CN106831857A - 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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- CN106831857A CN106831857A CN201710078832.9A CN201710078832A CN106831857A CN 106831857 A CN106831857 A CN 106831857A CN 201710078832 A CN201710078832 A CN 201710078832A CN 106831857 A CN106831857 A CN 106831857A
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- phosphite ester
- oil phase
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- sensitive
- acid
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- 150000008301 phosphite esters Chemical class 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 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 37
- 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
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- -1 phosphorous acid ester Chemical class 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 230000018044 dehydration Effects 0.000 claims description 19
- 238000006297 dehydration reaction Methods 0.000 claims description 19
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000926 separation method Methods 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 58
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 22
- 239000000047 product Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 9
- 239000012043 crude product Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000012267 brine Substances 0.000 abstract description 2
- 238000012824 chemical production Methods 0.000 abstract description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- 239000000203 mixture Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000376 reactant 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001577 simple distillation 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 technology 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 processed through diluted alkaline, concentrated base and solid caustic soda successively, reclaim triethylamine and drying and dehydrating obtains the triethylamine solution of product, last Distillation recovery triethylamine simultaneously obtains product.Technique of the invention can well protect phosphite ester from acidolysis and hydrolysis, and process conditions are gentle, and product yield is high; synthesis and alkali cleaning can be carried out at a temperature of nearly room temperature; 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 easy to management, and suitable industrial production is used.
Description
Technical field
The invention belongs to chemical production technical field, and in particular to a kind of production technology of acid-sensitive phosphite ester.
Background technology
Phosphite ester is widely used, especially Trimethyl phosphite and triethyl phosphite, can be used to manufacture plasticizer, resistance
Combustion agent, agricultural chemicals, medicine, rare metal extractant, organic synthesis intermediate etc..
Phosphite ester is generally obtained using alcohol with phosphorus trichloride reaction, and reaction equation is shown in (1), and the two reacts very acutely,
Even if can also carry out at low temperature.
PCl3+ 3ROH=(RO)3P+3HCl+Q1 (1)
In formula：R=CH3, C2H5。
From reaction (1) formula, 1 mole of phosphorus trichloride is often reacted it is necessary to generate 3 moles of hydrogen chloride (HCl).Chlorination
Hydrogen is sour gas, and its presence can degrade the phosphite ester of phosphite ester, especially lower aliphatic alcohols, and formula (2) is 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 ibid.
Yield influence of the presence of byproduct hydrogen chloride on target product phosphite ester is huge, especially Trimethyl phosphite
And triethyl phosphite.Synthetic reaction is carried out at a temperature of -10~25 DEG C, because reaction very exothermic has local mistake unavoidably
Heat, temperature is raised aggravates side reaction (2)~(4), particularly side reaction (2).Raw material phosphorus trichloride and product phosphite ester are met
Water facile hydrolysis, it is impossible to which hydrogen chloride is removed using inorganic base in the original location, because inorganic base and hcl reaction generate water.
In order to slow down reaction, it is easy to control low-temp reaction and avoids byproduct hydrogen chloride catabolite phosphite ester, generally
Solvent is made using aromatic hydrocarbons, triethylamine makees acid binding agent, and the need for the consumption of triethylamine is just met for binding hydrogen chloride, reaction equation is shown in
(5)。
N(C2H5)3+ HCl=N (C2H5)3·HCl+Q2 (5)
Reactant mixture contains Amine from Tertiary Amine Hydrochloride, reclaims triethylamine using diluted alkaline treatment first, and reaction equation is shown in (6)；Then
Using industrial dehydration of salt or azeotropic dehydration；Last separated obtains product.
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (6)
In place of traditional handicraft comes with some shortcomings, it is mainly shown as：(1) triethylamine consumption is few and aromatic solvent consumption very
It is many, hydrogen chloride generate phosphite ester while generate, i.e. chlorination hydrogen molecule near product molecule, in triethylamine molecule
During finding the reaction of chlorination hydrogen molecule, hydrogen chloride degrades portion of product, causes yield to reduce；(2) synthesize anti-
Should at low temperature carry out, can just reduce product acidolysis, and post-treatment caustic wash must also be carried out at low temperature, can just be reduced
Product is hydrolyzed, and low-temperature operation power consumption is more, and operating cost is higher；(3) dehydration is not thorough, when subsequent technique is heated, residual 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.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of production of acid-sensitive phosphite ester
Technique, specifically the production technology of lower aliphatic alcohols phosphite ester, is mainly used in organophosphorus compounds flame retardant intermediate
Production.Raw material type is reduced, synthetic reaction and post-treatment caustic wash need not be carried out at low temperature, improve yield, reduce operating cost,
It is adapted to industrial production to use.
The technical scheme that the present invention takes is：
A kind of production technology of acid-sensitive phosphite ester, specifically includes following steps：
(1) synthesize：In the reactor, the ertiary amine solution of alcohol is added, reactor is cooled down with ice salt bath, control the speed of agitator to be
60-120r/min, starts that phosphorus trichloride is added dropwise, and controls rate of addition, reaction temperature is maintained 5~40 DEG C, and feed molar is matched somebody with somebody
Than being tertiary amine:Alcohol:Phosphorus trichloride=6~30:3~3.3:1,0.5~3h of tear drop time, tear drop finish continuation and stir 0.5~1h；
(2) alkali cleaning：Speed of agitator is controlled for 60~120r/min, 5~40 DEG C of temperature, adds step (1) to synthesize diluted alkaline
Crude product in, feed molar proportioning be diluted alkaline:Phosphorus trichloride=3~3.15:1,1~10min is stirred, 1~15min is stood, point
Water outlet phase, retains oil phase；
(3) dry：In the oil phase of step (2), add concentrated base extraction dehydration, the volume ratio of concentrated base and oil phase for 0.01~
1 ︰ 1, stirs 1~10min, stands 1~15min, and layering, oil phase uses solid base adsorption dewatering again, and the two volume mass compares mL/g
It is 1~30 ︰ 1, stands 0.5~5h, separation of solid and liquid collects oil phase；
(4) distill：The oil phase that step (3) is collected is carried out into separated, phosphite ester product is obtained, the tertiary amine of recovery is straight
Female connector is used.
Further, in the step (1) alcohol ertiary amine solution, wherein, alcohol is methyl alcohol or ethanol, and carbon is former in tertiary amine molecule
Subnumber is 6~30.
Further, constant pressure funnel, agitator, thermometer are provided with the reactor in the step (1) and are returned
Flow condenser.
Further, raw material mol ratio is tertiary amine in the step (1):Alcohol:Phosphorus trichloride=18~22:3~3.15:
1。
Further, in the step (2) alkali cleaning temperature be 20~30 DEG C, mixing time be 5~8min, stand 8~
12min。
Further, concentrated base and the volume ratio of oil phase are 0.06~0.1 ︰ 1 in the step (3), stir 5~8min, quiet
8~12min is put, oil phase is 24~28 ︰ 1 than mL/g with the volume mass of solid base, stands 2~4h.
Further, the diluted alkaline in the step (2) is the NaOH of concentration 10%~20%, the concentrated base in step (3)
For concentration is 40%~70% NaOH, the solid base in step (3) is solid sodium hydroxide.
Further, in the step (3) after extraction dehydration layering, that reclaims that concentrated base is used for that preparation steps (2) to use is dilute
Alkali, after oil phase adsorption dewatering separation of solid and liquid, reclaiming solid base is used for the concentrated base that preparation steps (3) extract dehydration.
Further, the phosphite ester in the step (4) is Trimethyl phosphite or triethyl phosphite.
The present inventor's research finds that tertiary amine can protect phosphite ester, it is to avoid acidolysis and hydrolysis, the excessive more guarantors of tertiary amine occur
Shield effect is stronger, in the case of tertiary amine is large excess of, 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 is 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, it is allowed to which reaction is at a temperature of nearly room temperature using tertiary amine
Carry out, this is extremely important to energy-conservation.Because reaction PCl3+ 3ROH=(RO)3P+3HCl+Q1(1) with reaction N (C2H5)3+ HCl=N
(C2H5)3·HCl+Q2(5) while carrying out, very exothermic, the temperature of reactant mixture is raised naturally, can industrially use room temperature
Recirculated water replace circulating frozen brine-cooled reactant mixture.
Step (2) of the invention alkali cleaning, because, with the presence of substantial amounts of tertiary amine, improve phosphite ester in alkali cleaning in water
Stability, it is allowed to which alkali cleaning temperature is carried out at a temperature of nearly room temperature, because of reaction N (C2H5)3HCl+NaOH=N (C2H5)3+NaCl
+H2O (6) is neutralization reaction, and heat release raises the temperature of reactant mixture, without undue cooling, also can saving energy consumption.
The dry method of step (3) of the invention is divided into two steps：Dried using concentrated base first, then done 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 less than 0.2%.Solid base raw material is used to prepare the desiccant concentrated base of extraction after use, dense
Alkali is used to prepare the diluted alkaline for reclaiming tertiary amine after use, and a kind of material composition change is three kinds of raw materials, is sufficiently 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, or rectifying, or combination, can be with atmospheric operation, it is also possible to decompression operation.
Technique of the invention be applied to production Trimethyl phosphite and triethyl phosphite, it is necessary to raw alcohol be correspondingly
Methyl alcohol and ethanol；The tertiary amine for using can be aliphatic tertiary amine, can be cycloaliphatic amines, can be aromatic nitrile base, also may be used
To be other type tertiary amines, three groups on nitrogen-atoms can be the same or different, but regardless of tertiary amine, its molecule
In total carbon atom number in the range of 6~30.
The beneficial effects of the invention are as follows：
As a result of above-mentioned technique, reaction selectivity is good, and yield is higher than traditional technique；Synthesis and alkali cleaning can be
Carried out at a temperature of nearly room temperature, it is to avoid low-temperature operation, the recirculated water of industrial available room temperature replaces chilled brine, energy-saving
Substantially；Raw material is made the best use of everything, and reduces 1~2 kind, is easy to management.
Specific embodiment
Embodiment 1
(1) synthesize：In the 5000mL four-hole boiling flasks equipped with constant pressure funnel, agitator, thermometer and reflux condenser
In reactor, solution of 101g (3.15mol) methyl alcohol in 2024g (20mol) triethylamine is added, cooled down with ice salt bath and reacted
Device, controls speed of agitator for 100r/min, starts that 137g phosphorus trichlorides are added dropwise, and controls rate of addition, maintains reaction temperature
20~40 DEG C, tear drop time 2h, tear drop finishes continuation and stirs 0.5h；
(2) alkali cleaning：Speed of agitator is controlled for 80r/min, 20~40 DEG C of temperature, the NaOH of 500mL concentration 20% is dilute
Alkali is added in the crude product of first step synthesis, stirs 2min, stands 5min, separates water phase, retains oil phase；
(3) dry：In the oil phase of second step, the extraction dehydration of the NaOH concentrated bases of 215mL 40% is added, stirs 2min,
5min is stood, layering is reclaimed concentrated base for preparing 20% diluted alkaline that second step is used, oil phase and uses 122g solid base NaOH again
Adsorption dewatering, stands 2h, and separation of solid and liquid reclaims solid base for preparing 40% concentrated base of extraction dehydration, collects oil phase about
2850mL；
(4) distill：The oil phase that the 3rd step is collected first is carried out into rectifying, the cut of top temperature≤92 DEG C is collected, as reclaimed
Triethylamine, is directly applied mechanically, then residue distillation in reboiler is obtained into Trimethyl phosphite product 123g, purity 91%, yield
90.3%.
Embodiment 2
(1) synthesize：In the 5000mL four-hole boiling flasks equipped with constant pressure funnel, agitator, thermometer and reflux condenser
In reactor, solution of 145g (3.15mol) ethanol in 2024g (20mol) triethylamine is added, cooled down with ice salt bath and reacted
Device, controls speed of agitator for 100r/min, starts that 137g phosphorus trichlorides are added dropwise, and controls rate of addition, maintains reaction temperature
20~40 DEG C, tear drop time 2h, tear drop finishes continuation and stirs 0.5h；
(2) alkali cleaning：Speed of agitator is controlled for 80r/min, 20~40 DEG C of temperature, the NaOH of 500mL concentration 20% is dilute
Alkali is added in the crude product of first step synthesis, stirs 2min, stands 5min, separates water phase, retains oil phase；
(3) dry：In the oil phase of second step, the extraction dehydration of the NaOH concentrated bases of 215mL 40% is added, stirs 2min,
5min is stood, layering is reclaimed concentrated base for preparing 20% diluted alkaline that second step is used, oil phase and uses 122g solid base NaOH again
Adsorption dewatering, stands 3h, and separation of solid and liquid reclaims solid base for preparing 40% concentrated base of extraction dehydration, collects oil phase about
2900mL；
(4) distill：The oil phase that 3rd step is collected is distilled, top temperature≤91 DEG C of front-end volatiles are first collected, is as reclaimed
Triethylamine, directly apply mechanically, regather top 150~160 DEG C of positive cut of temperature and obtain triethyl phosphite product 170g, purity
90%, yield 92%.
Embodiment 3
(1) synthesize：In the 5000mL four-hole boiling flasks equipped with constant pressure funnel, agitator, thermometer and reflux condenser
In reactor, according to tertiary amine:Alcohol:Phosphorus trichloride=22:3:1, solution of the 3mol ethanol in 22mol triethylamines is added, use ice
Salt bath cools down reactor, controls speed of agitator for 100r/min, starts that 1mol phosphorus trichlorides are added dropwise, and controls rate of addition, makes anti-
Temperature is answered to maintain 20~40 DEG C, tear drop time 2h, tear drop finishes continuation and stirs 0.5h；
(2) alkali cleaning：Control speed of agitator for 80r/min, 30 DEG C of temperature, the NaOH diluted alkaline of 500mL concentration 20% is added
Enter in the crude product of first step synthesis, stir 8min, stand 10min, separate water phase, retain oil phase；
(3) dry：It is 0.08 ︰ 1 according to the volume ratio of concentrated base and oil phase in the oil phase of second step, adds 40% hydrogen-oxygen
Change the extraction dehydration of sodium concentrated base, stir 8min, stand 15min, layering, reclaiming concentrated base is used to preparing that second step uses to be 20% dilute
Alkali, is 28 ︰ 1 than mL/g according to the volume mass of oil phase and solid base, and oil phase uses solid base NaOH adsorption dewatering again, stands
3h, separation of solid and liquid, reclaiming solid base is used to prepare 40% concentrated base of extraction dehydration, collects oil phase about 2900mL；
(4) distill：The oil phase that 3rd step is collected is distilled, top temperature≤91 DEG C of front-end volatiles are first collected, is as reclaimed
Triethylamine, directly apply mechanically, regather top 150~160 DEG C of positive cut of temperature and obtain triethyl phosphite product 173.4g, purity
92%, yield 96%.
Embodiment 4
(1) synthesize：In the 5000mL four-hole boiling flasks equipped with constant pressure funnel, agitator, thermometer and reflux condenser
In reactor, solution of the 3.3mol ethanol in 30mol triethylamines is added, reactor is cooled down with ice salt bath, control speed of agitator
It is 120r/min, starts that 1mol phosphorus trichlorides are added dropwise, control rate of addition, reaction temperature is maintained 20~40 DEG C, during tear drop
Between 3h, tear drop finish continuation stir 0.5h；
(2) alkali cleaning：Speed of agitator is controlled for 120r/min, 20~40 DEG C of temperature, the NaOH of 500mL concentration 20% is dilute
Alkali is added in the crude product of first step synthesis, stirs 10min, stands 1min, separates water phase, retains oil phase；
(3) dry：It is 0.01 according to the volume ratio of concentrated base and oil phase in the oil phase of second step:1 adds 70% hydroxide
The extraction dehydration of sodium concentrated base, stirs 10min, stands 1min, layering, and reclaiming 70% concentrated base is used to preparing that second step uses to be 20% dilute
Alkali, is 1 than mL/g according to oil phase and solid base NaOH volume mass:1, solid base NaOH adsorption dewatering is added, it is quiet
5h is put, separation of solid and liquid reclaims solid base for preparing 70% concentrated base of extraction dehydration, collects oil phase；
(4) distill：The oil phase that 3rd step is collected is distilled, top temperature≤91 DEG C of front-end volatiles are first collected, is as reclaimed
Triethylamine, directly apply mechanically, regather top 150~160 DEG C of positive cut of temperature and obtain triethyl phosphite product 171.7g, purity
91%, yield 94%.
Embodiment 5
(1) synthesize：In the 5000mL four-hole boiling flasks equipped with constant pressure funnel, agitator, thermometer and reflux condenser
In reactor, solution of the 3mol ethanol in 6mol triethylamines is added, reactor is cooled down with ice salt bath, control the speed of agitator to be
60r/min, starts that 1mol phosphorus trichlorides are added dropwise, and controls rate of addition, reaction temperature is maintained 5~20 DEG C, tear drop time
0.5h, tear drop finishes continuation and stirs 1h；
(2) alkali cleaning：Speed of agitator is controlled for 60r/min, 5~20 DEG C of temperature, by the NaOH diluted alkaline of 500mL concentration 10%
Add in the crude product of first step synthesis, stir 1min, stand 15min, separate water phase, retain oil phase；
(3) dry：It is 1 according to the volume ratio of concentrated base and oil phase in the oil phase of second step:1 adds 40% NaOH
Concentrated base extraction dehydration, stirs 1min, stands 15min, is layered, and reclaiming concentrated base is used to prepare the diluted alkaline that second step uses 10%, presses
It is 30 than mL/g according to oil phase and solid base NaOH volume mass:1, solid base NaOH adsorption dewatering is added, stand
0.5h, separation of solid and liquid, reclaiming solid base is used to prepare extract dehydration 40% concentrated base, collects oil phase；
(4) distill：The oil phase that 3rd step is collected is distilled, top temperature≤91 DEG C of front-end volatiles are first collected, is as reclaimed
Triethylamine, directly apply mechanically, regather top 150~160 DEG C of positive cut 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 treatment, reclaims triethylamine and drying and dehydrating obtains the triethylamine solution of product, and last Distillation recovery triethylamine is simultaneously produced
Product.Technique of the invention can well protect phosphite ester from acidolysis and hydrolysis, and process conditions are gentle, and product yield is high, section
Can consumption reduction, suitable industrial production use.
The above is not limitation of the present invention, it should be pointed out that：Come for those skilled in the art
Say, on the premise of essential scope of the present invention is not departed from, some changes, remodeling, addition can also be made or replaced, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (9)
1. a kind of production technology of acid-sensitive phosphite ester, it is characterised in that specifically include following steps：
(1) synthesize：In the reactor, the ertiary amine solution of alcohol is added, reactor is cooled down with ice salt bath, it is 60- to control speed of agitator
120r/min, starts that phosphorus trichloride is added dropwise, and controls rate of addition, reaction temperature is maintained 5~40 DEG C, and feed molar proportioning is
Tertiary amine:Alcohol:Phosphorus trichloride=6~30:3~3.3:1,0.5~3h of tear drop time, tear drop finish continuation and stir 0.5~1h；
(2) alkali cleaning：Speed of agitator is controlled for 60~120r/min, 5~40 DEG C of temperature, diluted alkaline is added into the thick of step (1) synthesis
In product, feed molar proportioning is diluted alkaline:Phosphorus trichloride=3~3.15:1,1~10min is stirred, 1~15min is stood, separate water
Phase, retains oil phase；
(3) dry：In the oil phase of step (2), concentrated base extraction dehydration is added, concentrated base is 0.01~1 ︰ 1 with the volume ratio of oil phase,
1~10min of stirring, stands 1~15min, layering, and oil phase use solid base adsorption dewatering again, the two volume mass than mL/g for 1~
30 ︰ 1, stand 0.5~5h, and separation of solid and liquid collects oil phase；
(4) distill：The oil phase that step (3) is collected is carried out into separated, phosphite ester product is obtained, the tertiary amine of recovery directly covers
With.
2. a kind of production technology of acid-sensitive phosphite ester according to claim 1, it is characterised in that in the step (1)
The ertiary amine solution of alcohol, wherein, alcohol is methyl alcohol or ethanol, and carbon number is 6~30 in tertiary amine molecule.
3. a kind of production technology of acid-sensitive phosphite ester according to claim 1, it is characterised in that in the step (1)
Reactor be provided with constant pressure funnel, agitator, thermometer and reflux condenser.
4. a kind of production technology of acid-sensitive phosphite ester according to claim 1, it is characterised in that in the step (1)
Feed molar proportioning 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, it is characterised 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, it is characterised in that in the step (3)
Concentrated base is 0.06~0.1 ︰ 1 with the volume ratio of oil phase, stirs 5~8min, stands the volume matter of 8~12min, 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, it is characterised in that in the step (2)
Diluted alkaline be the NaOH of concentration 10%~20%, concentrated base in step (3) is 40%~70% NaOH, step for concentration
(3) solid base in is solid sodium hydroxide.
8. a kind of production technology of acid-sensitive phosphite ester according to claim 1, it is characterised in that in the step (3)
After extraction dehydration layering, reclaiming concentrated base is used for the diluted alkaline that preparation steps (2) are used, and after oil phase adsorption dewatering separation of solid and liquid, reclaims
Solid base is used for the concentrated base that preparation steps (3) extract dehydration.
9. a kind of production technology of acid-sensitive phosphite ester according to claim 1, it is characterised in that in the step (4)
Phosphite ester be Trimethyl phosphite or triethyl phosphite.
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| CN112028930A (en) * | 2020-09-09 | 2020-12-04 | 太仓康源化建医药有限公司 | Preparation method of triethyl phosphite |
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| US3057904A (en) * | 1958-09-04 | 1962-10-09 | Monsanto Chemicals | Preparation of esters of trivalent phosphorus acids |
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| 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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| CN112028930A (en) * | 2020-09-09 | 2020-12-04 | 太仓康源化建医药有限公司 | Preparation method of triethyl phosphite |
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