CN109503665A - Miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- and preparation method thereof - Google Patents
Miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- and preparation method thereof Download PDFInfo
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- CN109503665A CN109503665A CN201811566189.5A CN201811566189A CN109503665A CN 109503665 A CN109503665 A CN 109503665A CN 201811566189 A CN201811566189 A CN 201811566189A CN 109503665 A CN109503665 A CN 109503665A
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- methylol
- miscellaneous
- trimethylene
- fire retardant
- trimerization
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- -1 trimethylene phosphazene compound Chemical class 0.000 title claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- 239000003063 flame retardant Substances 0.000 title claims abstract description 38
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 11
- 230000006837 decompression Effects 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 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
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 238000005292 vacuum distillation Methods 0.000 description 9
- 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 class 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 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 3
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- ZSUFBRGARNXNBX-UHFFFAOYSA-N [P].C1=CC=NC=C1 Chemical compound [P].C1=CC=NC=C1 ZSUFBRGARNXNBX-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- SRLQRYLPGNFEAI-UHFFFAOYSA-N trihydroxy(methyl)-$l^{4}-sulfane Chemical compound CS(O)(O)O SRLQRYLPGNFEAI-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to miscellaneous trimethylene phosphazene compounds of the thio phosphono of a kind of fire retardant trimerization O, O-2- methylol -2- and preparation method thereof, and the structure of the compound is shown below:
Description
Technical field
The present invention relates to a kind of miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- and its systems
Preparation Method, the compound contain the triple ignition-proof elements of phosphorus, nitrogen, sulphur, can be used as polyester, polyamide, polyurethane, epoxy resin, no
The fire retardant of saturated resin, polyvinyl alcohol and coating etc..
Background technique
High molecular material is widely used in the fields such as automobile, electronics, electric appliance, weaving and building materials.But due to its tool
There is inflammability, Chang Yinqi fire brings threat to the lives and properties of people, to promote the development of fire retardant industry, halogen system
Fire retardant is due to having many advantages, such as that flame retarding efficiency is high, dosage is few and moderate, using relatively broad.But halogenated flame retardant exists
A large amount of dense smokes, nocuousness and corrosive gas can be generated when burning, and receive the query of people.Phosphorus-nitrogen expanding fire retardant tool
Have the advantages that efficiently, Halogen, low toxicity, when burning can form fine and close layer of charcoal on the surface of the material, and releasing largely can not combustion gas
Body effectively can prevent material from further burning, thus, the research of phosphorus-nitrogen containing flame retardant has become the hot spot of flame retardant area research
One of.
The miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- of the present invention belongs to the more sulphur of the more nitrogen of more phosphorus
Structure, phosphorus, sulfur content are high, and there are also fire-retardant nitrogen, three element cooperative flame retardant efficiency are high.The product structure symmetry is good, aromatic
To stablize, decomposition temperature is high, and it is good with high molecular material compatibility, adapt to the high temperature process of material；Its by hexachlorocyclotriph,sphazene and
Trihydroxy methyl phosphoric sulfide is made for raw material single step reaction, and raw material is easy to get, and has a wide range of application, and has the very big prospect of marketing.
Summary of the invention
It is an object of the present invention to propose a kind of miscellaneous trimethylene phosphorus of the thio phosphono of fire retardant trimerization O, O-2- methylol -2-
Nitrile compound, physical and chemical performance is stablized, nontoxic, and flame-retarded efficiency is high, good with high molecular material compatibility, can overcome in the prior art
Deficiency.
For achieving the above object, present invention employs following technical solutions:
A kind of miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2-, which is characterized in that the change
The structure for closing object is shown below:
Another object of the present invention is to propose a kind of miscellaneous trimethylene phosphorus of the thio phosphono of fire retardant trimerization O, O-2- methylol -2-
The preparation method of nitrile, simple process are easy to large-scale production, and raw material is cheap and easy to get, and equipment investment is few, low in cost, should
Method are as follows:
Hexachlorocyclotriph,sphazene is dissolved into organic solvent, acid binding agent is added, controls hexachlorocyclotriph,sphazene and trihydroxy methyl
Phosphoric sulfide and acid binding agent molar ratio are 1: 3: 6 reaction, and trihydroxy methyl phosphoric sulfide is added drop-wise in above-mentioned solution, under cooling condition,
40 DEG C are not higher than with rate of addition control reaction temperature, 100 DEG C~130 DEG C are warming up to after dripping off, insulation reaction 5-8h；Cooling
To 30 DEG C hereinafter, filtering the acid binding agent hydrochloride for removing and generating, it is evaporated under reduced pressure out organic solvent (recycling), is separately added into phase
Twice to the water washings of 2~3 times of volumes ml of quality grams of theoretical product, lower layer's organic phase is separated, opposite reason is added
It by the ethyl acetate of 2~3 times of volumes ml of quality grams of product, is dried, is filtered, filtrate decompression with anhydrous sodium sulfate
Ethyl acetate is distilled off, obtains the miscellaneous trimethylene phosphonitrile of the pale yellow transparent thio phosphono of viscous liquid trimerization O, O-2- methylol -2-.
This method may be used also are as follows:
Hexachlorocyclotriph,sphazene is dissolved into organic solvent, 3 times moles of hexachlorocyclotriph,sphazene of trihydroxy methyl vulcanization is added dropwise
Phosphorus under cooling condition, is not higher than 40 DEG C with rate of addition control reaction temperature, 100 DEG C~130 DEG C is warming up to after dripping off, heat preservation
8~11h is reacted, until releasing without hydrogen chloride；30 DEG C are cooled to hereinafter, be evaporated under reduced pressure out organic solvent (recycling), respectively plus
The water washing of 2~3 times of volumes ml of quality grams for entering relative theory product twice, separates lower layer's organic phase, is added opposite
The ethyl acetate of 2~3 times of volumes ml of quality grams of theoretical product, is dried with anhydrous sodium sulfate, is filtered, and filtrate subtracts
Ethyl acetate is distilled off in pressure, obtains the miscellaneous trimethylene phosphonitrile of the pale yellow transparent thio phosphono of viscous liquid trimerization O, O-2- methylol -2-.
Acid-binding agent as described above is triethylamine, n,N-Dimethylaniline or pyridine.
Organic solvent as described above is dioxane, toluene, ethylene glycol diethyl ether and chlorobenzene, the volume of organic solvent
It ml is 3: 1~5: 1 with the ratio between the quality grams of hexachlorocyclotriph,sphazene.
The miscellaneous trimethylene phosphonitrile of the thio phosphono of trimerization O, O-2- methylol -2- of the invention is pale yellow transparent viscous liquid, close
Degree is 1.386 (25 DEG C), index of refraction nD 25=1.2847, yield is 89.8%~95.6%, can be used as polyester, polyamide, gathers
The fire retardant of urethane, epoxy resin, unsaturated-resin, polyvinyl alcohol and coating etc..Fire retardant trimerization O, the O-2- methylol -2-
The preparation principle of the thio miscellaneous trimethylene phosphazene compound of phosphono is shown below:
Compared with prior art, the invention has the beneficial effects that:
1. the miscellaneous trimethylene phosphazene compound structure novel of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- of the present invention, phosphorus
Content is up to 26.8%, and nitrogen content is up to 6.1%, and sulfur content is up to 27.7%, and ignition-proof element total content is up to 60.6%.Structure
To weighing up, stability is high, can be suitably used for the high temperature process of various engineering plastics, three heavy element cooperative flame retardant efficiency of nitrogen phosphate and sulfur
Height has good plasticity；
2. the miscellaneous trimethylene phosphonitrile of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- of the present invention is halogen-free, be conducive to ring
It protects, belongs to the environmental-friendly fire retardant of intumescent；
3. the preparation method of the miscellaneous trimethylene phosphonitrile of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- of the present invention is that a step is anti-
It answers, simple process, synthesis process does not introduce impurity without adding catalyst；Equipment is simple, low in cost, is suitable for scale metaplasia
It produces, there is good application and development prospect.
Following spectrum data is provided in order to further illustrate the structure and performance spy of product.
1, the infared spectrum data of the miscellaneous trimethylene phosphonitrile of the thio phosphono of fire retardant trimerization O, O-2- methylol -2-:
3450.5cm-1Place is the stretching vibration peak of hydroxyl O-H key, 2897.5cm-1And 1500.7cm-1Place is that methylene c h bond absorbs
Peak, 1174.3cm-1And 1210.5cm-1The absorption peak of C-O, 1280.3cm-1For the stretching vibration absworption peak of phosphazene backbone P=N,
1020.3cm-1For the stretching vibration absworption peak of P-N on phosphazene backbone, 1400.5cm-1For the absorption peak of P=S, 1142.2cm-1
For the absorption peak of P-O, 840.4cm-1Place is the stretching vibration peak of C-P key.
2, the nuclear magnetic spectrum data of the miscellaneous trimethylene phosphonitrile of the thio phosphono of fire retardant trimerization O, O-2- methylol -2-: δ 3.10-
3.35 be-N=P-O-CH2On the peak H；δ 3.60-3.75 is HO-CH2On the peak methylene H；δ 4.10-4.23 is the H of hydroxyl
Peak.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is being equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tri- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, addition 10.42g (0.03mol) hexachlorocyclotriph,sphazene, 80ml dioxane and
After stirring dissolves hexachlorocyclotriph,sphazene, 14.05g (0.09mol) trihydroxy methyl sulphur is added dropwise in 18.18g (0.18mol) triethylamine
Change phosphorus, is not higher than 40 DEG C with rate of addition control reaction temperature, 100 DEG C is warming up to after dripping off, insulation reaction 8h；It is cooled to 30 DEG C
Hereinafter, filtering the triethylamine hydrochloride for removing and generating, vacuum distillation removes dioxane (recycling), is separately added into 35ml steaming
Distilled water washes twice, and separates lower layer's organic phase, and 35ml ethyl acetate is added, is dried with 1g anhydrous magnesium sulfate, filters, filtrate
Vacuum distillation removes ethyl acetate, obtains the thio miscellaneous trimethylene phosphorus of phosphono of pale yellow transparent viscous liquid trimerization O, O-2- methylol -2
Nitrile, yield: 90.5%, density is 1.386 (25 DEG C), index of refraction nD 25=1.2847.
Embodiment 2 is being equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tri- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, addition 10.42g (0.03mol) hexachlorocyclotriph,sphazene, 80ml toluene and
After stirring dissolves hexachlorocyclotriph,sphazene, 14.05g (0.09mol) three is added dropwise in 21.78g (0.18mol) n,N-Dimethylaniline
Methylol phosphoric sulfide is not higher than 40 DEG C with rate of addition control reaction temperature, 110 DEG C is warming up to after dripping off, insulation reaction 7h；Drop
For temperature to 30 DEG C hereinafter, filtering the n,N-Dimethylaniline hydrochloride for removing and generating, vacuum distillation removes toluene (recycling), point
Not Jia Ru 35ml distilled water wash twice, separate lower layer's organic phase, 35ml ethyl acetate be added, is done with 1g anhydrous magnesium sulfate
It is dry, it filters, filtrate decompression is distilled off ethyl acetate, it is thio to obtain pale yellow transparent viscous liquid trimerization O, O-2- methylol -2-
The miscellaneous trimethylene phosphonitrile of phosphono, yield: 92.1%, density is 1.386 (25 DEG C), index of refraction nD 25=1.2847.
Embodiment 3 is being equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tri- suitable for reading equipped with drying tube
In mouth bottle, with the air in nitrogen displacement bottle falling, 10.42g (0.03mol) hexachlorocyclotriph,sphazene, 80ml ethylene glycol diethyl is added
After stirring dissolves hexachlorocyclotriph,sphazene, 14.05g (0.09mol) trihydroxy methyl is added dropwise in ether and 14.22g (0.18mol) pyridine
Phosphoric sulfide is not higher than 40 DEG C with rate of addition control reaction temperature, 120 DEG C is warming up to after dripping off, insulation reaction 6h；It is cooled to
30 DEG C hereinafter, the pyridine hydrochloride that suction filtration removing generates, vacuum distillation remove ethylene glycol diethyl ether (recycling), are separately added into
35ml distilled water washes twice, and separates lower layer's organic phase, and 35ml ethyl acetate is added, is dried with 1g anhydrous magnesium sulfate, takes out
Filter, filtrate decompression are distilled off ethyl acetate, obtain the thio phosphono of pale yellow transparent viscous liquid trimerization O, O-2- methylol -2-
Miscellaneous trimethylene phosphonitrile, yield: 95.6%, density is 1.386 (25 DEG C), index of refraction nD 25=1.2847.
Embodiment 4 is being equipped with blender, thermometer and condenser pipe, and in the condenser pipe 250ml tri- suitable for reading equipped with drying tube
In mouthful bottle, with the air in nitrogen displacement bottle falling, addition 10.42g (0.03mol) hexachlorocyclotriph,sphazene, 80ml chlorobenzene and
After stirring dissolves hexachlorocyclotriph,sphazene, the vulcanization of 14.05g (0.09mol) trihydroxy methyl is added dropwise in 14.22g (0.18mol) pyridine
Phosphorus is not higher than 40 DEG C with rate of addition control reaction temperature, 130 DEG C is warming up to after dripping off, insulation reaction 5h；Be cooled to 30 DEG C with
Under, the pyridine hydrochloride for removing and generating is filtered, vacuum distillation removes chlorobenzene (recycling), is separately added into 35ml distillation water washing
Twice, lower layer's organic phase is separated, 35ml ethyl acetate is added, is dried with 1g anhydrous magnesium sulfate, is filtered, filtrate decompression distillation
Ethyl acetate is removed, obtains the miscellaneous trimethylene phosphonitrile of the pale yellow transparent thio phosphono of viscous liquid trimerization O, O-2- methylol -2-, yield:
94.2%, density is 1.386 (25 DEG C), index of refraction nD 25=1.2847.
Embodiment 5 equipped with blender, thermometer, high performance reflux condenser and hydrogen chloride absorption device reactor in,
Under nitrogen protection, 10.42g (0.03mol) hexachlorocyclotriph,sphazene and 80ml dioxane is added, stirring keeps hexachlorocyclotriph,sphazene molten
14.05g (0.09mol) trihydroxy methyl phosphoric sulfide is added dropwise in Xie Hou, is not higher than 40 DEG C with rate of addition control reaction temperature, drips off
After be warming up to 100 DEG C, insulation reaction 11h, until without hydrogen chloride release；30 DEG C are cooled to hereinafter, vacuum distillation removes dioxane
(recycling) is separately added into 35ml distilled water and washes twice, and separates lower layer's organic phase, and 35ml ethyl acetate is added, with 1g without
Water magnesium sulfate is dried, and filters, and filtrate decompression is distilled off ethyl acetate, obtains pale yellow transparent viscous liquid trimerization O, O-2-
The miscellaneous trimethylene phosphonitrile of the thio phosphono of methylol -2-, yield: 89.8%, density is 1.386 (25 DEG C), index of refraction nD 25=
1.2847。
Embodiment 6 equipped with blender, thermometer, high performance reflux condenser and hydrogen chloride absorption device reactor in,
Under nitrogen protection, 10.42g (0.03mol) hexachlorocyclotriph,sphazene and 80ml toluene is added, stirring dissolves hexachlorocyclotriph,sphazene
Afterwards, 14.05g (0.09mol) trihydroxy methyl phosphoric sulfide is added dropwise, is not higher than 40 DEG C, after dripping off with rate of addition control reaction temperature
110 DEG C, insulation reaction 10h are warming up to, until releasing without hydrogen chloride；30 DEG C are cooled to hereinafter, vacuum distillation removes toluene (recycling benefit
With), it is separately added into 35ml distilled water and washes twice, separate lower layer's organic phase, 35ml ethyl acetate is added, with 1g anhydrous magnesium sulfate
It is dried, filters, filtrate decompression is distilled off ethyl acetate, obtains pale yellow transparent viscous liquid trimerization O, O-2- methylol-
The miscellaneous trimethylene phosphonitrile of the thio phosphono of 2-, yield: 91.6%, density is 1.386 (25 DEG C), index of refraction nD 25=1.2847.
Embodiment 7 equipped with blender, thermometer, high performance reflux condenser and hydrogen chloride absorption device reactor in,
Under nitrogen protection, 10.42g (0.03mol) hexachlorocyclotriph,sphazene and 80ml ethylene glycol diethyl ether is added, stirring makes three phosphorus of chlordene ring
After nitrile dissolution, 14.05g (0.09mol) trihydroxy methyl phosphoric sulfide is not higher than 40 DEG C with rate of addition control reaction temperature, drips off
After be warming up to 120 DEG C, insulation reaction 9h, until without hydrogen chloride release；30 DEG C are cooled to hereinafter, vacuum distillation removes ethylene glycol diethyl
Ether (recycling) is separately added into 35ml distilled water and washes twice, and separates lower layer's organic phase, and 35ml ethyl acetate is added, uses 1g
Anhydrous magnesium sulfate is dried, and filters, and filtrate decompression is distilled off ethyl acetate, obtains pale yellow transparent viscous liquid trimerization O,
The miscellaneous trimethylene phosphonitrile of the thio phosphono of O-2- methylol -2-, yield: 94.7%, density is 1.386 (25 DEG C), index of refraction nD 25=
1.2847。
Embodiment 8 equipped with blender, thermometer, high performance reflux condenser and hydrogen chloride absorption device reactor in,
Under nitrogen protection, 10.42g (0.03mol) hexachlorocyclotriph,sphazene and 80ml chlorobenzene is added, stirring dissolves hexachlorocyclotriph,sphazene
Afterwards, 14.05g (0.09mol) trihydroxy methyl phosphoric sulfide is added dropwise, is not higher than 40 DEG C, after dripping off with rate of addition control reaction temperature
130 DEG C, insulation reaction 8h are warming up to, until releasing without hydrogen chloride；30 DEG C are cooled to hereinafter, vacuum distillation removes chlorobenzene (recycling benefit
With), it is separately added into 35ml distilled water and washes twice, separate lower layer's organic phase, 35ml ethyl acetate is added, with 1g anhydrous magnesium sulfate
It is dried, filters, filtrate decompression is distilled off ethyl acetate, obtains pale yellow transparent viscous liquid trimerization O, O-2- methylol-
The miscellaneous trimethylene phosphonitrile of the thio phosphono of 2-, yield: 93.3%, density is 1.386 (25 DEG C), index of refraction nD 25=1.2847.
1 preparation example main technologic parameters of table
Inventor also answers the miscellaneous trimethylene phosphonitrile of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- of above-mentioned synthesis
For in PVC, taking polyvinyl chloride (PVC), dioctyl phthalate (DOP), antimony oxide (Sb2O3) and product trimerization O,
The miscellaneous trimethylene phosphonitrile of the thio phosphono of O-2- methylol -2- in varing proportions after mixing, then with XJ-01 type extruder extrusion is made
Diameter 3mm, the batten of length 15cm.Reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample
The limit oxygen index of item.Test result is as shown in table 2:
The miscellaneous trimethylene phosphonitrile flame retardant property in PVC of the table thio phosphono of 2 fire retardant trimerization O, O-2- methylol -2-
As shown in Table 2, it is considered that the limit oxygen index of fire proofing, which reaches 27 or more, preferable flame retardant property.It is poly-
Vinyl chloride chlorinty itself is very high, is good fire proofing, but since the addition of inflammable plasticizer causes flame retardant property to reduce,
Table 2 shows that limit oxygen index only has 21 when 100 parts of plasticizer are added, and easily burns, but in air with trimerization O, O-2- hydroxyl
The increase of the miscellaneous trimethylene phosphonitrile of the thio phosphono of methyl -2-, limit oxygen index increase quickly, and limit oxygen index reaches when being added 10 parts
30, show that the product has very high flame-retarded efficiency；Simultaneously it was found that, the fire retardant also has preferable plasticity,
Usage amount of the plasticizer in polyvinyl chloride can be reduced.
Claims (5)
1. a kind of miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2-, which is characterized in that the chemical combination
The structure of object is shown below:
2. the miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- according to claim 1
Preparation method, which is characterized in that this method are as follows:
Hexachlorocyclotriph,sphazene is dissolved into organic solvent, acid binding agent is added, controls hexachlorocyclotriph,sphazene and trihydroxy methyl vulcanization
Phosphorus and acid binding agent molar ratio are 1: 3: 6 reaction, and trihydroxy methyl phosphoric sulfide is added drop-wise in above-mentioned solution, under cooling condition, with drop
Acceleration Control reaction temperature is not higher than 40 DEG C, 100 DEG C~130 DEG C is warming up to after dripping off, insulation reaction 5-8h；It is cooled to 30 DEG C
Hereinafter, filtering the acid binding agent hydrochloride for removing and generating, it is evaporated under reduced pressure out organic solvent, is separately added into relative product Theoretical Mass gram
The water washing of 2~3 times of volumes ml of number twice, separates lower layer's organic phase, adds relative product Theoretical Mass grams 2~3
The ethyl acetate of times volume ml, is dried with anhydrous sodium sulfate, is filtered, and filtrate decompression is distilled off ethyl acetate, obtains
The miscellaneous trimethylene phosphonitrile of the pale yellow transparent thio phosphono of viscous liquid trimerization O, O-2- methylol -2-.
3. the miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- according to claim 1
Preparation method, which is characterized in that this method are as follows:
Hexachlorocyclotriph,sphazene is dissolved into organic solvent, the trihydroxy methyl phosphoric sulfide of 3 times of moles of hexachlorocyclotriph,sphazene is added dropwise,
Under cooling condition, 40 DEG C are not higher than with rate of addition control reaction temperature, 100 DEG C~130 DEG C are warming up to after dripping off, insulation reaction
8~11h, until being released without hydrogen chloride；30 DEG C are cooled to hereinafter, be evaporated under reduced pressure out organic solvent, is separately added into relative product theory
The water washing of 2~3 times of volumes ml of quality grams twice, separates lower layer's organic phase, and relative product Theoretical Mass grams 2 is added
The ethyl acetate of~3 times of volumes ml, is dried with anhydrous sodium sulfate, is filtered, and ethyl acetate is distilled off in filtrate decompression,
Obtain the miscellaneous trimethylene phosphonitrile of the thio phosphono of pale yellow transparent viscous liquid trimerization O, O-2- methylol -2-.
4. the miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- according to claim 2
Preparation method, it is characterised in that: the acid-binding agent is triethylamine, n,N-Dimethylaniline or pyridine.
5. according to the miscellaneous trimethylene phosphazene compound of the thio phosphono of fire retardant trimerization O, O-2- methylol -2- described in claim 2 and 3
Preparation method, it is characterised in that: the organic solvent be dioxane, toluene, ethylene glycol diethyl ether and chlorobenzene, it is organic
The ratio between the volume ml of solvent and the quality grams of hexachlorocyclotriph,sphazene are 3: 1~5: 1.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4405738A (en) * | 1982-03-05 | 1983-09-20 | Akzona Incorporated | Flame retardant additives and flame retardant polyester compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4405738A (en) * | 1982-03-05 | 1983-09-20 | Akzona Incorporated | Flame retardant additives and flame retardant polyester compositions |
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