CN105001265B - The preparation method of the double phosphorus cage ring phosphate compounds of fire retardant - Google Patents
The preparation method of the double phosphorus cage ring phosphate compounds of fire retardant Download PDFInfo
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- CN105001265B CN105001265B CN201510404546.8A CN201510404546A CN105001265B CN 105001265 B CN105001265 B CN 105001265B CN 201510404546 A CN201510404546 A CN 201510404546A CN 105001265 B CN105001265 B CN 105001265B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 57
- 239000011574 phosphorus Substances 0.000 title claims abstract description 57
- 239000003063 flame retardant Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 title abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 235000021317 phosphate Nutrition 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000010792 warming Methods 0.000 claims abstract description 24
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 23
- 239000012265 solid product Substances 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000005292 vacuum distillation Methods 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 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 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000012065 filter cake Substances 0.000 description 38
- -1 octane compound Chemical class 0.000 description 23
- 238000000354 decomposition reaction Methods 0.000 description 22
- 239000007983 Tris buffer Substances 0.000 description 19
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical class OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 description 19
- 238000011084 recovery Methods 0.000 description 19
- 238000001291 vacuum drying Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 10
- 239000002032 methanolic fraction Substances 0.000 description 10
- 239000002031 ethanolic fraction Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008422 chlorobenzenes Chemical class 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate tribasic Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of preparation method of the double phosphorus cage ring phosphate compounds of fire retardant, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of preparation method of the double phosphorus cage ring phosphate compounds of organic phosphine fire retardant, and in particular to a kind of
1- oxygen -2, the preparation method of 6, the 7- trioxas-phosphabicyclo of Isosorbide-5-Nitrae-two [2.2.2] octane compound, compound is suitable as
The fire retardant of the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin.
Background technology
With the rapid advances of World Science technology, synthetic fibers, plastics, rubber Polymer material are more and more extensive
The every field of national economy is applied to, the living standard of people is drastically increased.However, the inflammability warp of macromolecular material
Often cause fire, the lives and properties for giving people bring serious threat.Therefore, promote and the flame-retardant modified of macromolecular material is ground
Study carefully, while fire retardant has also obtained development quickly.Phosphorus flame retardant with its low toxicity, low cigarette, decomposition temperature is high the advantages of it is more next
More it is valued by people.Particularly Organic phosphonate system fire retardant, because containing C-P keys, chemical stability enhancing, with resistance in structure
Water, solvent resistant extraction, the high and low cigarette of flame-retarded efficiency, the advantages of nontoxic, mechanical property is good, so, Organic phosphonate system fire retardant is ground
Study carefully one of direction for having turned into most promising.
The invention discloses a kind of preparation method of the double phosphorus cage ring phosphate compounds of organic phosphine fire retardant.The present invention is fire-retardant
Agent is cage structure, has the advantages that phosphorus content high, good stability, flame-retarded efficiency are high and material compatibility is good.Present invention reaction
The alcohol of generation can be recycled all, there is good economic benefit and environmental benefit, therefore, the product that the present invention is obtained has very
Good development prospect.
The content of the invention
Preparation method it is an object of the invention to propose a kind of double phosphorus cage ring phosphate compounds of organic phosphine fire retardant, should
Method is single step reaction, and process is simple, equipment investment is few, it is easy to large-scale production, can overcome deficiency of the prior art.Its skill
Art scheme is as follows：
The method is：
In the reactor equipped with efficient fractionating device, under nitrogen protection, equimolar tris hydroxymethyl phosphine and phosphorus are added
Sour three esters, under stirring, add a certain amount of catalyst, are warming up to 100-180 DEG C of reaction 8-12h, control column top temperature to want
The boiling temperature of generated alcohol is separated, reaction is stopped when the alcohol for fractionating out reaches theoretical amount, be cooled to less than 30 DEG C, purified place
Manage to obtain the double phosphorus cage ring phosphates of product.
The method can also be：
In the reactor equipped with efficient fractionating device, under nitrogen protection, organic solvent, equimolar three hydroxyls first are added
Base phosphine and phosphotriester, under stirring, add a certain amount of catalyst, are warming up to 100-160 DEG C of insulation reaction 5-10h, control
Column top temperature by separate generation alcohol boiling temperature, reaction, then vacuum distillation are stopped when the alcohol for fractionating out reaches theoretical amount
Organic solvent is removed, less than 30 DEG C are cooled to, purified treatment obtains the double phosphorus cage ring phosphates of product.
Phosphotriester as described above is trimethyl phosphate or triethyl phosphate.
Organic solvent as described above is dioxane, methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, two
Toluene or chlorobenzene, its consumption volume milliliter number are 4-9 times of tris hydroxymethyl phosphine quality grams.
A certain amount of catalyst as described above is sodium methoxide, triethylamine, pyridine or NaOH, and its consumption grams is three hydroxyls
The 1%-2% of methylphosphine quality grams.
Purification process as described above is to add 2-3 times of frozen water of volume milliliter number of product Theoretical Mass grams, stirring
10min, is dispersed in water white solid product, filtering, frozen water drip washing, drains, is vacuum dried.
The double phosphorus cage ring phosphates of organic phosphine fire retardant of the present invention are white solid, and product yield is 71.9%-88.2%, is melted
Point：77 ± 2 DEG C, decomposition temperature：269±5℃.It is suitable as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin
Deng the fire retardant of material, the preparation technology principle of the double phosphorus cage ring phosphates of the organic phosphine fire retardant is shown below：
R is-CH3Or-CH2CH3
Compared with prior art, the beneficial effects of the present invention are：
1. the double phosphorus cage ring phosphate compound phosphorus contents of organic phosphine fire retardant of the present invention are up to 36.9%, and flame-retarded efficiency is high,
It contains cage ring structure, and symmetry is good, and the organic phosphine key (C-P keys) in molecule can bring stability, decomposition temperature to compound
Height, and it is good with the compatibility of macromolecular material, and processing characteristics is excellent.
2. the alcohol for being produced in the preparation technology of the double phosphorus cage ring phosphate compounds of organic phosphine fire retardant of the present invention can be returned all
Receive and utilize, with good environmental benefit and economic benefit.
3. the preparation method of the double phosphorus cage ring phosphate compounds of organic phosphine fire retardant of the present invention is single step reaction, technique letter
Single, equipment investment is few, easy to operate, 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 double phosphorus cage ring phosphates, refers to Figure of description Fig. 1；
Fig. 1 shows, in 2973cm-1It is the stretching vibration peak of methylene c h bond to locate；1455cm-1It is methylene c h bond to locate
Flexural vibrations peak；1272cm-1It is the stretching vibration peak of P=O double bonds to locate；1153cm-1And 1126cm-1Locate stretching for C-O keys
Vibration peak；1024cm-1It is the stretching vibration peak of P-O keys to locate；818cm-1It is the stretching vibration peak of C-P keys to locate.
2nd, the nuclear magnetic spectrum figure of double phosphorus cage ring phosphates, refers to Figure of description Fig. 2；
Fig. 2 shows, solvent is made with deuterated dimethyl sulfoxide, is the H peaks of methylene at δ 4.06-4.43；It is deuterated at δ 2.50
The H peaks of dimethylsulfoxide solvent.
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 fractionating device with nitrogen
Air in bottle, adds 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.Under stirring, then add
Enter 0.24g Triethylamine catalysts, heat and be continually fed into nitrogen, be warming up to 110 DEG C of insulation reaction 10h, control column top temperature is not
Higher than 65 DEG C, the methyl alcohol (recovery is used) that reaction is produced is fractionated out, reaction is stopped when methanol fraction reaches theoretical amount, be cooled to
Less than 30 DEG C, 50ml frozen water is added, stir 10min, be dispersed in water white solid product, filtered, filter cake 10ml frozen water
Drip washing, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cage ring phosphates of white solid, and yield is 74.3%, fusing point：77±2
DEG C, decomposition temperature：269±5℃.
Embodiment 2 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.Under stirring, then add
Enter 0.14g sodium hydroxide catalysts, heat and be continually fed into nitrogen, be warming up to 130 DEG C of insulation reaction 9h, control column top temperature is not
Higher than 65 DEG C, the methyl alcohol (recovery is used) that reaction is produced is fractionated out, reaction is stopped when methanol fraction reaches theoretical amount, be cooled to
Less than 30 DEG C, 45ml frozen water is added, stir 10min, be dispersed in water white solid product, filtered, filter cake 10ml frozen water
Drip washing, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cage ring phosphates of white solid, and yield is 76.2%, fusing point：77±2
DEG C, decomposition temperature：269±5℃.
Embodiment 3 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.Under stirring, then add
Enter 0.15g sodium methoxide catalysts, heat and be continually fed into nitrogen, be warming up to 160 DEG C of insulation reaction 8h, control column top temperature is not high
In 65 DEG C, the methyl alcohol (recovery is used) that reaction is produced is fractionated out, reaction is stopped when methanol fraction reaches theoretical amount, be cooled to 30
Below DEG C, 40ml frozen water is added, stir 10min, be dispersed in water white solid product, filtered, filter cake 10ml frozen water drenches
Wash, compacting is drained, filter cake vacuum drying, obtain the double phosphorus cage ring phosphates of white solid, yield is 78.5%, fusing point：77 ± 2 DEG C,
Decomposition temperature：269±5℃.
Embodiment 4 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 90ml dioxane, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) tripotassium phosphate
Ester.Under stirring, 0.19g Triethylamine catalysts are added, heat and be continually fed into nitrogen, be warming up to 100 DEG C of insulation reaction 7h, controlled
Column top temperature is not higher than 65 DEG C, fractionates out the methyl alcohol (recovery is used) that reaction is produced, and stops when methanol fraction reaches theoretical amount
Reaction, then vacuum distillation eliminates dioxane, is cooled to less than 30 DEG C, adds 45ml frozen water, stirs 10min, makes white solid
Product is dispersed in water, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cages of white solid
Cyclic phosphate, yield is 85.1%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 5 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 80ml methyl phenyl ethers anisoles, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.
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 5h, control column
Top temperature is not higher than 65 DEG C, fractionates out the methyl alcohol (recovery is used) that reaction is produced, and stops when methanol fraction reaches theoretical amount anti-
Answer, then vacuum distillation eliminates methyl phenyl ethers anisole, is cooled to less than 30 DEG C, adds 45ml frozen water, stirs 10min, makes white solid product
It is dispersed in water, filters, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying obtains the double phosphorus cage ring phosphorus of white solid
Acid esters, yield is 87.7%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 6 is caught up with to the greatest extent in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 60ml diethylene glycol dimethyl ethers, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) phosphorus
Sour trimethyl.Under stirring, 0.23g sodium hydroxide catalysts are added, heat and be continually fed into nitrogen, be warming up to 160 DEG C of insulations anti-
Answer 5h, control column top temperature to be not higher than 65 DEG C, the methyl alcohol (recovery is used) that reaction is produced is fractionated out, when methanol fraction reaches theory
Stop reaction during amount, then vacuum distillation eliminates diethylene glycol dimethyl ether, is cooled to less than 30 DEG C, adds 50ml frozen water, stirring
10min, is dispersed in water white solid product, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying,
The double phosphorus cage ring phosphates of white solid are obtained, yield is 88.2%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 7 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 90ml ethylene glycol diethyl ethers, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) phosphoric acid
Trimethyl.Under stirring, 0.20g pyridine catalysts are added, heat and be continually fed into nitrogen, be warming up to 120 DEG C of insulation reaction 6h, controlled
Column top temperature processed is not higher than 65 DEG C, fractionates out the methyl alcohol (recovery is used) that reaction is produced, and stops when methanol fraction reaches theoretical amount
Only react, then vacuum distillation eliminates ethylene glycol diethyl ether, is cooled to less than 30 DEG C, adds 35ml frozen water, stirs 10min, makes white
Color solid product is dispersed in water, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains white solid
Double phosphorus cage ring phosphates, yield is 86.8%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 8 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 100ml toluene, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.
Under stirring, 0.15g pyridine catalysts are added, heat and be continually fed into nitrogen, be warming up to 110 DEG C of insulation reaction 7h, control capital
Temperature is not higher than 65 DEG C, fractionates out the methyl alcohol (recovery is used) that reaction is produced, and reaction is stopped when methanol fraction reaches theoretical amount,
Vacuum distillation again eliminates toluene, is cooled to less than 30 DEG C, adds 50ml frozen water, stirs 10min, is scattered in white solid product
In water, filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cage ring phosphates of white solid,
Yield is 85.9%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 9 is caught up with to the greatest extent in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 50ml dimethylbenzene, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.
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 5h, control column
Top temperature is not higher than 65 DEG C, fractionates out the methyl alcohol (recovery is used) that reaction is produced, and stops when methanol fraction reaches theoretical amount anti-
Answer, then vacuum distillation eliminates dimethylbenzene, is cooled to less than 30 DEG C, adds 35ml frozen water, stirs 10min, makes white solid product
It is dispersed in water, filters, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying obtains the double phosphorus cage ring phosphorus of white solid
Acid esters, yield is 86.0%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 10 is caught up with to the greatest extent in equipped with agitator, thermometer, the 200ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 70ml chlorobenzenes, 12.40g (0.1mol) tris hydroxymethyl phosphines and 14.00g (0.1mol) trimethyl phosphate.Stir
Mix down, add 0.18g sodium hydroxide catalysts, heat and be continually fed into nitrogen, be warming up to 130 DEG C of insulation reaction 6h, control column
Top temperature is not higher than 65 DEG C, fractionates out the methyl alcohol (recovery is used) that reaction is produced, and stops when methanol fraction reaches theoretical amount anti-
Answer, then vacuum distillation eliminates chlorobenzene, is cooled to less than 30 DEG C, adds 45ml frozen water, stirs 10min, makes white solid product point
Dissipate in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying obtains the double phosphorus cage ring phosphoric acid of white solid
Ester, yield is 85.6%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 11 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) triethyl phosphate.Under stirring, then add
Enter 0.18g pyridine catalysts, heat and be continually fed into nitrogen, be warming up to 120 DEG C of insulation reaction 12h, control column top temperature is not high
In 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, reaction is stopped when ethanol fraction reaches theoretical amount, be cooled to 30
Below DEG C, 40ml frozen water is added, stir 10min, be dispersed in water white solid product, filtered, filter cake 10ml frozen water drenches
Wash, compacting is drained, filter cake vacuum drying, obtain the double phosphorus cage ring phosphates of white solid, yield is 71.9%, fusing point：77 ± 2 DEG C,
Decomposition temperature：269±5℃.
Embodiment 12 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) triethyl phosphate.Under stirring, then add
Enter 0.20g sodium hydroxide catalysts, heat and be continually fed into nitrogen, be warming up to 150 DEG C of insulation reaction 11h, control column top temperature
Not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, reaction, cooling are stopped when ethanol fraction reaches theoretical amount
To less than 30 DEG C, 45ml frozen water is added, stir 10min, be dispersed in water white solid product, filtered, filter cake 10ml ice
Water wash, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cage ring phosphates of white solid, and yield is 73.1%, fusing point：77±2
DEG C, decomposition temperature：269±5℃.
Embodiment 13 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) triethyl phosphate.Under stirring, then add
Enter 0.24g sodium methoxide catalysts, heat and be continually fed into nitrogen, be warming up to 180 DEG C of insulation reaction 10h, control column top temperature is not
Higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, reaction is stopped when ethanol fraction reaches theoretical amount, be cooled to
Less than 30 DEG C, 50ml frozen water is added, stir 10min, be dispersed in water white solid product, filtered, filter cake 10ml frozen water
Drip washing, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cage ring phosphates of white solid, and yield is 75.7%, fusing point：77±2
DEG C, decomposition temperature：269±5℃.
Embodiment 14 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 100ml dioxane, 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) tricresyl phosphate second
Ester.Under stirring, 0.14g Triethylamine catalysts are added, heat and be continually fed into nitrogen, be warming up to 100 DEG C of insulation reaction 9h, controlled
Column top temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, and stops when ethanol fraction reaches theoretical amount
Reaction, then vacuum distillation eliminates dioxane, is cooled to less than 30 DEG C, adds 40ml frozen water, stirs 10min, makes white solid
Product is dispersed in water, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains the double phosphorus cages of white solid
Cyclic phosphate, yield is 82.0%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 15 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 80ml methyl phenyl ethers anisoles, 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) triethyl phosphate.
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 7h, control column
Top temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, and stops when ethanol fraction reaches theoretical amount anti-
Answer, then vacuum distillation eliminates methyl phenyl ethers anisole, is cooled to less than 30 DEG C, adds 45ml frozen water, stirs 10min, makes white solid product
It is dispersed in water, filters, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying obtains the double phosphorus cage ring phosphorus of white solid
Acid esters, yield is 85.8%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 16 is caught up with to the greatest extent in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 60ml diethylene glycol dimethyl ethers, 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) phosphorus
Triethylenetetraminehexaacetic acid ester.Under stirring, 0.24g sodium hydroxide catalysts are added, heat and be continually fed into nitrogen, be warming up to 160 DEG C of insulations anti-
Answer 7h, control column top temperature to be not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, when ethanol fraction reaches theory
Stop reaction during amount, then vacuum distillation eliminates diethylene glycol dimethyl ether, is cooled to less than 30 DEG C, adds 40ml frozen water, stirring
10min, is dispersed in water white solid product, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying,
The double phosphorus cage ring phosphates of white solid are obtained, yield is 86.1%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 17 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 90ml ethylene glycol diethyl ethers, 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) phosphoric acid
Triethyl.Under stirring, 0.23g pyridine catalysts are added, heat and be continually fed into nitrogen, be warming up to 120 DEG C of insulation reaction 9h, controlled
Column top temperature processed is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, and stops when ethanol fraction reaches theoretical amount
Only react, then vacuum distillation eliminates ethylene glycol diethyl ether, is cooled to less than 30 DEG C, adds 40ml frozen water, stirs 10min, makes white
Color solid product is dispersed in water, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying, obtains white solid
Double phosphorus cage ring phosphates, yield is 82.5%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 18 is caught up with to the greatest extent in equipped with agitator, thermometer, the 200ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 70ml chlorobenzenes, 12.40g (0.1mol) tris hydroxymethyl phosphines and 18.20g (0.1mol) triethyl phosphate.Stir
Mix down, add 0.15g sodium hydroxide catalysts, heat and be continually fed into nitrogen, be warming up to 130 DEG C of insulation reaction 8h, control column
Top temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, and stops when ethanol fraction reaches theoretical amount anti-
Should, less than 30 DEG C are cooled to, then vacuum distillation eliminates chlorobenzene, adds 50ml frozen water, stirs 10min, makes white solid product point
Dissipate in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying obtains the double phosphorus cage ring phosphoric acid of white solid
Ester, yield is 83.9%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 19 is caught up with to the greatest extent in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 50ml dimethylbenzene, 12.40g (0.1mol) tris hydroxymethyl phosphines and 16.60g (0.1mol) triethyl phosphate.
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 8h, control column
Top temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, and stops when ethanol fraction reaches theoretical amount anti-
Answer, then vacuum distillation eliminates dimethylbenzene, is cooled to less than 30 DEG C, adds 35ml frozen water, stirs 10min, makes white solid product
It is dispersed in water, filters, filter cake 10ml frozen water drip washing, compacting is drained, filter cake vacuum drying obtains the double phosphorus cage ring phosphorus of white solid
Acid esters, yield is 84.6%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Table 1 prepares embodiment main technologic parameters
Also be applied to the double phosphorus cage ring phosphates of the product 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 in PBT not on year-on-year basis
The product of example, or after product and MCA are compounded in different proportions, then be added in PBT in different proportions, at 225 DEG C,
Extruded with extruder, be made a length of 15cm, the batten of a diameter of 3mm, and its fire resistance is tested, the LOI for measuring
Result is as shown in table 2 and table 3：
Double fire-retardant data of the phosphorus cage ring phosphate in PBT of the product of table 2
| Addition % | LOI% | Drippage situation | Into charcoal |
| 0 | 21 | Fast drippage | Not into charcoal |
| 10 | 24 | Slow drippage | Not into charcoal |
| 20 | 29 | Do not drip | Into charcoal |
| 25 | 31 | Do not drip | Into charcoal |
As shown in Table 2, when the addition when double phosphorus cage ring phosphates in PBT is 20%, limited oxygen index value is 29%,
Fire retardant rank is reached, and has been dripped without melting, carbon-forming performance is fine.
The double fire-retardant data of phosphorus cage ring phosphate and MCA in PBT of the product of table 3
As shown in Table 3, double phosphorus cage ring phosphates have with MCA compoundings and preferably act synergistically, also good dilatancy, most
Good addition proportioning is 3：2, when total addition level is 25%, limited oxygen index is up to 31%, also good carbon-forming 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 the double phosphorus cage ring phosphorus of product
No matter acid esters is single use, or is compounded with MCA, there is preferable flame-retarded efficiency to PBT material.
Claims (3)
1. the preparation method of the double phosphorus cage ring phosphate compounds of a kind of organic phosphine fire retardant, it is characterised in that the method is：
In the reactor equipped with efficient fractionating device, under nitrogen protection, equimolar tris hydroxymethyl phosphine and tricresyl phosphate are added
Methyl esters or triethyl phosphate, under stirring, add catalyst sodium methoxide, three second relative to tris hydroxymethyl phosphine quality 1%-2%
Amine, pyridine or NaOH, be warming up to 100-180 DEG C reaction 8-12h, control column top temperature by separate generation alcohol boiling point
Temperature, reaction is stopped when the alcohol for fractionating out reaches theoretical amount, is cooled to less than 30 DEG C, adds 2-3 times of product Theoretical Mass grams
Volume milliliter number frozen water, stir 10min, be dispersed in water white solid product, filter, frozen water drip washing, drain, vacuum do
It is dry, the double phosphorus cage ring phosphates of product are obtained, the structure of the compound is shown below：
2. the preparation method of the double phosphorus cage ring phosphate compounds of a kind of organic phosphine fire retardant oxo, it is characterised in that the method is：
In the reactor equipped with efficient fractionating device, under nitrogen protection, organic solvent, equimolar tris hydroxymethyl phosphine are added
With trimethyl phosphate or triethyl phosphate, under stirring, the catalyst methyl alcohol relative to tris hydroxymethyl phosphine quality 1%-2% is added
Sodium, triethylamine, pyridine or NaOH, are warming up to 100-160 DEG C of insulation reaction 5-10h, and it is institute to be separated to control column top temperature
The boiling temperature of alcohol is generated, reaction is stopped when the alcohol for fractionating out reaches theoretical amount, then vacuum distillation removes organic solvent, is cooled to
Less than 30 DEG C, 2-3 times of frozen water of volume milliliter number of product Theoretical Mass grams is added, stir 10min, make white solid product point
Dissipate in water, filter, frozen water drip washing, drain, be vacuum dried, obtain the double phosphorus cage ring phosphates of product.
3. the preparation method of double phosphorus cage ring phosphate compounds as claimed in claim 2, it is characterised in that：The organic solvent is
Dioxane, methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene or chlorobenzene, its consumption volume milliliter
Number is 4-9 times of tris hydroxymethyl phosphine quality grams.
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| CN102140118A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant and preparation method thereof |
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| CN102140118A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant and preparation method thereof |
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| NMR PARAMETERS AND BONDING IN METAL, CHALCONIDE, BORANE AND CARBONIUM DERIVATIVES OF POLYCYCLIC PHOSPHORUS LIGANDS;D. A. ALLISON, et al.;《Phosphorus》;19731231;第2卷;257-264 * |
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