CN109503666B - Flame retardant trimerization O, O-propylene phosphazene compound and preparation method thereof - Google Patents
Flame retardant trimerization O, O-propylene phosphazene compound and preparation method thereof Download PDFInfo
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- CN109503666B CN109503666B CN201811568931.6A CN201811568931A CN109503666B CN 109503666 B CN109503666 B CN 109503666B CN 201811568931 A CN201811568931 A CN 201811568931A CN 109503666 B CN109503666 B CN 109503666B
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- hexachlorocyclotriphosphazene
- flame retardant
- ethyl acetate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 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 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 33
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 10
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 162
- 238000001816 cooling Methods 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000001035 drying Methods 0.000 claims description 39
- 239000000706 filtrate Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 26
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 26
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000967 suction filtration Methods 0.000 claims description 19
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 10
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 6
- UGPWRRVOLLMHSC-UHFFFAOYSA-N 2-[3-(2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound CC(C)(O)C1=CC=CC(C(C)(C)O)=C1 UGPWRRVOLLMHSC-UHFFFAOYSA-N 0.000 abstract description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 39
- 238000000354 decomposition reaction Methods 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 238000004064 recycling Methods 0.000 description 25
- 238000005406 washing Methods 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000001914 filtration Methods 0.000 description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000004821 distillation Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 9
- 229940035437 1,3-propanediol Drugs 0.000 description 9
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- QJVNPOHYEQDGJB-UHFFFAOYSA-N pentan-2-ylphosphane Chemical compound CCCC(C)P QJVNPOHYEQDGJB-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- -1 propylene phosphazene Chemical compound 0.000 description 6
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QVTPAZHGNYBKHE-UHFFFAOYSA-N dimethyl(propyl)phosphane Chemical compound CCCP(C)C QVTPAZHGNYBKHE-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a flame retardant trimerization O, O-propylene phosphazene compound and a preparation method thereof, wherein the structure of the compound is shown as the following formula:r is H or CH 3 . The preparation method comprises the following steps: controlling the mol ratio of hexachlorocyclotriphosphazene and metadiol to be 1:3 in an organic solvent, and reacting for 10-18 h at 60-100 ℃; purifying to obtain colorless transparent liquid, such as trimerized O, O-propylene phosphazene. The compound of the invention is an excellent halogen-free phosphorus-nitrogen synergistic flame retardant, can be used for flame retardance of polyester, polyamide, polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and the like, has simple process and low equipment investment, and is easy to realize industrial production.
Description
Technical Field
The invention relates to a flame retardant trimerization O, O-propylene phosphazene compound and a preparation method thereof, wherein the compound contains phosphorus and nitrogen dual flame retardant elements and can be used as flame retardants of polyester, polyamide, polyurethane, epoxy resin, unsaturated resin, polyvinyl alcohol, paint and the like.
Background
With the wide application of synthetic materials in the fields of electronic appliances, transportation, interior decoration and the like, the hidden danger of fire hazard brought by the synthetic materials is more and more, so that the flame retardance of the synthetic materials has become an important issue of concern. At present, the trend of flame retardant material development is to raise the flame retardant performance and simultaneously pay more attention to environmental protection and ecological safety. The phosphorus-nitrogen synergistic flame retardant has the characteristics of no halogen, low toxicity, high decomposition temperature, good machining performance and the like. Therefore, the application and research of the phosphorus-nitrogen flame retardant are getting more and more attention at home and abroad.
The invention discloses a flame retardant trimerization O, O-propylene phosphazene compound and a preparation method thereof, and the compound belongs to a polyphosphoric polynitrogen structure, has high phosphorus content and synergistic flame retardant element nitrogen. The product has good structural symmetry, stable aromaticity, high decomposition temperature and good compatibility with high polymer materials, and can adapt to high-temperature processing of the materials; the hexachlorocyclotriphosphazene and metadiol are used as raw materials for one-step reaction, and the raw materials are cheap and easy to obtain, so that the hexachlorocyclotriphosphazene and metadiol composite material has good application and development prospects.
Disclosure of Invention
The invention aims to provide a flame retardant trimerization O, O-propylene phosphazene compound which has stable physical and chemical properties, is nontoxic, has high flame retardant efficiency and good compatibility with high polymer materials, and can overcome the defects in the prior art.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a flame retardant trimerization O, O-propylene phosphazene compound is characterized in that the compound has the following structural formula:
wherein R is H or CH 3 。
The invention further aims to provide a preparation method of the flame retardant trimerization O, O-propylene phosphazene compound, which has the advantages of simple process, easy mass production, low-cost and easily obtained raw materials, low equipment investment and low cost, and the method comprises the following steps:
dissolving hexachlorocyclotriphosphazene into an organic solvent, adding an acid-binding agent, controlling the mol ratio of hexachlorocyclotriphosphazene to metadiol to the acid-binding agent to be 1:3:6 for reaction, dripping metadiol into the solution, controlling the reaction temperature to be not higher than 40 ℃ by dripping acceleration under the cooling condition, heating to 60-100 ℃ after dripping, and preserving heat for reaction for 10-15 hours; cooling to below 30 ℃, removing generated acid binding agent hydrochloride by suction filtration, distilling off an organic solvent under reduced pressure (recycling), respectively adding water with the volume milliliters of 2-3 times of the theoretical mass of the relative product, washing twice, separating out a lower organic phase, adding ethyl acetate with the volume milliliters of 2-3 times of the theoretical mass of the relative product, drying by using anhydrous sodium sulfate, performing suction filtration, distilling off the ethyl acetate from the filtrate under reduced pressure, and obtaining colorless transparent liquid trimerization O, O-propylene phosphazene.
The method can also be as follows:
dissolving hexachlorocyclotriphosphazene into an organic solvent, dropwise adding 3 times mol of m-glycol of hexachlorocyclotriphosphazene, controlling the reaction temperature to be not higher than 40 ℃ under the cooling condition, heating to 60-100 ℃ after dripping, and preserving heat for reaction for 13-18 h until no hydrogen chloride is released; cooling to below 30 ℃, distilling the organic solvent under reduced pressure (recycling), respectively adding water with the volume of 2-3 times of the volume milliliters of the theoretical mass of the relative product for washing twice, separating out the lower organic phase, adding ethyl acetate with the volume of 2-3 times of the volume milliliters of the theoretical mass of the relative product, drying with anhydrous sodium sulfate, carrying out suction filtration, and distilling the filtrate under reduced pressure to remove the ethyl acetate, thereby obtaining colorless transparent liquid trimeric O, O-propylene phosphazene.
The above-mentioned m-diol is 1, 3-propanediol, 1, 3-butanediol or 2, 4-pentanediol.
The acid binding agent is triethylamine, N-dimethylaniline or pyridine.
The organic solvent is tetrahydrofuran, chloroform, acetonitrile or dioxane, and the ratio of the volume milliliter number of the organic solvent to the mass gram number of hexachlorocyclotriphosphazene is 3:1-5:1.
The trimerization O, O-propylene phosphazene is colorless transparent liquid, wherein the decomposition temperature of the propylene phosphazene is 289+/-5 ℃, the density is 1.261 (25 ℃), and the refractive index is n D 25 = 1.3273; the decomposition temperature of the methylpropanephosphazene is 320+/-5 ℃, the density is 1.255 (25 ℃), and the refractive index is n D 25 = 1.3145; dimethylpropylphosphine has a decomposition temperature of 332+ -5deg.C, a density of 1.216 (25deg.C), and a refractive index of n D 25 = 1.3021. The yield is 89.3-95.8%, and can be used as flame retardants for polyesters, polyamides, polyurethanes, epoxy resins, unsaturated resins, polyvinyl alcohol, coatings and the like. The preparation principle of the flame retardant trimerization O, O-propylene phosphazene compound is shown as the following formula:
wherein R is H or CH 3 。
Compared with the prior art, the invention has the following advantages:
(1) the flame retardant trimerization O, O-propylene phosphazene compound has novel structure, the phosphorus content is up to 26.1 percent, the nitrogen content is up to 11.8 percent, and the total content of flame retardant elements is up to 37.9 percent. The structure is symmetrical, the stability is high, the high-temperature-resistant flame-retardant plastic composite material can be suitable for high-temperature processing of various engineering plastics, the nitrogen-phosphorus synergistic flame-retardant efficiency is high, and the high-temperature-resistant flame-retardant plastic composite material has good plasticity;
(2) the flame retardant trimerization O, O-propylene phosphazene does not contain halogen, and belongs to an intumescent environment-friendly flame retardant;
(3) the preparation method of the flame retardant trimerization O, O-propylene phosphazene is a one-step reaction, the process is simple, no catalyst is required to be added in the synthesis process, and no impurity is introduced; the equipment is simple, the cost is low, the method is suitable for large-scale production, and has good application and development prospects.
Drawings
The following figures are presented for further illustration of the structure and performance of the product.
Fig. 1 is an infrared spectrum of propionitrile: FIG. 1 shows that at 2968.4cm -1 Is a stretching vibration peak of methylene C-H bond, 1473.5cm -1 The bending vibration peak of the methylene C-H bond is 1221.7cm -1 A telescopic vibration absorption peak of 1026.9cm for phosphazene skeleton p=n -1 And 874.2cm -1 Is the P-N telescopic vibration absorption peak on the phosphazene skeleton, 996.9cm -1 Is a characteristic absorption peak of P-O-C.
FIG. 2 is a nuclear magnetic spectrum of propionitrile: FIG. 2 shows that with deuterated chloroform as the solvent, δ7.26 is the deuterated chloroform peak, δ3.76-3.84 is the oxygen-linked methylene hydrogen peak, and δ1.75-1.82 is the carbon-linked methylene hydrogen peak.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
Example 1 in a 250mL three-port flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of tetrahydrofuran, 12.12g (0.12 mol) of triethylamine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 4.56g (0.06 mol) of 1, 3-propanediol was added dropwise, the reaction temperature was controlled at not higher than 40℃by dropwise acceleration under cooling conditions, and after completion of the dropwise addition, the temperature was raised to 60℃and the reaction was maintained for 15 hours; cooling to below 30deg.C, suction filtering to remove generated triethylamine hydrochloride, and vacuum filteringTetrahydrofuran is distilled off (recycled), 20mL of water is added for washing twice respectively, the lower organic phase is separated, 15mL of ethyl acetate is added, drying is carried out by 1g of anhydrous magnesium sulfate, suction filtration is carried out, the filtrate is distilled off under reduced pressure to remove the ethyl acetate, and colorless transparent liquid propylene phosphazene is obtained, and the yield is: 90.3%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 2 in a 250mL three-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of chloroform, 12.12g (0.12 mol) of triethylamine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 4.56g (0.06 mol) of 1, 3-propanediol was added dropwise, the reaction temperature was controlled at not higher than 40℃by dropwise acceleration under cooling, and after completion of the dropwise addition, the temperature was raised to 60℃and the reaction was maintained for 15 hours; cooling to below 30 ℃, removing generated triethylamine hydrochloride by suction filtration, distilling filtrate under reduced pressure to remove chloroform (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 15mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, suction filtering, distilling filtrate under reduced pressure to remove ethyl acetate to obtain colorless transparent liquid propylenephosphazene, and obtaining the yield: 91.2%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 3 in a 250mL three-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of acetonitrile, 14.52g (0.12 mol) of N, N-dimethylaniline were added, and after dissolving hexachlorocyclotriphosphazene by stirring, 4.56g (0.06 mol) of 1, 3-propanediol was added dropwise, and under cooling conditions, the reaction temperature was controlled to not higher than 40℃at a dropping speed, and after completion of the dropping, the temperature was raised to 80℃and the reaction was maintained for 13 hours; cooling to below 30deg.C, suction filtering to remove generated N, N-dimethylaniline hydrochloride, vacuum distilling the filtrate to remove acetonitrile (recycling), respectively adding 20mL of water to wash twice, separating out lower organic phase, adding 15mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, suction filtering, vacuum distilling the filtrate to remove ethyl acetate to obtain colorless transparent liquid propylene phosphazene,yield: 95.8%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 4 in a 250mL three-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of dioxane, 9.48g (0.12 mol) of pyridine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 4.56g (0.06 mol) of 1, 3-propanediol was added dropwise, the reaction temperature was controlled to not higher than 40℃by dropwise acceleration under cooling, and after completion of the dropwise addition, the temperature was raised to 100℃and the reaction was continued for 10 hours; cooling to below 30 ℃, removing generated pyridine hydrochloride by suction filtration, removing dioxane (recycling) by vacuum distillation of filtrate, respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 15mL of ethyl acetate, drying by using 1g of anhydrous magnesium sulfate, suction filtering, removing ethyl acetate by vacuum distillation of filtrate, and obtaining colorless transparent liquid propylenephosphazene with yield: 93.3%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 5 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mL) of hexachlorocyclotriphosphazene and 60mL of tetrahydrofuran are added, after stirring to dissolve hexachlorocyclotriphosphazene, 4.56g (0.06 mol) of 1, 3-propanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, after the dripping is finished, the temperature is raised to 60 ℃, and the reaction is kept for 18 hours until no hydrogen chloride is released; cooling to below 30 ℃, distilling under reduced pressure to remove tetrahydrofuran (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 15mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate to obtain colorless transparent liquid propylenephosphazene, and obtaining the yield: 91.2%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 6 into a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorbing device, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60m were charged under the protection of nitrogen gasAfter dissolving hexachlorocyclotriphosphazene by stirring, dropwise adding 4.56g (0.06 mol) of 1, 3-propanediol, controlling the reaction temperature to be not higher than 40 ℃ at a dropwise speed under the cooling condition, heating to 60 ℃ after the dropwise adding is finished, and preserving heat for 18 hours until no hydrogen chloride is released; cooling to below 30 ℃, decompressing, distilling to remove chloroform (recycling), respectively adding 20mL of water for washing twice, separating out a lower organic phase, adding 15mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, filtering, decompressing and distilling the filtrate to remove the ethyl acetate to obtain colorless transparent liquid propylenephosphazene, and the yield is: 91.1%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 7 in a reactor equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of acetonitrile are added, after the hexachlorocyclotriphosphazene is dissolved by stirring, 4.56g (0.06 mol) of 1, 3-propanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, the temperature is raised to 80 ℃ after the dripping is finished, and the reaction is kept for 15 hours until no hydrogen chloride is released; cooling to below 30 ℃, decompressing, distilling to remove acetonitrile (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 15mL of ethyl acetate, drying by 1g of anhydrous magnesium sulfate, filtering, decompressing and distilling filtrate to remove the ethyl acetate to obtain colorless transparent liquid propylenephosphazene, and obtaining the yield: 94.5%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 8 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of dioxane are added, after stirring to dissolve hexachlorocyclotriphosphazene, 4.56g (0.06 mol) of 1, 3-propanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, after the dripping is finished, the temperature is raised to 100 ℃, and the reaction is kept for 13 hours until no hydrogen chloride is released; cooling to below 30deg.C, vacuum distilling to remove dioxane (recycling), adding 20mL water respectively, washing twice, separating lower organic phase, adding 15mL ethyl acetate, and drying with 1g anhydrous magnesium sulfateDrying, suction filtering, and distilling the filtrate under reduced pressure to remove ethyl acetate to obtain colorless transparent liquid propylene phosphazene, and the yield is: 93.5%, decomposition temperature 289.+ -. 5 ℃, density 1.261 (25 ℃ C.), refractive index n D 25 ＝1.3273。
Example 9 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of tetrahydrofuran, 12.12g (0.12 mol) of triethylamine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 5.40g (0.06 mL) of 1, 3-butanediol was added dropwise, the reaction temperature was controlled at not higher than 40℃by dropwise acceleration under cooling, and after completion of the dropwise addition, the temperature was raised to 60℃and the reaction was maintained for 15 hours; cooling to below 30 ℃, removing generated triethylamine hydrochloride by suction filtration, removing tetrahydrofuran by reduced pressure distillation (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, suction filtration, removing the ethyl acetate by reduced pressure distillation of filtrate to obtain colorless transparent liquid methylpropanephosphazene, and obtaining the yield: 90.7%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
Example 10 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of chloroform, 12.12g (0.12 mol) of triethylamine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 5.40g (0.06 mol) of 1, 3-butanediol was added dropwise, under cooling conditions, the reaction temperature was controlled at not higher than 40℃at a dropwise speed, and after completion of the dropwise addition, the temperature was raised to 60℃and the reaction was maintained for 15 hours; cooling to below 30 ℃, removing generated triethylamine hydrochloride by suction filtration, distilling under reduced pressure to remove chloroform (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, suction filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate to obtain colorless transparent liquid methylpropanephosphazene, and obtaining the yield: 91.3%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
Examples11. In a 250mL four-mouth bottle provided with a stirrer, a thermometer and a condenser, and a drying pipe at the upper opening of the condenser, air in the bottle is replaced by nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of acetonitrile and 14.52g (0.12 mol) of N, N-dimethylaniline are added, after the hexachlorocyclotriphosphazene is dissolved by stirring, 5.40g (0.06 mol) of 1, 3-butanediol is dropwise added, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃ by dropwise acceleration, and the temperature is raised to 80 ℃ after the completion of dropwise, and the reaction is kept for 13 hours; cooling to below 30 ℃, removing generated N, N-dimethylaniline hydrochloride by suction filtration, removing acetonitrile by reduced pressure distillation (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying by using 1g of anhydrous sodium sulfate, suction filtering, removing the ethyl acetate by reduced pressure distillation of filtrate to obtain colorless transparent liquid methylpropanephosphazene, and obtaining the yield: 95.1%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
Example 12 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of dioxane, 9.48g (0.12 mol) of pyridine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 5.40g (0.06 mol) of 1, 3-butanediol was added dropwise, the reaction temperature was controlled to not higher than 40℃by dropwise addition rate under cooling conditions, and the temperature was raised to 100℃after completion of dropwise addition, and the reaction was continued for 10 hours; cooling to below 30 ℃, removing generated pyridine hydrochloride by suction filtration, removing dioxane (recycling) by reduced pressure distillation, respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, suction filtration, removing the ethyl acetate by reduced pressure distillation of filtrate, and obtaining colorless transparent liquid methylpropanephosphazene with yield: 93.7%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
EXAMPLE 13 in a reactor equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorbing device, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of tetrahydrofuran were added under nitrogen protection, and after stirring to dissolve hexachlorocyclotriphosphazene, 5.40g (0.06 mol) ofl) 1, 3-butanediol, controlling the reaction temperature to be not higher than 40 ℃ under the cooling condition at the dropping speed, heating to 60 ℃ after the dropping, and preserving heat for reaction for 18 hours until no hydrogen chloride is released; cooling to below 30 ℃, distilling under reduced pressure to remove tetrahydrofuran (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate, and obtaining colorless transparent liquid methylpropanephosphazene with yield: 90.4%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
Example 14 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of chloroform are added, after stirring to dissolve hexachlorocyclotriphosphazene, 5.40g (0.06 mol) of 1, 3-butanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, after the dripping is finished, the temperature is raised to 60 ℃, and the reaction is kept for 18 hours until no hydrogen chloride is released; cooling to below 30deg.C, distilling under reduced pressure to remove chloroform (recycling), respectively adding 20mL of water, washing twice, separating lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, vacuum filtering, distilling filtrate under reduced pressure to remove ethyl acetate to obtain colorless transparent liquid methylpropanephosphazene, yield: 91.0%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), and refractive index n D 25 ＝1.3145。
Example 15 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of acetonitrile are added, after stirring to dissolve hexachlorocyclotriphosphazene, 5.40g (0.06 mol) of 1, 3-butanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, after the dripping is finished, the temperature is raised to 80 ℃, and the reaction is kept for 15 hours until no hydrogen chloride is released; cooling to below 30deg.C, distilling under reduced pressure to remove acetonitrile (recycling), respectively adding 20mL of water, washing twice, separating lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, vacuum filtering, and distilling filtrate under reduced pressure to remove ethyl acetate to obtain colorless transparent productLiquid methylpropanephosphazene, yield: 94.4%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
Example 16 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of dioxane are added, after stirring to dissolve hexachlorocyclotriphosphazene, 5.40g (0.06 mol) of 1, 3-butanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃ at the dropwise acceleration rate, the temperature is raised to 100 ℃ after the dropwise addition, and the reaction is kept for 13 hours until no hydrogen chloride is released; cooling to below 30 ℃, distilling under reduced pressure to remove dioxane (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate, and obtaining colorless transparent liquid methylpropanephosphazene with yield: 92.4%, decomposition temperature 320+ -5deg.C, density 1.255 (25deg.C), refractive index n D 25 ＝1.3145。
Example 17 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of tetrahydrofuran and 12.12g (0.12 mol) of triethylamine were added, after dissolving hexachlorocyclotriphosphazene by stirring, 6.24g (0.06 mol) of 2, 4-pentanediol was added dropwise, the reaction temperature was controlled at not higher than 40℃by dropwise addition rate under cooling conditions, and the temperature was raised to 60℃after completion of dropwise addition, and the reaction was continued for 15 hours; cooling to below 30 ℃, removing generated triethylamine hydrochloride by suction filtration, removing tetrahydrofuran by reduced pressure distillation (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, suction filtration, removing the ethyl acetate by reduced pressure distillation of filtrate to obtain colorless transparent liquid 1, 3-dimethylpropylphosphine, and obtaining the yield: 89.3%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Example 18 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, useThe air in the bottle is replaced by nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of chloroform and 12.12g (0.12 mol) of triethylamine are added, after the hexachlorocyclotriphosphazene is dissolved by stirring, 6.24g (0.06 mol) of 2, 4-pentanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃ by the dropping speed, and the temperature is raised to 60 ℃ after the dropping is finished, and the reaction is carried out for 15 hours; cooling to below 30 ℃, removing generated triethylamine hydrochloride by suction filtration, distilling under reduced pressure to remove chloroform (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, suction filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate to obtain colorless transparent liquid 1, 3-dimethylpropylphosphine, and obtaining the yield: 89.9%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Example 19 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of acetonitrile and 14.52g (0.12 mol) of N, N-dimethylaniline were added, after dissolving hexachlorocyclotriphosphazene by stirring, 6.24g (0.06 mol) of 2, 4-pentanediol was added dropwise, and under cooling, the reaction temperature was controlled at not higher than 40℃at a dropping speed, and after completion of the dropping, the temperature was raised to 80℃and the reaction was kept for 13 hours; cooling to below 30 ℃, removing generated N, N-dimethylaniline hydrochloride by suction filtration, removing acetonitrile by reduced pressure distillation (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying by using 1g of anhydrous magnesium sulfate, suction filtering, removing the ethyl acetate by reduced pressure distillation of filtrate to obtain colorless transparent liquid 1, 3-dimethylpropylphosphine, and obtaining the yield: 95.2%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
EXAMPLE 20 in a 250mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and equipped with a drying tube at the upper port of the condenser, the air in the flask was replaced with nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene, 60mL of dioxane and 9.48g (0.12 mol) of pyridine were added, and after dissolving hexachlorocyclotriphosphazene by stirring, 6.24g (0.06 mol) of 2, 4-pentanediol was added dropwise under cooling conditionsThe temperature is controlled to be not higher than 40 ℃, the temperature is raised to 100 ℃ after the dripping is finished, and the reaction is carried out for 10 hours; cooling to below 30 ℃, removing generated pyridine hydrochloride by suction filtration, removing dioxane (recycling) by reduced pressure distillation, respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, suction filtration, removing the ethyl acetate by reduced pressure distillation of filtrate to obtain colorless transparent liquid 1, 3-dimethylpropylphosphine, and obtaining the yield: 92.6%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Example 21 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of tetrahydrofuran are added, after stirring to dissolve hexachlorocyclotriphosphazene, 6.24g (0.06 mol) of 2, 4-pentanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃ by the dropping acceleration, the temperature is raised to 60 ℃ after the dropping is finished, and the reaction is kept for 18 hours until no hydrogen chloride is released; cooling to below 30 ℃, distilling under reduced pressure to remove tetrahydrofuran (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate, and obtaining colorless transparent liquid 1, 3-dimethylpropylphosphine, and the yield is: 90.4%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Example 22 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of chloroform are added, after stirring to dissolve hexachlorocyclotriphosphazene, 6.24g (0.06 mol) of 2, 4-pentanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, after the dripping is finished, the temperature is raised to 60 ℃, and the reaction is kept for 18 hours until no hydrogen chloride is released; cooling to below 30deg.C, distilling under reduced pressure to remove chloroform (recycling), respectively adding 20mL of water, washing twice, separating lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, vacuum filtering, and distilling filtrate under reduced pressure to remove ethyl acetate to obtain colorless transparent liquid1, 3-dimethylpropylphosphine as a body, yield: 90.7%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Example 23 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of acetonitrile are added, after stirring to dissolve hexachlorocyclotriphosphazene, 6.24g (0.06 mol) of 2, 4-pentanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, the temperature is raised to 80 ℃ after the completion of the dropwise addition, and the reaction is kept for 15 hours until no hydrogen chloride is released; cooling to below 30deg.C, distilling under reduced pressure to remove acetonitrile (recycling), respectively adding 20mL of water, washing twice, separating out lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, suction filtering, distilling filtrate under reduced pressure to remove ethyl acetate to obtain colorless transparent liquid 1, 3-dimethylpropylphosphine, yield: 93.8%, decomposition temperature 332+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Example 24 in a reactor equipped with a stirrer, a thermometer, a high-efficient reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, 6.95g (0.02 mol) of hexachlorocyclotriphosphazene and 60mL of dioxane are added, after stirring to dissolve hexachlorocyclotriphosphazene, 6.24g (0.06 mol) of 2, 4-pentanediol is added dropwise, under the cooling condition, the reaction temperature is controlled to be not higher than 40 ℃, after the completion of the dripping, the temperature is raised to 100 ℃, and the reaction is kept for 13 hours until no hydrogen chloride is released; cooling to below 30 ℃, distilling under reduced pressure to remove dioxane (recycling), respectively adding 20mL of water for washing twice, separating a lower organic phase, adding 20mL of ethyl acetate, drying with 1g of anhydrous magnesium sulfate, filtering, distilling the filtrate under reduced pressure to remove the ethyl acetate, thus obtaining colorless transparent liquid 1, 3-dimethylpropylphosphine, and the yield is: 92.2%, decomposition temperature 328+ -5deg.C, density 1.216 (25deg.C), refractive index n D 25 ＝1.3021。
Table 1 main process parameters of preparation examples
The inventor also applies the synthesized flame retardant trimerization O, O-propylene phosphazene to PVC, and takes polyvinyl chloride (PVC), dioctyl phthalate (DOP) and antimony trioxide (Sb) 2 O 3 ) And the product trimerization O, O-propylene phosphazene is evenly mixed according to different proportions, and then is extruded by an XJ-01 extruder to prepare a sample bar with the diameter of 3mm and the length of 15 cm. Reference is made to: GB/T2406-2008 "method for testing Plastic Combustion Performance-oxygen index method" limit oxygen index of test strips. The test results are shown in table 2:
TABLE 2 flame retardant trimerization of O, O-Prop-phosphazene flame retardant Properties in PVC
As is clear from Table 2, it is considered that the flame retardant material has a limiting oxygen index of 27 or more, i.e., a good flame retardant property. The polyvinyl chloride itself has very high chlorine content and is a good flame-retardant material, but the flame-retardant performance is reduced due to the addition of inflammable plasticizer, and Table 2 shows that the limiting oxygen index is only 21 when 100 parts of plasticizer are added, the polyvinyl chloride is very easy to burn in the air, but the limiting oxygen index is quickly increased along with the increase of the amount of the O-propylenephosphazene after trimerization, and the limiting oxygen index is more than 27 when 10 parts of plasticizer are added, so that the product has very high flame-retardant efficiency; meanwhile, experiments show that the flame retardant also has better plasticity, and can reduce the use amount of the plasticizer in polyvinyl chloride.
Claims (4)
1. A flame retardant trimerization O, O-propylene phosphazene compound is characterized in that the compound has the following structural formula:
wherein R is H or CH 3 And the compound is not H at the same time, and the name of the compound is trimerized O, O-methylpropanephosphazene or trimerized O, O-dimethylpropanephosphazene.
2. The method for preparing the flame retardant trimeric O, O-propylenephosphazene compound according to claim 1, which is characterized in that the method comprises the following steps:
dissolving hexachlorocyclotriphosphazene into an organic solvent, dropwise adding 3 times mol of m-glycol of hexachlorocyclotriphosphazene, controlling the reaction temperature to be not higher than 40 ℃ under the cooling condition, heating to 60-100 ℃ after dripping, and preserving heat for reaction for 13-18 h until no hydrogen chloride is released; cooling to below 30 ℃, distilling the organic solvent under reduced pressure, respectively adding water with the volume milliliters of 2-3 times of the theoretical mass of the relative product into the organic solvent for two times, separating out a lower organic phase, adding ethyl acetate with the volume milliliters of 2-3 times of the theoretical mass of the relative product, drying by using anhydrous sodium sulfate, carrying out suction filtration, and distilling the filtrate under reduced pressure to remove the ethyl acetate, thereby obtaining colorless transparent liquid trimeric O, O-propylene phosphazene.
3. The method for preparing the flame retardant trimeric O, O-propylenephosphazene compound according to claim 2, characterized by: the m-diol is 1, 3-butanediol or 2, 4-pentanediol.
4. The method for preparing the flame retardant trimeric O, O-propylenephosphazene compound according to claim 2, characterized by: the organic solvent is chloroform or dioxane, and the ratio of the volume milliliter number of the organic solvent to the mass gram number of hexachlorocyclotriphosphazene is 3:1-5:1.
Priority Applications (1)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3894121A (en) * | 1969-12-24 | 1975-07-08 | Sandoz Ltd | Phosphonitrilic esters |
| CN108467514A (en) * | 2018-04-13 | 2018-08-31 | 武汉工程大学 | A kind of Halogen phosphonitrile expansion type fire retardant and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3894121A (en) * | 1969-12-24 | 1975-07-08 | Sandoz Ltd | Phosphonitrilic esters |
| CN108467514A (en) * | 2018-04-13 | 2018-08-31 | 武汉工程大学 | A kind of Halogen phosphonitrile expansion type fire retardant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Phosphorus-nitrogen compounds. Part 58. The reactions of hexachlorocyclotriphosphazatriene with ethane-, 1,3-propane-, and 1,4-butanediols. Spiro, ansa, bridged and dangling derivatives and their phosphorus-31 and proton nuclear magnetic resonance spectra;Alkubaisi, Abdulla H et al.;《Heterocycles》;19891231;第347-358页 * |
| Theroleofthesubstitutedgrouponcompetitiveformationofansaandspiro isomers;Duygu Palabıyık et al.;《Inorganica Chimica Acta》;20181201;第15-23页 * |
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