CN105713042B - The preparation method of the double PEPA ester compounds of phenyl-phosphonic acid - Google Patents
The preparation method of the double PEPA ester compounds of phenyl-phosphonic acid Download PDFInfo
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- CN105713042B CN105713042B CN201610037026.2A CN201610037026A CN105713042B CN 105713042 B CN105713042 B CN 105713042B CN 201610037026 A CN201610037026 A CN 201610037026A CN 105713042 B CN105713042 B CN 105713042B
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- phosphonic acid
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- 101710130081 Aspergillopepsin-1 Proteins 0.000 title claims abstract description 38
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 title claims abstract description 38
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 PEPA ester compounds Chemical class 0.000 title claims abstract description 17
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 19
- 125000005499 phosphonyl group Chemical group 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000006073 displacement reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 11
- 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 description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 7
- 239000004743 Polypropylene Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 238000011109 contamination Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012360 testing method Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- 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)
Abstract
The present invention relates to a kind of preparation method of the double PEPA ester compounds of phenyl-phosphonic acid, the structural formula of the compound are as follows：
Description
Technical field
The present invention relates to a kind of preparation method of the double PEPA ester compounds of phenyl-phosphonic acid.The double double cages of PEPA esters category of phenyl-phosphonic acid
Shape phosphorus flame retardant, it is suitable as the fire retardant of the materials such as polyester PBT, polyester PET, polypropylene PP, polyurethane.
Background technology
The advantages of there is light, corrosion-resistant, easy processing and the irreplaceable other materials such as attractive in appearance due to high polymer material,
Very extensive application has been obtained in the production and life of people, but most of high polymer materials are not only inflammable, and in high temperature
When can melt drippage, cause second-time burning.The extensive use of fire retardant, can improve the inflammable characteristic of high polymer material, but one
As fire retardant the shortcomings that material at high temperature melting drippage can not be overcome to produce second-time burning, thus it is excellent to research and develop comprehensive cost performance
Good fire-retardant carbon forming agent has very strong market in urgent need.
Organic phosphorus flame retardant is wide in variety, and heat endurance is good, widely used, has the advantages that LSZH, has catered to resistance
The developing direction in agent market is fired, development prospect is very wide.It is and fire-retardant into charcoal effect by the PEPA of Material synthesis of pentaerythrite
It is good, but because its decomposition temperature is relatively low, the easy moisture absorption, using being restricted.
The invention discloses a kind of preparation method of the double PEPA ester compounds of phenyl-phosphonic acid, the compound decomposition temperature is high,
PEPA esterification encloses the polarity of hydroxyl, improves the water imbibition of itself, fire-retardant more preferable into charcoal effect, and the virtue in molecule
Ring and more ester structures can increase the compatibility of product and base material, generate unpredictable excellent fire-retardant into charcoal effect；Its
Preparation method technique is simple, easy to operate, and equipment investment is few, environment-friendly, has preferable application and development prospect.
The content of the invention
It is an object of the invention to propose a kind of preparation method of the double PEPA ester compounds of fire retardant phenyl-phosphonic acid, its technique
Simply, it is easy to large-scale production, this method is：
Equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading access one can extremely stretch it is swollen
In the reaction bulb of swollen soft seal set, nitrogen displacement falls air, at 20 DEG C, adds PEPA, organic solvent, under stirring, adds certain
The phenyl phosphonyl chloride of mol ratio, is started to warm up, and ammonia is continually fed on liquid level, keeps soft seal set micro- to be passed through speed
Rise constancy of volume, after being warming up to 60-80 DEG C of insulation reaction 3-4h, be evaporated under reduced pressure and remove organic solvent (recovery uses) and a small amount of low
Boiling point thing, purified processing, obtain the double PEPA esters of white solid phenyl-phosphonic acid.
This method is alternatively：
With nitrogen displacement fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air, add
PEPA, organic solvent, the sodium grain of equimolar amounts is added after being sufficiently stirred, be warming up to 30 DEG C of reactions to sodium and disappear, by certain mole
The phenyl phosphonyl chloride of ratio is added drop-wise in reaction system, after dripping off, after being warming up to 70-100 DEG C of reaction 4-6h, is evaporated under reduced pressure and is removed
Organic solvent (recovery uses) and a small amount of low boilers, purified processing, obtain the double PEPA esters of white solid phenyl-phosphonic acid.
This method can also be：
With nitrogen displacement fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air, add
PEPA, the hexane solution containing equivalent dibutyl zinc, after stirring makes PEPA fully dispersed, 60 DEG C of reaction 3h are warming up to, will
The phenyl phosphonyl chloride of certain mol proportion is added drop-wise in reaction system, after dripping off, reacts 6-7h at 60-70 DEG C, vacuum distillation removes
N-hexane (recovery uses) and a small amount of low boilers, purified processing are gone, obtains the double PEPA esters of white solid phenyl-phosphonic acid.
Organic solvent as described above is acetonitrile or dioxane, and its dosage volume milliliter number is PEPA quality grams
5-10 times.
The phenyl phosphonyl chloride of certain mol proportion as described above is 1: 2-1 for phenyl phosphonyl chloride and PEPA mol ratio
∶2.5。
For purification process as described above to add the distilled water of 4-6 times of product Theoretical Mass, stirring disperses solid product
Yu Shuizhong, filtering, washing, drying.
The double PEPA esters of phenyl-phosphonic acid of the present invention are white powdery solids, its fusing point：206 ± 2 DEG C, decomposition temperature：281
±5℃；Yield is 80.3%-88.3%, and it is suitable as the resistance of the materials such as polyester PBT, polyester PET, polypropylene PP, polyurethane
Combustion agent is used.
The preparation technology principle of the double PEPA esters of phenyl-phosphonic acid is shown below：
Compared with prior art, innovation of the invention is：
1. the preparation method reaction time of the present invention is short, reaction temperature is low, good reaction selectivity, and yield is high, accessory substance and molten
Agent is recyclable.
2. preparation method of the present invention mutually ties up the technique of acid using ammonia, ammonia is cheap, nontoxic, the hydrogen chloride discharged with system
Reaction generation ammonium chloride, can effectively facilitate the effusion of hydrogen chloride, and ammonia, not with acyl chloride reaction, ammonium chloride is with having on material liquid surface
Machine thing is immiscible, can be easily separated, and is used as Fertilizer application after can reclaiming.
3. being reacted in preparation method of the present invention using PEPA sodium salts and phenyl-phosphonic acid dichloro, make reaction be more prone to carry out,
Reaction is more complete, and the NaCl for reacting generation is easier to remove.
4. being reacted in preparation method of the present invention using PEPA zinc salts and phenyl-phosphonic acid dichloro, its zinc has self-catalysis work in itself
With, easily reacted very much, reacted more completely, and the ZnCl of reaction generation2Also easily remove.
5. preparation method technique of the present invention is simple, raw material is cheap and easy to get, and equipment investment is few, is easy to large-scale production.
Brief description of the drawings
In order to further illustrate that the structure of product and performance spy provide drawings described below.
Fig. 1 is the infrared spectrogram of the double PEPA esters of phenyl-phosphonic acid；Fig. 1 shows：851.2cm-1Locate as bicyclic-CH2- on C-
H flexural vibrations peaks；1037.0cm-1Locate the stretching vibration peak for P-O；1073.0cm-1Locate as the stretching vibration peak of C-O keys；
1172.8cm-1Locate the stretching vibration peak for P=O；1476.2cm-1Locate the skeleton stretching vibration peak for phenyl ring；2944.0cm-1Place
For the stretching vibration peak of c h bond.
Fig. 2 is the nuclear magnetic spectrum figure of the double PEPA esters of phenyl-phosphonic acid；Fig. 2 shows：With CD3SOCD3For solvent, δ3：7.76-
7.84 (q, 2H)；δ1：7.68-7.76 (t, 1H)；δ2：7.57-7.65 (q, 2H)；δ4：4.55-4.63 (d, 12H)；δ5：3.35-
3.49 (s, 4H).
Fig. 3 is the thermogravimetric spectrogram of the double PEPA esters of phenyl-phosphonic acid；Fig. 3 shows：Product starts weightless in 281 DEG C；Weight-loss ratio is
When 5%, temperature is 303 DEG C；When weight-loss ratio is 50%, temperature is 350 DEG C.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to one can extremely
In the 100mL four-hole boiling flasks of flexible expansion soft seal set, the air in logical nitrogen displacement bottle falling, 9.00g (0.050mol) is added
PEPA and 50mL dioxane, under stirring, 3.9g (0.02mol) phenyl phosphonyl chloride is added, is warming up to 60 DEG C, and to reaction bulb
Ammonia is continually fed on middle liquid level, keeps soft seal set to rise slightly constancy of volume to be passed through speed, after 60 DEG C of insulation reaction 4h, steams
Dioxane (recovery uses) and a small amount of low boilers are gone in distillation, add 50mL distilled water, and stirring makes product solid be scattered in water
In, filtering, washing, drying, obtain the double PEPA esters of white solid phenyl-phosphonic acid, yield 87.2%, fusing point：206 ± 2 DEG C, decompose
Temperature：281±5℃.
Embodiment 2 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to one can extremely
In the 100mL four-hole boiling flasks of flexible expansion soft seal set, the air in logical nitrogen displacement bottle falling, 8.64g (0.048mol) is added
PEPA and 50mL acetonitriles, under stirring, 3.9g (0.02mol) phenyl phosphonyl chloride is added, is warming up to 80 DEG C, and the liquid into reaction bulb
Ammonia is continually fed on face, keeps soft seal set to rise slightly constancy of volume to be passed through speed, after 80 DEG C of insulation reaction 3h, distillation removes
Acetonitrile (recovery uses) and a small amount of low boilers to be gone, add 50mL distilled water, stirring is dispersed in water product solid, filtering,
Washing, drying, obtain the double PEPA esters of white solid phenyl-phosphonic acid, yield 86.6%, fusing point：206 ± 2 DEG C, decomposition temperature：281
±5℃。
The nitrogen displacement of embodiment 3 fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air,
8.28g (0.046mol) PEPA, 50mL dioxane is added, 1.058g (0.046mol) sodium grain, heating are added after being sufficiently stirred
Disappeared to 30 DEG C of reactions to sodium, 3.9g (0.02mol) phenyl phosphonyl chloride is added dropwise in 1h, after dripping off, is warming up to 100 DEG C of reactions
4h, it is evaporated under reduced pressure and removes dioxane (recovery uses) and a small amount of low boilers, add 50mL distilled water, stirring consolidates product
Body is dispersed in water, and is filtered, washes, is dried, and obtains the double PEPA esters of white solid phenyl-phosphonic acid, yield 88.3%, fusing point：206
± 2 DEG C, decomposition temperature：281±5℃.
The nitrogen displacement of embodiment 4 fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air,
7.56g (0.042mol) PEPA, 50mL dioxane is added, 0.966g (0.042mol) sodium grain, heating are added after being sufficiently stirred
Disappeared to 30 DEG C of reactions to sodium, 3.9g (0.02mol) phenyl phosphonyl chloride is added dropwise in 1h, after dripping off, is warming up to 85 DEG C of reactions
5h, it is evaporated under reduced pressure and removes dioxane (recovery uses) and a small amount of low boilers, add 50mL distilled water, stirring consolidates product
Body is dispersed in water, and is filtered, washes, is dried, and obtains the double PEPA esters of white solid phenyl-phosphonic acid, yield 86.4%, fusing point：206
± 2 DEG C, decomposition temperature：281±5℃.
The nitrogen displacement of embodiment 5 fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air,
7.92g (0.044mol) PEPA, 50mL acetonitrile is added, 1.012g (0.044mol) sodium grain is added after being sufficiently stirred, is warming up to 30
DEG C reaction to sodium disappear, in 1h be added dropwise 3.9g (0.02mol) phenyl phosphonyl chloride, after dripping off, be warming up to 70 DEG C reaction 6h, subtract
Acetonitrile (recovery uses) and a small amount of low boilers are distilled off in pressure, add 50mL distilled water, and stirring is scattered in product solid
In water, filtering, washing, drying, the double PEPA esters of white solid phenyl-phosphonic acid, yield 84.1%, fusing point are obtained：206 ± 2 DEG C, point
Solve temperature：281±5℃.
The nitrogen displacement of embodiment 6 fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air,
The hexane solution that 7.56g (0.042mol) PEPA, 50mL contains 3.759g (0.021mol) dibutyl zinc is added, stirring makes
After PEPA is fully dispersed, 60 DEG C of reaction 3h are warming up to, 3.9g (0.02mol) phenyl phosphonyl chloride is added dropwise in 1h, after dripping off,
70 DEG C of reaction 6h, it is evaporated under reduced pressure and removes n-hexane (recovery uses) and a small amount of low boilers, add 50mL distilled water, stirring makes
Solid product is dispersed in water, and is filtered, washes, is dried, and is obtained the double PEPA esters of white solid phenyl-phosphonic acid, yield 83.1%, is melted
Point：206 ± 2 DEG C, decomposition temperature：281±5℃.
The nitrogen displacement of embodiment 7 fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air,
The hexane solution that 7.2g (0.04mol) PEPA, 50mL contains 3.58g (0.02mol) dibutyl zinc is added, stirring fills PEPA
After scattered, 60 DEG C of reaction 3h are warming up to, 3.9g (0.02mol) phenyl phosphonyl chloride is added dropwise in 1h, it is anti-at 60 DEG C after dripping off
7h is answered, is evaporated under reduced pressure and removes n-hexane (recovery uses) and a small amount of low boilers, add 40mL distilled water, stirring produces solid
Product are dispersed in water, and are filtered, wash, are dried, and obtain the double PEPA esters of white solid phenyl-phosphonic acid, yield 80.3%, fusing point：206
± 2 DEG C, decomposition temperature：281±5℃.
The nitrogen displacement of embodiment 8 fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air,
The hexane solution that 7.92g (0.044mol) PEPA, 50mL contains 3.938g (0.022mol) dibutyl zinc is added, stirring makes
After PEPA is fully dispersed, 60 DEG C of reaction 3h are warming up to, 3.9g (0.02mol) phenyl phosphonyl chloride is added dropwise in 1h, after dripping off,
60 DEG C of reaction 7h, it is evaporated under reduced pressure and removes n-hexane (recovery uses) and a small amount of low boilers, add 50mL distilled water, stirring makes
Solid product is dispersed in water, and is filtered, washes, is dried, and is obtained the double PEPA esters of white solid phenyl-phosphonic acid, yield 88.0%, is melted
Point：206 ± 2 DEG C, decomposition temperature：281±5℃.
The preparation example main technologic parameters of table 1
The double PEPA esters of the phenyl-phosphonic acid of above-mentioned preparation are 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 product fire retardant phenyl
After the double PEPA esters of phosphonic acids, PBT are well mixed in varing proportions, are extruded at 230 DEG C with extruder, a diameter of 3mm batten be made,
And its fire resistance is tested, part test result is as shown in table 2：
The double PEPA esters of the phenyl-phosphonic acid of table 2 are used for PBT fire resistance data
Table 2 shows that the double PEPA esters of phenyl-phosphonic acid are used for PBT, and when addition 20%, limited oxygen index is up to 29%, explanation
It has preferable fire resistance, also preferably into charcoal anti-drip energy.
Claims (2)
1. the preparation method of the double PEPA ester compounds of a kind of phenyl-phosphonic acid, it is characterised in that this method is：
With nitrogen displacement fall equipped with agitator, thermometer, high performance reflux condenser reaction bulb in air, add PEPA, then
The acetonitrile or dioxane organic solvent of PEPA mass 5-10 times of volume milliliter number of grams are added, equimolar is added after being sufficiently stirred
The sodium grain of amount, it is warming up to 30 DEG C of reactions to sodium and disappears, phenyl phosphonyl chloride is added dropwise, controls phenyl phosphonyl chloride and PEPA mole
Than 1: 2-1: 2.5, after dripping off, after being warming up to 70-100 DEG C of reaction 4-6h, adding the distilled water of 4-6 times of product Theoretical Mass,
Stirring is dispersed in water solid product, filters, washes, dries, and obtains the double PEPA esters of white solid phenyl-phosphonic acid.
2. the preparation method of the double PEPA ester compounds of a kind of phenyl-phosphonic acid, it is characterised in that this method is：Fall dress with nitrogen displacement
There is the air in the reaction bulb of agitator, thermometer, high performance reflux condenser, add PEPA, contain equivalent dibutyl zinc
Hexane solution, after stirring makes PEPA fully dispersed, 60 DEG C of reaction 3h are warming up to, phenyl phosphonyl chloride is added dropwise, controls Phenylphosphine
Acyl dichloro and PEPA mol ratio are 1: 2-1: 2.5, after dripping off, react 6-7h at 60-70 DEG C, be evaporated under reduced pressure remove n-hexane and
A small amount of low boilers, the distilled water of 4-6 times of product Theoretical Mass is added, stirring is dispersed in water solid product, filtering, water
Wash, dry, obtain the double PEPA esters of white solid phenyl-phosphonic acid.
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