CN103111253A - Method and equipment for perfluor polyether fluorination - Google Patents
Method and equipment for perfluor polyether fluorination Download PDFInfo
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- CN103111253A CN103111253A CN2013100818735A CN201310081873A CN103111253A CN 103111253 A CN103111253 A CN 103111253A CN 2013100818735 A CN2013100818735 A CN 2013100818735A CN 201310081873 A CN201310081873 A CN 201310081873A CN 103111253 A CN103111253 A CN 103111253A
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Abstract
The invention provides perfluor polyether fluorination reaction equipment which comprises a gas mixing system, a reaction kettle which is connected with the outlet of the gas mixing system, and a stirring device which is arranged inside the reaction kettle, wherein the stirring device comprises a hollow stirring rod and a hollow porous stirring paddle; the hollow porous stirring paddle is connected and communicated with the hollow stirring rod; and the hollow stirring rod is provided with an opening above the liquid level inside the reaction kettle. Due to the hollow stirring rod and the hollow porous stirring paddle, a fluridizer gas at the upper end of the liquid level of a material returns to the hollow stirring paddle through the hollow stirring rod and is further dispersed into the material through holes of the hollow stirring paddle, then the fluridizer can be repeatedly mixed and contacted with the material for multiple times, the maximum gas-liquid contact is achieved, and the utilization rate of the fluridizer is greatly improved.
Description
Technical field
The present invention relates to the PFPE technical field, relate in particular to the method and apparatus that a kind of PFPE is fluoridized.
Background technology
PFPE is a kind of water white perfluoro-polymer material.Compare with common pfpe molecule structure, PFPE has replaced c h bond with the C-F key, and the fluorine atom with strong electronegativity makes the attraction between molecule little, has less surface tension; Simultaneously the C-F key makes it have heat-resisting, resistance to oxidation, corrosion-resistant, anti-irradiation to the shielding action of main chain and the characteristic such as does not fire, and is widely used in the fields such as chemical industry, electronics, electrical equipment, machinery, nuclear industry, Aero-Space.
But the acid fluoride character of PFPE end group is comparatively active; in order to improve the stability of PFPE; just need to carry out stabilisation to its end group; at present; mainly the technology such as fluoridize by end group hydrogenation or end group the PFPE end group is carried out stabilisation; wherein fluoridizing the PFPE stability of acquisition by end group best, is therefore the major technique of the stable PFPE of industry preparation.
At present, the fluorization agent of PFPE end group fluorination technology use mainly contains AlF
3, SbF
5Or the mist of fluoro-gas and nitrogen, as F
2/ N
2Gaseous mixture wherein, uses AlF
3Or SbF
5As fluorization agent, carrying out technology that the PFPE end group fluoridizes, to have a fluorization agent expensive, the technological deficiency of product and separation of by-products difficulty; And the mist that uses fluoro-gas and nitrogen carries out the PFPE end group and fluoridizes, because the fluoro-gas activity is lower, be difficult for fully reacting with PFPE, and all there is the lower shortcoming of fluorization agent utilization rate in the fluorination reaction equipment that exists at present, therefore need a large amount of fluorization agents in fluorination process, the mol ratio of general fluoro-gas and PFPE needs to have higher conversion greater than 15 guarantee reactions, and this makes reaction cost increase, and is unfavorable for industrial production.
Summary of the invention
In view of this, the method and apparatus that provides a kind of PFPE to fluoridize is provided the technical problem to be solved in the present invention, improves the utilization rate of fluorization agent, thereby reduces the consumption of fluorization agent, utilizes less fluorization agent can make reaction have higher conversion ratio.
The invention provides a kind of PFPE fluorination reaction equipment, comprising:
Gas mixing system;
The reactor that is connected with the outlet of described gas mixing system;
Be arranged at the agitating device of reactor inside, described agitating device comprises hollow stirring rod and hollow porous paddle; Described hollow porous paddle is connected and communicates with described hollow stirring rod; Described hollow stirring rod has the opening that is positioned on the reactor liquid level.
Preferably, described hollow porous paddle comprises that upper strata four straight oars and lower floor's three leaves advance oar.
Preferably, be connected with the outlet of described gas mixing system bottom described reactor.
Preferably, described consersion unit also comprises the return tank that is connected with described reactor gas outlet.
Preferably, the liquid outlet of described return tank is connected with the reactor inlet.
Preferably, described return tank is provided with exhaust apparatus.
Preferably, be provided with check valve in described reactor and pipeline that gas mixing system is connected.
Preferably, described gas mixing system comprises the gas blending tank of two series connection.
The present invention also provides a kind of and has adopted above-mentioned consersion unit to carry out the method that PFPE is fluoridized, and it is characterized in that, comprising:
PFPE is added in reactor, and reactor is vacuumized; Pass in reactor after fluoro-gas is mixed in gas mixing system with nitrogen, open agitating device, carry out fluorination reaction, the PFPE that obtains fluoridizing.
Preferably, in the mist of described fluoro-gas and nitrogen, the mol ratio of described fluoro-gas and PFPE is 1～12:1.
Preferably, described fluoro-gas is selected from F
2, SF
4, SF
6And BF
3In any one or a few.
Preferably, the temperature of described fluorination reaction is 100 ℃～300 ℃.
The invention provides a kind of PFPE fluorination reaction equipment, comprising: gas mixing system; The reactor that is connected with the outlet of described gas mixing system; Be arranged at the agitating device of reactor inside, described agitating device comprises hollow stirring rod and hollow porous paddle; Described hollow porous paddle is connected and communicates with described hollow stirring rod; Described hollow stirring rod has the opening that is positioned on the reactor liquid level.Wherein, hollow stirring rod and hollow porous paddle can make the fluorization agent gas of material liquid surface upper end get back in hollow paddle by hollow stirring rod, pore by hollow paddle is dispersed in material again again, fluorization agent gas can repeatedly be contacted with mixing of materials repeatedly, reach gas-liquid contact and maximize, larger raising the utilization rate of fluorization agent.
Utilize PFPE fluorination reaction equipment provided by the invention to carry out the PFPE fluorination reaction, due to the utilization rate that has improved fluorization agent, therefore utilize less fluorization agent can make reaction have higher conversion ratio, experimental result shows, in the present invention, the mol ratio of fluoro-gas and PFPE is no more than 12:1, and the conversion ratio of PFPE can reach 100%.
Description of drawings
Fig. 1 is PFPE fluorination reaction equipment structure chart provided by the invention;
Fig. 2 is in PFPE fluorination reaction equipment provided by the invention, the inside top view of reactor.
The specific embodiment
The invention provides a kind of PFPE fluorination reaction equipment, comprising:
Gas mixing system;
The reactor that is connected with the outlet of described gas mixing system;
Be arranged at the agitating device of reactor inside, described agitating device comprises hollow stirring rod and hollow porous paddle; Described hollow porous paddle is connected and communicates with described hollow stirring rod; Described hollow stirring rod has the opening that is positioned on the reactor liquid level.
Wherein, hollow stirring rod and hollow porous paddle can make the fluorization agent gas of material liquid surface upper end get back in hollow paddle by hollow stirring rod, pore by hollow paddle is dispersed in material again again, fluorization agent gas can repeatedly be contacted with mixing of materials repeatedly, reach gas-liquid contact and maximize, larger raising the utilization rate of fluorization agent; In addition, the mode by air inlet at the bottom of still makes fluorization agent enter reactor from the bottom, reacts with material, makes reaction without dead material district, and has increased the time of contact of fluorization agent gas and material, has improved the utilization rate of fluorization agent.
Referring to Fig. 1, Fig. 1 is PFPE fluorination reaction equipment structure chart provided by the invention, wherein, 1 is gas mixer, and 2 is the fluoro-gas air accumulator, and 3 is the nitrogen storage gas tank, 4 is flowmeter, and 5 is device for pressure measurement, and 6 is reactor, 7 is gas valve, and 8 is check valve, and 9 is baiting valve, 10 is hollow stirring rod, 11 is hollow porous paddle, and 12 is return tank, and 13 is counterbalance valve; 14 is gas valve, and 15 is gas vent.
Fluorination reaction equipment provided by the present invention comprises gas mixing system, and the effect of gas mixing system is fluorization agent gas is mixed, and plays cushioning effect, makes the conveying of gas comparatively stable.In the present embodiment, gas mixing system comprises gas mixer 1, and it can be gas mixer well known to those skilled in the art, is preferably the gas blending tank.In the present invention, described gas mixer preferably includes the gas blending tank of two series connection.Described gas mixing system can also comprise caisson, described caisson can be caisson well known to those skilled in the art, preferably, comprise fluoro-gas air accumulator 2 and nitrogen storage gas tank 3, the outlet of described fluoro-gas air accumulator and nitrogen storage gas tank is connected with the entrance of described gas blending tank respectively, two interior gases of air accumulator enter blending tank, can be used as fluorization agent after fully mixing and use.In other embodiments, be provided with flowmeter 4 between described caisson and gas mixer, be used for the accurate quantitative analysis gas volume; Described gas blending tank is provided with device for pressure measurement 5, is used for measurement gas blending tank internal pressure value.
The effect of reactor 6 is to provide reacting environment for PFPE carries out fluorination reaction, and its air inlet is connected with the gas outlet of described gas mixing system.For fluorization agent gas is fully contacted with material, the air inlet of described reactor is arranged at its bottom, and namely the gas outlet of described gas mixing system is connected with the bottom of described reactor.At this moment, mist enters reactor from the bottom, reacts with material, and at the bottom of still, the mode of air inlet makes reaction without dead material district, and has increased the time of contact of fluorization agent gas and material, has improved the utilization rate of fluorization agent; Simultaneously, the mode of air inlet at the bottom of still has been avoided pipeline is stretched into from the reactor top gas bottom and has been supplied gas, and pipeline easily and the shortcoming that bumps of agitating device.In other embodiments of the invention, described reactor bottom also is provided with bubbling device, and gas enters reactor by the mode of bubbling from the bottom, to improve the contact area of gas and material.
In other embodiments of the invention, can also be provided with gas valve 7 between described gas mixing system and reactor, be used for controlling the mist flow velocity; Can also be provided with check valve 8 between described gas mixing system and reactor, be used for avoiding back flow of gas.Described reactor bottom also is provided with baiting valve 9, described baiting valve is connected with the air inlet pipeline of reactor bottom, when reaction is in air-suction state, to close described baiting valve and keep system airtight, gas enters reactor and reacts, after reaction finishes, close the gas trap in gas piping, make mist stop passing into, open simultaneously baiting valve, emit product, the check valve in gas piping can effectively prevent driving in the wrong direction of gas.
In other embodiments, be provided with exhaust apparatus in reactor provided by the present invention, make reactor to communicate with ambient atmosphere; Preferably, be provided with gas valve on described exhaust apparatus, be used for controlling the still internal gas pressure.
Be provided with agitating device in described reactor, referring to Fig. 2, Fig. 2 is in PFPE fluorination reaction equipment provided by the invention, the inside top view of reactor, and wherein, 6 is reactor, and 11 is hollow porous paddle, and 16 is the top end opening of hollow stirring rod.
Described agitating device comprises hollow stirring rod 10 and hollow porous paddle 11, described hollow stirring rod has the opening 16 that is positioned on the reactor liquid level, make that the gas on liquid level can enter in reactor, this opening is preferably placed at the hollow stirring rod top, and namely hollow stirring rod is through-hole structure; Described hollow porous paddle is connected and communicates with described hollow stirring rod, and the gas in hollow stirring rod can be entered in hollow porous paddle; In the present invention, described hollow stirring rod can connect one group of paddle, also can connect many group paddles, and the present invention there is no specific (special) requirements to this, can decide according to reactor volume, and the present invention preferably arranges two groups of hollow porous paddles; More preferably four straight oars are adopted on the upper strata, and lower floor adopts three leaves to advance oar, and two groups of paddle actings in conjunction make the more even of reactant liquor dispersion; The present invention all without particular restriction, can be the general shape well known to those skilled in the art such as circular, square, oval to the shape of pore on described blade, quantity, size; The present invention to the diameter of described blade also without specific (special) requirements, can be according to the reactor size adjustment; The present invention there is no particular restriction to the connected mode of described hollow stirring rod and hollow porous paddle, can be general welding, only puddler and paddle is communicated, and makes gas enter paddle by puddler and gets final product.In the present invention, described hollow stirring rod and hollow porous paddle can make the fluorization agent gas of material liquid surface upper end get back in hollow paddle by hollow stirring rod, pore by hollow paddle is dispersed in material again again, fluorization agent gas can repeatedly be contacted with mixing of materials repeatedly, reach gas-liquid contact and maximize, larger raising the utilization rate of fluorization agent.The diameter of propeller blade of described hollow porous paddle can be according to the size adjustment of reactor, and the present invention is to this and indefinite.
Described fluorination reaction equipment also comprises return tank 12, and it can make the fluorization agent recycling, and described return tank 12 is connected with the gas outlet of reactor; The liquid outlet of described return tank is connected with the reactor inlet, makes condensed liquid can enter reactor and again reacts with PFPE; Preferably, described return tank is provided with exhaust apparatus, is used for gas is discharged; Described exhaust apparatus also comprises counterbalance valve 13, is used for the gas in return tank is discharged through counterbalance valve.Described exhaust apparatus preferably communicates with the exhaust apparatus of reactor, and gas can be discharged by gas outlet 15 simultaneously.
In a specific embodiment of the present invention, connecting line between described each device is the 316L stainless steel, agitating device in described reactor and reactor is the MONEL alloy, and described return tank is Hastelloy, and special substance makes the corrosion resistance of consersion unit greatly improve.
PFPE provided by the invention is fluoridized device and is used in accordance with the following methods:
Open caisson 2,3, fluoro-gas and N
2After gas process flowmeter 4 accurate quantitative analysis, fully mix in gas blending tank 1 by a certain percentage, form fluorization agent gas, described fluorization agent gas enters reactor by pipeline and PFPE carries out fluorination reaction.
The present invention also provides a kind of and has adopted above-mentioned consersion unit to carry out the method that PFPE is fluoridized, and comprising:
PFPE is added in reactor, and reactor is vacuumized; Pass in reactor after fluoro-gas is mixed in gas mixing system with nitrogen, open agitating device, carry out fluorination reaction, the PFPE after being fluoridized.
At first PFPE is added in described reactor, the off-response still, and reactor is vacuumized; Then reactor is heated, the temperature of described heating is preferably 100 ℃～300 ℃, more preferably 150 ℃～250 ℃; Open simultaneously N
2The valve of the valve of air accumulator and fluoro-gas air accumulator makes gas pass into gas by flowmeter in the gas blending tank, makes fluoro-gas and N
2Mix according to the volume ratio of 1:2～6, when the pressure of tank to be mixed is 0.1MPa～2MPa, stop ventilation; When question response still temperature reaches target temperature, with fluoro-gas and N
2Mist pass in reactor, open agitating device, carry out fluorination reaction; In the present invention, described fluoro-gas is preferably F
2, SF
4And SF
6In any one, F more preferably
2Described fluoro-gas and N
2Mist in, the mol ratio of fluoro-gas and described PFPE is preferably 1～12:1, more preferably 2.5～7.5:1; Described fluoro-gas and N
2Mist and the mol ratio of PFPE be preferably 1～50:1,10～30:1 more preferably; After reaction a period of time, open return tank and reflux; Material sampled and detected by infrared spectrum, after reaction finishes, temperature of reaction kettle is down to room temperature (25 ℃), opening the baiting valve blowing at the bottom of still, the PFPE product after being fluoridized.Preferably, before reacting, consersion unit is carried out drying, the present invention there is no specific (special) requirements to the mode of described drying, can be the mode of dry reaction equipment well known to those skilled in the art, as heat drying or with N
2Purge and all can.
Prepare fluoridize after the PFPE product have the structure shown in formula (I):
Wherein, 5≤n≤60.
Detect by nuclear-magnetism, according to F atomic features peak, the conversion ratio of PFPE is detected, experimental result shows, in the present invention, the mol ratio of fluoro-gas and PFPE is no more than 12:1, and the conversion ratio of PFPE can reach 100%.
The invention provides a kind of PFPE fluorination reaction equipment, comprising: gas mixing system; The reactor that is connected with the outlet of described gas mixing system; Be arranged at the agitating device of reactor inside, described agitating device comprises hollow stirring rod and hollow porous paddle; Described hollow porous paddle is connected and communicates with described hollow stirring rod; Described hollow stirring rod has the opening that is positioned on the reactor liquid level.Wherein, hollow stirring rod and hollow porous paddle can make the fluorization agent gas of material liquid surface upper end get back in hollow paddle by hollow stirring rod, pore by hollow paddle is dispersed in material again again, fluorization agent gas can repeatedly be contacted with mixing of materials repeatedly, reach gas-liquid contact and maximize, larger raising the utilization rate of fluorization agent; In addition, the mode by air inlet at the bottom of still makes fluorization agent enter reactor from the bottom, reacts with material, makes reaction without dead material district, and has increased the time of contact of fluorization agent gas and material, has improved the utilization rate of fluorization agent.
In order to further illustrate the present invention, the method and apparatus of PFPE provided by the invention being fluoridized below in conjunction with embodiment is described in detail.
Embodiment 1
The fluorination reaction device structure is seen accompanying drawing 1, and accompanying drawing 1 is the structure chart of fluorination reaction equipment provided by the invention, and described consersion unit comprises: the gas blending tank 1 of two series connection; Fluorine gas air accumulator 2, nitrogen storage gas tank 3, its outlet is connected with the air inlet of gas blending tank respectively; The reactor 6 that the bottom is connected with gas blending tank gas outlet; Be arranged at the agitating device of reactor inside, comprise hollow stirring rod 10 and hollow porous paddle 11, described hollow stirring rod has the opening that is positioned on the reactor liquid level, and described hollow porous paddle is connected and communicates with described hollow stirring rod; Described reactor volume is 0.5L, and described hollow porous paddle is the individual layer paddle, and blade is four straight leaf formulas, and diameter of stirring paddle 5cm has the hollow pore of 3 circles, diameter 2mm on each blade; The return tank 12 that is connected with the reactor gas outlet, the liquid outlet of described return tank is connected with the inlet of reactor.
Described fluorine gas air accumulator, nitrogen storage gas tank, gas blending tank and the pipeline that is attached thereto are the 316L stainless steel, and the agitating device in described reactor and reactor is the MONEL alloy, and described return tank is Hastelloy.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 160mL/min, F
2The speed of gas 40mL/min, the 6h that ventilates under 100 ℃ opens return tank, then with identical gas speed, the 12h that ventilates under 150 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens bleeder valve, and blowing obtains product 505g, and productive rate is 97.5%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 83.2%.
Embodiment 2
Fluorination reaction equipment comprise air accumulator, two series connection gas blending tank, reactor, be arranged at the agitating device of reactor inside, comprise hollow stirring rod and hollow porous paddle.Wherein reactor volume is 0.5L; Hollow porous paddle is two-layer paddle, and lower floor is that three leaves advance the oar formulas, and diameter of stirring paddle 5cm has the hollow pore of 3 circles, diameter 2mm on each blade; The upper strata is four straight oar formulas, and diameter of stirring paddle 6cm has the hollow pore of 3 circles, diameter 2mm on each blade.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 160mL/min, F
2The speed of gas 40mL/min, the 6h that ventilates under 100 ℃, then with identical gas speed, the 12h that ventilates under 150 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 505g, and productive rate is 97.5%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 90.9%.
Embodiment 3
Fluorination reaction equipment comprises that air accumulator, two gas blending tanks, bottoms mix tank connected reactor, be arranged at the agitating device of reactor inside with gas, comprises hollow stirring rod and hollow porous paddle; The reactor gas outlet is connected with return tank, and the liquid outlet of described return tank is connected with the inlet of reactor; Described return tank is provided with exhaust apparatus, and described exhaust apparatus is provided with gas trap and counterbalance valve.Described Polycondensation Reactor and Esterification Reactor is provided with bubbling device.Wherein reactor volume is 0.5L; Hollow porous paddle is two-layer paddle, and lower floor is that three leaves advance the oar formulas, and diameter of stirring paddle 5cm has the hollow pore of 3 circles, diameter 2mm on each blade; The upper strata is four straight oar formulas, and diameter of stirring paddle 6cm has the hollow pore of 3 circles, diameter 2mm on each blade.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0.5MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 160mL/min, F
2The speed of gas 40mL/min, the 6h that ventilates under 150 ℃ opens return tank, then with identical gas speed, the 12h that ventilates under 180 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 501g, and productive rate is 96.7%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 98.5%.
Embodiment 4
The fluorination reaction equipment that adopts embodiment 3 to provide carries out fluorination reaction.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0.5MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and SF
4Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 160mL/min, SF
4The speed of gas 40mL/min, the 6h that ventilates under 150 ℃ opens return tank, then with identical gas speed, the 12h that ventilates under 180 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 501g, and productive rate is 96.7%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 93.5%.
Embodiment 5
The fluorination reaction equipment that adopts embodiment 3 to provide carries out fluorination reaction.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0.5MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 160mL/min, F
2The speed of gas 40mL/min, the 6h that ventilates under 185 ℃ opens return tank, then with identical gas speed, the 12h that ventilates under 210 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 498g, and productive rate is 94.3%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 94.5%.
The fluorination reaction equipment that adopts embodiment 3 to provide carries out fluorination reaction.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0.5MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 160mL/min, F
2The speed of gas 40mL/min, the 12h that ventilates under 150 ℃ opens return tank, then with identical gas speed, the 6h that ventilates under 185 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 508g, and productive rate is 98.1%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 99.2%.
Embodiment 7
The fluorination reaction equipment that adopts embodiment 3 to provide carries out fluorination reaction.
Add the 518g PFPE in reactor, the mean value of its n is 10.5, and the pressure of gas reactor is 0.5MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 120mL/min, F
2The speed of gas 30mL/min, the 16h that ventilates under 150 ℃ opens return tank, then with identical gas speed, the 8h that ventilates under 185 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 495g, and productive rate is 95.5%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 100%.
Embodiment 8
Fluorination reaction equipment comprises air accumulator, two gas blending tanks, reactors, is arranged at the agitating device of reactor inside, comprises hollow stirring rod and hollow porous paddle; The reactor gas outlet is connected with return tank, and the liquid outlet of described return tank is connected with the inlet of reactor; Described return tank is provided with exhaust apparatus, and described exhaust apparatus is provided with counterbalance valve; Described reactor is provided with exhaust apparatus, and described exhaust apparatus is provided with gas trap.Wherein reactor volume is 2L; Hollow porous paddle is two-layer paddle, and lower floor is that three leaves advance the oar formulas, and diameter of stirring paddle 8cm has the hollow pore of 5 circles, diameter 3mm on each blade; The upper strata is four straight oar formulas, and diameter of stirring paddle 10cm has the hollow pore of 4 circles, diameter 3mm on each blade.
Add the 2500g PFPE in reactor, the mean value of its n is 38.2, and the pressure of gas reactor is 0.5MPa, and opens agitating device; Open the air accumulator valve, make N
2Gas and F
2Then gas enter reactor by Bubbling method at the bottom of still and react, at first with N through the gas blending tank
2Gas 120mL/min, F
2The speed of gas 30mL/min, the 20h that ventilates under 100 ℃ opens return tank, then with identical gas speed, the 10h that ventilates under 185 ℃, by the infrared spectroscopy monitor reaction process, reaction passes into N after finishing in reactor
2Gas carries out cooling down to reaction system, opens baiting valve, and blowing obtains product 2485g, and productive rate is 99.4%.Detect by nuclear-magnetism, according to F atomic features peak, the PFPE conversion ratio is detected, result shows that the conversion ratio of PFPE is 100%.
By above-described embodiment as can be known, fluorination reaction equipment provided by the invention, employing comprises the mixing plant of hollow stirring rod and hollow porous paddle, realized repeatedly recycling of fluorization agent gas, and adopted the mode of air inlet at the bottom of still, adopted counterbalance valve that reaction is under setting pressure, carried out fluorination reaction, improve the utilization rate of fluorization agent, used less fluorization agent can make PFPE have higher conversion ratio.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (12)
1. PFPE fluorination reaction equipment comprises:
Gas mixing system;
The reactor that is connected with the outlet of described gas mixing system;
Be arranged at the agitating device of reactor inside, described agitating device comprises hollow stirring rod and hollow porous paddle; Described hollow porous paddle is connected and communicates with described hollow stirring rod; Described hollow stirring rod has the opening that is positioned on the reactor liquid level.
2. consersion unit according to claim 1, is characterized in that, described hollow porous paddle comprises that upper strata four straight oars and lower floor's three leaves advance oar.
3. consersion unit according to claim 1, is characterized in that, described reactor bottom is connected with the outlet of described gas mixing system.
4. consersion unit according to claim 1, is characterized in that, also comprises the return tank that is connected with described reactor gas outlet.
5. consersion unit according to claim 4, is characterized in that, the liquid outlet of described return tank is connected with the reactor inlet.
6. consersion unit according to claim 4, is characterized in that, described return tank is provided with exhaust apparatus.
7. consersion unit according to claim 1, is characterized in that, is provided with check valve in described reactor and pipeline that gas mixing system is connected.
8. consersion unit according to claim 1, is characterized in that, described gas mixing system comprises the gas blending tank of two series connection.
9. one kind is adopted the described consersion unit of claim 1～8 any one to carry out the method that PFPE is fluoridized, and it is characterized in that, comprising:
PFPE is added in reactor, and reactor is vacuumized; Pass in reactor after fluoro-gas is mixed in gas mixing system with nitrogen, open agitating device, carry out fluorination reaction, the PFPE that obtains fluoridizing.
10. method according to claim 9, is characterized in that, in the mist of described fluoro-gas and nitrogen, the mol ratio of described fluoro-gas and PFPE is 1～12:1.
11. method according to claim 9 is characterized in that, described fluoro-gas is selected from F
2, SF
4, SF
6And BF
3In any one or a few.
12. method according to claim 9 is characterized in that, the temperature of described fluorination reaction is 100 ℃～300 ℃.
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| CN201310081873.5A Active CN103111253B (en) | 2013-03-14 | 2013-03-14 | The method and apparatus that PFPE is fluoridized |
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| CN106311097A (en) * | 2016-09-06 | 2017-01-11 | 天津长芦新材料研究院有限公司 | Application of gas-liquid contact reaction device to fluorination of perfluoropolyether acid |
| CN106397761A (en) * | 2016-09-06 | 2017-02-15 | 天津长芦新材料研究院有限公司 | Fluorination method for end groups of perfluoropolyether acid |
| CN106633023A (en) * | 2016-11-25 | 2017-05-10 | 江苏梅兰化工有限公司 | Preparation method of perfluoropolyether |
| CN110054768A (en) * | 2019-05-30 | 2019-07-26 | 上海欧勒奋生物科技有限公司 | A method of improving out-phase contacting efficiency |
| CN110092901A (en) * | 2019-05-30 | 2019-08-06 | 上海欧勒奋生物科技有限公司 | A kind of flaorination process of perfluoropolyether unstable end-group |
| CN110183643A (en) * | 2019-05-30 | 2019-08-30 | 上海欧勒奋生物科技有限公司 | A kind of fluorinated systems of perfluoropolyether unstable end-group |
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| CN106311097A (en) * | 2016-09-06 | 2017-01-11 | 天津长芦新材料研究院有限公司 | Application of gas-liquid contact reaction device to fluorination of perfluoropolyether acid |
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| CN110092901A (en) * | 2019-05-30 | 2019-08-06 | 上海欧勒奋生物科技有限公司 | A kind of flaorination process of perfluoropolyether unstable end-group |
| CN110183643A (en) * | 2019-05-30 | 2019-08-30 | 上海欧勒奋生物科技有限公司 | A kind of fluorinated systems of perfluoropolyether unstable end-group |
| CN110092901B (en) * | 2019-05-30 | 2021-11-19 | 上海欧勒奋生物科技有限公司 | Fluorination process of unstable end group of perfluoropolyether |
| CN110183643B (en) * | 2019-05-30 | 2021-12-14 | 上海欧勒奋生物科技有限公司 | Fluorination system of unstable terminal group of perfluoropolyether |
| CN110054768B (en) * | 2019-05-30 | 2022-01-04 | 上海欧勒奋生物科技有限公司 | Method for improving heterogeneous contact efficiency |
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