CN104926881B - The preparation method of the miscellaneous cage ring phosphate compound of the phosphono of fire retardant 4 - Google Patents
The preparation method of the miscellaneous cage ring phosphate compound of the phosphono of fire retardant 4 Download PDFInfo
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 41
- 239000010452 phosphate Substances 0.000 title claims abstract description 41
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- -1 phosphate compound Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 title abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- DKRWGRQBYLWNKR-UHFFFAOYSA-N OC(O)(O)[PH2]=O Chemical compound OC(O)(O)[PH2]=O DKRWGRQBYLWNKR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001256 steam distillation Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 235000021317 phosphate Nutrition 0.000 description 32
- 239000012065 filter cake Substances 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of preparation method of the miscellaneous cage ring phosphate compound of the phosphono of fire retardant 4, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of preparation method of the miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos, and in particular to
A kind of Isosorbide-5-Nitrae-dioxy -2, the preparation method of 6, the 7- trioxas-phosphabicyclo of Isosorbide-5-Nitrae-two [2.2.2] octane compound, the compound
It is suitable as the fire retardant of the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin.
Background technology
The life that macromolecular material gives people in daily life brings many facilities, but these macromolecular materials are most
All it is inflammable, often causes fire, the security of the lives and property of people has been arrived in serious harm.Therefore, flame retarded polymeric material and resistance
The research and application for firing agent are developed.With in world wide, the enhancing of people's awareness of safety and some flame retardant regulations
Promulgation, it is also proposed requirement higher to fire retardant, market has very strong urgency to its environment friendly flame retardant, low toxicity,
Efficient flame-retarding agent is the important directions of development.Because phosphorus system particularly Organic phosphonate system fire retardant has the advantages that low cigarette, low toxicity,
The non-halogen cry of fire retardant high today, gradually it is valued by people, the research to Organic phosphonate system fire retardant has turned into most
One of direction with development prospect.
The invention discloses a kind of preparation method of the miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos,
K.J.Coskran and J.G.Verkade is disclosed by raw material of tris hydroxymethyl phosphine in nineteen sixty-five and is prepared 4- phosphines by two-step reaction
The method of the miscellaneous cage ring phosphate of acyl, ultimate yield only has 33.2%, does not have the value of industrialization；The present invention is with three hydroxyls of stabilization
Methyl oxidation phosphine is raw material, and one-step method prepares the compound, and process is simple, equipment investment is few, easy to operate, low cost, is easily turned
Turn to industrialized production；The phenol that present invention reaction is produced can be recycled all, high financial profit, before having extraordinary development
Scape.
The content of the invention
It is new it is an object of the invention to propose a kind of preparing for miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos
Method, the method is single step reaction, process is simple, it is easy to large-scale production, and raw material is cheap and easy to get, and equipment investment is few, cost
It is cheap, deficiency of the prior art can be overcome.Its technical scheme is as follows：
The method is：
In equipped with agitator, thermometer, the reactor of reflux condensate device, under nitrogen protection, add equimolar
Triphenyl phosphate and trihydroxy methyl phosphine oxide, add a certain amount of catalyst, are warming up to 120-170 DEG C of reaction 8-14h, remove
The phenol of generation is reacted, product crystallize in frozen water, filtering, is drained, is vacuum dried at frozen water drip washing, obtains white solid 4- phosphonos
Miscellaneous cage ring phosphate.
The method is specially：
In equipped with agitator, thermometer, the reactor of efficient backflow condensing unit, under nitrogen protection, addition etc. rubs
Your triphenyl phosphate and trihydroxy methyl phosphine oxide, adds a certain amount of catalyst, is warming up to 120-170 DEG C of reaction 8-14h,
Stop reaction, add 1-2 times of water of volume milliliter number of product Theoretical Mass grams, water flowing steam under liquid level to carry out vapor steaming
Evaporate, after phenol is all steamed, stirring is cooled to less than 10 DEG C, separate out white particulate solid product, filtering, frozen water drip washing,
Drain, be vacuum dried, obtain the white solid miscellaneous cage ring phosphate of product 4- phosphonos.
The method can also be specifically：
In equipped with agitator, thermometer, the reactor of efficient backflow condensing unit, under nitrogen protection, add organic
Solvent, equimolar triphenyl phosphate and trihydroxy methyl phosphine oxide, under stirring, add a certain amount of catalyst, are warming up to
120-160 DEG C of reaction 8-12h, vacuum distillation removes organic solvent and phenol, adds 2-3 times of volume of product Theoretical Mass grams in the least
The frozen water of number is risen, stirring is cooled to less than 10 DEG C, is dispersed in water white particulate solid product, filtering, is taken out at frozen water drip washing
Dry, vacuum drying, obtains the white solid miscellaneous cage ring phosphate of product 4- phosphonos.
A certain amount of catalyst as described above is sodium methoxide, triethylamine, pyridine or NaOH, and its consumption is trihydroxy methyl
The 1%-2% of phosphine oxide quality.
Organic solvent as described above is methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethylbenzene or chlorobenzene, its
Consumption volume milliliter number is 5-8 times of trihydroxy methyl phosphine oxide quality grams.
The miscellaneous cage ring phosphate of organic phosphine fire retardant 4- phosphonos of the present invention is white solid, and product yield is 84.3%-
93.2%, fusing point：211 ± 2 DEG C, decomposition temperature：305±5℃.It is suitable as polyester, polyurethane, epoxy resin, unsaturation
The fire retardant of the materials such as resin, polyolefin, the organic phosphine miscellaneous cage ring phosphate synthesis technological principle of fire retardant 4- phosphonos is as follows
Shown in formula：
Compared with prior art, the beneficial effects of the present invention are：
1. the miscellaneous cage ring phosphate compound phosphorus content of organic phosphine fire retardant 4- phosphonos of the present invention is up to 33.7%, flame-retarded efficiency
Height, the organic phosphine key (C-P keys) in its molecule brings stability to compound, and phospha cage ring structural symmetry is good, to compound
Stability also contribute, product stabilization, decomposition temperature is high and good with the compatibility of macromolecular material, there is fine processability
Energy.
2. the raw material trihydroxy methyl phosphine oxide that the miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos of the present invention is used
Inherently a kind of excellent response type organic phosphine fire retardant, with phosphate reaction, introduces many ester structures, while improve again again
The content of phosphorus, makes product obtain preferable fire resistance.
3. the nitrogenated flame retardant such as the miscellaneous cage ring phosphate of organic phosphine fire retardant 4- phosphonos of the present invention and MCA compounding has preferably association
Same-action, also good dilatancy, can effectively reduce fire proofing production cost, there is good application prospect.
4. the phenol for being produced in the preparation technology of the miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos of the present invention can
All recycle, with good environmental benefit and economic benefit.
5. the preparation method of the miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos of the present invention is single step reaction, technique
Simply, equipment investment is few, easy to operate, and raw material is easy to get, low cost, it is easy to which scale is converted and produced.
Brief description of the drawings
In order to the structure and performance spy that further illustrate product provide drawings described below.
1st, the infrared spectrogram of the miscellaneous cage ring phosphate of 4- phosphonos, refers to Figure of description Fig. 1；
Fig. 1 shows, in 2887cm-1It is the stretching vibration peak of methylene c h bond to locate；1483cm-1It is methylene c h bond to locate
Flexural vibrations peak；1317cm-1Place is the stretching vibration peak of the P=O double bonds being connected with oxygen；1263cm-1Place is with carbon phase even
The stretching vibration peak of P=O double bonds；1206cm-1And 1114cm-1It is the stretching vibration peak of C-O keys to locate；1005cm-1It is P-O keys to locate
Stretching vibration peak；852cm-1It is the stretching vibration peak of C-P keys to locate.
2nd, the nuclear magnetic spectrum figure of the miscellaneous cage ring phosphate of 4- phosphonos, refers to Figure of description Fig. 2；
Fig. 2 shows that deuterated dimethyl sulfoxide makees solvent, is the H peaks of methylene at δ 4.83-5.10；It is deuterated two at δ 2.50
The H peaks of first sulfoxide solvent.
3rd, the differential thermal figure of the miscellaneous cage ring phosphate of 4- phosphonos, refers to Figure of description Fig. 3；
From the figure 3, it may be seen that temperature is 305 DEG C starts weightlessness；During weight-loss ratio 50%, temperature is 479 DEG C；To final temperature 800
DEG C when still have 33% residue, illustrate that product has preferable heat endurance.
Specific embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 14.00g (0.1mol) trihydroxy methyls phosphine oxide, 32.63g (0.1mol) triphenyl phosphates and 0.20g pyrroles
Pyridine catalyst, heating stirring is simultaneously continually fed into nitrogen, is warming up to 130 DEG C of insulation reaction 14h, stops reaction, adds 20ml water, liquid
Water flowing steam under face, carries out steam distillation, and after phenol is all steamed, stirring is cooled to less than 10 DEG C, consolidates white particulate
Body product is separated out, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains the white solid miscellaneous cage of 4- phosphonos
Cyclic phosphate, yield is 84.3%, fusing point：211 ± 2 DEG C, decomposition temperature：305±5℃.
Embodiment 2 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 14.00g (0.1mol) trihydroxy methyls phosphine oxide, 32.63g (0.1mol) triphenyl phosphates and 0.18g first
Alcohol sodium catalyst, heating stirring is simultaneously continually fed into nitrogen, is warming up to 170 DEG C of insulation reaction 10h, stops reaction, adds 20ml water,
Water flowing steam under liquid level, carries out steam distillation, and after phenol is all steamed, stirring is cooled to less than 10 DEG C, makes white particulate
Solid product is separated out, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains white solid 4- phosphonos miscellaneous
Cage ring phosphate, yield is 87.7%, fusing point：211 ± 2 DEG C, decomposition temperature：305±5℃.
Embodiment 3 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 80ml methyl phenyl ethers anisoles, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 32.63g (0.1mol) tricresyl phosphate
Phenyl ester.Under stirring, 0.22g sodium methoxide catalysts are added, heat and be continually fed into nitrogen, be warming up to 150 DEG C of insulation reaction 8h, stopped
Only react, vacuum distillation removes methyl phenyl ethers anisole and phenol (recovery is used), add 45ml frozen water, stirring is cooled to less than 10 DEG C,
White particulate solid product is dispersed in water, is filtered, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying is obtained
The miscellaneous cage ring phosphate of white solid 4- phosphonos, yield is 93.2%, fusing point：211 ± 2 DEG C, decomposition temperature：305±5℃.
Embodiment 4 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 100ml diethylene glycol dimethyl ethers, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 32.63g
(0.1mol) triphenyl phosphate.Under stirring, 0.28g sodium hydroxide catalysts are added, heat and be continually fed into nitrogen, be warming up to
160 DEG C of insulation reaction 8h, stop reaction, and vacuum distillation removes diethylene glycol dimethyl ether and phenol (recovery is used), adds
40ml frozen water, stirring is cooled to less than 10 DEG C, is dispersed in water white particulate solid product, filters, filter cake 10ml frozen water
Drip washing, compacting is drained, filter cake vacuum drying, obtains the miscellaneous cage ring phosphate of white solid 4- phosphonos, and yield is 92.6%, fusing point：211
± 2 DEG C, decomposition temperature：305±5℃.
Embodiment 5 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 110ml ethylene glycol diethyl ethers, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 32.63g (0.1mol)
Triphenyl phosphate.Under stirring, 0.20g Triethylamine catalysts are added, heat and be continually fed into nitrogen, be warming up to 120 DEG C of insulations anti-
10h is answered, stops reaction, vacuum distillation removes ethylene glycol diethyl ether and phenol (recovery is used), adds 55ml frozen water, stirs cold
But to less than 10 DEG C, white particulate solid product is dispersed in water, is filtered, filter cake 10ml frozen water drip washing, compacting is drained, filtered
Cake is vacuum dried, and obtains the miscellaneous cage ring phosphate of white solid 4- phosphonos, and yield is 90.5%, fusing point：211 ± 2 DEG C, decomposition temperature：
305±5℃。
Embodiment 6 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 90ml dimethylbenzene, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 32.63g (0.1mol) tricresyl phosphate
Phenyl ester.Under stirring, 0.20g sodium methoxide catalysts are added, heat and be continually fed into nitrogen, be warming up to 140 DEG C of insulation reaction 9h, stopped
Only react, vacuum distillation removes removal xylene and phenol (recovery is used), add 40ml frozen water, stirring is cooled to less than 10 DEG C,
White particulate solid product is dispersed in water, is filtered, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying is obtained
The miscellaneous cage ring phosphate of white solid 4- phosphonos, yield is 91.4%, fusing point：211 ± 2 DEG C, decomposition temperature：305±5℃.
Embodiment 7 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient backflow device with nitrogen
Air in bottle, adds 70ml chlorobenzenes, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 32.63g (0.1mol) phosphoric acid triphen
Ester.Under stirring, 0.16g pyridine catalysts are added, heat and be continually fed into nitrogen, be warming up to 130 DEG C of insulation reaction 10h, stopped
Reaction, vacuum distillation removes chlorobenzene and phenol (recovery is used), adds 50ml frozen water, and stirring is cooled to less than 10 DEG C, makes white
Color tablets shape solid product is dispersed in water, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains white
The miscellaneous cage ring phosphate of solid 4- phosphonos, yield is 91.0%, fusing point：211 ± 2 DEG C, decomposition temperature：305±5℃.
Table 1 prepares embodiment main technologic parameters
Also be applied to the miscellaneous cage ring phosphate of product 4- phosphonos of above-mentioned preparation 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.Added not in PBT
Product in proportion, or after product and MCA are compounded in different proportions, then be added in PBT in different proportions, 225
At DEG C, extruded with extruder, be made a length of 15cm, the batten of a diameter of 3mm, and its fire resistance is tested, measured
LOI results as shown in table 2 and table 3：
The fire-retardant data that the miscellaneous cage ring phosphate of product 4- phosphonos of table 2 is used in PBT
| Addition % | LOI% | Drippage situation | Into charcoal |
| 0 | 21 | Fast drippage | Not into charcoal |
| 10 | 24 | Slow drippage | Not into charcoal |
| 20 | 30 | Do not drip | Into charcoal |
| 25 | 32 | Do not drip | Into charcoal |
As shown in Table 2, when the addition when the miscellaneous cage ring phosphate of 4- phosphonos in PBT is 20%, limited oxygen index value is
30%, fire retardant rank has been reached, and dripped without melting, carbon-forming performance is fine.
The miscellaneous cage ring phosphate of product 4- phosphonos of table 3 and MCA compound for PBT in fire-retardant data
As shown in Table 3, the miscellaneous cage ring phosphate of product 4- phosphonos has preferably synergy with MCA compoundings, also well
Dilatancy, when product addition accounts for 55%, and total addition level is when being 25%, limited oxygen index up to 33%, also well into
Charcoal performance；And the price of MCA is very cheap, the production cost of fire proofing can be greatly lowered.Thus it can be seen that product 4-
No matter the miscellaneous cage ring phosphate of phosphono is single use, or is compounded with MCA, there is preferable flame retardant effect to PBT material.
Claims (4)
1. a kind of preparation method of the miscellaneous cage ring phosphate compound of organic phosphine fire retardant 4- phosphonos, it is characterised in that the method is：
In equipped with agitator, thermometer, the reactor of reflux condensate device, under nitrogen protection, equimolar phosphoric acid is added
Triphenylmethyl methacrylate and trihydroxy methyl phosphine oxide, add sodium methoxide, triethylamine, pyridine or NaOH as catalyst, are warming up to
120-170 DEG C of reaction 8-14h, except the phenol of dereaction generation, product crystallize in frozen water, filtering, frozen water drip washing, drains, very
Sky is dried, and obtains the miscellaneous cage ring phosphate of white solid 4- phosphonos, and the structure of the compound is shown below：
2. the preparation method of the miscellaneous cage ring phosphate compound of 4- phosphonos as claimed in claim 1, it is characterised in that the method is：
In equipped with agitator, thermometer, the reactor of efficient backflow condensing unit, under nitrogen protection, add equimolar
Triphenyl phosphate and trihydroxy methyl phosphine oxide, add sodium methoxide, three second relative to trihydroxy methyl phosphine oxide quality 1%-2%
Amine, pyridine or NaOH are warming up to 120-170 DEG C of reaction 8-14h as catalyst, stop reaction, add product theory matter
1-2 times of water of volume milliliter number of amount grams, water flowing steam under liquid level carries out steam distillation, after phenol is all steamed, stirring
Less than 10 DEG C are cooled to, solid product is separated out, filtered, frozen water drip washing, drained, be vacuum dried, obtain the product miscellaneous cage ring of 4- phosphonos
Phosphate.
3. the preparation method of the miscellaneous cage ring phosphate compound of 4- phosphonos as claimed in claim 1, it is characterised in that the method is：
In equipped with agitator, thermometer, the reactor of efficient backflow condensing unit, under nitrogen protection, addition organic solvent,
Equimolar triphenyl phosphate and trihydroxy methyl phosphine oxide, under stirring, add relative to trihydroxy methyl phosphine oxide quality 1%-
2% sodium methoxide, triethylamine, pyridine or NaOH are warming up to 120-160 DEG C of insulation reaction 8-12h as catalyst, depressurize
Organic solvent and phenol is distilled off, 2-3 times of frozen water of volume milliliter number of product Theoretical Mass grams is added, stirring is cooled to 10
Below DEG C, solid product is dispersed in water, filtered, frozen water drip washing, drained, be vacuum dried, obtain the miscellaneous cage ring phosphorus of product 4- phosphonos
Acid esters.
4. the preparation method of the miscellaneous cage ring phosphate compound of 4- phosphonos as claimed in claim 3, it is characterised in that：It is described organic molten
Agent is methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethylbenzene or chlorobenzene, and its consumption volume milliliter number is three hydroxyl first
5-8 times of base phosphine oxide quality grams.
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Denomination of invention: Preparation method of flame retardant 4-phosphonyl heterocyclic phosphate compounds Granted publication date: 20170630 Pledgee: Zhejiang Nanxun Rural Commercial Bank branch Linghu Limited by Share Ltd. Pledgor: Zhejiang Rui hi tech materials Limited by Share Ltd. Registration number: Y2024330000544 |