CN107344998A - A kind of metal complex fire retardant and preparation method thereof - Google Patents
A kind of metal complex fire retardant and preparation method thereof Download PDFInfo
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- CN107344998A CN107344998A CN201710344578.2A CN201710344578A CN107344998A CN 107344998 A CN107344998 A CN 107344998A CN 201710344578 A CN201710344578 A CN 201710344578A CN 107344998 A CN107344998 A CN 107344998A
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- fire retardant
- metal complex
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- acetate
- complex fire
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 159000000021 acetate salts Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 229960004979 fampridine Drugs 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- -1 lead acetate Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 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 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000003340 retarding agent Substances 0.000 abstract description 2
- 150000003928 4-aminopyridines Chemical class 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000013904 zinc acetate Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZRHANBBTXQZFSP-UHFFFAOYSA-M potassium;4-amino-3,5,6-trichloropyridine-2-carboxylate Chemical compound [K+].NC1=C(Cl)C(Cl)=NC(C([O-])=O)=C1Cl ZRHANBBTXQZFSP-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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)
Abstract
The present invention discloses a kind of metal complex fire retardant and preparation method thereof, is to use hexachlorocyclotriph,sphazene and 4 aminopyridines, synthesizes the organometallic ligand based on the phosphonitrile of ring three；Then part carries out complexation reaction with metal acetate salt again, obtains the metal complex fire retardant of a kind of high thermal stability, high carbon residue.The synthesis technique is easily operated, and product postprocessing is simple, is adapted to industrialized production；The fire-retardant advantage of the fire retardant combination metal catalytic and phosphazene flame retardant, fire retardant addition can be effectively reduced, be a kind of Halogen, efficient environmental protection fire retarding agent.
Description
Technical field
The present invention relates to a kind of metal complex fire retardant and preparation method thereof, belong to the synthesis skill of material science fire retardant
Art field.
Background technology
High polymer material is widely used in production, scientific research and each department of national defence and people's daily life, but
Common high polymer material has the inflammability of height, and this undoubtedly leaves great potential safety hazard to the lives and properties of people.
Therefore, the heat endurance of material is improved, the flame resistance of reinforcing material turns into the focus of present material study on the modification.Fire retardant conduct
A kind of auxiliary agent that can effectively prevent material from being ignited and suppress flame propagation and be widely used in lifted material refractory ability,
The important auxiliary agent of synthesis high polymer material is turned into.Halogenated flame retardant is one of organic fire-retardant that global yield is maximum at present,
But some bromide fire retardants and its fire-retardant material generate bioxin in the process of photodissociation or burning, to human health, safety and
There is potential hazard in environment, caused the great attention of environmental protection organization and national governments and be vigilant.Halogen-free organophosphorous flame retardant
The fire retardant laid equal stress on halogenated flame retardant, because its is wide in variety, purposes is wide, efficiently, enjoy user and researcher blue or green low toxicity
Look at.
In recent years, either in the research of halogen flame-retardant system or halogen-free flame-retardant system, catalytic flame retardancy technology is increasingly drawn
The interest of numerous researchers is played.Catalysis technique relates generally to metal ion, including transition metal ions, alkali metal ion and
Rare earth ion, wherein, bivalent metal ion, such as Zn (II), Ca (II) and Mg (II) can be used as resin crosslinks, dehydrogenation reaction
Catalyst, the metal ion of variable valency can be used as free radical scavenger or oxidation catalyst.Such as in order to improve chemically expansible
The flame retarding efficiency of fire retardant, scientific researchers thermally decompose from the fire retardant in the condensed phase of flame-retardant system, ester decomposes, aromatisation
And set out on the chemical reaction mechanism of foamed char, " synergist ", " carbon forming agent " or " catalyst " is found to accelerate chemistry
The catalysis carbon-forming effect of expanding fire retardant, improves the intensity and compactness of carbon residue, reduces addition of fire retardant etc..
Although inorganic metal compound is serving certain effect with conventional flame retardant cooperative flame retardant polymer, by
It is larger in the polarity of inorganic metal compound and the different polarities of polymeric matrix, easily reunite.Simultaneously because organic molecule hinders
Easily there is the phenomenon migrated in combustion agent, therefore the metal complex with catalytic flame retardancy performance occurs in flame retardant area
Using.However, the species of metal complex fire retardant is relatively limited, metal complex fire retardant is strongly limit in macromolecule material
Expect the application in flame retardant area.Therefore, design, fire retardant of the synthesis with autocatalytic cleavage energy just turns into committed step.The phosphorus of ring three
Nitrile is a kind of compound being alternately arranged with P, N element as basic framework, the aza hexatomic ring conjugated structure of its unique phosphorus
With good heat endurance and anti-flammability, and based on the ring triphosphine carbonitrile derivatives with coordination ability, synthesis is designed
Metal-complexing ring triphosphine nitrile compounds, there will be the catalysis expansion type flame retardant of huge applications prospect as one kind, it is right at present
The research of this kind of complex is still rare.
The content of the invention
In view of the existing problems, the present invention provides a kind of new Halogen, non-corrosiveness, there is catalytic flame retardancy effect
Metal complex fire retardant, the fire retardant is a kind of metal ligand compound constructed based on ring triphosphine nitrile nitrogen heterocycles part
Thing.
To solve above technical problem, the present invention adopts the technical scheme that：
A kind of metal complex fire retardant, its general structure are shown below：
Wherein, M Zn2+、Ca2+、Co2+、Ni2+、Mn2+、Fe3+、Cu2+、Pb2+、Pd2+、Ba2+In one or more.
The invention also discloses the synthetic method of the metal complex fire retardant, comprise the following steps：
(1) in N2Under protection, hexachlorocyclotriph,sphazene (HCCP) is substantially dissolved in tetrahydrofuran, adds acid binding agent stirring
Uniformly；The tetrahydrofuran solution of 4-aminopyridine is added dropwise thereto again, is warming up to backflow, after reacting 8~24h, solution is cooled down
To room temperature, filtering, filter cake is washed for several times with solvent, and 80 DEG C of 10~30h of vacuum drying obtain part six (4-aminopyridine) ring three
Phosphonitrile.
(2) in N2Under protection, using absolute ethyl alcohol as solvent, part six (4-aminopyridine) ring prepared by step (1) is added
Three phosphonitriles and metal acetate salt are in reaction vessel；It is sufficiently stirred, until completely dissolved, rises to back the temperature in reaction vessel
Stream mode；After reacting 8~24h, solution is cooled to room temperature, filters, is cleaned with ethanol and distilled water, 80 DEG C of vacuum drying 10~
30h obtains target product metal complex fire retardant (metal-ring triphosphine nitrile complex).
The preparation reaction equation of the metal complex fire retardant is：
The mol ratio of hexachlorocyclotriph,sphazene and 4-aminopyridine described in step (1) of the present invention is 1:6~1:8, preferably
1:7.2~1:7.5；Described acid binding agent and the mol ratio of 4-aminopyridine are 0.5~1.5:1；Described acid binding agent is carbonic acid
One kind in potassium, sodium carbonate, sodium acid carbonate, sodium hydroxide, triethylamine；Described solvent is tetrahydrofuran, N, N- dimethyl methyls
One or more combinations in acid amides, dimethyl sulfoxide, water, chloroform.
Metal acetate salt described in step (2) of the present invention is zinc acetate, calcium acetate, cobalt acetate, nickel acetate, manganese acetate, vinegar
One or more in sour iron, copper acetate, lead acetate, palladium, barium acetate；(the 4- ammonia of part six described in step (2) of the present invention
Yl pyridines) ring three the mol ratio of phosphonitrile and metal acetate salt be 1:3~1:7.Using said ratio, metal-complexing can be closed
Reason, it both can guarantee that product had best fire resistance, while and can ensures the raising of heat endurance and carbon left.
The beneficial effects of the present invention are：
1. the metal complex fire retardant combination metal catalytic of the present invention is fire-retardant excellent into charcoal and phosphorus nitrogen synergistic type fire retardant
Point, peak heat release during material combustion can be effectively reduced, more preferable fire-retardant effect is obtained with relatively low addition
Fruit.
It is one 2. the metal complex fire retardant of the present invention has high heat endurance, resistance to water soak and matrix compatibility
The high environmental protection fire retarding agent of efficient, the low cigarette of kind, heat endurance, can be applied to the fire-retardant of the higher polymer of decomposition temperature or to moisture absorption
Property require in harsh material.
3. there are multiple groups that can be coordinated with metallic element in the metal complex flame retardant mechanism of the present invention, because
This can be by controlling the content of metallic element, to regulate and control the heat endurance of complex fire retardant and fire resistance, so as to assign
The based flame retardant adapts to the application flexibility of different materials.
4. the synthesis technique of the metal complex fire retardant of the present invention is simply easily operated, without anti-at high temperature under high pressure
Should, product postprocessing is simple, and products therefrom is easy to purify, and yield is high.
Brief description of the drawings
Fig. 1 is the phosphonitrile (SFACP) of part six (4-aminopyridine) ring three and metal-complexing prepared by the embodiment of the present invention 1
The infrared spectrum of compound fire retardant (Zn-SFACP)；
Fig. 2 is the phosphonitrile (SFACP) of part six (4-aminopyridine) ring three and metal-complexing prepared by the embodiment of the present invention 1
The thermal weight loss spectrogram of compound fire retardant (Zn-SFACP).
Embodiment
Embodiment 1
0.1mol HCCP are substantially dissolved in 60ml tetrahydrofurans, 0.4mol sodium carbonate is added and stirs, fill N2
30min；The tetrahydrofuran solution 50ml of the 4-aminopyridine containing 0.72mol is added dropwise thereto again, is warming up to backflow, reacts 10h
Afterwards, solution is cooled to room temperature, filters, washed three times with tetrahydrofuran, 80 DEG C of vacuum drying 24h obtain (the 4- amino of part six
Pyridine) three phosphonitrile (SFACP) of ring, yield 95%.In N2Under protection, by 0.1mol SFACP, 0.55mol zinc acetates, 300ml second
Alcohol is added in 500ml three-necked flask, is sufficiently stirred, and until completely dissolved, is warming up to backflow, after reacting 18h, solution is delayed
Slow cool down is to room temperature, filtering, is washed twice with ethanol, distilled water washed once, and 80 DEG C of vacuum drying 24h obtain target product gold
Belong to complex fire retardant Zn-SFACP, yield 87%.(SFACP and Zn-SFACP infrared spectrum are shown in Fig. 1, hot weightless picture
Spectrogram is shown in Fig. 2).
Embodiment 2
0.1mol HCCP are substantially dissolved in 60ml tetrahydrofurans, 0.9mol sodium hydroxides is added and stirs, fill N2
30min；The tetrahydrofuran solution 60ml of the 4-aminopyridine containing 0.74mol is added dropwise thereto again, is warming up to backflow, reacts 17h
Afterwards, solution is cooled to room temperature, filters, washed three times with tetrahydrofuran, 80 DEG C of vacuum drying 24h obtain (the 4- amino of part six
Pyridine) three phosphonitrile (SFACP) of ring, yield 97%.In N2Under protection, by 0.1mol SFACP, 0.45mol palladiums, 300ml second
Alcohol is added in 500ml three-necked flask, is sufficiently stirred, and until completely dissolved, is warming up to backflow, after reacting 24h, solution is delayed
Slow cool down is to room temperature, filtering, is washed twice with ethanol, distilled water washed once, and 80 DEG C of vacuum drying 24h obtain target product gold
Belong to complex fire retardant Pd-SFACP, yield 80%.
Embodiment 3
In N2Under protection, by 0.2molHCCP, 1.3mol 4-aminopyridine, 0.7mol triethylamines, 160ml tetrahydrofurans
It is added in reaction vessel, is warming up to back flow reaction 12h, cooling, filtering, tetrahydrofuran washing filter cake twice, wash by dichloromethane
Wash once, 80 DEG C of vacuum drying 24h obtain the phosphonitrile (SFACP) of part six (4-aminopyridine) ring three, yield 96%.In N2Protection
Under, 0.1mol SFACP, 0.2mol cobalt acetates, 0.2mol nickel acetates, 300ml ethanol are added in 500ml three-necked flask,
Dissolving is sufficiently stirred, backflow is warming up to and continues to react 24h, solution is slowly cooled to room temperature, filtered, washed twice with ethanol,
Distilled water washed once, and 80 DEG C of vacuum drying 24h obtain target product metal complex fire retardant, yield 86%.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, to any modifications and changes of the invention made, protection scope of the present invention is suitable for.
Claims (9)
1. a kind of metal complex fire retardant, it is characterised in that general structure is：
Wherein, M Zn2+、Ca2+、Co2+、Ni2+、Mn2+、Fe3+、Cu2+、Pb2+、Pd2+、Ba2+In one or more.
A kind of 2. preparation method of the metal complex fire retardant described in claim 1, it is characterised in that：This method includes as follows
Step：
(1) in N2Under protection, hexachlorocyclotriph,sphazene (HCCP) is substantially dissolved in tetrahydrofuran, acid binding agent is added and stirs；
The tetrahydrofuran solution of 4-aminopyridine is added dropwise thereto again, is warming up to backflow, after reacting 8~24h, solution is cooled to room
Temperature, filtering, filter cake are washed for several times with solvent, and 80 DEG C of 10~30h of vacuum drying obtain the phosphonitrile of part six (4-aminopyridine) ring three；
(2) in N2Under protection, using absolute ethyl alcohol as solvent, metal acetate salt and (the 4- amino of part six of step (1) preparation are added
Pyridine) ring three phosphonitrile in reaction vessel；It is sufficiently stirred, until completely dissolved, the temperature in reaction vessel is risen to backflow shape
State；After reacting 8~24h, solution is cooled to room temperature, filtered, with ethanol and distillation water washing, 80 DEG C are dried in vacuo 10~30h,
Obtain metal complex fire retardant.
3. the preparation method of metal complex fire retardant according to claim 2, it is characterised in that：Described in step (1)
Hexachlorocyclotriph,sphazene and 4-aminopyridine mol ratio be 1:6~1:8.
4. the preparation method of metal complex fire retardant according to claim 3, it is characterised in that：Described in step (1)
Hexachlorocyclotriph,sphazene and 4-aminopyridine mol ratio be 1:7.2~1:7.5.
5. the preparation method of metal complex fire retardant according to claim 2, it is characterised in that：Step ties up acid in (1)
The mol ratio of agent and 4-aminopyridine is 0.5~1.5:1.
6. the preparation method of metal complex fire retardant according to claim 2, it is characterised in that：Described in step (1)
Acid binding agent be potassium carbonate, sodium carbonate, sodium acid carbonate, sodium hydroxide, one kind in triethylamine.
7. the preparation method of metal complex fire retardant according to claim 2, it is characterised in that：Described in step (1)
Solvent be tetrahydrofuran, DMF, dimethyl sulfoxide, water, one or more combinations in chloroform.
8. the preparation method of metal complex fire retardant according to claim 2, it is characterised in that：Described in step (2)
Metal acetate salt is zinc acetate, calcium acetate, cobalt acetate, nickel acetate, manganese acetate, ferric acetate, copper acetate, lead acetate, palladium, vinegar
One or more in sour barium.
9. the preparation method of metal complex fire retardant according to claim 2, it is characterised in that：Part in step (2)
The mol ratio of the phosphonitrile of six (4-aminopyridine) ring three and metal acetate salt is 1:3~1:7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110396202A (en) * | 2019-08-26 | 2019-11-01 | 北京理工大学 | ZIF-67 nanocrystal surface modifies six imidazole rings, three phosphonitrile fire retardant and preparation method thereof |
| CN111423618A (en) * | 2020-05-20 | 2020-07-17 | 中国科学技术大学 | Nitrogen heterocyclic aromatic amine-metal ion complex flame retardant and application thereof in preparation of flame-retardant epoxy resin |
| CN115058017A (en) * | 2022-06-28 | 2022-09-16 | 河北大学 | Preparation method of hexa (4-carboxyphenoxy) cyclotriphosphazene based zinc ion complex flame retardant and flame-retardant epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110396202A (en) * | 2019-08-26 | 2019-11-01 | 北京理工大学 | ZIF-67 nanocrystal surface modifies six imidazole rings, three phosphonitrile fire retardant and preparation method thereof |
| CN110396202B (en) * | 2019-08-26 | 2020-08-14 | 北京理工大学 | ZIF-67 nanocrystalline surface modified hexa-imidazole cyclotriphosphazene flame retardant and preparation method thereof |
| CN111423618A (en) * | 2020-05-20 | 2020-07-17 | 中国科学技术大学 | Nitrogen heterocyclic aromatic amine-metal ion complex flame retardant and application thereof in preparation of flame-retardant epoxy resin |
| CN111423618B (en) * | 2020-05-20 | 2021-07-06 | 中国科学技术大学 | Nitrogen heterocyclic aromatic amine-metal ion complex flame retardant and application thereof in preparation of flame-retardant epoxy resin |
| CN115058017A (en) * | 2022-06-28 | 2022-09-16 | 河北大学 | Preparation method of hexa (4-carboxyphenoxy) cyclotriphosphazene based zinc ion complex flame retardant and flame-retardant epoxy resin |
| CN115058017B (en) * | 2022-06-28 | 2024-02-06 | 河北大学 | Preparation method of hexa (4-carboxyphenoxy) cyclotriphosphazene zinc ion complex flame retardant and flame-retardant epoxy resin |
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