CN109734552A - The controllable polymerization method and device of hexafluoropropylene trimer - Google Patents
The controllable polymerization method and device of hexafluoropropylene trimer Download PDFInfo
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- CN109734552A CN109734552A CN201811459912.XA CN201811459912A CN109734552A CN 109734552 A CN109734552 A CN 109734552A CN 201811459912 A CN201811459912 A CN 201811459912A CN 109734552 A CN109734552 A CN 109734552A
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Abstract
The invention belongs to fluorine chemical fields, and in particular to a kind of controllable polymerization method and device of hexafluoropropylene trimer are obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene；Reaction temperature is 260-320 DEG C, time of contact 0.1s-30s；The load capacity of ionic fluorides is 10%-20%；Carrier is activated carbon, aluminum oxide, silica or magnesia；Ionic fluorides are AgF, NaF, KF, RbF or CsF.The characteristics of variation route of the invention is applicable to the enterprise of existing production fluorinated product, and realization is recycled for a long time, at low cost, remarkable in economical benefits.
Description
Technical field
The invention belongs to fluorine chemical fields, and in particular to a kind of controllable polymerization method and device of hexafluoropropylene trimer.
Background technique
It is particularly useful industrial chemicals that oligomerization of hexafluoropropylene, which obtains dimer and trimer all, can be derived many fluorine-containing
Surfactant.There is the perfluor carbochain of hexafluoropropene oligomers hydrophobic height to be branched, living with general straight chain perfluorosurf
Property agent is compared, and some special physical properties are added.It can be used alone can also make jointly with other surfaces activating agent
With so as to which in detergent, plastic paint, weaving, leather, petroleum, electronics, the fields such as pigment play unique effect.Example
Such as: the perfluoroalkyl ether that the oligomer and phenol reactant of hexafluoropropene generate reacts with oleum, can be made into sulfonate type
Fluorinated surfactant.Perfluoroalkyl ether is reacted with chlorosulfonic acid, and sulfuryl chlorio can be introduced on phenyl ring, and further reaction can be made into
Various fluorinated surfactants.Being had by the fluorine-containing surfactant that oligomerization of hexafluoropropylene derivative is prepared reduces interface table
Face tension and in the solution oriented attachment and the characteristic for forming micella, thus make its be widely applied with washing, plastics, metal,
The fields such as coating, textile, leather, household article, petroleum product, electronics industry.
Currently, hexafluoropropylene dimmer, tripolymer mainly use liquid phase method to synthesize, liquid phase method oligomerization of hexafluoropropylene technique
It is that catalyst and its additive are dissolved in aprotic polar solvent, then leads to people's hexafluoropropene and react, process can be with
It is being also possible to continuously for interval.The product of oligomerisation reaction is substantially insoluble in a solvent, after the completion of reaction, can
To form apparent two-phase, convenient separation, but in product phase, necessarily contain a small amount of solvent and catalyst, therefore carries out product
Before rectifying, it is necessary to be washed, to remove solvent and catalyst.The solvent that washing removes can not generally recycle, wherein being catalyzed
The recycling of agent is also very difficult.
The preparation method of hexafluoropropylene dimmer also includes vapor phase method: usually catalyst being loaded in tubular reactor, gas
The hexafluoropropene of state carries out successive reaction by catalyst layer.The post-processing of reaction is to condense reaction gas directly to carry out rectifying.
Catalyst used in gas phase polymerization technique is the fluoride of alkali metal, mainly the CsF to be adsorbed on activated carbon or nickel oxide
Or KF is catalyst, or directly makees catalyst with activated carbon, and the gas of hexafluoropropene is passed through at 410~420 DEG C of temperature
Product is obtained in heat-resistant tube equipped with activated carbon granule.
Vapor phase method and liquid phase method have his own strong points.Vapor phase method high degree of automation, convenient post-treatment are suitable for extensive life
It produces, but conversion per pass is lower, equipment investment is larger.Conversion ratio of liquid phase method and yield are higher, by adjusting technological parameter
Have preferable selectivity, the requirement to reaction controlling is lower than vapor phase method, pilot plant small investment, but to raw material, catalyst,
Solvent requirement is anhydrous, post-processes more cumbersome.
Summary of the invention
It is an object of the invention to overcome in the prior art, a kind of the controllable poly- of hexafluoropropylene trimer is provided
Close method and device.
To achieve the above object, the technical solution adopted by the present invention are as follows:
Hexafluoropropylene trimer is obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene；Reaction
Temperature is 260-320 DEG C, time of contact 0.1s-30s；The load capacity of support type ionic fluorides is 10%-20%；Carrier
For activated carbon, aluminum oxide, silica or magnesia；Ionic fluorides are AgF, NaF, KF, RbF or CsF.
Hexafluoropropylene trimer is obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene；Reaction
Temperature is 300 DEG C, time of contact 10s；The load capacity of support type ionic fluorides is 15%；Carrier is activated carbon, three oxidations
Two aluminium, silica or magnesia；Ionic fluorides are AgF, NaF or KF.
The invention also includes a kind of devices of controllable polymerization for the hexafluoropropylene trimer, including sequentially connect
Hexafluoropropene air accumulator, catalytic reaction tube, condenser and the product fluid reservoir connect；The hexafluoropropene air accumulator and institute
The bottom for the catalytic reaction tube stated is connected to, the gas access at the top of the catalytic reaction tube and the condenser side
Connection；
The condenser external is provided with condensation collet；Heating mantle is provided with outside the catalytic reaction tube；It is described
Condenser lower end condensed fluid outlet be connected to the product fluid reservoir.The condenser is passed through 10 DEG C cold
Condensate, the heating temperature of catalytic reaction tube are 260-320 DEG C.
The gas vent of the upper end of the condenser is connected to for hexafluoropropene with the bottom of the catalytic reaction tube
Recycling.
Compared with prior art, the beneficial effects of the present invention are:
Hexafluoropropylene trimer produced by the invention, can by controlling reaction condition using hexafluoropropene gas as raw material
With the hexafluoropropylene trimer that obtains of high yield, controllability is strong；Meanwhile the present invention also provides a kind of production hexafluoropropene trimerizations
The device of body separates product and raw material hexafluoropropene that condenser condenses, and the hexafluoropropene after separation, which returns to, urges
Change reaction tube to continue to participate in reaction, realization is applied, and promotes the utilization rate of hexafluoropropene gas greatly.New road of the invention
Line is applicable to the enterprise of existing production fluorinated product, and realization is recycled for a long time, at low cost, the spy of remarkable in economical benefits
Point.
Detailed description of the invention
Fig. 1 is the device of the invention structural schematic diagram.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, with reference to the accompanying drawing and
The present invention is described in further detail for most preferred embodiment.
Fig. 1 shows a kind of device of controllable polymerization for the hexafluoropropylene trimer, and six including sequential connection
Fluoropropene air accumulator 1, catalytic reaction tube 2, condenser 3 and product fluid reservoir 5；The hexafluoropropene air accumulator with it is described
Catalytic reaction tube bottom connection, the gas access of the top of the catalytic reaction tube and the condenser side connects
It is logical；The condensed fluid outlet of the lower end of the condenser 4 is connected to the product fluid reservoir.The condenser is passed through
10 DEG C of condensed water, the heating temperature of catalytic reaction tube are 260-320 DEG C.The gas vent of the upper end of the condenser with
The bottom connection of the catalytic reaction tube is recycled for hexafluoropropene.
Embodiment 1: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being catalyzed equipped with NaF/Al2O3
The catalytic reaction tube of agent, the load capacity of catalyst are 10%, and the temperature of catalyst reaction tube is 260 DEG C, and time of contact is
0.1s；Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, not instead
The hexafluoropropene answered is recycled to catalyst reaction tube through outlet.The liquid hexafluoropropylene trimer in detection condenser
Purity is 99.3%.The yield of hexafluoropropylene trimer is shown in Table 1.
Embodiment 2: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being equipped with AgF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 15%, and the temperature of catalyst reaction tube is 300 DEG C, time of contact 10s；
Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, and unreacted six
Fluoropropene is recycled to catalyst reaction tube through outlet.The purity of liquid hexafluoropropylene trimer is in detection condenser
99.3%.The yield for applying rear hexafluoropropylene trimer is shown in Table 1.
Embodiment 3: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being equipped with KF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 20%, and the temperature of catalyst reaction tube is 320 DEG C, time of contact 30s；
Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, and unreacted six
Fluoropropene is recycled to catalyst reaction tube through outlet.The purity of liquid hexafluoropropylene trimer is in detection condenser
99.3%.The yield for applying rear hexafluoropropylene trimer is shown in Table 1.
Comparative example 1: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being catalyzed equipped with NaF/Al2O3
The catalytic reaction tube of agent, the load capacity of catalyst are 10%, and the temperature of catalyst filling column is 150 DEG C, and time of contact is
0.1s；Mixed gas after reaction enters the condenser with cooling jacket by port entrance, and condensate temperature is 10 DEG C, not
The hexafluoropropene of reaction is recycled to catalytic reaction tube through gas vent.The liquid hexafluoropropene two in detection condenser receiver
The purity of aggressiveness is 99.3%.The yield of hexafluoropropylene dimmer is shown in Table 1.
Comparative example 2: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being equipped with AgF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 15%, and the temperature of catalyst filling column is 180 DEG C, time of contact 10s；Reaction
Mixed gas afterwards enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, unreacted hexafluoro third
Alkene is recycled to catalytic reaction tube column through outlet.The purity of liquid hexafluoropropylene dimmer is 99.2% in detection condenser.Set
1 is shown in Table with the yield of rear hexafluoropropylene dimmer.
Comparative example 3: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being equipped with KF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 20%, and the temperature of catalyst filling column is 220 DEG C, time of contact 30s；Reaction
Mixed gas afterwards enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, unreacted hexafluoro third
Alkene is recycled to catalytic reaction tube through outlet.The purity of liquid hexafluoropropylene dimmer is 99.3% in detection condenser.It applies
The yield of hexafluoropropylene dimmer is shown in Table 1 afterwards.
Table 1
| Serial number | T(℃) | Trimer (%) | Dimer (%) | COF2 (%) | HFP single transformation rate (%) |
| Comparative example 1 | 150 | 3 | 95 | 2 | 60 |
| Comparative example 2 | 180 | 3 | 95 | 2 | 80 |
| Comparative example 3 | 200 | 14 | 85 | 2 | 95 |
| Embodiment 1 | 260 | 90 | 8 | 2 | 95 |
| Embodiment 2 | 300 | 95 | 3 | 2 | 97 |
| Embodiment 3 | 320 | 90 | 5 | 5 | 98 |
Variation route of the invention is applicable to the enterprise of existing production fluorinated product, and realization is recycled for a long time, cost
It is low, the characteristics of remarkable in economical benefits.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (4)
1. the controllable polymerization method of hexafluoropropylene trimer according to claim 1, which is characterized in that hexafluoropropene trimerization
Body is obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene；Reaction temperature is 260-320 DEG C；When contact
Between be 0.1s-30s；The load capacity of support type ionic fluorides is 10%-20%；Carrier is activated carbon, aluminum oxide, dioxy
SiClx or magnesia；Ionic fluorides are AgF, NaF, KF, RbF or CsF.
2. the controllable polymerization method of hexafluoropropylene trimer described in claim 1, which is characterized in that hexafluoropropylene trimer by
Hexafluoropropene obtains under the catalysis of support type ionic fluorides through gas phase reaction；Reaction temperature is 300 DEG C；Time of contact is 10s；
The load capacity of support type ionic fluorides is 15%；Carrier is activated carbon, aluminum oxide, silica or magnesia；From
Sub- fluoride is AgF, NaF or KF.
3. a kind of device of the controllable polymerization for the described in any item hexafluoropropylene trimers of claim 1-2, feature exist
In hexafluoropropene air accumulator, catalytic reaction tube, condenser and product fluid reservoir including sequential connection；The hexafluoro third
Alkene air accumulator is connected to the bottom of the catalytic reaction tube, the top of the catalytic reaction tube and the condenser side
Gas access connection；The condensed fluid outlet of the lower end of the condenser is connected to the product fluid reservoir.
4. the device of the controllable polymerization according to claim 3 for hexafluoropropylene trimer, which is characterized in that described
The gas vent of the upper end of condenser is connected to the bottom of the catalytic reaction tube to be recycled for hexafluoropropene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110577460A (en) * | 2019-09-24 | 2019-12-17 | 浙江诺亚氟化工有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4296265A (en) * | 1979-07-19 | 1981-10-20 | Daikin Kogyo Co., Ltd. | Process for preparing hexafluoropropene oligomers |
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2018
- 2018-11-30 CN CN201811459912.XA patent/CN109734552A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4296265A (en) * | 1979-07-19 | 1981-10-20 | Daikin Kogyo Co., Ltd. | Process for preparing hexafluoropropene oligomers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110577460A (en) * | 2019-09-24 | 2019-12-17 | 浙江诺亚氟化工有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
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Application publication date: 20190510 |