CN106831857B - A kind of production technology of acid-sensitive phosphite ester - Google Patents
A kind of production technology of acid-sensitive phosphite ester Download PDFInfo
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- CN106831857B CN106831857B CN201710078832.9A CN201710078832A CN106831857B CN 106831857 B CN106831857 B CN 106831857B CN 201710078832 A CN201710078832 A CN 201710078832A CN 106831857 B CN106831857 B CN 106831857B
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- 150000008301 phosphite esters Chemical class 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- 239000002585 base Substances 0.000 claims abstract description 60
- 239000007787 solid Substances 0.000 claims abstract description 28
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 238000004064 recycling Methods 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 64
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 22
- 239000000047 product Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 9
- 239000012043 crude product Substances 0.000 abstract description 8
- -1 phosphorous acid ester Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000012267 brine Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 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 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of production technologies of phosphite ester, belong to chemical production technical field, technique of the invention makees acid binding agent and solvent synthesizing phosphorous acid ester using tertiary amine, crude product is successively handled through diluted alkaline, concentrated base and solid caustic soda, simultaneously drying and dehydrating obtains the triethylamine solution of product to recycling triethylamine, is finally distilled to recover triethylamine and obtains product.Technique of the invention can protect well phosphite ester from acidolysis and hydrolysis, and process conditions are mild, and product yield is high; synthesis and alkali cleaning can nearly room temperature at a temperature of carry out; low-temperature operation is avoided, the recirculated water of industrial available room temperature replaces chilled brine, energy-saving obvious；Raw material is made the best use of everything, and is suitable for that industrial production uses convenient for management.
Description
Technical field
The invention belongs to chemical production technical fields, and in particular to a kind of production technology of acid-sensitive phosphite ester.
Background technique
Phosphite ester is widely used, especially Trimethyl phosphite and triethyl phosphite, can be used for manufacturing plasticizer, resistance
Fire agent, pesticide, medicine, rare metal extractant, organic synthesis intermediate etc..
Phosphite ester generally uses alcohol to react with phosphorus trichloride and is made, and reaction equation is shown in (1), and the two reaction is very violent,
Even if also can be carried out at low temperature.
PCl3+ 3ROH=(RO)3P+3HCl+Q1 (1)
In formula: R=CH3, C2H5。
From reaction (1) formula as it can be seen that the phosphorus trichloride of every 1 mole of reaction is it is necessary to generating 3 moles of hydrogen chloride (HCl).Chlorination
Hydrogen is sour gas, its presence can degrade the phosphite ester of phosphite ester, especially lower aliphatic alcohols, and formula (2) are shown in side reaction
~(4).
(RO)3P+HCl=(RO)2POH+RCl (2)
(RO)2POH+HCl=RO (OH)2+RCl (3)
ROP(OH)2+ HCl=P (OH)3+RCl (4)
In formula: R is same as above.
The presence of byproduct hydrogen chloride is huge on the influence of the yield of target product phosphite ester, especially Trimethyl phosphite
And triethyl phosphite.Synthetic reaction carries out at a temperature of -10~25 DEG C, since reaction very exothermic inevitably has local mistake
Heat, temperature raising aggravate side reaction (2)~(4), especially side reaction (2).Raw material phosphorus trichloride and product phosphite ester are met
Water facile hydrolysis cannot remove in situ hydrogen chloride using inorganic base, because inorganic base and hcl reaction generate water.
In order to slow down reaction, convenient for controlling low-temp reaction and avoiding byproduct hydrogen chloride catabolite phosphite ester, usually
Solvent is made using aromatic hydrocarbons, triethylamine makees acid binding agent, and the dosage of triethylamine is just met for binding the needs of hydrogen chloride, and reaction equation is shown in
(5)。
N(C2H5)3+ HCl=N (C2H5)3·HCl+Q2 (5)
Reaction mixture contains Amine from Tertiary Amine Hydrochloride, and first using diluted alkaline processing recycling triethylamine, reaction equation is shown in (6)；Then
Using industrial dehydration of salt or azeotropic dehydration；Finally distill isolated product.
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (6)
Traditional handicraft comes with some shortcomings place, is mainly shown as: (1) triethylamine dosage few and aromatic solvent dosage very
More, hydrogen chloride is generated while generating phosphite ester, i.e. chlorination hydrogen molecule is near product molecule, in triethylamine molecule
During finding the reaction of chlorination hydrogen molecule, hydrogen chloride degrades portion of product, and yield is caused to reduce；(2) synthesis is anti-
It must should carry out at low temperature, can just reduce product acidolysis, and post-treatment caustic wash must also carry out at low temperature, can just reduce
Product hydrolysis, low-temperature operation energy consumption is more, and operating cost is higher；(3) dehydration is not thorough, and when subsequent technique is heated, remains water
Dividing causes portion of product to hydrolyze, and can also reduce yield.
Therefore, to traditional phosphite ester production technology, there is necessity of Improvement.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of productions of acid-sensitive phosphite ester
Technique, specifically the production technology of lower aliphatic alcohols phosphite ester, is mainly used for organophosphorus compounds flame retardant intermediate
Production.Raw material type is reduced, synthetic reaction and post-treatment caustic wash need not carry out at low temperature, and yield is improved, operating cost is reduced,
It is suitble to industrial production to use.
The technical scheme adopted by the invention is as follows:
A kind of production technology of acid-sensitive phosphite ester, specifically includes the following steps:
(1) it synthesizes: in the reactor, the ertiary amine solution of alcohol is added, with the cooling reactor of ice salt bath, control speed of agitator is
60-120r/min starts that phosphorus trichloride is added dropwise, controls rate of addition, so that reaction temperature is maintained 5~40 DEG C, feed molar is matched
Than for tertiary amine: alcohol: phosphorus trichloride=6~30:3~3.3:1,0.5~3h of tear drop time, tear drop, which finishes, continues 0.5~1h of stirring；
(2) alkali cleaning: control speed of agitator is 60~120r/min, 5~40 DEG C of temperature, and step (1) synthesis is added in diluted alkaline
Crude product in, feed molar proportion be diluted alkaline: phosphorus trichloride=3~3.15:1, stir 1~10min, stand 1~15min, point
Water phase out retains oily phase；
(3) dry: in the oily phase of step (2), be added concentrated base extraction dehydration, the volume ratio of concentrated base and oily phase for 0.01~
1 ︰ 1 stirs 1~10min, stands 1~15min, layering, oily Xiang Zaiyong solid base adsorption dewatering, the two volume mass ratio mL/g
For 1~30 ︰ 1,0.5~5h is stood, is separated by solid-liquid separation, oily phase is collected；
(4) distill: the oil that step (3) are collected mutually carries out distillation separation, obtains phosphite ester product, the tertiary amine of recycling is straight
Female connector is used.
Further, in the step (1) alcohol ertiary amine solution, wherein alcohol is methanol or ethyl alcohol, and carbon is former in tertiary amine molecule
Subnumber is 6~30.
Further, it is provided with constant pressure funnel, blender, thermometer in the reactor in the step (1) and returns
Flow condenser.
Further, raw material mol ratio is tertiary amine: alcohol: phosphorus trichloride=18~22:3~3.15 in the step (1):
1。
Further, in the step (2) alkali cleaning temperature be 20~30 DEG C, mixing time be 5~8min, stand 8~
12min。
Further, the volume ratio of concentrated base and oily phase is 0.06~0.1 ︰ 1 in the step (3), stirs 5~8min, quiet
8~12min is set, oil is mutually 24~28 ︰ 1 with the volume mass ratio mL/g of solid base, stands 2~4h.
Further, the diluted alkaline in the step (2) is 10%~20% sodium hydroxide of concentration, the concentrated base in step (3)
It is 40%~70% sodium hydroxide for concentration, the solid base in step (3) is solid sodium hydroxide.
Further, in the step (3) after extraction dehydration layering, recycling concentrated base uses dilute for preparation steps (2)
Alkali, after oily phase adsorption dewatering is separated by solid-liquid separation, concentrated base of the recycling solid base for preparation steps (3) extraction dehydration.
Further, the phosphite ester in the step (4) is Trimethyl phosphite or triethyl phosphite.
The present inventor, which studies discovery tertiary amine, can protect phosphite ester, avoid that acidolysis and hydrolysis, the excessive more guarantors of tertiary amine occur
Shield effect is stronger, in the large excess of situation of tertiary amine, suitably improves reaction temperature to yield substantially without influence.Based on this,
Aromatic solvent is saved, solvent and acid binding agent are doubled as using excessive tertiary amine.Although tertiary amine than the price of aromatic solvent, by
In almost can whole recoveries, cost of material do not increase.
Step (1) synthesis of the invention, doubles as solvent and acid binding agent using tertiary amine, allow to react nearly room temperature at a temperature of
It carries out, this is extremely important to energy conservation.Because reacting PCl3+ 3ROH=(RO)3P+3HCl+Q1(1) with react N (C2H5)3+ HCl=N
(C2H5)3·HCl+Q2(5) it carries out simultaneously, very exothermic, the temperature of reaction mixture increases naturally, can industrially use room temperature
Recirculated water replace the cooling reaction mixture of circulating frozen brine.
Step (2) alkali cleaning of the invention, because with the presence of a large amount of tertiary amine, improving in alkali cleaning phosphite ester in water
Stability, allow alkali cleaning temperature nearly room temperature at a temperature of carry out, because react N (C2H5)3HCl+NaOH=N (C2H5)3+NaCl
+H2O (6) is neutralization reaction, and heat release increases the temperature of reaction mixture, can also energy saving without excessively cooling.
The dry method of step (3) of the invention is divided into two steps: it is dry using concentrated base first, it is then dry using solid base
It is dry.Concentrated base and solid base have strong water imbibition, and, to be pre-dried, the latter is further dried for the former, the two combination drying effect
Fruit is good, moisture can be taken off to 0.2% or less.Solid base raw material is used to prepare after use the desiccant concentrated base of extraction, dense
Alkali is used to prepare after use the diluted alkaline of recycling tertiary amine, and a kind of material composition change is three kinds of raw materials, is adequately applied.
Step (4) distillation of the invention, is separated according to tertiary amine with the boiling-point difference of product phosphite ester, can be simple
Distillation, is also possible to rectifying or combination, can be with atmospheric operation, can also be with decompression operation.
Technique of the invention is suitable for production Trimethyl phosphite and triethyl phosphite, the raw alcohol needed are correspondingly
Methanol and ethyl alcohol；The tertiary amine used can be aliphatic tertiary amine, can be cycloaliphatic amines, can be aromatic nitrile base, can also
To be other type tertiary amines, three groups on nitrogen-atoms can be the same or different, but regardless of tertiary amine, molecule
In total carbon atom number in 6~30 ranges.
The beneficial effects of the present invention are:
Due to using above-mentioned technique, reaction selectivity is good, and yield is higher than traditional technique；Synthesis and alkali cleaning can be
It is carried out at a temperature of nearly room temperature, avoids low-temperature operation, the recirculated water of industrial available room temperature replaces chilled brine, energy-saving
Obviously；Raw material is made the best use of everything, and reduces 1~2 kind, convenient for management.
Specific embodiment
Embodiment 1
(1) it synthesizes: in the 5000mL four-hole boiling flask that constant pressure funnel, blender, thermometer and reflux condenser are housed
In reactor, solution of 101g (3.15mol) methanol in 2024g (20mol) triethylamine is added, is reacted with ice salt bath is cooling
Device, control speed of agitator are 100r/min, start that 137g phosphorus trichloride is added dropwise, control rate of addition, maintain reaction temperature
20~40 DEG C, tear drop time 2h, tear drop, which finishes, to be continued to stir 0.5h；
(2) alkali cleaning: control speed of agitator be 80r/min, 20~40 DEG C of temperature, 20% sodium hydroxide of 500mL concentration is dilute
Alkali is added in the crude product of first step synthesis, stirs 2min, stands 5min, separates water phase, retains oily phase；
(3) dry: in the oily phase of second step, the extraction dehydration of 40% sodium hydroxide concentrated base of 215mL is added, stirs 2min,
5min, layering are stood, recycling concentrated base mutually uses 122g solid base sodium hydroxide for preparing 20% diluted alkaline that second step uses, oil again
Adsorption dewatering stands 2h, is separated by solid-liquid separation, and recycling solid base is used to prepare 40% concentrated base of extraction dehydration, collects oil and makes an appointment
2850mL；
(4) distill: the oil for first collecting third step mutually carries out rectifying, collects top temperature≤92 DEG C of fraction, as recycles
Triethylamine is directly applied, then residue in reboiler is distilled to obtain Trimethyl phosphite product 123g, purity 91%, yield
90.3%.
Embodiment 2
(1) it synthesizes: in the 5000mL four-hole boiling flask that constant pressure funnel, blender, thermometer and reflux condenser are housed
In reactor, solution of 145g (3.15mol) ethyl alcohol in 2024g (20mol) triethylamine is added, is reacted with ice salt bath is cooling
Device, control speed of agitator are 100r/min, start that 137g phosphorus trichloride is added dropwise, control rate of addition, maintain reaction temperature
20~40 DEG C, tear drop time 2h, tear drop, which finishes, to be continued to stir 0.5h；
(2) alkali cleaning: control speed of agitator be 80r/min, 20~40 DEG C of temperature, 20% sodium hydroxide of 500mL concentration is dilute
Alkali is added in the crude product of first step synthesis, stirs 2min, stands 5min, separates water phase, retains oily phase；
(3) dry: in the oily phase of second step, the extraction dehydration of 40% sodium hydroxide concentrated base of 215mL is added, stirs 2min,
5min, layering are stood, recycling concentrated base mutually uses 122g solid base sodium hydroxide for preparing 20% diluted alkaline that second step uses, oil again
Adsorption dewatering stands 3h, is separated by solid-liquid separation, and recycling solid base is used to prepare 40% concentrated base of extraction dehydration, collects oil and makes an appointment
2900mL；
(4) distill: the oil that third step is collected mutually distills, first collect top it is warm≤91 DEG C of front-end volatiles, as recycle
Triethylamine, directly apply, regather top 150~160 DEG C of positive fraction of temperature and obtain triethyl phosphite product 170g, purity
90%, yield 92%.
Embodiment 3
(1) it synthesizes: in the 5000mL four-hole boiling flask that constant pressure funnel, blender, thermometer and reflux condenser are housed
In reactor, according to tertiary amine: alcohol: phosphorus trichloride=22:3:1 is added solution of the 3mol ethyl alcohol in 22mol triethylamine, uses ice
Salt bath cools down reactor, and control speed of agitator is 100r/min, starts that 1mol phosphorus trichloride is added dropwise, controls rate of addition, makes anti-
Temperature is answered to maintain 20~40 DEG C, tear drop time 2h, tear drop, which finishes, to be continued to stir 0.5h；
(2) alkali cleaning: control speed of agitator is 80r/min, 30 DEG C of temperature, and 20% sodium hydroxide diluted alkaline of 500mL concentration is added
In the crude product for entering first step synthesis, 8min is stirred, stands 10min, separates water phase, retains oily phase；
(3) dry: in the oily phase of second step, the volume ratio according to concentrated base and oily phase is 0.08 ︰ 1, and 40% hydrogen-oxygen is added
Change the extraction of sodium concentrated base to be dehydrated, stir 8min, stand 15min, layering, recycling concentrated base is used to prepare second step uses 20% dilute
Alkali, the volume mass ratio mL/g according to oily phase and solid base is 28 ︰ 1, and oily Xiang Zaiyong solid base sodium hydroxide adsorption dewatering is stood
3h is separated by solid-liquid separation, and recycling solid base is used to prepare 40% concentrated base of extraction dehydration, and collection oil is makeed an appointment 2900mL；
(4) distill: the oil that third step is collected mutually distills, first collect top it is warm≤91 DEG C of front-end volatiles, as recycle
Triethylamine, directly apply, regather top 150~160 DEG C of positive fraction of temperature and obtain triethyl phosphite product 173.4g, purity
92%, yield 96%.
Embodiment 4
(1) it synthesizes: in the 5000mL four-hole boiling flask that constant pressure funnel, blender, thermometer and reflux condenser are housed
In reactor, solution of the 3.3mol ethyl alcohol in 30mol triethylamine is added, with the cooling reactor of ice salt bath, controls speed of agitator
For 120r/min, start that 1mol phosphorus trichloride is added dropwise, control rate of addition, reaction temperature is made to maintain 20~40 DEG C, when tear drop
Between 3h, tear drop finish continues stir 0.5h；
(2) alkali cleaning: control speed of agitator be 120r/min, 20~40 DEG C of temperature, 20% sodium hydroxide of 500mL concentration is dilute
Alkali is added in the crude product of first step synthesis, stirs 10min, stands 1min, separates water phase, retains oily phase；
(3) dry: in the oily phase of second step, the volume ratio according to concentrated base and oily phase is that 70% hydroxide is added in 0.01:1
The extraction dehydration of sodium concentrated base, stirs 10min, stands 1min, be layered, 70% concentrated base of recycling is dilute for preparing second step uses 20%
Alkali is 1:1 according to oily phase and solid base sodium hydroxide volume mass ratio mL/g, and solid base sodium hydroxide adsorption dewatering is added, quiet
5h is set, is separated by solid-liquid separation, recycling solid base is used to prepare 70% concentrated base of extraction dehydration, collects oily phase；
(4) distill: the oil that third step is collected mutually distills, first collect top it is warm≤91 DEG C of front-end volatiles, as recycle
Triethylamine, directly apply, regather top 150~160 DEG C of positive fraction of temperature and obtain triethyl phosphite product 171.7g, purity
91%, yield 94%.
Embodiment 5
(1) it synthesizes: in the 5000mL four-hole boiling flask that constant pressure funnel, blender, thermometer and reflux condenser are housed
In reactor, solution of the 3mol ethyl alcohol in 6mol triethylamine is added, with the cooling reactor of ice salt bath, control speed of agitator is
60r/min starts that 1mol phosphorus trichloride is added dropwise, controls rate of addition, so that reaction temperature is maintained 5~20 DEG C, the tear drop time
0.5h, tear drop, which finishes, to be continued to stir 1h；
(2) alkali cleaning: control speed of agitator is 60r/min, 5~20 DEG C of temperature, by 10% sodium hydroxide diluted alkaline of 500mL concentration
It is added in the crude product of first step synthesis, stirs 1min, stand 15min, separate water phase, retain oily phase；
(3) dry: in the oily phase of second step, the volume ratio according to concentrated base and oily phase is that 40% sodium hydroxide is added in 1:1
Concentrated base extraction dehydration, stirs 1min, stands 15min, layering, and recycling concentrated base is used to prepare the diluted alkaline that second step uses 10%, presses
Taking oily picture with solid base sodium hydroxide volume mass ratio mL/g is 30:1, and solid base sodium hydroxide adsorption dewatering is added, stands
0.5h is separated by solid-liquid separation, and recycling solid base is used to prepare 40% concentrated base of extraction dehydration, collects oily phase；
(4) distill: the oil that third step is collected mutually distills, first collect top it is warm≤91 DEG C of front-end volatiles, as recycle
Triethylamine, directly apply, regather top 150~160 DEG C of positive fraction of temperature and obtain triethyl phosphite product 160g, purity
90%, yield 86.7%.
Technique of the invention makees acid binding agent and solvent synthesizing phosphorous acid ester using tertiary amine, crude product successively through diluted alkaline, concentrated base and
Solid caustic soda processing, simultaneously drying and dehydrating obtains the triethylamine solution of product to recycling triethylamine, is finally distilled to recover triethylamine and is produced
Product.Technique of the invention can protect well phosphite ester from acidolysis and hydrolysis, and process conditions are mild, and product yield is high, section
It can lower consumption, be suitable for that industrial production uses.
The above is not limitation of the present invention, it should be pointed out that: those skilled in the art are come
It says, under the premise of not departing from essential scope of the present invention, several variations, modifications, additions or substitutions can also be made, these improvement
It also should be regarded as protection scope of the present invention with retouching.
Claims (7)
1. a kind of production technology of acid-sensitive phosphite ester, which is characterized in that specifically includes the following steps:
(1) it synthesizes: in the reactor, the ertiary amine solution of alcohol is added, with the cooling reactor of ice salt bath, control speed of agitator is 60-
120r/min starts that phosphorus trichloride is added dropwise, controls rate of addition, and reaction temperature is made to maintain 5~40 DEG C, and feed molar proportion is
Tertiary amine: alcohol: phosphorus trichloride=6~30:3~3.3:1,0.5~3h of tear drop time, tear drop, which finishes, continues 0.5~1h of stirring；
(2) alkali cleaning: control speed of agitator is 60~120r/min, 5~40 DEG C of temperature, and the thick of step (1) synthesis is added in diluted alkaline
In product, feed molar proportion is diluted alkaline: phosphorus trichloride=3~3.15:1, stirs 1~10min, stands 1~15min, separates water
Phase retains oily phase；
(3) dry: in the oily phase of step (2), concentrated base extraction is added and is dehydrated, the volume ratio of concentrated base and oily phase is 0.01~1 ︰ 1,
Stir 1~10min, stand 1~15min, layering, oily Xiang Zaiyong solid base adsorption dewatering, the two volume mass ratio mL/g be 1~
30 ︰ 1 stand 0.5~5h, are separated by solid-liquid separation, and collect oily phase；
(4) distill: the oil that step (3) are collected mutually carries out distillation separation, obtains phosphite ester product, the tertiary amine of recycling directly covers
With；
Diluted alkaline in the step (2) is 10%~20% sodium hydroxide of concentration, the concentrated base in step (3) be concentration be 40%~
70% sodium hydroxide, the solid base in step (3) are solid sodium hydroxide；
Phosphite ester in the step (4) is Trimethyl phosphite or triethyl phosphite.
2. a kind of production technology of acid-sensitive phosphite ester according to claim 1, which is characterized in that in the step (1)
The ertiary amine solution of alcohol, wherein alcohol is methanol or ethyl alcohol, and carbon atom number is 6~30 in tertiary amine molecule.
3. a kind of production technology of acid-sensitive phosphite ester according to claim 1, which is characterized in that in the step (1)
Reactor be equipped with constant pressure funnel, blender, thermometer and reflux condenser.
4. a kind of production technology of acid-sensitive phosphite ester according to claim 1, which is characterized in that in the step (1)
Feed molar proportion is tertiary amine: alcohol: phosphorus trichloride=18~22:3~3.15:1.
5. a kind of production technology of acid-sensitive phosphite ester according to claim 1, which is characterized in that in the step (2)
Alkali cleaning temperature is 20~30 DEG C, and mixing time is 5~8min, stands 8~12min.
6. a kind of production technology of acid-sensitive phosphite ester according to claim 1, which is characterized in that in the step (3)
The volume ratio of concentrated base and oil phase is 0.06~0.1 ︰ 1, stirs 5~8min, stands 8~12min, the volume matter of oil phase and solid base
Amount is 24~28 ︰ 1 than mL/g, stands 2~4h.
7. a kind of production technology of acid-sensitive phosphite ester according to claim 1, which is characterized in that in the step (3)
After extraction dehydration layering, recycling concentrated base is used for the diluted alkaline that preparation steps (2) use, after oily phase adsorption dewatering is separated by solid-liquid separation, recycling
Concentrated base of the solid base for preparation steps (3) extraction dehydration.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3057904A (en) * | 1958-09-04 | 1962-10-09 | Monsanto Chemicals | Preparation of esters of trivalent phosphorus acids |
| CN1724546A (en) * | 2005-06-27 | 2006-01-25 | 罗方明 | Production method of triethyl phosphite |
| CN101486729A (en) * | 2008-12-12 | 2009-07-22 | 荆州市沙市东方有机化工研究所 | Production method of O, O-dialkyl thiophosphoryl chloride |
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2017
- 2017-02-14 CN CN201710078832.9A patent/CN106831857B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3057904A (en) * | 1958-09-04 | 1962-10-09 | Monsanto Chemicals | Preparation of esters of trivalent phosphorus acids |
| CN1724546A (en) * | 2005-06-27 | 2006-01-25 | 罗方明 | Production method of triethyl phosphite |
| CN101486729A (en) * | 2008-12-12 | 2009-07-22 | 荆州市沙市东方有机化工研究所 | Production method of O, O-dialkyl thiophosphoryl chloride |
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| Title |
|---|
| 亚磷酸二乙酯的合成;姬学仪;《江苏化工》;19961231;第24卷;第21-25页 |
| 无溶剂法合成亚磷酸二乙酯;陶贤平等;《南通工学院学报》;20001231;第16卷;第21-24页 |
| 用二甲基苯胺作脱盐酸剂合成亚磷酸三乙酯;朱新宝;《化学工业与工程技术》;19951231;第16卷;第17-20页 |
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