CN107312040A - A kind of phosphazene compound, Preparation method and use - Google Patents
A kind of phosphazene compound, Preparation method and use Download PDFInfo
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- CN107312040A CN107312040A CN201610264487.3A CN201610264487A CN107312040A CN 107312040 A CN107312040 A CN 107312040A CN 201610264487 A CN201610264487 A CN 201610264487A CN 107312040 A CN107312040 A CN 107312040A
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- substituted
- phosphonitrile
- unsubstituted
- phosphazene compound
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- -1 phosphazene compound Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 13
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 229920006351 engineering plastic Polymers 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 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 3
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 125000004430 oxygen atom Chemical group O* 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 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 description 8
- 239000002585 base Substances 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BXJGUBZTZWCMEX-UHFFFAOYSA-N 2,3-dimethylbenzene-1,4-diol Chemical group CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-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
- 238000004378 air conditioning Methods 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K13/04—Ingredients characterised by their shape and organic or 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
- C08K3/34—Silicon-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
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of phosphazene compound, the phosphazene compound has formula (I) structure：Wherein, Y and R1It is each independently selected from organic group；M is phosphazenium groups；X1、X2It is optionally O or S independently of one another with A；R is selected from sub- organic group；A be selected from 0~5 integer, b be selected from 1~6 integer, and meet a and b plus and equal to 2 times of number of phosphorus atoms in phosphazenium groups；C is >=0 integer.The present invention on phosphazenium groups by introducing ammonium salt, realize the Synergistic with phosphazenium groups P, N, improve its heat endurance, flame retardant type and the compatibility with other components, with good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property, so as to expand its application.
Description
Technical field
The invention belongs to the technical field of fire retardant matter, it is related to phosphazene compound, Preparation method and use, and in particular to one
Plant phosphonitrile ammonium salt compound, preparation method and the application in engineering plastics, coating and building element.
Background technology
Using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, sound
The various products that articles for use etc. use for family expenses, office electric equipment products and the other field of representative are rung, for safety, significant portion
Product require that it possesses different degrees of fire resistance.
In order that product reaches required fire resistance or grade, traditional technology is usually used to be added into material system
Plus such as inorganic fire-retarded thing of the class such as the metal hydroxides of aluminium hydroxide hydrate, magnesium hydroxide hydrate containing the crystallization water
Matter and into system material add such as brominated amount of brominated bisphenol A, brominated bisphenol a type epoxy resin it is higher or containing halogen
The higher organic chemicals of amount, in order to improve the anti-flammability of these organic chemicals for containing halogen, also usually in body
Such as antimony oxide is added in system to the disagreeableness inorganic chemistry fire retardant material of environment.
Due to using halogen-containing fire retardant matter, it can produce the noxious material such as two of no degradability or difficult degradation when burning
Dislike English class organic halogen chemical contamination environment, the influence mankind and animal health.
For the purpose of environmental protection, made using the not halogen-containing compound such as phosphorous, nitrogenous instead of halogen contained compound
For fire retardant, particularly on electronics, electric, Electric Industrial, phosphonitrilic polymer is a kind of fire-retardant high polymer, its phosphorus nitrogen having
Coordination system makes its flame retardant effect fine.
As electronic product is to short, small, thin, high multiple stratification, the further raising of high reliability request, civilian consumer electronics
Popularization use and the factor such as increasingly severeer pressure of environmental pollution requirement, market is good in the urgent need to material has
Anti-flammability, heat resistance, the cheap anti-flammability material of good mechanical performance.
The content of the invention
It is an object of the invention to provide a kind of phosphazene compound, the phosphazene compound has formula (I) structure：
Wherein, Y and R1It is each independently selected from organic group；
M is phosphazenium groups；
X1、X2It is optionally any one in the 6th major element independently of one another with A；
R is selected from sub- organic group；
A be selected from 0~5 integer, b be selected from 1~6 integer, and meet a and b plus and equal to phosphorus atoms in phosphazenium groups
2 times of number；
C is >=0 integer.
For the difference of phosphorus atoms ratio in M, a is different with b value, it is only necessary to meet adding and equal to phosphonitrile base for a and b
2 times of number of phosphorus atoms in group.
Preferably, the M is selected from the cyclic phosphazene with formula (II) structure, or the linear phosphonitrile with formula (III) structure；
In formula (II) or formula (III), n1And n2It is each independently selected from 3~10 integer, such as 4,5,6,7,8,9
Deng n1It is preferred that 3 or 4, n2It is preferred that 5,6,7 or 8；
It is preferred that the phosphonitrile base M of ring three1, the phosphonitrile base M of ring four2Or non-annularity polyphosphazene base M3In any a kind or at least two kinds of
Combination；It is preferred that M is the phosphonitrile base M of ring three1。
Note, M1、M2In the expression of structural formula, there is symbolOnly to one kind of " ring-type " structure
Signal.
Here it is possible to understand, Y-X1More example is phenoxy group.
Preferably, Y and R1Selected from substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted branched hydrocarbyl or substitution or
Unsubstituted aromatic radical；It is preferred that C1~C30Substituted or unsubstituted straight-chain alkyl, C1~C30Substituted or unsubstituted branched-chain hydrocarbons
Base or C6~C30Substituted or unsubstituted aromatic radical；Further preferred C1~C10Substituted or unsubstituted straight-chain alkyl, C1~
C10Substituted or unsubstituted branched hydrocarbyl or C6~C16Substituted or unsubstituted aromatic radical；Particularly preferred R1Selected from methyl, ethyl,
N-propyl, normal-butyl, isopropyl or isobutyl group；Particularly preferred Y be selected from phenyl, benzyl, phenethyl, to 3,5-dimethylphenyl.
It is further preferred that R1For H.
It is further preferred that Y is phenyl.
Preferably, R be selected from substituted or unsubstituted straight chain alkylene group, substituted or unsubstituted branched alkylene, substitution or
Unsubstituted arylene；It is preferred that C1~C30Substituted or unsubstituted straight chain alkylene group, C1~C30Substituted or unsubstituted branch
Chain alkylene, C6~C30Substituted or unsubstituted arylene；Further preferred C1~C10Substituted or unsubstituted straight chain it is sub-
Alkyl, C1~C10Substituted or unsubstituted branched alkylene, C6~C16Substituted or unsubstituted arylene；Particularly preferred methylene
Base, ethylidene, propylidene, sub- normal-butyl or isopropylidene.
Preferably, X1、X2It is O with A.
Preferably, c is 0,1,2,3,4 or 5.
Preferably, the phosphazene compound is selected fromWherein a be selected from 0~
5 integer, b be selected from 1~6 integer, and meet a and b plus and equal to 2 times of number of phosphorus atoms in phosphazenium groups M.
Preferably, the phosphazene compound is selected fromWherein a is selected from 0
~5 integer, b be selected from 1~6 integer, and meet a and b plus and equal to 2 times of number of phosphorus atoms in phosphazenium groups M.
Preferably, M includes at least 50wt% n1The phosphonitrile, at most 30wt% n of=3 formula (II) structure1>=4 formula
(II) phosphonitrile of structure and the at most phosphonitrile of 45wt% formula (III) structure.
If n1The phosphonitrile content of=3 formula (II) structure is less than 50wt%, or n1The phosphonitrile of >=4 formula (II) structure is more
In 30wt%, then heat resistance, water resistance and mechanical performance etc. will be damaged in use with the reacted product of epoxy resin
Must performance；The content of the phosphonitrile of formula (III) structure comprises up to the 45% of phosphazenium groups gross mass, if exceeding the content, with
The reacted product of epoxy resin would be possible to because viscosity is excessive, inconvenient for use in use, and because molecular weight is excessive and
The bad result such as make its performance suffer damage.
The two of the object of the invention are to provide a kind of a kind of preparation method of the phosphazene compound as described in the first purpose, described
Method comprises the following steps：
Phosphonitrile chloride and the first starting compound are subjected to nucleophilic substitution, obtained described in one of Claims 1 to 4
Phosphazene compound；
The phosphonitrile chloride is M (Cl)m, the m values are 2 times of phosphorus atoms in M；
First starting compound is Y-X1- H andWherein, X1、X2, A, M, c and R1
With with the identical meanings described in one of Claims 1 to 4, preferably X1、X2, A be O, R1For H.
The instantiation of the catalyst of nucleophilic substitution has the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride, trifluoro
Change the lewis base such as boron and its complex compound, sodium hydroxide.These catalyst one or more can be used in mixed way, in the present invention
Have no special regulation.Phosphonitrile chloride can be using most commonly used hexachlorocyclotriph,sphazene of originating.
It is described phosphonitrile chloride and the first starting compound are subjected to nucleophilic substitution during, the first raw material chemical combination
In thing Y-X1-H andIt can simultaneously add, can also add in two steps, it is first anti-with Y-X1-H
Should, Ran HouyuReaction.
The three of the object of the invention are to provide a kind of another preparation method of the phosphazene compound as described in the first purpose, institute
The method of stating comprises the following steps：
(1) phosphonitrile chloride and the second starting compound are subjected to nucleophilic substitution；
The phosphonitrile chloride is M (Cl)m, the m values are 2 times of phosphorus atoms in M；
Second starting compound is Y-X1- H andWherein, X1、X2, A, M, c and R1
With with the identical meanings described in one of Claims 1 to 4；It is preferred that X1、X2, A be O；
(2) product for obtaining step (1) reacts the phosphazene compound obtained described in one of Claims 1 to 4 with ammoniacal liquor.
It is described phosphonitrile chloride and the second starting compound are subjected to nucleophilic substitution during, the second raw material chemical combination
Y-X in thing1- H andIt can simultaneously add, can also add in two steps, elder generation and Y-X1- H reacts,
Then withReaction.
The four of the object of the invention are to provide a kind of engineering plastics, include the phosphonitrile ammonium salts described in the first purpose.
Above-mentioned phosphonitrile ammonium salts are added in the engineering plastics, fire retardant is served as.
As for the resin in engineering plastics, nucleator, antioxidant, coupling agent etc., other auxiliary agents can be using known material.
The five of the object of the invention are to provide a kind of coating, include the phosphonitrile ammonium salts described in the first purpose.
Phosphonitrile ammonium salts are added in the coating, fire retardant or catalyst is served as.
Other auxiliary agents such as emulsion, dispersant, defoamer, coupling agent in the coating can use known technology.
The six of the object of the invention are to provide a kind of building element, and the surface of the building element is coated with described in the fifth purpose
Coating.
The building element has preferably anti-flammability, heat resistance and mechanical performance.
Term " ××× base or group " of the present invention refer to sloughed in ××× molecular structure of compounds it is one or more
Remaining part after hydrogen atom or other atoms or atomic group.
Compared with prior art, the invention has the advantages that：
The present invention realizes the Synergistic with phosphazenium groups P, N, improves it by introducing ammonium salt on phosphazenium groups
Heat endurance, flame retardant type and the compatibility with other components, with good heat resistance, water resistance, cohesiveness and mechanicalness
Energy, electrical property, so as to expand its application.
Embodiment
Technical scheme is further illustrated below by embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
Embodiment 1
A kind of phosphazene compound 1, with following structure：
Preparation method is：
(1) in the reactor, the ammonia spirit of the hydroquinones of the amount part of 8 materials is dissolved in dioxane, then
The sodium carbonate of the hexachlorocyclotriph,sphazene of the amount part of 1 material and the amount part of 0.5 material is added, nitrogen protection is passed through, in reflux temperature
Lower reaction 24 hours, obtains phosphazene compound 1, yield 80%.
Performance characterization：
Infrared spectrum is：1198cm-1(P=O)；1203cm-1、1184cm-1、1162cm-1(P=N)；3084cm-1、
1590cm-1、1489cm-1、1451cm-1(phenyl ring)；
1H-NMR (DMSO-d6, ppm) nuclear magnetic spectrum is：7.0~7.2 (the O atom ortho position being connected on phenyl ring with ammonium salt
Hydrogen, 12H), 6.6~6.8 (hydrogen at the O atom ortho position being connected on phenyl ring with the phosphonitrile of ring three, 12H).
Embodiment 2
A kind of phosphazene compound 2, with following structure：
Preparation method is：
(1) in the reactor, the phenol of the amount part of 1 material is dissolved in dioxane, then adds the amount part of 1 material
Hexachlorocyclotriph,sphazene and 0.5 material amount part sodium carbonate, be passed through nitrogen protection, react 24 hours at a reflux temperature；
(2) by the amount 1 of step (1) and hydroquinones according to material:6 mixing, are passed through nitrogen protection, at a reflux temperature instead
Answer 24 hours；Washing removes the raw materials such as unnecessary excessive hydroquinones；
(3) product for adding ammoniacal liquor neutralization procedure (2) obtains phosphazene compound 2；
Performance characterization：
Infrared spectrum is：1198cm-1(P=O)；1203cm-1、1184cm-1、1162cm-1(P=N)；3084cm-1、
1590cm-1、1489cm-1、1451cm-1(phenyl ring)；
1H-NMR (DMSO-d6, ppm) nuclear magnetic spectrum is：7.0~7.2 (the O atom ortho position being connected on phenyl ring with ammonium salt
Hydrogen, 12H), 6.6~6.8 (hydrogen at the O atom ortho position being connected on phenyl ring with the phosphonitrile of ring three, 12H), 6.8~6.9 (with ring on phenyl ring
The hydrogen of the O atom contraposition of three phosphonitriles connection, 1H).
Embodiment 3
A kind of phosphazene compound 3, with following structure：
Preparation method is：
(1) in the reactor, the phenol of the amount part of 1 material is dissolved in dioxane, then adds the amount part of 1 material
The phosphonitrile of eight chlorine ring four and 0.5 material amount part sodium carbonate, be passed through nitrogen protection, react 24 hours at a reflux temperature；
(2) by the amount 1 of step (1) and adjacent dimethyl hydroquinones according to material:8 mixing, are passed through nitrogen protection, in backflow
At a temperature of react 24 hours；Washing removes the raw materials such as unnecessary adjacent dimethyl hydroquinones；
(3) product for adding ammoniacal liquor neutralization procedure (2) obtains phosphazene compound 3；
Performance characterization：
Infrared spectrum is：1198cm-1(P=O)；1203cm-1、1184cm-1、1162cm-1(P=N)；3084cm-1、
1590cm-1、1489cm-1、1451cm-1(phenyl ring)；2800cm-1、1300cm-1(methyl)
1H-NMR (DMSO-d6, ppm) nuclear magnetic spectrum is：6.1~6.2 (the O atom ortho position being connected on phenyl ring with ammonium salt
Hydrogen, 10H), 6.6~6.8 (hydrogen at the O atom ortho position being connected on phenyl ring with the phosphonitrile of ring three, 12H), 7.05~7.12 (on phenyl ring with
The hydrogen of the O atom meta of the phosphonitrile of ring three connection, 12H), 6.8~6.9 (O atom that be connected on phenyl ring with the phosphonitrile of ring three is aligned
Hydrogen, 1H), 2.33~2.37 (hydrogen of methyl, 6H).
Application examples 1
A kind of engineering plastics, raw materials by weight portion includes following component：
The parts by weight of nylon 66 resin 100
Glass fibre (being specially boron trioxide) 100 parts by weight
Antioxidant (being specially antioxidant 1010) 10 parts by weight
Nucleator (being specially talcum powder) 10 parts by weight
The parts by weight of phosphazene compound 100 that embodiment is prepared；
Preparation method is：Extruder blending extrusion is used after raw material is mixed according to formula rate, you can obtain engineering plastics,
Engineering plastics 1 (embodiment 1), engineering plastics 2 (embodiment 2), engineering plastics 3 (embodiment 3) are designated as respectively.
Application examples 2
A kind of coating, raw materials by weight portion includes following component：
The parts by weight of elastic polyurethane emulsion 50
Curing agent (being specially dimethylaniline) 5 parts by weight
The parts by weight of expanded graphite 5
The parts by weight of phenolic group propane epoxy resin 20
Solvent (being specially isopropyl acetate) 60 parts by weight
The parts by weight of phosphazene compound 5 that embodiment is prepared；Preparation method is：Raw material is mixed according to formula rate
Stir afterwards and, through high speed it is scattered after coating is made, coating 1 (embodiment 1), coating 2 (embodiment 2), coating 3 are designated as respectively
(embodiment 3).
The performance test results：
The performance comparision for the engineering plastics that the application examples of table -1 is provided
| Test event | Engineering plastics 1 | Engineering plastics 2 | Engineering plastics 3 |
| Tg(DSC)(℃) | 151 | 153 | 154 |
| Saturated water absorption (%) | 0.30 | 0.31 | 0.33 |
| Heat decomposition temperature (DEG C) | 391 | 395 | 397 |
| Bending strength (kg/mm2) | 11.9 | 12.2 | 12.3 |
| Flammability (UL-94) | V-0 | V-0 | V-0 |
The performance comparision for the coating that the application examples of table -2 is provided
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Peel strength (kg/mm2) | 1.85 | 1.85 | 1.88 |
| Interlaminar strength (kg/mm2) | 1.62 | 1.65 | 1.70 |
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (9)
1. a kind of phosphazene compound, it is characterised in that the phosphazene compound has formula (I) structure：
Wherein, Y and R1It is each independently selected from organic group；
M is phosphazenium groups；
X1、X2It is optionally any one in the 6th major element independently of one another with A；
R is selected from sub- organic group；
A be selected from 0~5 integer, b be selected from 1~6 integer, and meet a and b plus and equal to number of phosphorus atoms in phosphazenium groups
2 times；
C is >=0 integer.
2. phosphazene compound as claimed in claim 1, it is characterised in that the M is selected from the ring-type phosphorus with formula (II) structure
Nitrile, or the linear phosphonitrile with formula (III) structure；
In formula (II) or formula (III), n1And n2It is each independently selected from 3~10 integer, n1It is preferred that 3 or 4, n2It is preferred that 5,6,
7 or 8；
It is preferred that the phosphonitrile base M of ring three1, the phosphonitrile base M of ring four2Or non-annularity polyphosphazene base M3In any a kind or at least two kinds of of combination；
It is preferred that M is the phosphonitrile base M of ring three1；
Preferably, Y and R1Do not take selected from substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted branched hydrocarbyl or substitution or
The aromatic radical in generation；It is preferred that C1~C30Substituted or unsubstituted straight-chain alkyl, C1~C30Substituted or unsubstituted branched hydrocarbyl or
C6~C30Substituted or unsubstituted aromatic radical；Further preferred C1~C10Substituted or unsubstituted straight-chain alkyl, C1~C10Take
Generation or unsubstituted branched hydrocarbyl or C6~C16Substituted or unsubstituted aromatic radical；Particularly preferred R1Selected from methyl, ethyl, positive third
Base, normal-butyl, isopropyl or isobutyl group；Particularly preferred Y be selected from phenyl, benzyl, phenethyl, to 3,5-dimethylphenyl；
It is further preferred that R1For H；
It is further preferred that Y is phenyl；
Preferably, R is selected from substituted or unsubstituted straight chain alkylene group, substituted or unsubstituted branched alkylene, substitution or not taken
The arylene in generation；It is preferred that C1~C30Substituted or unsubstituted straight chain alkylene group, C1~C30Substituted or unsubstituted side chain is sub-
Alkyl, C6~C30Substituted or unsubstituted arylene；Further preferred C1~C10Substituted or unsubstituted straight chain alkylene group,
C1~C10Substituted or unsubstituted branched alkylene, C6~C16Substituted or unsubstituted arylene；Particularly preferred methylene, Asia
Ethyl, propylidene, sub- normal-butyl or isopropylidene；
Preferably, X1、X2It is O with A；
Preferably, c is 0,1,2,3,4 or 5.
3. phosphazene compound as claimed in claim 1 or 2, it is characterised in that the phosphazene compound is selected fromWherein, a is selected from 0~5 integer, and b is selected from 1~6 integer, and meets a
With b's plus and equal to 2 times of number of phosphorus atoms in phosphazenium groups M；
Preferably, the phosphazene compound is selected fromWherein a is selected from 0~5
Integer, b be selected from 1~6 integer, and meet a and b plus and equal to 2 times of number of phosphorus atoms in phosphazenium groups M.
4. the non-reacted phosphazene compound according to one of claims 1 to 3, it is characterised in that M includes at least 50wt%
N1The phosphonitrile, at most 30wt% n of=3 formula (II) structure1The phosphonitrile of >=4 formula (II) structure and at most 45wt%'s
The phosphonitrile of formula (II) structure.
5. a kind of preparation method of phosphazene compound as described in one of Claims 1 to 4, it is characterised in that methods described bag
Include following steps：
Phosphonitrile chloride and the first starting compound are subjected to nucleophilic substitution, the phosphorus described in one of Claims 1 to 4 is obtained
Nitrile compound；
The phosphonitrile chloride is M (Cl)m, the m values are 2 times of phosphorus atoms in M；
First starting compound is Y-X1- H andWherein, X1、X2, A, M, c and R1Have
With the identical meanings described in one of Claims 1 to 4, preferably X1、X2, A be O, R1For H.
6. a kind of preparation method of phosphazene compound as described in one of Claims 1 to 4, it is characterised in that methods described bag
Include following steps：
(1) phosphonitrile chloride and the second starting compound are subjected to nucleophilic substitution；
The phosphonitrile chloride is M (Cl)m, the m values are 2 times of phosphorus atoms in M；
Second starting compound is Y-X1- H andWherein, X1、X2, A, M, c and R1With with
Identical meanings described in one of Claims 1 to 4；, preferably X1、X2, A be O；
(2) product for obtaining step (1) reacts the phosphazene compound obtained described in one of Claims 1 to 4 with ammoniacal liquor.
7. a kind of engineering plastics, it is characterised in that include the phosphonitrile ammonium salts described in one of claims 1 to 3.
8. a kind of coating, it is characterised in that include the phosphonitrile ammonium salts described in one of claims 1 to 3.
9. a kind of building element, it is characterised in that the surface of the building element is coated with the coating described in claim 8.
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Citations (2)
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|---|---|---|---|---|
| US20030152777A1 (en) * | 2002-02-07 | 2003-08-14 | Shoichi Osada | Semiconductor encapsulating flame retardant epoxy resin composition and semiconductor device |
| CN103665359A (en) * | 2013-10-16 | 2014-03-26 | 上海大学 | Preparation method of phosphorus and nitrogen-containing liquid crystal copolyester material |
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2016
- 2016-04-26 CN CN201610264487.3A patent/CN107312040A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030152777A1 (en) * | 2002-02-07 | 2003-08-14 | Shoichi Osada | Semiconductor encapsulating flame retardant epoxy resin composition and semiconductor device |
| CN103665359A (en) * | 2013-10-16 | 2014-03-26 | 上海大学 | Preparation method of phosphorus and nitrogen-containing liquid crystal copolyester material |
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| Title |
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| C. Y. YUAN ET AL: "Thermally stable and flame-retardant aromatic phosphate and cyclotriphosphazene-containing polyurethanes: synthesis and properties", 《POLYM. ADV. TECHNOL.》 * |
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