CN102807581B - The preparation method of Lewis acid ion liquid catalyst synthesis phosphotriester - Google Patents
The preparation method of Lewis acid ion liquid catalyst synthesis phosphotriester Download PDFInfo
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- CN102807581B CN102807581B CN201210306486.2A CN201210306486A CN102807581B CN 102807581 B CN102807581 B CN 102807581B CN 201210306486 A CN201210306486 A CN 201210306486A CN 102807581 B CN102807581 B CN 102807581B
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Abstract
The invention discloses the preparation method of a kind of Lewis acid ion liquid catalyst synthesis phosphotriester, catalyst phosphorus oxychloride and epoxide ring-opening reaction is adopted to generate phosphotriester, wherein catalyzer is ionic liquid [the A]-x [Lewis acid] that Lewis acid is formed with A, and A represents amine and derivative, imidazole and its derivants or pyridine and its derivatives.In the preparation method of phosphotriester of the present invention, cheaper starting materials, the catalytic efficiency of catalyzer are high, consumption is few, environmentally friendly, and technique is simple, and the quality of obtained phosphate flame retardant product is good, and acid number is little, and color and luster is good, and product purity is high.
Description
Technical field
The present invention relates to a kind of preparation technology of fire retardant phosphoric acid ester, particularly relate to the preparation method that a kind of Lewis acid ion liquid catalyst phosphorus oxychloride and epoxide ring-opening reaction synthesize fire retardant phosphotriester.
Background technology
Phosphoric acid ester is widely used in synthetic materials, building decoration, cable, battery, the excellent flame retardant of soft (firmly) matter polyurethane foam etc., and in rigid polyurethane foam, have good thermal conductance, stability to hydrolysis and low viscosity at low temperatures.Flame retardant effect is remarkable, has plasticising, protection against the tide, the effect such as antistatic, therefore has good development prospect.
A kind of preparation method of phosphoric acid ester is, phosphorus oxychloride and epoxide obtain phosphotriester through ring-opening reaction under the effect of catalyzer.For tricresyl phosphate (chloropropyl) Lipase absobed method: with phosphorus oxychloride, propylene oxide feedstock, ring-opening reaction synthesis under different types of catalyst.Its catalyst type roughly can be divided three classes: 1.Lewis acid, as anhydrous AlCl
3, MgCl
2deng (Shen Qi, Zhou Lequn, enemy state just waits preparation method [P] .CN101007952A of .TCPP fire retardant), these catalyzer itself are unstable, are very easily hydrolyzed in atmosphere; Post-reaction treatment difficulty, cannot reclaim and contaminate environment.2. the heterogeneous catalyst (T ties up this, W Ge Lapei, R dust Bert etc., preparation [P] .CN1834103A of tricresyl phosphate (chloropropyl) ester) of metal oxide, 3. immobilized multi-acid salt catalysis (Yang Jinfei, TiSiW
12o
40/ TiO
2catalyze and synthesize tricresyl phosphate-(β-chloropropyl) ester [J]. applied chemistry, 2003,20 (2): 201-202).
On the other hand, Lewis acid ion liquid is as the existing application of catalyzer, can effective catalysis aryl oxide cleavage reaction (GerardusJ.Kemperman, TheodorusA.Roeters, PeterW.Hilberink.CleavageofAromaticMethylEthersbyChloroa luminateIonicLiquidReagents.Eur.J.Org.Chem.2003,1681-1686).
The present invention is intended to the shortcoming for Lewis acid catalyst, and the method for phosphorus oxychloride and open loop of epoxy compound being synthesized to phosphotriester is improved.
Summary of the invention
The shortcoming that the preparation method that the present invention is directed to existing phosphoric acid ester exists, a kind of preparation method of phosphotriester is provided, adopt Lewis acid ion liquid as catalyzer, can the ring-opening reaction of efficient catalytic phosphorus oxychloride and epoxy compounds, simplify being separated of catalyzer and product, purification process, few and the environmental friendliness of catalyst levels, product yield is high.
For solving the problems of the technologies described above and realizing goal of the invention, the present invention by the following technical solutions:
A kind of preparation method of Lewis acid ion liquid catalyst synthesis phosphotriester, it is characterized in that, under catalyst effect, phosphorus oxychloride and epoxide ring-opening reaction generate phosphotriester, described catalyzer is ionic liquid [the A]-x [Lewis acid] that Lewis acid is formed with A, A is selected from amine and derivative thereof, imidazole and its derivants, or pyridine and its derivatives.
Described Lewis acid is selected from AlCl
3, FeCl
3, MgCl
2, ZnCl
2, SnCl
2or TiCl
4.
Described amine and derivative thereof are trialkylamine or benzyl amine.Wherein, in trialkylamine, alkyl is ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, sec.-propyl, isobutyl-, isopentyl or iso-octyl; Benzyl amine is N, N-dimethyl benzylamine, N, N-dibenzyl thanomin, N-benzyl ethyl alcohol amine, adjacent benzylaniline or benzyltriethylammoinium chloride.
Described imidazole and its derivants is imidazoles, N-alkyl imidazole or 1,3-Dialkyl-imidazolium, and wherein alkyl is methyl, ethyl, propyl group or butyl.
Described pyridine and its derivatives is pyridine, alkyl pyridine or haloalkylpyridin, and wherein alkyl is methyl, ethyl, propyl group or butyl, and halogeno-group is chloro or bromo.
In described ionic liquid, x is preferably the molar fraction that 30% ~ 90%(x represents Lewis acid in the ionic liquid of formation).
Described ionic-liquid catalyst can be prepared by the following method, in organic solvent, reacts, except obtaining Lewis acid ion liquid catalyst after desolventizing under A and Lewis acid normal temperature.Organic solvent used is selected from ethylene dichloride, benzene or hexanaphthene etc.Lewis acid is 1:0.5 ~ 1:4.5 with the ratio of the amount of substance of A, preferred 1:1 ~ 1:3.5.
With AlCl
3react for example with benzyltriethylammoinium chloride (BTEAC) or triethylamine, the synthetic route of Lewis acid ion liquid is as follows:
Catalyzer 1
Formula 1
Catalyzer 2
AlCl
3+N(C
2H
5)
3→N(C
2H
5)
3～xAlCl
3
Formula 2
Adopt above-mentioned Lewis acid ion liquid catalyst, the method preparing phosphotriester is specially, under condition of heating and stirring, to in the mixture of phosphorus oxychloride and Lewis acid ion liquid catalyst, drip epoxide, drip off the certain temperature of reaction of rear maintenance and continue reaction, until reacted, steam unnecessary epoxide, obtain object phosphotriester.
The consumption of Above-mentioned catalytic agent is 0.0001% ~ 2.0% of reaction raw materials gross weight.
Aforementioned epoxy compound is 0.5:1 ~ 5:1 with the ratio of the amount of substance of chlorethoxyfos, preferred 3:1 ~ 5:1.
Described epoxide is oxyethane, propylene oxide, epoxy chloropropane, alkane (virtue) hexadecyl ethylene oxide, alkane (virtue) basic ring Ethylene Oxide, a halogenated oxirane, a halogenated epoxy propane, dihalo oxyethane, dihalo propylene oxide, tetrahydrofuran (THF), alkyl tetrahydro furans, wherein alkyl is methyl, ethyl, propyl group or butyl, and halogeno-group is chloro or bromo.
In described method, the dropping temperature of epoxide is 35 DEG C ~ 90 DEG C, and epoxide and phosphorus oxychloride reaction temperature are 60 DEG C ~ 120 DEG C.
By technique scheme, the present invention at least has following advantages:
1, the total recovery of preparation method's products obtained therefrom of phosphoric acid ester of the present invention is 85 ~ 98%, usually can reach more than 90%.
The Lewis acid ion liquid catalyst catalytic efficiency used in the preparation method of 2, phosphoric acid ester of the present invention is high, and consumption is few, is generally only 0.01% of raw material total mass.
The cheaper starting materials of catalyzer in the preparation method of 3, phosphoric acid ester of the present invention, technique are simple, have good industrial prospect.
The quality of the phosphate flame retardant product 4, obtained by the present invention is good, and acid number is little, and product purity is high, and color and luster is better, does not need other desolventing technology.
5, the preparation process environmentally safe of synthesis of the present invention and catalyzer, meets the requirement of Green Chemistry.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, be described in detail as follows below with preferred embodiment of the present invention.
Embodiment
For further setting forth the present invention for the technique means reaching predetermined goal of the invention and take and effect, to its embodiment of preparation method of a kind of phosphoric acid ester proposed according to the present invention, feature and effect thereof, be described in detail as follows.
Embodiment 1 ~ 14 relates to the preparation of Lewis acid ion liquid catalyst.
Embodiment 1
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds BTEAC22.78g (0.1mol), CH
2cl
230mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 92%.
Embodiment 2
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds BTEAC45.56g (0.2mol), CH
2cl
240mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 90%.
Embodiment 3
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (250mL) adds BTEAC68.34g (0.3mol), CH
2cl
250mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 89%.
Embodiment 4
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (250mL) adds BTEAC91.12g (0.4mol), CH
2cl
2260mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 90%.
Embodiment 5
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds triethylamine 0.1mol, CH
2cl
230mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 92%.
Embodiment 6
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds triethylamine 0.2mol, CH
2cl
240mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 90%.
Embodiment 7
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (250mL) adds triethylamine 0.3mol, CH
2cl
250mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 89%.
Embodiment 8
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (250mL) adds triethylamine 0.4mol, CH
2cl
2260mL, then adds AlCl
313.34g (0.1mol), normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 90%.
Embodiment 9
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds BTEAC22.78g (0.1mol), CH
2cl
230mL, then adds TiCl
40.1mol, normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 92%.
Embodiment 10
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds BTEAC45.56g (0.2mol), CH
2cl
240mL, then adds TiCl
40.1mol, normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 90%.
Embodiment 11
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (250mL) adds BTEAC68.34g (0.3mol), CH
2cl
250mL, then adds TiCl
40.1mol, normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 89%.
Embodiment 12
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds triethylamine 22.78g (0.1mol), CH
2cl
230mL, then adds MgCl
20.1mol, normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 92%.
Embodiment 13
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (100mL) adds triethylamine 45.56g (0.2mol), CH
2cl
240mL, then adds MgCl
20.1mol, normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 90%.
Embodiment 14
In the three-necked flask that prolong (suitable for reading connect device for absorbing tail gas) and thermometer are housed, (250mL) adds triethylamine 68.34g (0.3mol), CH
2cl
250mL, then adds MgCl
20.1mol, normal-temperature reaction 5h, stopped reaction, cooling, except desolventizing obtains the finished product, productive rate 89%.
Embodiment 15 ~ 35 relates to the preparation of phosphotriester.
Embodiment 15
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip propylene oxide (C
3h
6o) 44.0g (0.75mol), makes temperature of reaction control between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be tricresyl phosphate (2-chloropropyl) ester (TCPP), productive rate 90%, acid number < 0.1mgKOH/g.
Embodiment 16
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 96%, acid number < 0.1mgKOH/g.
Embodiment 17
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtains water white liquid and is TCPP, productive rate 95.5%, acid number < 0.1mgKOH/g.
Embodiment 18
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=67%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 91%, acid number < 0.1mgKOH/g.
Embodiment 19
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=67%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 96%, acid number < 0.1mgKOH/g.
Embodiment 20
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=67%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtains water white liquid and is TCPP, productive rate 98%, acid number < 0.1mgKOH/g.
Embodiment 21
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 2(x=75%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 93%, acid number < 0.1mgKOH/g.
Embodiment 22
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 2(x=75%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 96.5%, acid number < 0.1mgKOH/g.
Embodiment 23
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 2(x=75%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtains water white liquid and is TCPP, productive rate 97.5%, acid number < 0.1mgKOH/g.
Embodiment 24
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=80%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 93%, acid number < 0.1mgKOH/g.
Embodiment 25
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=80%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 96%, acid number < 0.1mgKOH/g.
Embodiment 26
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=80%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip C
3h
6o44.0g (0.75mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtains water white liquid and is TCPP, productive rate 95.5%, acid number < 0.1mgKOH/g.
Embodiment 27
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 2(x=50%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o29.4g (0.5mol), makes temperature of reaction control between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 91%, acid number < 0.1mgKOH/g.
Embodiment 28
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 2(x=50%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o29.4g (0.5mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 95%, acid number < 0.1mgKOH/g.
Embodiment 29
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 2(x=50%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip C
3h
6o29.40g (0.5mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtains water white liquid and is TCPP, productive rate 95%, acid number < 0.1mgKOH/g.
Embodiment 30
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o14.7g (0.25mol), makes temperature of reaction control between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 90%, acid number < 0.1mgKOH/g.
Embodiment 31
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip C
3h
6o14.7g (0.25mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtain water white liquid and be TCPP, productive rate 94%, acid number < 0.1mgKOH/g.
Embodiment 32
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip C
3h
6o14.7g (0.25mol), makes temperature of reaction control between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, propylene oxide 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary propylene oxide, obtains water white liquid and is TCPP, productive rate 95.5%, acid number < 0.1mgKOH/g.
Embodiment 33
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.005g, start to stir, heating in water bath, to about 45 DEG C, starts to drip oxyethane 0.75mol, and temperature of reaction is controlled between 50 DEG C ~ 72 DEG C.Drip off rear continuation reaction two hours.Oxyethane 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary oxyethane, obtain water white liquid and be object phosphotriester, productive rate 92%, acid number < 0.1mgKOH/g.
Embodiment 34
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer 1(x=50%) 0.01g, start to stir, heating in water bath, to about 45 DEG C, starts to drip epoxy chloropropane 0.75mol, and temperature of reaction is controlled between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours.Epoxy chloropropane 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary epoxy chloropropane, obtain water white liquid and be object phosphotriester, productive rate 94%, acid number < 0.1mgKOH/g.
Embodiment 35
POCl is added in the four neck flasks (250mL) that ground thermometer, serpentine condenser and constant pressure funnel are housed
338.5g (0.25mol), catalyzer (x=50%) 0.015g, start to stir, heating in water bath, to about 50 DEG C, starts to drip methyl oxirane 0.75mol, and temperature of reaction is controlled between 55 DEG C ~ 70 DEG C.Drip off rear continuation reaction two hours, methyl oxirane 10mL is added again in four neck flasks, improve bath temperature to 80 DEG C ~ 100 DEG C reaction 1 ~ 1.5 hour, treat substantially without backflow, stopped reaction, normal pressure steams unnecessary methyl oxirane, obtains water white liquid and is object phosphotriester, productive rate 95.6%, acid number < 0.1mgKOH/g.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (5)
1. the preparation method of a Lewis acid ion liquid catalyst synthesis phosphotriester, it is characterized in that, under catalyst effect, phosphorus oxychloride and epoxide ring-opening reaction generate phosphotriester, described catalyzer is ionic liquid [the A]-x [Lewis acid] that Lewis acid is formed with A, and wherein A is selected from amine and derivative, imidazole and its derivants or pyridine and its derivatives;
Described Lewis acid is AlCl
3, FeCl
3, MgCl
2, ZnCl
2, SnCl
2or TiCl
4;
Described amine and derivative thereof are trialkylamine or benzyl amine, and wherein alkyl is ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, sec.-propyl, isobutyl-, isopentyl or iso-octyl; Benzyl amine is N, N-dimethyl benzylamine, N, N-dibenzyl thanomin, N-benzyl ethyl alcohol amine, adjacent benzylaniline or benzyltriethylammoinium chloride;
Described imidazole and its derivants is imidazoles, N-alkyl imidazole or 1,3-Dialkyl-imidazolium, and wherein alkyl is methyl, ethyl, propyl group or butyl;
Described pyridine and its derivatives is pyridine, alkyl pyridine or haloalkylpyridin, and wherein alkyl is methyl, ethyl, propyl group or butyl, and halogeno-group is chloro or bromo;
In described ionic liquid, the molar fraction x of Lewis acid is 30% ~ 90%.
2. the preparation method of phosphotriester according to claim 1, is characterized in that: described ionic-liquid catalyst is prepared by the following method, in organic solvent, reacts, except obtaining Lewis acid ion liquid catalyst after desolventizing under A and Lewis acid normal temperature; Described organic solvent is selected from ethylene dichloride, benzene or hexanaphthene, and Lewis acid is 1:0.5 ~ 1:4.5 with the ratio of the amount of substance of A.
3. the preparation method of phosphotriester according to claim 1, is characterized in that: the consumption of described Lewis acid ion liquid catalyst is 0.0001% ~ 2.0% of reaction raw materials gross weight; Described epoxide is 0.5:1 ~ 5:1 with the ratio of the amount of substance of described chlorethoxyfos.
4. the preparation method of phosphotriester according to claim 1, it is characterized in that: described epoxide is oxyethane, propylene oxide, epoxy chloropropane, alkyl epoxy ethane/aryl rings oxidative ethane, alkyl epoxy propane/aryl rings Ethylene Oxide, a halogenated oxirane, a halogenated epoxy propane, dihalo oxyethane, dihalo propylene oxide, tetrahydrofuran (THF) or alkyl tetrahydro furans, wherein alkyl is methyl, ethyl, propyl group or butyl, and halogeno-group is chloro or bromo.
5. the preparation method of phosphotriester according to claim 1, it is characterized in that: under condition of heating and stirring, to in the mixture of phosphorus oxychloride and Lewis acid ion liquid catalyst, drip epoxide, drip off the certain temperature of reaction of rear maintenance and continue reaction, until reacted, steam unnecessary epoxide, obtain object phosphotriester; The dropping temperature of described epoxide is 35 DEG C ~ 90 DEG C, and described epoxide and described phosphorus oxychloride reaction temperature are 60 DEG C ~ 120 DEG C.
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| CN103480412A (en) * | 2013-08-13 | 2014-01-01 | 滨海雅克化工有限公司 | Ionic liquid catalyst used in preparation of bisphenol A (phenyl polyphosphate) and preparation method thereof |
| CN103554467B (en) * | 2013-10-31 | 2015-10-21 | 淄博德信联邦化学工业有限公司 | The preparation method of phosphorous chloride flame retardant polyether polyol |
| CN105131688B (en) * | 2015-09-17 | 2017-08-29 | 莆田学院 | A kind of photocuring expandable flame retardant coating of stanniferous ionic liquid fire retardant and the application fire retardant |
| CN105440071A (en) * | 2015-11-06 | 2016-03-30 | 南京师范大学 | Preparation method of phosphate or phosphite flame retardant with low acid value and high stability |
| CN106366122B (en) * | 2016-08-24 | 2017-12-01 | 浙江万盛股份有限公司 | Three（2,3 2 chloropropyls）The continuous preparation method of phosphate |
| CN107445985B (en) * | 2017-08-18 | 2020-04-21 | 南京师范大学 | Preparation method and application of polyhydroxy phosphate |
| CN109232639B (en) * | 2018-10-11 | 2021-02-09 | 山东泰和水处理科技股份有限公司 | Preparation method of tris (1, 3-dichloropropyl) phosphonate |
| CN112920218B (en) * | 2021-02-05 | 2023-10-24 | 南京师范大学 | Tert-butylphenyl phosphate and preparation method and application thereof |
| CN113333019A (en) * | 2021-04-29 | 2021-09-03 | 佳化化学（抚顺）新材料有限公司 | Method for synthesizing organic phosphorus flame retardant by catalysis of Lewis acid ionic liquid |
| CN113717218B (en) * | 2021-09-07 | 2024-05-28 | 三峡大学 | Preparation method of tri (2-chloropropyl) phosphate |
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