CN106543235B - A kind of metal complex and preparation method thereof that concerted catalysis containing P/N/Si/S/Ni is fire-retardant - Google Patents
A kind of metal complex and preparation method thereof that concerted catalysis containing P/N/Si/S/Ni is fire-retardant Download PDFInfo
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- CN106543235B CN106543235B CN201610968443.9A CN201610968443A CN106543235B CN 106543235 B CN106543235 B CN 106543235B CN 201610968443 A CN201610968443 A CN 201610968443A CN 106543235 B CN106543235 B CN 106543235B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 58
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 21
- 230000002153 concerted effect Effects 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 189
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 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 19
- 230000000694 effects Effects 0.000 abstract description 12
- 238000002485 combustion reaction Methods 0.000 abstract description 9
- 239000005864 Sulphur Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000002341 toxic gas Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229920000742 Cotton Polymers 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- 239000007787 solid Substances 0.000 description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 18
- 239000012046 mixed solvent Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 10
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 9
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- OZECFIJVSAYAPH-UHFFFAOYSA-N ethyl-di(propan-2-yl)azanium;chloride Chemical compound Cl.CCN(C(C)C)C(C)C OZECFIJVSAYAPH-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- -1 sulphur anion Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
Abstract
The present invention relates to a kind of intumescent metal based flame retardant, the fire-retardant metal complex and preparation method thereof of specifically a kind of concerted catalysis containing P/N/Si/S/Ni.Intermediate II of the invention can be used for preparing the fire-retardant metal complex of a variety of concerted catalysis containing P/N/Si/S/Ni；Four kinds of phosphorus, nitrogen, silicon, sulphur ignition-proof element set into a molecule and are coordinated in metallic atom simultaneously by the metal complex, a variety of ignition-proof elements collaboration expandable flame retardants and metal catalized at carbon flame-proof are given full play to, its flame retardant effect as fire retardant is substantially increased；Halogen-free atom and the siloxy group decomposed containing easily reaction in the molecule of the fire retardant, therefore in combustion without toxic gas and formaldehydeless release, exactly meet the environmentally protective requirement of modern fire retardant combustion process；It can be used for carrying out various cotton fabric matrixes durable flame-retardant processing in the case where usage amount is less and can reach good expected flame retardant effect simultaneously.
Description
Technical field
The present invention relates to a kind of intumescent metal based flame retardant, specifically a kind of concerted catalysis containing P/N/Si/S/Ni is fire-retardant
Metal complex and preparation method thereof.
Background technique
With the rapid development of science and technology, high molecular material kind quantity and use scope increasingly increase, but they have
One general character is exactly inflammable or flammable, and fire retardant is a kind of material can be prevented to ignite or inhibit the active principle of flame propagation.
Therefore, the design with preparation of fire retardant have become the research hotspot problem in flame retarded polymeric material field and are concerned.Referring to:
Chen,L.；Wang,Y.Z.Polym.Adv.Technol.,2010,21,1-19.
In the development and application of fire retardant, halogenated flame retardant is still current because of advantages such as its additive amount is few, good flame retardation effects
The maximum organic based flame retardant of dosage in the world, but since it can discharge many cigarettes in fire-retardant combustion process and corrosivity is toxic
Gas, life security and environment to the mankind cause high risks and gradually by Halogen (low halogen) intumescent of rising in recent years
Fire retardant is replaced.Referring to: Laoutid, F.；Bonnaud,L.；Alexandre M.；Lopez-Cuesta,J.M.；
Dubois,P.Mat.Sci.Eng.R.,2009,63,100-119；Liang,S.；Neisius,N.M.；Gaan,
S.Prog.Org.Coat.,2013,76,1642-1665。
Intumescent organic fire-retardant is due to integrating acid source, carbon source, gas source Intumescent Retardant System and the resistance such as play phosphorus, nitrogen
The effect of cooperative flame retardant between combustion element and there is it during fire-retardant stability is good, should not disappear, to polymeric matrix
Performance influences the advantages such as small；But in order to significantly improve flame retardant effect, then the usage amount of fire retardant is needed to cause fire-retardant greatly very much
The problem that the physical property of matrix is evidently poor.In consideration of it, scientific research personnel introduces the ignition-proof elements such as silicon, sulphur to expansion type flame-retarding body
Its flame retardant effect is further promoted in system, wherein being introduced into for element silicon can form Si-O by material surface in fire-retardant combustion process
Or the inorganic protective layer of Si-C key, the introducing of element sulphur can be used as acid source similar to P elements and form acid in combustion
Matter catalysis protection layer of charcoal quickly generates, these a large amount of generations for further burning and avoid toxic gas to matrix is blocked
And the effect of playing good cooperative flame retardant, fire retardant effect can be further increased and reduce its usage amount.Referring to:
Nguyen,T.M.D.；Chang,S.C.；Condon,B.；Uchimiya,M.；Fortier,C.Polym.Adv.Technol.,
2012,23,1555-1563；Zhao,P.H.；Zhang,M.；Wu,D.H.Korean J.Chem.Eng.,2013,30,1678-
1690；Li,X.H.；Chen,H.Y.；Wang,W.T.；Zhao,P.H.Polym.Degrad.Stabil.,2015,120,193-
202；Zhao,P.H.；Liu,S.N.；Xiong,K.K.；Wang,W.T.Fiber Polym.,2016,17,569-575.
Meanwhile scientific research personnel shows some metal oxides and metal salt compounding into Intumscent Flame Retardant System in recent years
Good flame retardant effect out then hinders in right system molecule it is contemplated that metallic element is introduced directly into intumescent, plays class
It is similar to function of the organometallic complex as the catalyst of a large amount of organic reactions, it is made to be catalyzed quickening in fire-retardant combustion process
At charcoal react carry out and quickly generate protection layer of charcoal and play the role of well it is heat-insulated oxygen barrier, show efficient flame retardant effect.
Summary of the invention
For the above technical background, the present invention has acyclic guaranteed costs such as cigarette is toxic and swollen in order to solve halogenated flame retardant
Not the problems such as flame retarding efficiency of swollen type organic fire-retardant is not good enough, usage amount is big, and provide a kind of intermediate II and preparation method thereof,
The fire-retardant metal complex of the and target product of the intermediate II --- concerted catalysis containing P/N/Si/S/Ni and its preparation side
Method.
The present invention is achieved by the following technical solutions: a kind of metal that concerted catalysis containing P/N/Si/S/Ni is fire-retardant is matched
Close the intermediate II of object, structural formula are as follows:
X is Cl, Br, I (iodine) in the structural formula.
In addition, the present invention provides a kind of preparation method of the intermediate II of metal complex, in the metal complex
Mesosome II is as described above, the preparation method includes the following steps:
(1) 3-aminopropyltriethoxysilane, diphenyl phosphorus chloride, triethylamine are sequentially added into methylene chloride
In, after solution room temperature reaction overnight, by crude product by sand core filtering, concentrated by rotary evaporation, tetrahydrofuran washing, methylene chloride weight
Crystallization, vacuum drying, obtain intermediate compound I；
(2) dihalide nickel and intermediate compound I are sequentially added in the first solvent, solution reacts 0.5h at 25 DEG C -35 DEG C
Stop reaction afterwards, crude product is successively washed by concentrated by rotary evaporation, dehydrated alcohol and methylene chloride, anhydrous methanol recrystallizes, true
Sky is dry, obtains intermediate II.
The reason of recrystallize with dichloromethane is used in the preparation method of intermediate II of the present invention, in the step (1)
Being intermediate compound I easily reaches saturated solution state very well in the dissolubility of methylene chloride, and additional amount is those skilled in the art
It is easy to control realization.In the step (2) dihalide nickel be six hydration Nickel Chlorides, it is anhydrous Nickel Bromide, anhydrous diiodinating
For nickel as reaction raw materials, the purpose is to intermediate IIs generated to have separately included the visibly different three halogen (I of reactivity
> Br > Cl), this is because the atomic radius of Cl, Br, I are sequentially increased, the Ni-X key formed with metal core successively weakens, and is reacting
The leaving away property of Cl, Br, I successively enhance that (i.e. reactivity successively increases when the sulphur anion attack core center Ni of dithiol in the process
Greatly), therefore the yield of generation metal target complex successively improves.
It is that dehydrated alcohol removing on a small quantity may be not anti-that dehydrated alcohol and methylene chloride, which successively wash purpose, in the step (2)
The dihalide nickel and methylene chloride answered are gone out a small amount of unreacted intermediate compound I (excess), and additional amount is those skilled in the art
It is easy to control realization.The reason of being recrystallized in the step (2) using anhydrous methanol is intermediate II in the molten of anhydrous methanol
Solution property preferably easily reaches saturated solution state, and additional amount is that those skilled in the art are easy to control realization.
When it is implemented, in order to improve the yield of intermediate II, it is preferred that the 3-aminopropyltriethoxysilane,
Diphenyl phosphorus chloride, triethylamine molar ratio be 1:2.3:2.2；The molar ratio of the dihalide nickel and intermediate compound I is 1:1.1.
Further, first solvent is the mixture, anhydrous methanol and methylene chloride of dehydrated alcohol and methylene chloride
Mixture.Foregoing first solvents are relative to other solvents, both mixed solvents are relative to single used in general literature
For reaction dissolvent, it more can guarantee the abundant dissolution of each reaction raw materials, its reaction process allowed to carry out in homogeneous system, because
Dihalide nickel inorganic salts are soluble in dehydrated alcohol and anhydrous methanol and are insoluble in common organic solvents, other reaction raw materials such as 3-
Dissolubility is best in methylene chloride for aminopropyltriethoxywerene werene and diphenyl phosphorus chloride.
In addition, the dihalide nickel is six hydration Nickel Chlorides, anhydrous Nickel Bromide or anhydrous diiodinating nickel.
Another object of the present invention is to provide the target product of above-mentioned intermediate II --- it is cooperateed with containing P/N/Si/S/Ni
The metal complex of catalytic flame retardancy, structural formula are as follows:
It is fire-retardant to provide a kind of concerted catalysis containing P/N/Si/S/Ni for clearer its technology contents of explanation by the present invention
Metal complex preparation method, the metal complex it has been observed that intermediate II used by the preparation method it has been observed that should
Preparation method includes the following steps:
Intermediate II is dissolved in the second solvent, be then stirred at room temperature down be successively added dropwise 2- it is thio -1,3- dimercaptopropane and
Acid binding agent, react 0.5-1.5h after, by crude product by sand core filtering, concentrated by rotary evaporation, dehydrated alcohol, tetrahydrofuran and ether according to
Secondary washing, recrystallize with dichloromethane, vacuum drying, obtain metal complex.
In the preparation method of metal complex of the present invention, anhydrous methanol, tetrahydrofuran and ether successively wash purpose
It is: a small amount of possible unreacted intermediate II of dehydrated alcohol removing, a small amount of remaining acid binding agent hydrochloride of tetrahydrofuran removing, two
Chloromethanes is gone out a small amount of unreacted intermediate compound I (excess), and each additional amount is easy to control realization for those skilled in the art.Make
Being metal complex with the reason of recrystallize with dichloromethane preferably easily reaches saturated solution state in the dissolubility of methylene chloride,
Its additional amount is that those skilled in the art are easy to control realization.
The synthetic route of the metal complex is as follows:
In order to improve the yield of metal complex of the present invention, it is preferred that the intermediate II, 2- be thio -1,3-, the third two sulphur
The molar ratio of pure and mild acid binding agent is 1:1.1~1.3:2~4.
Preferably, second solvent is mixture, the tetrahydro of methylene chloride, tetrahydrofuran, methylene chloride and ether
The mixture of furans and ether.Foregoing second solvents can fully ensure that each reaction raw materials relative to other solvents, these types of solvent
Abundant dissolution, allow its reaction process to carry out in homogeneous system, because intermediate II is in methylene chloride and tetrahydrofuran
Dissolubility is maximum and other organic solvent indissolubles, raw material dithiol in ether dissolubility preferably while can also be dissolved in methylene chloride
And tetrahydrofuran.
When it is implemented, the acid binding agent is triethylamine, pyridine and diisopropylethylamine.
The present invention has the following beneficial effects with respect to the prior art:
1. intermediate II provided by the invention can be used for preparing the fire-retardant metal of a variety of concerted catalysis containing P/N/Si/S/Ni and match
Close object；
2. four kinds of phosphorus, nitrogen, silicon, sulphur ignition-proof element set into a molecule and are coordinated in by the metal complex simultaneously
Metallic atom gives full play to a variety of ignition-proof elements collaboration expandable flame retardants and metal catalized at carbon flame-proof, greatly improves
Its flame retardant effect as fire retardant；
3. halogen-free atom and the siloxy group decomposed containing easily reaction in the molecule of the fire retardant, therefore it is in combustion process
Middle no toxic gas and formaldehydeless release exactly meet the environmentally protective requirement of modern fire retardant combustion process；
It can be used for carrying out various cotton fabric matrixes durable flame-retardant processing in the case where usage amount is less and can reach good simultaneously
Good expection flame retardant effect；
4. synthetic technological condition of the invention it is mild and stablizes, reaction process is simple and easy to control, raw material inexpensively and be easy to get,
Convenient post-treatment and it is quick, a variety of [SiP can be prepared2NS2M] metal complexes are hindering with expanding intumescent metal based flame retardant
Fire the application of polymeric material field.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of intermediate II described in the embodiment of the present invention 1.
Fig. 2 is the nuclear magnetic resonance phosphorus spectrogram of intermediate II described in the embodiment of the present invention 1.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of metal complex described in the embodiment of the present invention 1.
Fig. 4 is the nuclear magnetic resonance phosphorus spectrogram of metal complex described in the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
A kind of metal complex that concerted catalysis containing P/N/Si/S/Ni is fire-retardant the preparation method comprises the following steps:
(1) in the methylene chloride of 30mL, the 3-aminopropyltriethoxysilane of 2.3mL (10mmol) is first added, then
It is slowly added to the diphenyl phosphorus chloride of 4.1mL (23mmol), is then slowly added to the triethylamine of 3.1mL (22mmol)；Room temperature is stirred
After mixing reaction overnight, obtain faint yellow suspension, by its by sand core be filtered to remove triethylamine hydrochloride solid obtain it is faint yellow
Liquid is rotated removing methylene chloride and obtains solid crude product；Finally pass it through tetrahydrofuran washing, methylene chloride is tied again
It is brilliant and be dried in vacuo to obtain pale white solid, as intermediate compound I (yield 89%)；Fusing point is 66-68 DEG C.
(2) in the in the mixed solvent of 35mL dehydrated alcohol+10mL methylene chloride, six water of 1.19g (5.0mmol) are first added
It is anti-at 25 DEG C -35 DEG C after conjunction Nickel Chloride is vigorously stirred the intermediate compound I for adding 3.25g (5.5mmol) to being completely dissolved
It answers stopping reaction after 0.5h to obtain brick-red turbid solution, is removed mixed solvent and obtains sticky solid, finally pass it through nothing
Water-ethanol and methylene chloride successively wash, anhydrous methanol recrystallization, are dried in vacuo to obtain brick-red powder solid, as intermediate II
(yield 90%)；Fusing point is greater than 250 DEG C.
The structural characterization data of intermediate II (X=Cl) are as follows:1H-NMR(CD2Cl2,400MHz,TMS)δH/ ppm:
7.99-7.94(m,8H,4C6 H 5-o),7.67-7.52(m,12H,4C6 H 5- m, p), 3.56 (q, J=7.2Hz, 6H,
3OCH 2CH3),2.81-2.74(m,2H,NCH 2CH2CH2Si),1.22-1.14(m,2H,NCH2CH 2CH2), Si 1.02 (t, J=
7.2Hz,9H,3OCH2CH 3), 0.14 (t, J=8.0Hz, 2H, NCH2CH2CH 2Si).31P-NMR(CDCl3, 162MHz, 85%
H3PO4)δp/ ppm:41.46 (s)
(3) under nitrogen atmosphere protection, the intermediate II (brick-red powder) by 1.44g (2.0mmol) containing double chlorine is added
In 35mL methylene chloride and stirring and dissolving, then be slowly injected into 0.2mL (2.4mmol) 2- it is thio -1,3- dimercaptopropane, it is then slow
The slow triethylamine acid binding agent that 0.8mL (6.0mmol) is added dropwise, red reaction solution, which is stirred at room temperature in reaction process, becomes dark solution,
Stop reacting to obtain black turbid solution after room temperature reaction 1h, it is filtered to remove triethylamine hydrochloride by sand core and obtains black liquid
Body, revolving remove methylene chloride and obtain sticky solid；Finally pass it through anhydrous methanol, tetrahydrofuran and ether successively wash, two
Chloromethanes recrystallization, vacuum drying obtain black solid, as metal complex (yield 85%).
The structural characterization data of metal complex are as follows:1H-NMR(CD2Cl2,400MHz,TMS)δH/ ppm:8.00-7.81
(m,8H,4C6 H 5-o),7.67-7.46(m,12H,4C6 H 5- m, p), 3.56 (q, J=7.2Hz, 6H, 3OCH 2CH3),2.90-
2.80(m,2H,NCH 2CH2CH2Si),1.25-1.16(m,4H,2SCH 2), 1.03 (t, J=7.2Hz, 9H, 3OCH2CH 3),
0.88-0.85(m,2H,NCH2CH 2CH2), Si 0.14 (t, J=8.0Hz, 2H, NCH2CH2CH 2Si).31P-NMR(CDCl3,
162MHz, 85%H3PO4)δp/ ppm:63.13 (s)
Embodiment 2
A kind of metal complex that concerted catalysis containing P/N/Si/S/Ni is fire-retardant the preparation method comprises the following steps:
(1) in the methylene chloride of 30mL, the 3-aminopropyltriethoxysilane of 2.3mL (10mmol) is first added, then
It is slowly added to the diphenyl phosphorus chloride of 4.1mL (23mmol), is then slowly added to the triethylamine of 3.1mL (22mmol)；Room temperature is stirred
After mixing reaction overnight, obtain faint yellow suspension, by its by sand core be filtered to remove triethylamine hydrochloride solid obtain it is faint yellow
Liquid is rotated removing methylene chloride and obtains solid crude product；Finally pass it through tetrahydrofuran washing, methylene chloride is tied again
It is brilliant and be dried in vacuo to obtain pale white solid, as intermediate compound I (yield 88%).
(2) in the in the mixed solvent of 35mL dehydrated alcohol+10mL methylene chloride, the anhydrous of 1.10g (5.0mmol) is first added
After Nickel Bromide is vigorously stirred the intermediate compound I for adding 3.25g (5.5mmol) to being completely dissolved, reacted at 25 DEG C -35 DEG C
Stop reaction after 0.5h and obtain red turbid solution, is removed mixed solvent and obtains sticky solid, finally pass it through anhydrous second
Pure and mild methylene chloride successively washs, anhydrous methanol recrystallization, is dried in vacuo to obtain red powder solid, as intermediate II (yield
For 87%).
(3) under nitrogen atmosphere protection, the intermediate II (red powder) by 1.62g (2.0mmol) containing double bromines is added
In 35mL methylene chloride and stirring and dissolving, then be slowly injected into 0.2mL (2.4mmol) 2- it is thio -1,3- dimercaptopropane, it is then slow
The slow triethylamine acid binding agent that 0.8mL (6.0mmol) is added dropwise, red reaction solution, which is stirred at room temperature in reaction process, becomes dark solution,
Stop reacting to obtain black turbid solution after room temperature reaction 1h, it is filtered to remove triethylamine hydrochloride by sand core and obtains black liquid
Body, revolving remove methylene chloride and obtain sticky solid；Finally pass it through anhydrous methanol, tetrahydrofuran and ether successively wash, two
Chloromethanes recrystallization, vacuum drying obtain black solid, as metal complex (yield 89%).
Embodiment 3
A kind of metal complex that concerted catalysis containing P/N/Si/S/Ni is fire-retardant the preparation method comprises the following steps:
(1) in the methylene chloride of 30mL, the 3-aminopropyltriethoxysilane of 2.3mL (10mmol) is first added, then
It is slowly added to the diphenyl phosphorus chloride of 4.1mL (23mmol), is then slowly added to the triethylamine of 3.1mL (22mmol)；Room temperature is stirred
After mixing reaction overnight, obtain faint yellow suspension, by its by sand core be filtered to remove triethylamine hydrochloride solid obtain it is faint yellow
Liquid is rotated removing methylene chloride and obtains solid crude product；Finally pass it through tetrahydrofuran washing, methylene chloride is tied again
It is brilliant and be dried in vacuo to obtain pale white solid, as intermediate compound I (yield 91%).
(2) in the in the mixed solvent of 35mL anhydrous methanol+10mL methylene chloride, the anhydrous of 1.34g (5.0mmol) is first added
After diiodinating nickel is vigorously stirred the intermediate compound I for adding 3.25g (5.5mmol) to being completely dissolved, reacted at 25 DEG C -35 DEG C
Stop reaction after 0.5h and obtain peony turbid solution, is removed mixed solvent and obtains sticky solid, finally pass it through anhydrous
Ethyl alcohol and methylene chloride successively wash, anhydrous methanol recrystallization, are dried in vacuo to obtain dark red powder solid, as intermediate II
(yield 85%).
(3) under nitrogen atmosphere protection, the intermediate II (dark red powder) by 1.73g (2.0mmol) containing double iodine is added
In 35mL methylene chloride and stirring and dissolving, then be slowly injected into 0.2mL (2.4mmol) 2- it is thio -1,3- dimercaptopropane, it is then slow
The slow triethylamine acid binding agent that 0.8mL (6.0mmol) is added dropwise, red reaction solution, which is stirred at room temperature in reaction process, becomes dark solution,
Stop reacting to obtain black turbid solution after room temperature reaction 1h, it is filtered to remove triethylamine hydrochloride by sand core and obtains black liquid
Body, revolving remove methylene chloride and obtain sticky solid；Finally pass it through anhydrous methanol, tetrahydrofuran and ether successively wash, two
Chloromethanes recrystallization, vacuum drying obtain black solid, as metal complex (yield 92%).
Embodiment 4
A kind of metal complex that concerted catalysis containing P/N/Si/S/Ni is fire-retardant the preparation method comprises the following steps:
(1) in the methylene chloride of 50mL, the 3-aminopropyltriethoxysilane of 4.6mL (20mmol) is first added, then
It is slowly added to the diphenyl phosphorus chloride of 8.2mL (46mmol), is then slowly added to the triethylamine of 6.2mL (44mmol)；Room temperature is stirred
After mixing reaction overnight, obtain faint yellow suspension, by its by sand core be filtered to remove triethylamine hydrochloride solid obtain it is faint yellow
Liquid is rotated removing methylene chloride and obtains solid crude product；Finally pass it through tetrahydrofuran washing, methylene chloride is tied again
It is brilliant and be dried in vacuo to obtain pale white solid, as intermediate compound I (yield 85%).
(2) in the in the mixed solvent of 35mL anhydrous methanol+10mL methylene chloride, six water of 1.79g (7.5mmol) are first added
It is anti-at 25 DEG C -35 DEG C after conjunction Nickel Chloride is vigorously stirred the intermediate compound I for adding 4.89g (8.3mmol) to being completely dissolved
It answers stopping reaction after 0.5h to obtain brick-red turbid solution, is removed mixed solvent and obtains sticky solid, finally pass it through nothing
Water-ethanol and methylene chloride successively wash, anhydrous methanol recrystallization, are dried in vacuo to obtain brick-red powder solid, as intermediate II
(yield 88%).
(3) under nitrogen atmosphere protection, the intermediate II (brick-red powder) by 1.44g (2.0mmol) containing double chlorine is added
In 35mL tetrahydrofuran and stirring and dissolving, then be slowly injected into 0.18mL (2.2mmol) 2- it is thio -1,3- dimercaptopropane, then
The triethylamine acid binding agent of 0.53mL (4.0mmol) is slowly added dropwise, red reaction solution is stirred at room temperature in reaction process, and to become black molten
Liquid stops reacting to obtain black turbid solution, it is filtered to remove triethylamine hydrochloride by sand core and obtains black after reacting at room temperature 1h
Liquid, revolving remove methylene chloride and obtain sticky solid；Finally pass it through anhydrous methanol, tetrahydrofuran and ether successively wash,
Recrystallize with dichloromethane, vacuum drying obtain black solid, as metal complex (yield 80%).
Embodiment 5
A kind of metal complex that concerted catalysis containing P/N/Si/S/Ni is fire-retardant the preparation method comprises the following steps:
(1) in the methylene chloride of 35mL, the 3-aminopropyltriethoxysilane of 3.45mL (15mmol) is first added, then
It is slowly added to the diphenyl phosphorus chloride of 6.20mL (35mmol), is then slowly added to the triethylamine of 4.70mL (33mmol)；Room temperature
After being stirred overnight reaction, obtain faint yellow suspension, by its by sand core be filtered to remove triethylamine hydrochloride solid obtain it is yellowish
Color liquid is rotated removing methylene chloride and obtains solid crude product；Finally pass it through tetrahydrofuran washing, methylene chloride weight
Crystallize and be dried in vacuo and to obtain pale white solid, as intermediate compound I (yield 83%).
(2) in the in the mixed solvent of 45mL anhydrous methanol+10mL methylene chloride, the anhydrous of 1.32g (6.0mmol) is first added
After Nickel Bromide is vigorously stirred the intermediate compound I for adding 3.90g (6.6mmol) to being completely dissolved, reacted at 25 DEG C -35 DEG C
Stop reaction after 0.5h and obtain red turbid solution, is removed mixed solvent and obtains sticky solid, finally pass it through anhydrous second
Pure and mild methylene chloride successively washs, anhydrous methanol recrystallization, is dried in vacuo to obtain red powder solid, as intermediate II (yield
For 85%).
(3) under nitrogen atmosphere protection, the intermediate II (red powder) by 1.62g (2.0mmol) containing double bromines is added
In 30mL tetrahydrofuran+5mL ether and stirring and dissolving, then be slowly injected into 0.18mL (2.2mmol) 2- it is thio -1,3-, the third two sulphur
The pyridine acid binding agent of 0.53mL (4.0mmol) is then slowly added dropwise in alcohol, and red reaction solution, which is stirred at room temperature in reaction process, becomes black
Color solution, react at room temperature 1h after stop react to obtain black turbid solution, by its by sand core be filtered to remove pyridine hydrochloride obtain it is black
Color liquid, revolving remove methylene chloride and obtain sticky solid；Anhydrous methanol, tetrahydrofuran and ether is finally passed it through successively to wash
It washs, recrystallize with dichloromethane, vacuum drying obtain black solid, as metal complex (yield 84%).
Embodiment 6
A kind of metal complex that concerted catalysis containing P/N/Si/S/Ni is fire-retardant the preparation method comprises the following steps:
(1) in the methylene chloride of 60mL, the 3-aminopropyltriethoxysilane of 6.9mL (30mmol) is first added, then
It is slowly added to the diphenyl phosphorus chloride of 12.3mL (69mmol), is then slowly added to the triethylamine of 6.3mL (66mmol)；Room temperature is stirred
After mixing reaction overnight, obtain faint yellow suspension, by its by sand core be filtered to remove triethylamine hydrochloride solid obtain it is faint yellow
Liquid is rotated removing methylene chloride and obtains solid crude product；Finally pass it through tetrahydrofuran washing, methylene chloride is tied again
It is brilliant and be dried in vacuo to obtain pale white solid, as intermediate compound I (yield 82%).
(2) in the in the mixed solvent of 45mL anhydrous methanol+10mL methylene chloride, the anhydrous of 1.61g (6.0mmol) is first added
After diiodinating nickel is vigorously stirred the intermediate compound I for adding 3.90g (6.6mmol) to being completely dissolved, reacted at 25 DEG C -35 DEG C
Stop reaction after 0.5h and obtain peony turbid solution, is removed mixed solvent and obtains sticky solid, finally pass it through anhydrous
Ethyl alcohol and methylene chloride successively wash, anhydrous methanol recrystallization, are dried in vacuo to obtain dark red powder solid, as intermediate II
(yield 83%).
(3) under nitrogen atmosphere protection, the intermediate II (dark red powder) by 1.73g (2.0mmol) containing double iodine is added
The in the mixed solvent and stirring and dissolving of 30mL methylene chloride+10mL ether, then it is slowly injected into the 2- sulphur of 0.21mL (2.2mmol)
Generation -1,3- dimercaptopropane, is then slowly added dropwise the diisopropylethylamine acid binding agent of 1.06mL (8.0mmol), reaction is stirred at room temperature
Red reaction solution becomes dark solution in the process, stops reacting to obtain black turbid solution after reacting at room temperature 1h, it is passed through sand core mistake
It filters out diisopropylethylamine hydrochloride and obtains black liquor, revolving removes methylene chloride and obtains sticky solid；Finally pass it through
Anhydrous methanol, tetrahydrofuran and ether successively wash, recrystallize with dichloromethane, vacuum drying obtain black solid, as metal
Complex (yield 85%).
Claims (5)
1. a kind of fire-retardant metal complex of concerted catalysis containing P/N/Si/S/Ni, which is characterized in that its structural formula are as follows:
。
2. a kind of preparation method of the fire-retardant metal complex of concerted catalysis containing P/N/Si/S/Ni, which is characterized in that the metal is matched
Conjunction object is as described in claim 1, which includes the following steps:
Intermediate II is dissolved in the second solvent, be then stirred at room temperature down be successively added dropwise 2- it is thio -1,3- dimercaptopropane and tie up acid
Agent, after reacting 0.5-1.5h, by crude product by sand core filtering, concentrated by rotary evaporation, dehydrated alcohol, tetrahydrofuran, ether are successively washed
It washs, recrystallize with dichloromethane, is dried in vacuo, obtains metal complex；Its structural formula of the intermediate II are as follows:
X is Cl, Br, I in the structural formula.
3. a kind of preparation method of the fire-retardant metal complex of concerted catalysis containing P/N/Si/S/Ni according to claim 2,
It is characterized in that, the intermediate II, 2- it is thio-molar ratio of 1,3- dimercaptopropane and acid binding agent is 1:1.1~1.3:2~4.
4. a kind of preparation method of the fire-retardant metal complex of concerted catalysis containing P/N/Si/S/Ni according to claim 2,
It is characterized in that, second solvent is mixture, the tetrahydrofuran of methylene chloride, tetrahydrofuran, methylene chloride and ether
With the mixture of ether.
5. a kind of preparation method of the fire-retardant metal complex of concerted catalysis containing P/N/Si/S/Ni according to claim 2,
It is characterized in that, the acid binding agent is triethylamine, pyridine and diisopropylethylamine.
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