CN109705165A - A kind of synthesis of high purity dicyclo phosphonate ester and purification process - Google Patents
A kind of synthesis of high purity dicyclo phosphonate ester and purification process Download PDFInfo
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Abstract
A kind of synthesis of high purity dicyclo phosphonate ester and purification process are related to synthesis and the purification process of a kind of dicyclic phosphonate.Low the invention aims to solve existing annular phosphonate synthetic method target product purity, thermal stability is poor, is organized into the bad problem of flame retardant effect after fabric.Method: one, under nitrogen protection, by dimethyl methyl phosphonate, trimethylolpropane and ionic liquid [Bmim] BF4Mixed liquor is formed after stirring 15min~25min, nitrogen is continually fed into and is heated to 140 DEG C~170 DEG C, continues stirring and constant temperature distillation 14h~30h, obtains pale yellow solution；Two, gas chromatographic analysis is carried out to pale yellow solution, then pillar layer separation is carried out, again through eluent, it is formed using gas chromatography detection eluant, eluent, eluant, eluent is evaporated off in temperature condition backspin by the eluant, eluent containing target product in the vacuum degree of 0.065MPa~0.09MPa and 60 DEG C~80 DEG C, obtains target product dicyclic phosphonate.The present invention can get synthesis and the purification process of a kind of high purity dicyclo phosphonate ester.
Description
Technical field
The present invention relates to a kind of synthesis of dicyclic phosphonate and purification process.
Background technique
The one kind of phosphonate ester as fire retardant not only has hypotoxicity and does not pollute compared to traditional halogen flame
The characteristics of environment, and it is low in cost.Although early have foreign literature with bicyclic phosphinate and dimethyl methyl phosphonate in N2Item
Under part, with two-step method synthesizing cyclic phosphonate, but reaction step is more, the reaction time in 30h or more, and reaction temperature compared with
Height, requires a great deal of time and heat.There are also the domestic scholars bicyclic phosphinate of ionic liquid-catalyzed ethyl and
DMMP uses two-step method synthesizing cyclic phosphonate, but cumbersome and higher cost at 185 DEG C.
In recent years, there is domestic scholars proposition one-step synthesis method annular phosphonate, but lack effective method of purification, therefore
Acquisition target product purity is not also high, and thermal stability is poor, and then influences annular phosphonate and be organized into after fabric most as fire retardant
Whole flame retardant effect.
Summary of the invention
Low the invention aims to solve existing annular phosphonate synthetic method target product purity, thermal stability is poor,
It is organized into the bad problem of flame retardant effect after fabric, and synthesis and the purification process of a kind of high purity dicyclo phosphonate ester are provided.
A kind of synthesis of high purity dicyclo phosphonate ester and purification process, are completed by the following steps:
Under nitrogen protection, by dimethyl methyl phosphonate, trimethylolpropane and ionic liquid [Bmim] BF4It is added to anti-
It answers in container, forms mixed liquor after stirring 15min~25min, be continually fed into nitrogen and be heated to 140 DEG C~170 DEG C, continue to stir
It mixes and constant temperature distills 14h~30h, terminate and react after being exhausted using gas chromatography tracking reaction to dimethyl methyl phosphonate, obtain
To pale yellow solution, gas chromatographic analysis is carried out to the pale yellow solution, then carries out pillar layer separation, then through eluant, eluent
Elution, using gas chromatography detection elution after eluant, eluent form, by the eluant, eluent containing target product 0.065MPa~
Under the conditions of the vacuum degree of 0.09MPa and 60 DEG C~80 DEG C of temperature, revolving removes eluant, eluent, obtains the bicyclic phosphonic acids of target product
Ester, the purity > 90% of the dicyclic phosphonate；
The mass ratio of the material of the dimethyl methyl phosphonate and trimethylolpropane is 1~2: 1, the ionic liquid
The total mass ratio of [Bmim] BF4 and dimethyl methyl phosphonate and trimethylolpropane is 0.005~0.015:1.
For the stationary phase that the pillar layer separation uses for silica gel, the eluant, eluent is to contain ethyl acetate, glacial acetic acid
With the mixture of distilled water, the ratio of the ethyl acetate, glacial acetic acid and distilled water is 3:5:1.
Synthesize the reaction equation of dicyclic phosphonate are as follows:
Advantages of the present invention:
The high purity dicyclo phosphonate ester of the present invention after purification collects acid source and charcoal derived from all over the body, itself is in combustion
It can be good at being dehydrated into charcoal.Dicyclic phosphonate has twin nuclei, and chemical property is stablized, and after the processing of purified means,
It shows that purity reaches 90% or more through gas chromatography testing result, keeps its thermal stability outstanding.According to national standard GB/
The standard of T5455-1997 " textile combustion performance test normal beam technique " carries out vertical burn test, and high purity dicyclo phosphonate ester is whole
After flame time and smoldering time after managing into fabric are 0s, damage a length of 6.0cm of charcoal, and flame retardant rating reaches B1Grade, LOI value can
Up to 36%, tearing brute force retention rate influences the feel of fabric smaller 84% or so.With traditional low-purity annular phosphonate
Fire retardant B3The flame retardant property of grade is compared, and the flame retardant property of high purity dicyclo phosphonate fire retardant is more efficient, reliable.
Secondly, the present invention uses ionic liquid [Bmim] BF4It is not only environmentally protective as catalyst, and itself can also rise
It to fire retardation, therefore need not be separated from target product, simplify synthesis step.
The present invention can get synthesis and the purification process of a kind of high purity dicyclo phosphonate ester.
Detailed description of the invention
Fig. 1 is the FTIR spectrum spectrogram of dicyclic phosphonate reaction mixture；
Fig. 2 is the gas chromatogram of dicyclic phosphonate eluent；
Fig. 3 is the 1H nmr spectrum of dicyclic phosphonate；
Fig. 4 is the 13C nmr spectrum of dicyclic phosphonate；
Fig. 5 is the 31P nmr spectrum of dicyclic phosphonate.
Specific embodiment
Specific embodiment 1: present embodiment is synthesis and the purification process of a kind of high purity dicyclo phosphonate ester, be by
What following steps were completed:
Under nitrogen protection, by dimethyl methyl phosphonate, trimethylolpropane and ionic liquid [Bmim] BF4It is added to anti-
It answers in container, forms mixed liquor after stirring 15min~25min, be continually fed into nitrogen and be heated to 140 DEG C~170 DEG C, continue to stir
It mixes and constant temperature distills 14h~30h, terminate and react after being exhausted using gas chromatography tracking reaction to dimethyl methyl phosphonate, obtain
To pale yellow solution, purification process is carried out to pale yellow solution, obtains target product dicyclic phosphonate, the dicyclic phosphonate
Purity > 90%；
The mass ratio of the material of the dimethyl methyl phosphonate and trimethylolpropane is 1~2: 1, the ionic liquid
[Bmim]BF4It is 0.005~0.015:1 with the total mass ratio of dimethyl methyl phosphonate and trimethylolpropane.
A kind of synthesis of high purity dicyclo phosphonate ester of present embodiment and purification process, high purity dicyclo phosphonic acids after purification
Ester collects acid source and charcoal derived from all over the body, itself can be good at being dehydrated into charcoal in combustion.Dicyclic phosphonate has bicyclic
Structure, chemical property are stablized, and after the processing of purified means, show that purity reaches 90% through gas chromatography testing result
More than, keep its thermal stability outstanding.According to the mark of national standard GB/T5455-1997 " textile combustion performance test normal beam technique "
Standard carries out vertical burn test, and high purity dicyclo phosphonate ester is organized into the after flame time after fabric and smoldering time is 0s, damage
The a length of 6.0cm of charcoal is ruined, flame retardant rating reaches B1Grade, LOI value is up to 36%, and tearing brute force retention rate is 84% or so, and to knitting
The feel of object influences smaller.With traditional low-purity annular phosphonate fire retardant B3The flame retardant property of grade is compared, high purity dicyclo
The flame retardant property of phosphonate fire retardant is more efficient, reliable.
Secondly, the present invention uses ionic liquid [Bmim] BF4It is not only environmentally protective as catalyst, and itself can also rise
It to fire retardation, therefore need not be separated from target product, simplify synthesis step.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: to the pale yellow solution
Gas chromatographic analysis is carried out, pillar layer separation is then carried out, then through eluent, after gas chromatography detection elution
Eluant, eluent composition, by the eluant, eluent containing target product in the vacuum degree of 0.065MPa~0.09MPa and 60 DEG C~80 DEG C of temperature
Under the conditions of, revolving removes eluant, eluent, obtains target product dicyclic phosphonate.Other steps are same as the specific embodiment one.
Specific embodiment 3: present embodiment is with specific embodiment one or two differences: the column chromatography point
From the stationary phase used for silica gel.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: the elution
Agent is the mixture containing ethyl acetate, glacial acetic acid and distilled water.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: the elution
The ratio of ethyl acetate, glacial acetic acid and distilled water is 3:5:1 in agent.Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: described will contain
Eluant, eluent is evaporated off in the temperature condition backspin of the vacuum degree of 0.08MPa and 70 DEG C in the eluant, eluent of target product, obtains target production
Object dicyclic phosphonate.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: the methyl
The mass ratio of the material of dimethyl phosphonate and trimethylolpropane is 1.5: 1.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: the ion
Liquid [Bmim] BF4It is 0.01:1 with the total mass ratio of dimethyl methyl phosphonate and trimethylolpropane.Other steps and specific
Embodiment one to seven is identical.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: described persistently to lead to
Enter nitrogen and is heated to 141 DEG C.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: described to continue to stir
It mixes and constant temperature distills 15h.Other steps are identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of synthesis of high purity dicyclo phosphonate ester and purification process are completed by the following steps:
One, under nitrogen protection, dimethyl methyl phosphonate, trimethylolpropane and ionic liquid [Bmim] BF4 are added
Into reaction vessel, mixed liquor is formed after stirring 17min, after dimethyl methyl phosphonate and trimethylolpropane are completely dissolved,
It is continually fed into nitrogen and is heated to 145 DEG C, continue stirring and constant temperature distillation 16h, track reaction process using gas chromatography, until
Dimethyl methyl phosphonate terminates reaction after exhausting, and obtains pale yellow solution；
The mass ratio of the material of the dimethyl methyl phosphonate and trimethylolpropane is 1.5: 1, the ionic liquid
The total mass ratio of [Bmim] BF4 and dimethyl methyl phosphonate and trimethylolpropane is 0.009:1.
Two, gas chromatographic analysis is carried out to pale yellow solution, confirms the retention time of its main component, then carry out column color
Spectrum separation, then through eluent, formed using gas chromatography detection eluant, eluent, the eluant, eluent containing target product is existed
Eluant, eluent is evaporated off in the vacuum degree of 0.07MPa and 65 DEG C of temperature condition backspin, obtains target product dicyclic phosphonate；
For the stationary phase that the pillar layer separation uses for silica gel, the eluant, eluent is to contain ethyl acetate, glacial acetic acid
With the mixture of distilled water, the ratio of the ethyl acetate, glacial acetic acid and distilled water is 3:5:1.
It will be seen from figure 1 that vmax/cm-1: absorption peak is in 2884cm-1, 2934cm-1Peak is that methyl and methylene C-H are flexible
Vibration peak, 1186cm-1For the absorption peak of phosphorus oxygen double bond P=O, 984cm-1For the corresponding characteristic absorption peak of C-O-P.Result above
Confirm the presence of target product dicyclic phosphonate；
Target product integrating peak areas is as a result, target product retention time is 7.9-8.2mim, in bimodal, peak according to fig. 2
Area accounting 91.63%；
In Fig. 3: have abc three classes H atom in compound, the chemical shift of a between 0.8~1.7ppm, b 3.0~
Between 4.3ppm, c is in 2.0ppm or so.Three classes H atom number ratio 10:12:9, and associated quad area ratio 1.00:1.15:
0.79 matches；
There is five class C atom of abcde in Fig. 4, in compound, number ratio is 2:2:2:6:3, and the chemical shift of a is on the left side 60ppm
The right side, b is in 23ppm or so, and c is between 6.0~7.0ppm, and d is in 70ppm or so, and e is in 10ppm or so.Five class C atoms accordingly accumulate
Point area ratio 1.00:1.04:1.08:2.91:1.41 matches with the ratio between corresponding C atom number；
In Fig. 5, there are three P atoms in compound molecule, and chemical environment is essentially identical, and chemical shift appears in the left side 30ppm
It is right；
Vertical burn test result:
A kind of synthesis of high purity dicyclo phosphonate ester of the present embodiment and purification process, high purity dicyclo phosphonic acids after purification
Ester shows that purity reaches 92% through gas chromatography testing result.According to national standard GB/T5455-1997 " textile combustion performance
Test normal beam technique " standard carry out vertical burn test, high purity dicyclo phosphonate ester is organized into the flame retardant rating after fabric and reaches
B1Grade, LOI value is up to 36%, tearing brute force retention rate 85%, and influences on the feel of fabric smaller.It is cyclic annular with traditional low-purity
Phosphonate fire retardant B3The flame retardant property of grade is compared, and the flame retardant property of high purity dicyclo phosphonate fire retardant is more efficient, reliable.
Secondly, the present embodiment uses ionic liquid [Bmim] BF4 as catalyst, itself can also play fire retardation, because
This need not be separated from target product, simplify synthesis step.
Embodiment two: a kind of synthesis of high purity dicyclo phosphonate ester and purification process are completed by the following steps:
One, under nitrogen protection, dimethyl methyl phosphonate, trimethylolpropane and ionic liquid [Bmim] BF4 are added
Into reaction vessel, mixed liquor is formed after stirring 22min, after dimethyl methyl phosphonate and trimethylolpropane are completely dissolved,
It is continually fed into nitrogen and is heated to 160 DEG C, continue stirring and constant temperature distillation 18h, track reaction process using gas chromatography, until
Dimethyl methyl phosphonate terminates reaction after exhausting, and obtains pale yellow solution；
The mass ratio of the material of the dimethyl methyl phosphonate and trimethylolpropane is 1.8: 1, the ionic liquid
The total mass ratio of [Bmim] BF4 and dimethyl methyl phosphonate and trimethylolpropane is 0.012:1.
Two, gas chromatographic analysis is carried out to pale yellow solution, confirms the retention time of its main component, then carry out column color
Spectrum separation, then through eluent, formed using gas chromatography detection eluant, eluent, the eluant, eluent containing target product is existed
Eluant, eluent is evaporated off in the vacuum degree of 0.08MPa and 75 DEG C of temperature condition backspin, obtains target product dicyclic phosphonate；
For the stationary phase that the pillar layer separation uses for silica gel, the eluant, eluent is to contain ethyl acetate, glacial acetic acid
With the mixture of distilled water, the ratio of the ethyl acetate, glacial acetic acid and distilled water is 3:5:1.
Vertical burn test result:
A kind of synthesis of high purity dicyclo phosphonate ester of the present embodiment and purification process, high purity dicyclo phosphonic acids after purification
Ester shows that purity reaches 93% through gas chromatography testing result.According to national standard GB/T5455-1997 " textile combustion performance
Test normal beam technique " standard carry out vertical burn test, high purity dicyclo phosphonate ester is organized into the flame retardant rating after fabric and reaches
B1Grade, up to 36%, tearing brute force retention rate influences the feel of fabric smaller LOI value 86%.With traditional low-purity ring
Shape phosphonate fire retardant B3The flame retardant property of grade is compared, and the flame retardant property of high purity dicyclo phosphonate fire retardant is more efficient, can
It leans on.
Secondly, the present embodiment uses ionic liquid [Bmim] BF4 as catalyst, itself can also play fire retardation, because
This need not be separated from target product, simplify synthesis step.
Claims (10)
1. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester, it is characterised in that it is completed by the following steps:
Under nitrogen protection, by dimethyl methyl phosphonate, trimethylolpropane and ionic liquid [Bmim] BF4Reaction is added to hold
In device, mixed liquor is formed after stirring 15min~25min, nitrogen is continually fed into and is heated to 140 DEG C~170 DEG C, continues stirring simultaneously
Constant temperature distills 14h~30h, terminates and reacts after being exhausted using gas chromatography tracking reaction to dimethyl methyl phosphonate, obtains shallow
Yellow solution carries out purification process to pale yellow solution, obtains target product dicyclic phosphonate, the purity of the dicyclic phosphonate
> 90%；
The mass ratio of the material of the dimethyl methyl phosphonate and trimethylolpropane is 1~2: 1, the ionic liquid
[Bmim]BF4It is 0.005~0.015:1 with the total mass ratio of dimethyl methyl phosphonate and trimethylolpropane.
2. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 1, it is characterised in that by with
Lower step carries out purification process:
Gas chromatographic analysis is carried out to the pale yellow solution, then carries out pillar layer separation, then through eluent, utilize
Eluant, eluent composition after gas chromatography detection elution, by the eluant, eluent containing target product in the true of 0.065MPa~0.09MPa
Under the conditions of reciprocal of duty cycle and 60 DEG C~80 DEG C of temperature, revolving removes eluant, eluent, obtains target product dicyclic phosphonate.
3. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 2, it is characterised in that described
The stationary phase that uses of pillar layer separation for silica gel.
4. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 2, it is characterised in that described
Eluant, eluent be the mixture containing ethyl acetate, glacial acetic acid and distilled water.
5. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 2, it is characterised in that described
Eluant, eluent in ethyl acetate, glacial acetic acid and distilled water ratio be 3:5:1.
6. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 2, it is characterised in that described
The temperature condition backspin by the eluant, eluent containing target product in the vacuum degree of 0.08MPa and 70 DEG C eluant, eluent is evaporated off, obtain
Target product dicyclic phosphonate.
7. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 1, it is characterised in that described
Dimethyl methyl phosphonate and trimethylolpropane the mass ratio of the material be 1.5: 1.
8. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 1, it is characterised in that described
Ionic liquid [Bmim] BF4It is 0.01:1 with the total mass ratio of dimethyl methyl phosphonate and trimethylolpropane.
9. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 1, it is characterised in that continue
It is passed through nitrogen and is heated to 141 DEG C.
10. synthesis and the purification process of a kind of high purity dicyclo phosphonate ester according to claim 1, it is characterised in that continue
It stirs and constant temperature distills 15h.
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