CN104529694B - A kind of preparation method of long chain fluorine-containing alkene - Google Patents
A kind of preparation method of long chain fluorine-containing alkene Download PDFInfo
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- CN104529694B CN104529694B CN201410775913.0A CN201410775913A CN104529694B CN 104529694 B CN104529694 B CN 104529694B CN 201410775913 A CN201410775913 A CN 201410775913A CN 104529694 B CN104529694 B CN 104529694B
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Abstract
The present invention relates to a kind of preparation method of long chain fluorine-containing alkene, comprise the steps: 1) addition reaction: in the reactor containing perfluoroalkyl iodine solution, radical initiator, pass into fluorochemical monomer continuously, the flow rate regulating the pressure reduction of fluorochemical monomer before and after reactor to control fluorochemical monomer carries out addition reaction by Bubbling method, prepare affixture, after reaction terminates, by reaction solution by rectification under vacuum, obtain the adduct of certain purity; 2) eliminative reaction: by adduct cancellation HI in the basic conditions, rectifying, obtains long-chain olefin product.The present invention adopts perfluoroalkyl iodides and fluorochemical monomer as raw material, can obtain the Fluorine containing olefine containing long-chain by addition and elimination two-step reaction, and high, the simple environmental protection of the method selectivity, be easy to realize.
Description
Technical field
The invention belongs to the synthesis field of organic compound, be specifically related to a kind of preparation method of long chain fluorine-containing alkene.
Background technology
Long chain fluorine-containing olefin(e) compound contains longer fluorine-containing side chain relative to common Fluorine containing olefine, by improving the moulding processability of various fluoropolymer, creep resistance, resistance to cracking energy and light transmission with common Fluorine containing olefine copolymerization, its general structure is:
Wherein R
ffor fluoridized alkyl group, X
1, X
2, X
3for halogen atom, hydrogen atom etc., wherein at least one is F atom.
The preparation method of conventional Fluorine containing olefine mainly contains cracking fluorochlorohydrocarbon method, acyl fluorides (or acyl chlorides) class fluorochemicals decarboxylation method and perfluoroalkyl iodides and ethene telomerizes dehydroiodination method etc.
Cracking fluorochlorohydrocarbon method can be prepared as tetrafluoroethylene (hereafter claiming TFE), vinylidene (hereafter claiming VDF), trifluorochloroethylene (hereafter claiming CTFE), trifluoro-ethylene (hereafter claiming TrFE), R 1216 (hereafter claiming HFP), the Fluorine containing olefines such as tetrafluoeopropene, wherein Honeywell Inc. patent US2005020862A1 (Processforthemanufactureof1, 3, 3, 3-tetrafluoropropene) adopt 1-chloro-1, 3, 3, 3-tetrafluoropropane (hereafter claiming HCFC-244fa) obtains tetrafluoeopropene by removing HCl, but because restriction the method for raw material can only prepare simple Fluorine containing olefine, be restricted when preparing the Fluorine containing olefine of long-chain.
Summary of the invention
Can only prepare the defect of the shorter simple Fluorine containing olefine of chain length for cracking fluorochlorohydrocarbon method in prior art, the invention provides a kind of preparation method of long chain fluorine-containing alkene, the method step is simple, technique environmental protection, is easy to realize, comprises the steps:
1) addition reaction
In the reactor containing perfluoroalkyl iodides, radical initiator, pass into gaseous fluorinated monomer continuously, carry out addition reaction by Bubbling method, after reaction terminates, by reaction solution by rectification under vacuum, obtain adduct;
2) eliminative reaction
By described adduct cancellation HI in the basic conditions, rectifying, obtains long chain fluorine-containing alkene.
In the present invention, the general formula of described perfluoroalkyl iodides is R
fi; Wherein atomic iodine I is at the end of carbochain, R
ffor the perfluorinated alkyl group of carbonatoms between 2-8; For example can but be not limited only to: C
2f
5i, C
3f
7i, C
4f
9i, C
5f
11i, C
6f
13i, C
7f
15i, C
8f
17i.
In the present invention, the general formula of described gaseous fluorinated monomer is X
ax
bc=CX
cx
d, wherein, X
a, X
b, X
c, X
dfor halogen atom, hydrogen atom etc., wherein at least one is expressed as F atom, for example can be vinylidene (hereafter claiming VDF), 1,2-difluoroethylene, trifluoro-ethylene (hereafter claiming TrFE), vinyl fluoride (hereafter claiming VF).
In the present invention, described radical initiator is organic superoxide; For example can be but be not limited only to: diisopropyl peroxide, di-t-butyl peroxide, diacetyl peroxide, dipropyonyl peroxide, dibutyrylperoxide, dibenzoyl peroxide, benzoylperoxy acetyl, peroxysuccinic acid, peroxy dicarbonate methyl esters, peroxy dicarbonate isopropyl ester (hereinafter claiming IPP), peroxy dicarbonate tertiary butyl ester.Described radical initiator in every 100 molar part perfluoroalkyl iodides consumptions for 0.001-1.0 part, preferred 0.01-0.5 part.
In the present invention, the alkaline reagents that described alkaline condition uses includes but are not limited to NaOH, KOH, CH
3oNa, C
2h
5oNa, C
4h
9oNa; In 100 molar part adducts, the consumption of alkaline reagents is 100-150 part, preferred 100-120 part.
In the present invention, described addition reaction condition: temperature-80 ~ 100 DEG C, preferably-30 ~ 50 DEG C.
In the present invention, described elimination reaction condition is: temperature 20 ~ 100 DEG C, preferably 40 ~ 80 DEG C, and before and after reactor, the pressure reduction of fluorochemical monomer is 0.1-1.5MPa, preferred 0.1-1.0MPa.
Reactor of the present invention is preferably nickelalloy material, and inside leads to circulatory mediator with coil pipe, to control temperature of reaction system.
Adopt preparation method of the present invention can obtain the good long chain fluorine-containing alkene of polymerizability, object lesson has CHF=CHC
2f
5, CHF=CHC
3f
7, CHF=CHC
4f
9, CHF=CHC
5f
11, CHF=CHC
6f
13, CHF=CFC
2f
5, CHF=CFC
3f
7, CHF=CFC
4f
9, CHF=CFC
5f
11, CHF=CFC
6f
13, CF
2=CHC
2f
5, CF
2=CHC
3f
7, CF
2=CHC
4f
9, CF
2=CHC
5f
11, CF
2=CHC
6f
13, CF
2=CFC
2f
5, CF
2=CFC
3f
7, CF
2=CFC
4f
9, CF
2=CFC
5f
11, CF
2=CFC
6f
13, preferred CHF=CHC
4f
9, CHF=CFC
4f
9, CF
2=CHC
4f
9, CF
2=CFC
4f
9.
Use present method synthesis long chain fluorine-containing alkene, step is simple, and production cost is low, is a kind of production method of simple environmental protection.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
1) addition reaction
Have in the 1L nickelalloy reaction tubes of coil pipe in inside, add 700g (2.0mol) perfluoro butyl iodine (CF
3cF
2cF
2cF
2i) and 0.5g dibenzoyl peroxide, be cooled to-40 DEG C, pass through N
2air in system of draining, is then warming up to 0 DEG C.
By compressor, fluorochemical monomer vinylidene VDF is entered reactor from liquid phase valve gate open, unabsorbed VDF gas enters gas-liquid separator by gaseous phase outlet, gets back to VDF storage tank.Controlled by pneumavalve in reaction process, ensure that storage tank and compressor outlet gas pressure difference are 0.5MPa all the time.After storage tank quality no longer reduces, stop compressor, successively close the import and export of the gentle phase valve of liquid phase valve and storage tank, the low 119g of VDF storage tank quality co-falling before and after reaction.Temperature of reactor is down to-40 DEG C, gas in system of draining, collects reaction solution, by mainly containing two kinds of material compositions in gas chromatograph-mass spectrometer analytical reaction liquid, 91.4% is CF
3cF
2cF
2cF
2cH
2cF
2i, 8.5% is unreacted raw material CF
3cF
2cF
2cF
2i, a small amount of impurity does not detect structure.
By rectification under vacuum, under the pressure of 10KPa, collect the cut of 59-60 DEG C, weighing quality is 734.6g, by CF
3cF
2cF
2cF
2i calculated yield is 89.61%.
2) eliminative reaction
12g sodium butylate is dissolved in 500ml propyl carbinol, obtains sodium butylate solution.Get the adduct CF that 410g (1.0mol) rectifying obtains
3cF
2cF
2cF
2cH
2cF
2i, adduct and sodium butylate solution are joined 1000mL with stir and reflux exchanger three-necked flask in, open stir, be warming up to 50 DEG C start react.After completion of the reaction reaction solution is transferred to Rotary Evaporators, collect the low-boiling-point substance of 50-60 DEG C, then collect 63-64 DEG C of cut through rectification and purification, weighing quality is 264.8g, passes through
1h,
13c,
19the NMR of F analyzes and determines that structure is CF
3cF
2cF
2cF
2cH=CF
2, be 93.90% by calculated yield, the total recovery of two-step reaction is 84.14%.
Embodiment 2
1) addition reaction
According to the reaction conditions of embodiment 1, use equal difluoroethylene instead as addition alkene, react under 20 DEG C of conditions, other conditions are constant, and obtaining reaction solution is 87.9%CF
3cF
2cF
2cF
2cFHCFHI and 12.1% unreacted CF
3cF
2cF
2cF
2i, does not detect impurity.
By rectifying under the pressure of 10KPa, collect the cut of 59-60 DEG C, weighing quality is 705.03g, by CF
3cF
2cF
2cF
2i calculated yield is 86.00%.
2) eliminative reaction
Get the adduct CF that 410g (1.0mol) rectifying obtains
3cF
2cF
2cF
2cFHCFHI, in three-necked flask, according to the reaction conditions of embodiment 1, obtains the product 234.8g that boiling range is 66-68 DEG C, passes through
1h,
13c,
19the NMR of F analyzes and determines that structure is CF
3cF
2cF
2cF
2cF=CFH is 83.26% by calculated yield, and the total recovery of two-step reaction is 71.60%.
Embodiment 3
1) addition reaction
According to the reaction conditions of embodiment 1, except using TrFE instead as addition alkene, react under-10 DEG C of conditions, other conditions are constant, obtain reaction solution by 97.7%CF
3cF
2cF
2cF
2cFHCF
2i and 2.1% unreacted raw material CF
3cF
2cF
2cF
2i forms, remaining as dimer CF
3cF
2cF
2cF
2(CFHCF
2)
2i.By rectifying under the pressure of 10KPa, collect the cut of 59-60 DEG C, weighing quality is 811.94g, by CF
3cF
2cF
2cF
2i calculated yield is 94.87%.
2) eliminative reaction
Get the adduct CF that 428g (1.0mol) rectifying obtains
3cF
2cF
2cF
2cFHCF
2i, in three-necked flask, according to the reaction conditions of embodiment 1, obtains the product 285.4g that boiling range is 72 ~ 73 DEG C, passes through
1h,
13c,
19the NMR of F analyzes and determines that structure is CF
3cF
2cF
2cF
2cF=CF
2, be 95.13% by calculated yield, the total recovery of two-step reaction is 90.25%.
Embodiment 4
1) addition reaction
According to the reaction conditions of embodiment 1, except using FE instead as addition alkene, storage tank and compressor outlet gas pressure difference are down to 0.2MPa, react under 20 DEG C of conditions, and other conditions are constant, obtain reaction solution by 92.9%CF
3cF
2cF
2cF
2cH
2cFHI and 7.1% unreacted raw material CF
3cF
2cF
2cF
2i forms, and does not detect other impurity.By rectifying under the pressure of 5KPa, collect the cut of 59 ~ 60 DEG C, weighing quality is 667.25g, by CF
3cF
2cF
2cF
2i calculated yield is 85.13%.
2) eliminative reaction
Get the adduct CF that 392g (1.0mol) rectifying obtains
3cF
2cF
2cF
2cH
2cFHI, in three-necked flask, according to the reaction conditions of embodiment 1, obtains the product 217.83g that boiling range is 54 ~ 55 DEG C, passes through
1h,
13c,
19the NMR of F analyzes and determines that structure is CF
3cF
2cF
2cF
2cH=CFH is 82.51% by calculated yield, and the total recovery of two-step reaction is 70.24%.
Embodiment 5
1) addition reaction
According to the reaction conditions of embodiment 1, remove 700g (2.0mol) CF
3cF
2cF
2cF
2i changes 592g (2.0mol) perfluoro propyl iodine (CF into
3cF
2cF
2i), other conditions are constant, obtain reaction solution by 97.7%CF
3cF
2cF
2cH
2cF
2i and 2.1% unreacted raw material CF
3cF
2cF
2i forms.By rectifying under the pressure of 1KPa, collect the cut of 59 ~ 60 DEG C, weighing quality is 665.82g, by CF
3cF
2cF
2i calculated yield is 92.50%.
2) eliminative reaction
Get the adduct CF that 360g (1.0mol) rectifying obtains
3cF
2cF
2cH
2cF
2i, in three-necked flask, according to the reaction conditions of embodiment 1, obtains the product 215.99g that boiling range is 49 ~ 50 DEG C, passes through
1h,
13c,
19the NMR of F analyzes and determines that structure is CF
3cF
2cF
2cF
2cF=CF
2, be 93.10% by calculated yield, the total recovery of two-step reaction is 86.12%.
As seen from the above embodiment, use present method synthesis long chain fluorine-containing alkene, on the one hand, the simple environmental protection of synthesis step, easy handling.On the other hand, in synthesized material, C-H content is less, has higher copolymerizable, is the good material of carrying out polyreaction further.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (1)
1. a preparation method for long chain fluorine-containing alkene, is characterized in that, comprises the steps:
1) addition reaction
In the reactor containing perfluoroalkyl iodides, radical initiator, pass into gaseous fluorinated monomer continuously, carry out addition reaction by Bubbling method, after reaction terminates, by reaction solution by rectification under vacuum, obtain adduct;
2) eliminative reaction
By described adduct cancellation HI in the basic conditions, rectifying, obtains long chain fluorine-containing alkene;
Wherein, the general formula of described perfluoroalkyl iodides is R
fi; Wherein atomic iodine I is at the end of carbochain, R
ffor the perfluorinated alkyl group of carbonatoms between 2-8;
The general formula of described gaseous fluorinated monomer is X
ax
bc=CX
cx
d, wherein, X
a, X
b, X
c, X
dindependently be expressed as halogen atom, hydrogen atom, wherein at least one is F atom;
Described radical initiator is organic superoxide; Described radical initiator is in every 100 molar part perfluoroalkyl iodides, and consumption is 0.01-0.5 part;
The alkaline reagents that described alkaline condition uses is selected from NaOH, KOH, CH
3oNa, C
2h
5oNa, C
4h
9oNa; Described alkaline reagents is in 100 molar part adducts, and the consumption of alkaline reagents is 100-120 part;
Described addition reaction condition: temperature-30 ~ 50 DEG C, before and after reactor, the pressure reduction of fluorochemical monomer is 0.1-1.0MPa;
Described elimination reaction condition is: temperature 40 ~ 80 DEG C.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001081464A1 (en) * | 2000-04-19 | 2001-11-01 | Dupont Dow Elastomers L.L.C. | Fluoroelastomer composition having excellent processability |
WO2013157456A1 (en) * | 2012-04-19 | 2013-10-24 | ダイキン工業株式会社 | Method for utilizing fluoroalkyl iodide |
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2014
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WO2001081464A1 (en) * | 2000-04-19 | 2001-11-01 | Dupont Dow Elastomers L.L.C. | Fluoroelastomer composition having excellent processability |
WO2013157456A1 (en) * | 2012-04-19 | 2013-10-24 | ダイキン工業株式会社 | Method for utilizing fluoroalkyl iodide |
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