CN105384780B - The preparation method of aryl silicon ring phosphine compound - Google Patents
The preparation method of aryl silicon ring phosphine compound Download PDFInfo
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- CN105384780B CN105384780B CN201510707743.7A CN201510707743A CN105384780B CN 105384780 B CN105384780 B CN 105384780B CN 201510707743 A CN201510707743 A CN 201510707743A CN 105384780 B CN105384780 B CN 105384780B
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- phosphine compound
- silicon ring
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- fire retardant
- ring phosphine
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- -1 aryl silicon ring phosphine compound Chemical class 0.000 title claims abstract description 40
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005054 phenyltrichlorosilane Substances 0.000 claims abstract description 10
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000004677 Nylon Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920001778 nylon Polymers 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 3
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000007977 PBT buffer Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 abstract 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical 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 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-L methylphosphonate(2-) Chemical compound CP([O-])([O-])=O YACKEPLHDIMKIO-UHFFFAOYSA-L 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of fire retardant aryl silicon ring phosphine compound, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant aryl silicon ring phosphine compound, and in particular to a kind of fire retardant phenyl
Three (1- oxygen -1- methyl -4- ethyl -1- phospha -2,6- dioxa-cyclohexyls -<4>- methoxyl group) silane compound preparation
Method, the compound contain the dual ignition-proof element of phosphorus, silicon, and the collaboration of phosphorus silicon has higher flame-retarded efficiency, be suitable as polyester PBT,
The fire retardant of the materials such as PET, polyurethane, nylon, epoxy resin, polyvinyl chloride.
Background technology
Due to a large amount of uses of inflammable organic synthesis high polymer material, the research and development of fire proofing has been promoted.Fire-retardant
In material, halogenated flame retardant is the maximum fire retardant of usage amount, its good flame retardation effect, applied widely.But because halogen system hinders
Combustion agent can discharge a large amount of pernicious gases in burning, and the life security of people can be caused greatly to threaten, thus this is fire-retardant
The use of agent receives increasing restriction, and halogen-free flame retardants has very strong market in urgent need.Due to organic phosphorus flame retardant
Flame retardant effect is excellent, applied widely, is developed rapidly.But traditional organophosphorous fire retardant still have polarity it is big,
Easy to migrate, the deficiencies of electric property is poor.Silicone flame retardant is a kind of new halogen-free flame retardants, has efficient, nontoxic, suppression
Cigarette, advantages of environment protection, but there is the problems such as expensive in it, limit its development.Silicon, can produce can not be pre- for phosphorus collaboration
The effect of material, the research are a significantly problems.
The invention discloses a kind of preparation method of fire retardant aryl silicon ring phosphine compound.Contain in the molecular structure of compounds
Two kinds of silicon, phosphorus excellent ignition-proof elements, the advantages of possessing silicon-series five-retardant and phosphorus flame retardant, show again preferably into charcoal
With the processing characteristics of close friend, multiple phosphine rings contain in its molecular structure, decomposition temperature height, Stability Analysis of Structures, good flame retardation effect, are one
Kind is efficient, suppression cigarette, nontoxic fire retardant, there is application and DEVELOPMENT PROSPECT well.
The content of the invention
It is an object of the invention to propose a kind of preparation method of fire retardant aryl silicon ring phosphine compound, its technique is simple,
Equipment investment is few, is easy to large-scale production, can overcome deficiency of the prior art.Its technical scheme is as follows：
This method is：
Fall the air in the reactor with hydrogen chloride absorption device with nitrogen displacement, add organic solvent and 1- oxygen -1-
Methyl -4- ethyl -4- methylol -2,6- dioxa -1- phospha cyclohexanes are (referred to as：4- methylols -4- ethyls-Cyclic methyl phosphine
Acid esters), under stirring, phenyl trichlorosilane is added drop-wise in reaction system, control phenyl trichlorosilane and 4- methylol -4- second
The mol ratio of base-Cyclic methyl phosphonate ester is 1: 3-1: 3.8, and controls dropping temperature to be no more than 60 DEG C, in 100-150 after dripping off
DEG C reaction 13-21h, after hydrogen to be chlorinated discharges, is evaporated under reduced pressure and removes organic solvent (recovery use), purified processing, obtain aryl
Silicon ring phosphine compound, the structure of the compound are shown below：
Organic solvent as described above is diethylene glycol dimethyl ether, dimethylbenzene, tetrachloroethanes, ethylene glycol diethyl ether or benzene first
Ether, its dosage are 3-8 times that organic solvent volume milliliter number is phenyl trichlorosilane quality grams.
Purification process as described above stirs to add the distilled water of product Theoretical Mass 1-2 times of volume milliliter number of grams
Solid is dispersed in water, is filtered, water wash to pH=7, drying.
Fire retardant aryl silicon ring phosphine compound of the present invention is white solid, and its yield is 80.6%-93.5%, fusing point：150
± 2 DEG C, decomposition temperature：335 ± 5 DEG C, it is suitable as the materials such as polyester PBT, PET, polyurethane, nylon, epoxy resin, polyvinyl chloride
The fire retardant of material.
The preparation technology principle of aryl silicon ring phosphine compound is shown below：
Compared with prior art, beneficial innovation of the invention is：
1. fire retardant aryl silicon ring phosphine compound of the present invention contains two kinds of phosphorus, silicon ignition-proof elements, under high temperature, P elements conversion
The formation for facilitating charcoal can be catalyzed for phosphoric acid or polyphosphoric acid, the polyphosphoric acid film of formation has heat-insulated anoxybiotic to act on；Silicon forms densification with carbon
Silicon layer of charcoal, can effectively prevent melting drip generation.Phosphorus, silicon can be played higher fire-retardant from different mechanism cooperative flame retardants
Efficiency.
2. contain stable C-P keys, C-Si keys and six in fire retardant aryl silicon ring phosphine compound molecular structure of the present invention
Ring structure, these design features cause the compound physical stable chemical performance, and decomposition temperature is high, adapts in more
Engineering plastics high temperature process.
3. the phenyl contained in fire retardant aryl silicon ring phosphine compound molecular structure of the present invention has the multidirectional of electronic structure
Property, its compatibility with material can be increased, good dispersion, to the Effect on Mechanical Properties very little of material, so as to promote fire-retardant effect
The raising of fruit.
Brief description of the drawings
In order to further illustrate that the structure of product and performance spy provide drawings described below.
1st, the infrared spectrogram of aryl silicon ring phosphine compound, refers to Figure of description Fig. 1：
Fig. 1 shows, 3093cm-1(stretching vibration of c h bond on phenyl ring)；3000cm-1And 2963cm-1(c h bond it is flexible
Vibration)；1442cm-1(flexural vibrations of c h bond)；1250cm-1(stretching vibration of P=O keys)；1175cm-1(Si-O-C keys
Stretching vibration)；998cm-1(flexural vibrations of Si-O-C keys)；900cm-1(stretching vibration of P-O-C keys)；730cm-1(Si-C keys
Stretching vibration).
2nd, the nuclear magnetic spectrum figure of aryl silicon ring phosphine compound, refers to Figure of description Fig. 2：
Fig. 2 shows that deuterochloroform is solvent, and δ 0.82-1.00 are C-CH2CH3The methyl hydrogen peak of upper and carbon phase even；δ1.22-
1.33 it is C-CH2CH3The methylene hydrogen peak of upper and carbon phase even；δ 1.54-1.71 are O=P-CH3The upper methyl hydrogen being connected with phosphorus oxygen
Peak；δ 4.18-4.36 are Si-OCH2The upper methylene hydrogen peaks being connected with silica of C；δ 4.48-4.60 are (CH2O)2- P=O (- CH3)
The methylene epoxide hydrogen peak being connected on phosphine ring with oxygen；δ 7.32-7.50 are hydrogen peak on phenyl ring；δ 7.26 is what solvent carbon deuterium chloride exchanged
Proton peak.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 is in tetra- mouthfuls of the 200ml equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device
In flask, with air in nitrogen displacement bottle falling, 60ml ethylene glycol diethyl ethers and 34.92g (0.18mol) 4- methylols -4- are added
Ethyl-Cyclic methyl phosphonate ester, stirs lower dropwise addition 10.58g (0.05mol) phenyl trichlorosilane, and control dropping temperature is no more than
60 DEG C, 110 DEG C are warming up to after dripping off, reacts 19h, after hydrogen to be chlorinated discharges, makes vacuum distillation apparatus into, is evaporated under reduced pressure and removes second
Glycol diethyl ether (recovery uses), adds 55ml distilled water, and stirring is dispersed in water solid, filtered, water wash to pH
=7, drying, obtain white solid aryl silicon ring phosphine compound, product yield 90.5%.
Embodiment 2 is in tetra- mouthfuls of the 200ml equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device
In flask, with air in nitrogen displacement bottle falling, 70ml dimethylbenzene and 31.04g (0.16mol) 4- methylols -4- ethyls-ring are added
Shape methyl phosphonate, lower dropwise addition 10.58g (0.05mol) phenyl trichlorosilane is stirred, control dropping temperature is no more than 60 DEG C, drop
100 DEG C are warming up to after complete, reacts 21h, after hydrogen to be chlorinated discharges, makes vacuum distillation apparatus into, is evaporated under reduced pressure except removal xylene (returns
Receive and use), 70ml distilled water is added, stirring is dispersed in water solid, filters, water wash to pH=7, drying, obtains white
Color solid aryl silicon ring phosphine compound, product yield 84.2%.
Embodiment 3 is in tetra- mouthfuls of the 200ml equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device
In flask, with air in nitrogen displacement bottle falling, add 50ml diethylene glycol dimethyl ethers and 32.98g (0.17mol) 4- methylols-
4- ethyls-Cyclic methyl phosphonate ester, stir lower dropwise addition 10.58g (0.05mol) phenyl trichlorosilane, and control dropping temperature does not surpass
60 DEG C are crossed, 150 DEG C are warming up to after dripping off, reacts 13h, after hydrogen to be chlorinated discharges, makes vacuum distillation apparatus into, is evaporated under reduced pressure and removes
Diethylene glycol dimethyl ether (recovery uses), adds 60ml distilled water, and stirring is dispersed in water solid, filtered, water wash
To pH=7, drying, white solid aryl silicon ring phosphine compound, product yield 86.0% are obtained.
Embodiment 4 is in tetra- mouthfuls of the 200ml equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device
In flask, with air in nitrogen displacement bottle falling, 80ml methyl phenyl ethers anisoles and 36.86g (0.19mol) 4- methylols -4- ethyls-ring are added
Shape methyl phosphonate, lower dropwise addition 10.58g (0.05mol) phenyl trichlorosilane is stirred, control dropping temperature is no more than 60 DEG C, drop
140 DEG C are warming up to after complete, reacts 16h, after hydrogen to be chlorinated discharges, makes vacuum distillation apparatus into, removing methyl phenyl ethers anisole is evaporated under reduced pressure and (returns
Receive and use), 45ml distilled water is added, stirring is dispersed in water solid, filters, water wash to pH=7, drying, obtains white
Color solid aryl silicon ring phosphine compound, product yield 93.5%.
Embodiment 5 is in tetra- mouthfuls of the 150ml equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device
In flask, with air in nitrogen displacement bottle falling, add 40ml tetrachloroethanes and 29.10g (0.15mol) 4- methylol -4- ethyls -
Cyclic methyl phosphonate ester, lower dropwise addition 10.58g (0.05mol) phenyl trichlorosilane being stirred, control dropping temperature is no more than 60 DEG C,
130 DEG C are warming up to after dripping off, reacts 18h, after hydrogen to be chlorinated discharges, makes vacuum distillation apparatus into, is evaporated under reduced pressure and removes four chloroethenes
Alkane (recovery uses), 35ml distilled water being added, stirring is dispersed in water solid, filtered, water wash to pH=7, drying,
Obtain white solid aryl silicon ring phosphine compound, product yield 80.6%.
The preparation example main technologic parameters of table 1
The aryl silicon ring phosphine compound of above-mentioned preparation is also applied in polyester PBT by inventor.Reference：GB/
T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limited oxygen index of test sample product.Take the collaboration resistance of product phosphorus silicon
After combustion agent aryl silicon ring phosphine compound and polyester PBT are well mixed with different weight percentage, squeezed with extruder at 230 DEG C
Go out, a diameter of 3mm batten is made, and its fire resistance is tested, result of the test is as shown in table 2：
The aryl silicon ring phosphine compound of table 2 is applied to PBT fire resistance data
As can be seen from Table 2 when fire retardant aryl silicon ring phosphine compound addition of the present invention is up to 20%, the pole of flame-retardant PBT
Limited oxygen index reaches 30%, is provided with good flame retardant effect, and have in heated or burning the defects of easily melting drippage to it
Improved.Therefore, fire retardant of the present invention has good fire resistance and very wide into charcoal anti-drip energy, application prospect.
Claims (1)
1. a kind of preparation method of fire retardant aryl silicon ring phosphine compound, it is characterised in that this method is：
Fall the air in the reactor with hydrogen chloride absorption device with nitrogen displacement, it is phenyl trichlorine silicon to add volume milliliter number
Dimethylbenzene, tetrachloroethanes or the methyl phenyl ethers anisole of 3-8 times of alkane quality grams make solvent and 1- oxygen -1- methyl -4- ethyl -4- methylols -
2,6- dioxa -1- phospha cyclohexanes, under stirring, phenyl trichlorosilane is added drop-wise in reaction system, controls phenyl trichlorine silicon
The mol ratio of alkane and 1- oxygen -1- methyl -4- ethyl -4- methylol -2,6- dioxa -1- phospha cyclohexanes is 1: 3-1: 3.8, and
Control dropping temperature to be no more than 60 DEG C, react 13-21h at 100-150 DEG C after dripping off, after hydrogen to be chlorinated discharges, vacuum distillation removes
Organic solvent to be removed, adds the distilled water of product Theoretical Mass 1-2 times of volume milliliter number of grams, stirring is dispersed in water solid,
Filter, water wash to pH=7, drying, obtain aryl silicon ring phosphine compound, the structure of the compound is shown below：
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