flame-retardant polypropylene by extrusion injection molding. The pyridine functional group-containing cyclotriphosphazene derivative has a synergistic effect on ammonium polyphosphate flame retardant polypropylene, the oxygen index is improved and the processability is improved.
Description
Technical field
The present invention relates to a kind of application of the phosphazene derivative of ring three containing pyridine functional groups, belongs to processing aid technology neck
Domain.According to its construction features, biology, medicine and pesticide field are also apply be applicable to.
Background technology
Phosphazene compound is while phosphorous, two kinds of ignition-proof elements of nitrogen, are that a kind of very promising New Phosphorus/nitrogen system bittern-free is fire-retardant
Agent.By phosphorus, the difference of nitrogen frame configuration, cyclic phosphazene and the big class of linear phosphonitrile two can be divided into.Cyclic phosphazene is that the mono- double bond of P, N is handed over
For the six-membered cyclic compound that connection is formed, two chlorine atoms are connected with each phosphorus atoms, because chlorine in side chain atom is lived
Property it is very high and unstable, SN2 nucleophilic substitutions occur by organic molecules with active hydrogen with some can be had concurrently
The phosphazene derivative of inorganic matters and Organic Compound energy.In recent years, due to the unique structure of phosphonitrile and its derivant and performance, in resistance
The fields such as combustible material, biomaterial for medical purpose, liquid crystal material have all been applied, and have obtained the concern of increasing researcher.
The class phenyl ring rigid structure that molecule containing pyridine contains, can improve the heat stability of target product；Pyridine groups
Belong to nitrogen heterocyclic ring, nitrogen is conducive to improving flame retardant effect as ignition-proof element；And pyridine ring is a kind of good part, can
To be combined with coordinating metal, more structures are derived on this basis.
The content of the invention
The invention aims to propose a kind of phosphazene derivative of ring three containing pyridine functional groups preparation method and its
Using, with 2- hydroxyl -5-X pyridines, sodium class compound and hexachlorocyclotriph,sphazene as raw material, at a certain temperature, make hydroxyl with
There is nucleophilic substitution in hexachlorocyclotriph,sphazene, after certain hour reaction, sense containing pyridine is collected from reactant mixture
The phosphazene derivative of group.
The purpose of the present invention is achieved through the following technical solutions.
A kind of application of the phosphazene derivative of ring three containing pyridine functional groups：
(1) phosphazene derivative of pyridine functional groups ring three and epoxy resin, firming agent will be contained according to obtaining fire-retardant ring after compounding
Oxygen tree fat；The mass ratio of the phosphazene derivative of the ring containing pyridine functional groups three, epoxy resin and firming agent is 1~6:73~76:
21~23；The phosphazene derivative of ring three containing pyridine functional groups improves to a certain extent the heat resistance and anti-flammability of epoxy resin
Energy.
(2) extrusion injection after the phosphazene derivative of pyridine functional groups ring three is compounded with APP, polypropylene, antioxidant will be contained
Obtain polypropylene flame redardant.The polypropylene and the phosphazene derivative of ring containing pyridine functional groups three and the quality of the mixture of APP
Than for 70:30；The phosphazene derivative of ring containing pyridine functional groups three is 2~8 with the mass ratio of APP:22~28；Antioxidant is
The 0.3%~0.6% of the phosphazene derivative of ring containing pyridine functional groups three, APP and polypropylene three's mass sum；
As a result show, the phosphazene derivative of ring containing pyridine functional groups three serves synergistic work to Flame Retardant Modification of PP by Ammonium Polyphosphate
With, oxygen index (OI) is improve, improve processing characteristics.
The antioxidant is the quality of the mixture of 1010 antioxidant and 168 antioxidant, 1010 antioxidant and 168 antioxidant
Than for 1:2~4.
A kind of phosphazene derivative of ring three containing pyridine functional groups of the present invention, the phosphonitrile of ring three for containing pyridine functional groups derives
Thing main component is following material, shown in its structural formula such as formula (1)：
Wherein, X is nitro, amino, cyano group, carboxyl, aldehyde radical, alkoxyl or alkyl；Alkoxyl is methoxyl group, ethoxy
Base, methoxy ethoxy, isopropoxy, isopropyl alkenyloxy group, t-butylperoxy or diacetylmonoxime；Alkyl is methyl, ethyl, methyl
Ethyl, isopropyl or butyl.
A kind of preparation method of phosphazene derivative of ring three containing pyridine functional groups according to the present invention, its concrete preparation process
For：
1) under inert gas atmosphere, 2- hydroxyl -5-X pyridines and solvent are added in reactor, sodium class is subsequently adding
Compound, stirring is subsequently adding hexachlorocyclotriph,sphazene, and reaction temperature is 20~120 DEG C, and the response time is 12~48 hours；
To reactant liquor；
2) to step 1) in obtain reacting liquid filtering, with eluent solvent, washing, remove by-product, then solvent is evaporated off,
Finally obtain the phosphazene derivative of ring three containing pyridine functional groups；
Above-mentioned steps 1) in solvent be C1~C3Alcohol, acetone, dichloromethane, chloroform, benzene,toluene,xylene,
Tetrahydrofuran or its mixture；
Above-mentioned steps 1) in 2- hydroxyl -5-X pyridines and solvent ratio be 1g:12~15ml；
Above-mentioned steps 1) in 2- hydroxyl -5-X pyridines structural formula such as formula (2)：
Above-mentioned steps 1) in the mol ratio of hexachlorocyclotriph,sphazene and 2- hydroxyl -5-X pyridines be 1:6~9；
Above-mentioned steps 1) in sodium class compound be sodium hydride, SODIUM METAL, sodium carbonate or sodium bicarbonate；
Above-mentioned steps 1) in the mol ratio of sodium class compound and 2- hydroxyl -5-X pyridines be 1.2~2:1.
Beneficial effect
1st, fire retarding epoxide resin is prepared.The addition of the phosphazene derivative of ring three containing pyridine functional groups, delays epoxy
The decomposition temperature of resin, promotes combustion product into charcoal, largely improves the thermostability of epoxy resin, also makes epoxy resin
Oxygen index (OI) be improved；And with the increase of the phosphazene derivative content of ring three containing pyridine functional groups, MPOCP promotes into charcoal
Effect also become better and better, the layer of charcoal of generation is also more and more stable, and oxygen index (OI) more and more higher, fire resistance is become better and better.
2nd, polypropylene flame redardant is prepared.The phosphazene derivative of ring three containing pyridine functional groups is added to as a kind of synergist
In polypropylene flame redardant system, there can be oxygen index (OI) as the toughener of polypropylene flame redardant system and fire retardant, the polypropylene for obtaining
It is high, the characteristics of elongation at break is high.
3rd, the present invention is a kind of phosphazene derivative of ring three containing pyridine functional groups of synthesis, used as a kind of new containing pyridine ring
Three phosphonitrile organic inorganic hybridization things, in being added to Polymer Systems.The characteristics of due to molecular structure, it is not only able to improve high score
The compatibility of subsystem, and be conducive to improving macromolecular material heat stability, improve the thermal behavior of macromolecular material, in material
It is heated and promotes condensed phase charring in combustion process, improves the fire resistance of macromolecular material.
4th, the present invention has the features such as reaction condition is gentle, easily controllable, reproducible, last handling process is simple.
5th, in the derivative molecular phosphonitrile structure and the property feature of pyridine functional groups so that it is also expected to be applied to life
The fields such as thing, medicine and pesticide.
Description of the drawings
Fig. 1 is the phosphazene derivative MPOCP of ring three containing pyridine functional groups and hexachlorocyclotriph,sphazene HCCP prepared by embodiment 1
Contrast infared spectrum；
Fig. 2 is the phosphazene derivative MPOCP of ring three containing pyridine functional groups and 2- hydroxy-5-methyl base pyrroles prepared by embodiment 1
Pyridine MP contrasts infared spectrum；
Fig. 3 is the phosphazene derivative nmr spectrum of ring containing pyridine functional groups three prepared by embodiment 1, and 6.31ppm is P-
The peak of O-C keys；
The mass spectrum of the phosphazene derivative of ring containing pyridine functional groups three that Fig. 4 is prepared for embodiment 1, its middle-molecular-weihydroxyethyl 784.5
For the peak of hexasubstitution.
Specific embodiment
Below by embodiment, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
Infrared spectrum adopts NICOLET 6700IR type determination of infrared spectroscopy；Nuclear magnetic resonance map adopts Germany Bruker
DMX600 nuclear magnetic resonance spectrometers, scanning times are 64 times；Mass spectrum adopts Germany Bruker Daltonics Inc.BIFLEX
Type III MALDI-TOF mass spectrograph；Thermogravimetric analyzer adopts the TG 209F1 of Nai Chi companies of GermanyType thermogravimetric analyzer.
Embodiment 1
8.730g2- hydroxy-5-methyl yl pyridines are dissolved in 140ml tetrahydrofurans, 2.327g sodium hydrides, magnetic force is added
Stirring makes fully dissolving, one hour of normal-temperature reaction；In addition 3.482g hexachlorocyclotriph,sphazenes are dissolved in into 60ml tetrahydrofuran solutions
In, instilled in above-mentioned tetrahydrofuran solution with constant pressure funnel, more than 20h is reacted under the conditions of 67 DEG C.After reaction is terminated
The mixture for obtaining is filtered by kieselguhr, removes excessive 2- hydroxy-5-methyl yl pyridines salt, while with eluent methylene chloride,
Obtain the dichloromethane solution of product.Washing 3-5 time.Excessive moisture is filtered to remove, the ring three containing pyridine functional groups is finally given
Phosphazene derivative, the isolation of the phosphazene derivative of ring three containing pyridine functional groups is air-dried preservation.
The characterize data of the phosphazene derivative of ring three containing pyridine functional groups is shown in Fig. 1, Fig. 2, Fig. 3.
Spectral data is：
FT-IR(cm-1):800-1400 (P-N, P=N), 953,905,522 (P-O-C)
31P NMR(CDCl3,δ,ppm,TMS):6.31(6P,-P-O-C)。
By epoxy resin E-44, MPOCP (this contains the phosphazene derivative of pyridine functional groups) and firming agent DDS (diaminourea two
Phenylsulfone) according to mass ratio be 76.15：1：Prepared by 22.85 ratio, obtain fire retarding epoxide resin.The epoxy of MPOCP is not added
Resin is EP (only adding epoxy resin E-44 and firming agent DDS).
The preparation process of fire retarding epoxide resin can be divided into the mixing of fire retardant and epoxy resin, the addition of firming agent, high temperature
Three steps of solidification, wherein the requirement of the control and time to temperature is particularly strict.
(1) mixing of MPOCP and E-44 epoxy resin
E-44 and mould are placed in drying oven, heating a period of time, treats that E-44 viscosity degradation is arrived at a temperature of 80 DEG C
Take out from drying baker after appropriate level；Quantitative MPOCP and E-44 is weighed respectively, is mixed in oblique there-necked flask, be placed in
In 140 DEG C of oil bath, 30min is sufficiently stirred for.
(2) addition of firming agent
After MPOCP and E-44 are sufficiently mixed 30min, quantitative firming agent DDS is weighed, be added to fill mixture three mouthfuls
In flask, continue stir about 15min.After DDS is completely dissolved, evacuation process is carried out to there-necked flask with vacuum pump, to go
Except the gas of residual in resin.
(3) hot setting
After bubble-free in resin is produced, stop evacuation, unload there-necked flask；The mould that taking-up is placed in advance in drying baker
Tool, and mould is loaded into before it is cured, in being placed in drying baker, 4h is incubated at 180 DEG C, until resin is fully cured,
Obtain fire retarding epoxide resin.
The TG data such as table 1 of the EP of MPOCP, EP and addition 1%MPOCP, it can be seen that the addition of MPOCP, postpones
The heat decomposition temperature of EP, promotes combustion product into charcoal, improves the thermal stability of epoxy resin.
The MPOCP of table 1, EP, the TG data of the EP of addition 1%MPOCP
According to GB/T 2046.2-2009, with oxygen index instrument the limited oxygen index of the EP for adding 1%MPOCP, the limit are characterized
Oxygen index (OI) is 26.9%, the limited oxygen index value 25% higher than EP.
Compare with the epoxy resin of MPOCP is not added, hot property and fire resistance are significantly improved.
Embodiment 2
MPOCP used in the embodiment and the process of fire retarding epoxide resin is prepared with embodiment 1.
By epoxy resin E-44, MPOCP and firming agent DDS according to mass ratio 74.61：3：Prepared by 22.39 ratio, obtain
Fire retarding epoxide resin.
The TG data such as table 2 of the EP of MPOCP, EP and addition 3%MPOCP, it can be seen that the addition of MPOCP, postpones
The heat decomposition temperature of EP, promotes combustion product into charcoal, improves the thermal stability of epoxy resin.
The TG data of the EP of table 2 MPOCP, EP and addition 3%MPOCP
According to GB/T 2046.2-2009, with oxygen index instrument the limited oxygen index of the EP for adding 3%MPOCP, the limit are characterized
Oxygen index (OI) is 28.5%, the limited oxygen index value 25% higher than EP.
Compare with the epoxy resin of MPOCP is not added, hot property and fire resistance are significantly improved.
Embodiment 3
MPOCP used in the embodiment and the process of fire retarding epoxide resin is prepared with embodiment 1.
By epoxy resin E-44, MPOCP and firming agent DDS according to mass ratio 73.08：5：Prepared by 21.92 ratio, obtain
Fire retarding epoxide resin.
The TG data such as table 3 of the EP of MPOCP, EP and addition 1%MPOCP, it can be seen that the addition of MPOCP, postpones
The heat decomposition temperature of EP, promotes combustion product into charcoal, improves the thermal stability of epoxy resin.
The TG data of the EP of table 3 MPOCP, EP and addition 5%MPOCP
According to GB/T 2046.2-2009, with oxygen index instrument the limited oxygen index of the EP for adding 5%MPOCP, the limit are characterized
Oxygen index (OI) is 29.4%, the limited oxygen index value 25% higher than EP.
Compare with the epoxy resin of MPOCP is not added, hot property and fire resistance are significantly improved.
Embodiment 4
8.730g2- hydroxy-5-methyl yl pyridines are dissolved in 120ml tetrahydrofurans, 2.327g sodium hydrides, magnetic force is added
Stirring makes fully dissolving, one hour of normal-temperature reaction；In addition 3.482g hexachlorocyclotriph,sphazenes are dissolved in into 50ml tetrahydrofuran solutions
In, instilled in above-mentioned tetrahydrofuran solution with constant pressure funnel, more than 20h is reacted under the conditions of 67 DEG C.After reaction is terminated
The mixture for obtaining is filtered by kieselguhr, removes excessive 2- hydroxy-5-methyl yl pyridines salt, while with eluent methylene chloride,
Obtain the dichloromethane solution of product.Washing 3-5 time.Excessive moisture is filtered to remove, product is finally given, product isolation air is done
Dry preservation.
By ring three phosphazene derivative MPOCP, 22g APPs of the 6g of above-mentioned synthesis containing pyridine functional groups and 70g poly- third
Alkene is compounded, and is subsequently adding the antioxidant of 0.1g 1010 and the antioxidant of 0.2g 168, extrusion temperature condition is 165 DEG C, 170 DEG C, 175
DEG C, 180 DEG C, 175 DEG C, 170 DEG C, injection temperature condition be 190 DEG C, 195 DEG C, 200 DEG C, 195 DEG C, 190 DEG C, obtain flame-retardant polypropylene
Alkene test bars.
By GB/T 1040.2-2006, its mechanical property is characterized with electronic tension tester, elongation at break is
82.12%, according to GB/T 2046.2-2009, its limited oxygen index is characterized with oxygen index instrument, limited oxygen index is 25.9%.
Embodiment 5
MPOCP used in the embodiment is with embodiment 4.
Ring three phosphazene derivatives of the 5g of above-mentioned synthesis containing pyridine functional groups, 24g APPs and 70g polypropylene are answered
Match somebody with somebody, be subsequently adding the antioxidant of 0.1g 1010 and the antioxidant of 0.2g 168, extrusion temperature condition is 165 DEG C, 170 DEG C, 175 DEG C,
180 DEG C, 175 DEG C, 170 DEG C, injection temperature condition is 190 DEG C, 195 DEG C, 200 DEG C, 195 DEG C, 190 DEG C, obtains polypropylene flame redardant
Test bars.
By GB/T 1040.2-2006, its mechanical property is characterized with electronic tension tester, elongation at break is
83.50%, according to GB/T 2046.2-2009, its limited oxygen index is characterized with oxygen index instrument, limited oxygen index is 24.1%.
Embodiment 6
MPOCP used in the embodiment is with embodiment 4.
Ring three phosphazene derivatives of the 4g of above-mentioned synthesis containing pyridine functional groups, 26g APPs and 70g polypropylene are answered
Match somebody with somebody, be subsequently adding the antioxidant of 0.1g 1010 and the antioxidant of 0.2g 168, extrusion temperature condition is 165 DEG C, 170 DEG C, 175 DEG C,
180 DEG C, 175 DEG C, 170 DEG C, injection temperature condition is 190 DEG C, 195 DEG C, 200 DEG C, 195 DEG C, 190 DEG C, obtains polypropylene flame redardant
Test bars.
By GB/T 1040.2-2006, its mechanical property is characterized with electronic tension tester, elongation at break is
79.86%, according to GB/T 2046.2-2009, its limited oxygen index is characterized with oxygen index instrument, limited oxygen index is 22.0%.
Claims (9)
1. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups, it is characterised in that：The phosphorus of pyridine functional groups ring three will be contained
Carbonitrile derivatives and epoxy resin, firming agent after compounding according to obtaining fire retarding epoxide resin；The phosphonitrile of the ring containing pyridine functional groups three
The mass ratio of derivant, epoxy resin and firming agent is 1~6:73~76:21~23.
2. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups, it is characterised in that：The phosphorus of pyridine functional groups ring three will be contained
Carbonitrile derivatives extrude injection and obtain polypropylene flame redardant after compounding with APP, polypropylene, antioxidant；The polypropylene with contain pyrrole
The mass ratio of the mixture of the phosphazene derivative of pyridine functional group ring three and APP is 70:30；The phosphonitrile of ring containing pyridine functional groups three
Derivant is 2~8 with the mass ratio of APP:22~28；Antioxidant is the phosphazene derivative of ring containing pyridine functional groups three, poly- phosphorus
The 0.3%~0.6% of sour ammonium and polypropylene three's mass sum.
3. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 2, it is characterised in that：It is described
It is 1 that antioxidant is the mass ratio of the mixture of 1010 antioxidant and 168 antioxidant, 1010 antioxidant and 168 antioxidant:2~4.
4. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 1 or 2, it is characterised in that：
The structural formula such as formula (1) of the phosphazene derivative of ring three containing pyridine functional groups is as follows：
Wherein, X is nitro, amino, cyano group, carboxyl, aldehyde radical, alkoxyl or alkyl；Alkoxyl is methoxyl group, ethyoxyl, first
Epoxide ethyoxyl, isopropoxy, isopropyl alkenyloxy group, t-butylperoxy or diacetylmonoxime；Alkyl be methyl, ethyl, Methylethyl,
Isopropyl or butyl.
5. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 4, it is characterised in that：It is described
The preparation method of the phosphazene derivative of ring three containing pyridine functional groups, its concrete preparation process is：
1) under inert gas atmosphere, 2- hydroxyl -5-X pyridines and solvent are added in reactor, sodium class chemical combination is subsequently adding
Thing, stirring is subsequently adding hexachlorocyclotriph,sphazene, and reaction temperature is 20~120 DEG C, and the response time is 12~48 hours；Obtain anti-
Answer liquid；
2) to step 1) in obtain reacting liquid filtering, with eluent solvent, washing, remove by-product, then solvent is evaporated off, finally
Obtain the phosphazene derivative of ring three containing pyridine functional groups.
6. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 5, it is characterised in that：It is described
Step 1) in solvent be C1~C3Alcohol, acetone, dichloromethane, chloroform, benzene,toluene,xylene, tetrahydrofuran or its
Mixture.
7. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 5, it is characterised in that：It is described
Step 1) in 2- hydroxyl -5-X pyridines and solvent ratio be 1g:12~15ml；Above-mentioned steps 1) in hexachlorocyclotriph,sphazene with
The mol ratio of 2- hydroxyl -5-X pyridines is 1:6~9；Above-mentioned steps 1) in sodium class compound and 2- hydroxyl -5-X pyridines mole
Than for 1.2~2:1.
8. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 5, it is characterised in that：It is described
Step 1) in 2- hydroxyl -5-X pyridines structural formula such as formula (2)：
。
9. a kind of application of the phosphazene derivative of ring three containing pyridine functional groups as claimed in claim 5, it is characterised in that：It is described
Step 1) in sodium class compound be sodium hydride, SODIUM METAL, sodium carbonate or sodium bicarbonate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111116663A (en) * | 2019-12-11 | 2020-05-08 | 华南理工大学 | Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof |
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| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
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| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
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