CN107649112B - A kind of catalyst produced for fluoro phosphonitrile and its derivatives industry metaplasia - Google Patents
A kind of catalyst produced for fluoro phosphonitrile and its derivatives industry metaplasia Download PDFInfo
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- CN107649112B CN107649112B CN201710874578.3A CN201710874578A CN107649112B CN 107649112 B CN107649112 B CN 107649112B CN 201710874578 A CN201710874578 A CN 201710874578A CN 107649112 B CN107649112 B CN 107649112B
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- phosphonitrile
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- -1 fluoro phosphonitrile Chemical compound 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 206010054949 Metaplasia Diseases 0.000 title abstract description 8
- 230000015689 metaplastic ossification Effects 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 9
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 20
- 235000013024 sodium fluoride Nutrition 0.000 claims description 18
- 239000011775 sodium fluoride Substances 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GRPIQKZLNSCFTB-UHFFFAOYSA-N n-[bis(dimethylamino)-fluoroimino-$l^{5}-phosphanyl]-n-methylmethanamine Chemical class CN(C)P(=NF)(N(C)C)N(C)C GRPIQKZLNSCFTB-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 238000003682 fluorination reaction Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 25
- 239000013078 crystal Substances 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 14
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 239000003444 phase transfer catalyst Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WCQRWCFGZARAMR-UHFFFAOYSA-N [F].[F] Chemical compound [F].[F] WCQRWCFGZARAMR-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- BTAGRXWGMYTPBY-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,4-trichlorophenyl)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1C1=CC=C(Cl)C(Cl)=C1Cl BTAGRXWGMYTPBY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst produced for fluoro phosphonitrile and its derivatives industry metaplasia, the catalyst is applied to chloro phosphonitrile and its derivative prepares the fluorination reaction of fluoro phosphonitrile and its derivative, and the catalyst is the mixture of one or more of technical grade graphene, graphene oxide, fullerene, Mxene, hydroxyl carbon nano tube, expanded graphite.It is simple using catalyst separation, increase the purity of product, can reuse, reduces the use cost of catalyst.
Description
Technical field
The present invention relates to industrialized production fluoro phosphonitrile and its derivatives, and in particular to one kind is for fluoro phosphonitrile and its spreads out
The catalyst that biological industry metaplasia produces.
Background technique
Phosphazene compound is a kind of skeleton by phosphorus and the alternately arranged inorganic-organic hybridization compound of nitrogen, can be divided into ring phosphorus
Nitrile and polyphosphazene.Wherein, chloro phosphonitrile is most representative compound in cyclic phosphazene compound, since chlorine atom has very by force
Activity, it is easy to replaced various nucleopilic reagents.Therefore, using chloro phosphonitrile as intermediate, can synthesize has with various
The fluoro phosphine nitrile and its phosphazene derivative of machine functional group.Compatibility of the chlorine atom in lithium battery electrolytes is poor, and fluoro phosphorus
Nitrile and its derivative then have good electrochemistry compatibility.
Currently, the synthesis of fluoro phosphonitrile and its derivative mainly with chloro phosphonitrile and villiaumite carry out fluorination reaction yield compared with
It is low, in order to accelerate the speed and yield of fluorination reaction, need to add catalyst into reaction system, catalyst mainly has tetramethyl
Ammonium chloride, 4 bromide, 18- crown- 6 and phosphonium bromide and polyethylene glycol etc..
Chinese patent (application number CN201610164612.3), which discloses, can greatly improve fluoro phosphonitrile and its derivative
The polyethylene glycols catalyst of yield can make fluoro phosphonitrile and its derivative yield be promoted to 99% using the catalyst.
Since fluoro phosphonitrile and its derivative then have good electrochemistry compatibility, thus present inventor uses
Polyethylene glycols catalyst optimizes the industrialized producing technology of existing fluoro phosphonitrile and its derivative, however uses poly-
Glycols catalyst is the industrialized production the problem of are as follows: and polyethylene glycols catalyst is a kind of phase transfer catalyst,
There is good dissolubility in organic solvent and water, so that there are a large amount of polyethylene glycols catalyst in product, from product
It is middle that the separation of polyethylene glycols catalyst is relatively difficult, cause product purity to reduce, both influences polyethylene glycols catalyst in work
Application in industry, and recycling and reusing can not be carried out to polyethylene glycols catalyst, if being carried out again to the product in product pure
Change, and recycle polyethylene glycols catalyst, not only needs to increase research and development cost, but also need to increase separation purifying technique,
Increase process costs.It although can be improved the yield of fluoro phosphonitrile and its derivative using polyethylene glycols catalyst, but by
It is much higher than the raising bring income of yield in its bring increased costs of the above problem.So as to cause use catalyst in industry
The bottleneck generated in the technique research and development of metaplasia production fluoro phosphonitrile and its derivative raising Business Economic Benefit.
Summary of the invention
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of for fluoro phosphonitrile and its derivative
The catalyst of object industrialized production.It is simple using catalyst separation, increase the purity of product, can reuse, reduction is urged
The use cost of agent.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of catalyst produced for fluoro phosphonitrile and its derivatives industry metaplasia, the catalyst are applied to chloro phosphonitrile
And its derivative prepares the fluorination reaction of fluoro phosphonitrile and its derivative, the catalyst is technical grade graphene, graphite oxide
The mixture of one or more of alkene, fullerene, Mxene, hydroxyl carbon nano tube, expanded graphite.
Either catalyst or the polyethylene glycol such as tetramethyl ammonium chloride, 4 bromide, 18- crown- 6 and phosphonium bromide
Class catalyst is a kind of phase transfer catalyst, and Catalysis Principles is: the fluorization agents such as potassium fluoride, sodium fluoride are inorganic matters, difficult
To be dissolved in organic solvent, and fluorization agent is carried out fluorinated being by fluorine ion on the position P to chloro phosphonitrile and its derivative
Chlorine carry out nucleophilic displacement of fluorine, phase transfer catalyst can be dissolved in organic solvent, at the same its there is also hydrophilic radicals, can be by fluorine
Fluorine ion in agent is transferred in organic solvent, thus accelerate the bombardment to P of fluorine ion, so that catalytic action is played,
Thus phase transfer catalyst thinks optimal catalytic effect to be achieved, guarantees that it in the solubility of organic solvent is the most important condition.
And according to solid catalyst, since it cannot be dissolved in organic solvent, thus it is the same without image of Buddha phase transfer catalyst, leads to
It crosses phase transfer catalyst fluorine ion is transferred to realize catalytic performance in organic solvent, so solid catalyst pair can not be used
The fluorination reaction of chloro phosphonitrile and its derivative carries out catalytic applications.
Technical grade graphene that the present invention uses, graphene oxide, fullerene, Mxene, hydroxyl carbon nano tube, expansion
Contain aerobic or hydroxyl in graphite, the affinity interaction of catalyst and solvent can be reinforced, increase contact of the catalyst with raw material
Probability, and in these catalyst contain a large amount of conjugated structure, and in phosphonitrile contain nitrogen phosphorus double bond, can in catalyst
Substance form the pi-conjugated structure of π-, enable catalyst raw material to form stronger molecular separating force, and have in itself in catalyst
Fluorine ion can directly be bombarded P by catalyst to which nucleophilic displacement of fluorine occur by electric conductivity.
Since the present invention uses graphene, graphene oxide, fullerene, Mxene, hydroxyl carbon nano tube, expanded graphite
As catalyst, organic solvent is not dissolved in, thus catalyst only may separate out by filtering after fully reacting, to improve
The purity of product.
The second object of the present invention is to provide the synthetic method of a kind of fluoro phosphonitrile and its derivative, chloro phosphonitrile is dissolved
In organic solvent, fluorization agent is added and above-mentioned catalyst is reacted, to get fluoro phosphonitrile and its derivative after filtering distillation
Object.
The third object of the present invention is to provide a kind of above-mentioned synthetic method and is preparing fluoro phosphonitrile and its derivative species battery
Application in electrolyte.
The fourth object of the present invention is to provide above-mentioned synthetic method in preparing fluoro phosphonitrile and its derivative species battery
Using.
The invention has the benefit that
1. the separation for the catalyst that the present invention uses is simple, the purity for greatly improving product can be improved, using the present invention
Catalyst the purity of product can be improved to 99%.
2. reaction condition of the present invention is mild, operability is good, is suitable for industrialization large-scale production.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
The general formula of chloro phosphonitrile and its derivative described herein is
Wherein, R1~R6It may be the same or different, being selected from is chlorine element, alkyl, chloro alkyl, chloro alcoxyl
Base, askarel, alkoxy, alkyl silicon, chloroalkene base, xenyl phenyl, chlorophenyl, alkyl phosphate, alkoxyl silicone,
Boron alkoxide or amide groups, R1~R6In at least one be chlorine element, work as R1~R6It is chloro phosphonitrile when being chlorine element.
As background technique is introduced, exists in the prior art and contain in the product for preparing fluoro phosphonitrile and its derivative
Be difficult to the deficiency of isolated catalyst, in order to solve technical problem as above, present applicant proposes one kind for fluoro phosphonitrile and
The catalyst that its derivatives industry metaplasia produces.
A kind of exemplary embodiment of the application is provided and a kind of is produced for fluoro phosphonitrile and its derivatives industry metaplasia
Catalyst, the catalyst is applied to chloro phosphonitrile and its derivative prepares the fluorination reaction of fluoro phosphonitrile and its derivative, institute
Catalyst is stated as one in technical grade graphene, graphene oxide, fullerene, Mxene, hydroxyl carbon nano tube, expanded graphite
Kind or two or more mixtures.
Either catalyst or the polyethylene glycol such as tetramethyl ammonium chloride, 4 bromide, 18- crown- 6 and phosphonium bromide
Class catalyst is a kind of phase transfer catalyst, and Catalysis Principles is: the fluorization agents such as potassium fluoride, sodium fluoride are inorganic matters, difficult
To be dissolved in organic solvent, and fluorization agent is carried out fluorinated being by fluorine ion on the position P to chloro phosphonitrile and its derivative
Chlorine carry out nucleophilic displacement of fluorine, phase transfer catalyst can be dissolved in organic solvent, at the same its there is also hydrophilic radicals, can be by fluorine
Fluorine ion in agent is transferred in organic solvent, thus accelerate the bombardment to P of fluorine ion, so that catalytic action is played,
Thus phase transfer catalyst thinks optimal catalytic effect to be achieved, guarantees that it in the solubility of organic solvent is the most important condition.
And according to solid catalyst, since it cannot be dissolved in organic solvent, thus it is the same without image of Buddha phase transfer catalyst, leads to
It crosses phase transfer catalyst fluorine ion is transferred to realize catalytic performance in organic solvent, so solid catalyst pair can not be used
The fluorination reaction of chloro phosphonitrile and its derivative carries out catalytic applications.
Since the present invention is using industry grade graphene, graphene oxide, fullerene, Mxene, hydroxyl carbon nano tube, expansion
Graphite does not dissolve in organic solvent as catalyst, thus only may separate out catalyst by filtering after fully reacting, thus
Improve the purity of product.
Another exemplary embodiment of the application provides the synthetic method of a kind of fluoro phosphonitrile and its derivative, will
Chloro phosphonitrile or fluoro phosphazene derivative are dissolved in organic solvent, and fluorization agent is added and above-mentioned catalyst is reacted, filters
To get fluoro phosphonitrile and its derivative after distillation.
In order to guarantee fully reacting, the application is preferred, and the reaction time is 1~20h.
Preferably, the reaction temperature is 30~120 DEG C.
In order to guarantee the catalytic effect of catalyst, the application is preferred, the additional amount of the catalyst be chloro phosphonitrile and
The 1~20% of 1~20% or fluoro phosphazene derivative and fluorization agent gross mass of fluorization agent gross mass.
Preferably, the ratio between amount of substance of the chloro phosphonitrile or fluoro phosphazene derivative and fluorization agent is 1:1~1.5.
Improve the conversion ratio of chloro phosphonitrile.
Preferably, the fluorization agent is one of sodium fluoride and potassium fluoride or its two kinds mixture.
Preferably, the organic solvent is tetrahydrofuran, n-hexane, toluene, chlorobenzene, petroleum ether, pyridine, N, N- diformazan
The mixture of one or more of base formamide (DMF), acetonitrile or benzonitrile.
Embodiment there is provided a kind of above-mentioned synthetic methods to prepare fluoro phosphonitrile or derivatives thereof for the third of the application
Application in class battery electrolyte.
Embodiment there is provided a kind of above-mentioned synthetic methods to prepare fluoro phosphonitrile or derivatives thereof for the 4th kind of the application
Application in class battery.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
Embodiment 1:
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution, Xiang Rong in 200mL tetrahydrofuran
27g sodium fluoride is added in liquid, 2g technical grade graphene is added as catalyst as fluorization agent, and is anti-under the conditions of 30 DEG C of temperature
Answer 10h, filtered, be evaporated under reduced pressure after obtain three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 98%.
Embodiment 2
Three phosphonitrile dissolution of crystals of 27.5g ethyoxyl pentachloro- ring is formed into ethyoxyl pentachloro- ring three in 200mL tetrahydrofuran
Phosphonitrile solution 27g sodium fluoride is added into solution, 2g technical grade graphene is added as catalyst as fluorization agent, and 30
React 15h under the conditions of DEG C temperature, filtered, be evaporated under reduced pressure after obtain five fluorine ring of phosphazene derivative ethyoxyl, three phosphonitrile, yield
99%, purity 97%.
Embodiment 3
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution in 200mL DMF, into solution
27g sodium fluoride is added as fluorization agent, 2g graphene oxide is added as catalyst, and under the conditions of 60 DEG C of temperature and reacts 5h,
Filtered, be evaporated under reduced pressure after obtain three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 98%.
Embodiment 4
Three phosphonitrile dissolution of crystals of 27.5g ethyoxyl pentachloro- ring is formed into three phosphonitrile of ethyoxyl pentachloro- ring in 200mL DMF
Solution 27g sodium fluoride is added into solution, 2g graphene oxide is added as catalyst as fluorization agent, and in 60 DEG C of temperature
Under the conditions of react 5h, filtered, be evaporated under reduced pressure after obtain five fluorine ring of phosphazene derivative ethyoxyl, three phosphonitrile, yield 99%, purity
It is 98%.
Embodiment 5
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution in 200mL petroleum ether, to solution
Middle addition 27g sodium fluoride is added 2g fullerene as catalyst, and under the conditions of 100 DEG C of temperature and reacts 3h, pass through as fluorization agent
Three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 97% are obtained after filtering, vacuum distillation.
Embodiment 6
Three phosphonitrile dissolution of crystals of 27.5g ethyoxyl pentachloro- ring is formed into three phosphorus of ethyoxyl pentachloro- ring in 200mL petroleum ether
Nitrile solution 27g sodium fluoride is added into solution, 2g fullerene is added as catalyst as fluorization agent, and in 100 DEG C of temperature strips
React 5h under part, filtered, be evaporated under reduced pressure after obtain five fluorine ring of phosphazene derivative ethyoxyl, three phosphonitrile, yield 99%, purity is
97%.
Embodiment 7
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution in 200mL n-hexane, to solution
Middle addition 27g sodium fluoride is added 2g Mxene as catalyst, and under the conditions of 120 DEG C of temperature and reacts 2h, pass through as fluorization agent
Three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 98% are obtained after filtering, vacuum distillation.
Embodiment 8
Three phosphonitrile dissolution of crystals of 27.5g ethyoxyl pentachloro- ring is formed into three phosphorus of ethyoxyl pentachloro- ring in 200mL n-hexane
Nitrile solution 27g sodium fluoride is added into solution, 2g Mxene is added as catalyst as fluorization agent, and in 120 DEG C of temperature strips
React 2h under part, filtered, be evaporated under reduced pressure after obtain five fluorine ring of phosphazene derivative ethyoxyl, three phosphonitrile, yield 99%, purity is
98%.
Embodiment 9
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution in 200mL toluene, into solution
27g sodium fluoride is added as fluorization agent, 2g hydroxyl carbon nano tube is added and is reacted as catalyst, and under the conditions of 80 DEG C of temperature
4h, filtered, be evaporated under reduced pressure after obtain three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 98%.
Embodiment 10
Three phosphonitrile dissolution of crystals of 27.5g ethyoxyl pentachloro- ring is formed into three phosphonitrile of ethyoxyl pentachloro- ring in 200mL toluene
Solution 27g sodium fluoride is added into solution, 2g hydroxyl carbon nano tube is added as catalyst as fluorization agent, and at 80 DEG C
4h is reacted under the conditions of temperature, filtered, be evaporated under reduced pressure after obtain five fluorine ring of phosphazene derivative ethyoxyl, three phosphonitrile, yield 99%,
Purity is 98%.
Embodiment 11
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution in 200mL acetonitrile, into solution
27g sodium fluoride is added as fluorization agent, 2g expanded graphite is added as catalyst, and under the conditions of 30 DEG C of temperature and reacts 20h, passes through
Three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 97% are obtained after filtering, vacuum distillation.
Embodiment 12
Three phosphonitrile dissolution of crystals of 27.5g ethyoxyl pentachloro- ring is formed into three phosphonitrile of ethyoxyl pentachloro- ring in 200mL acetonitrile
Solution 27g sodium fluoride is added into solution, 2g expanded graphite is added as catalyst as fluorization agent, and in 30 DEG C of temperature strips
React 20h under part, filtered, be evaporated under reduced pressure after obtain five fluorine ring of phosphazene derivative ethyoxyl, three phosphonitrile, yield 99%, purity is
97%.
Embodiment 13
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution, Xiang Rong in 200mL tetrahydrofuran
27g sodium fluoride is added in liquid 2g poly glycol monomethyl ether 800 is added and is used as catalyst as fluorization agent, and in 30 DEG C of temperature strips
React 1h under part, filtered, be evaporated under reduced pressure after obtain three phosphonitrile of phosphazene derivative hexafluoro ring, yield 99%, purity 85%.
Embodiment 14
34.7g hexachlorocyclotriph,sphazene dissolution of crystals is formed into hexachlorocyclotriph,sphazene solution, Xiang Rong in 200mL tetrahydrofuran
27g sodium fluoride is added in liquid as fluorization agent, using the filtered obtained precipitating of embodiment 1 as catalyst, and in 30 DEG C of temperature
10h is reacted under the conditions of degree, filtered, be evaporated under reduced pressure after obtain three phosphonitrile of phosphazene derivative hexafluoro ring, yield 98%, purity is
97%.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (9)
1. the synthetic method of a kind of fluoro phosphonitrile and its derivative, characterized in that chloro phosphonitrile or chloro phosphazene derivative is molten
Solution is added fluorization agent and catalyst and is reacted in organic solvent, to get fluoro phosphonitrile and its derivative after filtering distillation,
The catalyst is technical grade graphene, in graphene oxide, fullerene, Mxene, hydroxyl carbon nano tube, expanded graphite
One or more kinds of mixtures.
2. synthetic method as described in claim 1, characterized in that the reaction time is 1~20h.
3. synthetic method as described in claim 1, characterized in that the reaction temperature is 30~120 DEG C.
4. synthetic method as described in claim 1, characterized in that the additional amount of the catalyst is chloro phosphonitrile and fluorization agent
The 1~20% of 1~20% or fluoro phosphazene derivative and fluorization agent gross mass of gross mass.
5. synthetic method as described in claim 1, characterized in that the chloro phosphonitrile or fluoro phosphazene derivative and fluorization agent
The ratio between the amount of substance be 1:1~1.5.
6. synthetic method as described in claim 1, characterized in that the fluorization agent be one of sodium fluoride and potassium fluoride or
Its two kinds mixture.
7. synthetic method as described in claim 1, characterized in that the organic solvent be tetrahydrofuran, n-hexane, toluene,
The mixture of one or more of chlorobenzene, petroleum ether, pyridine, N,N-dimethylformamide, acetonitrile or benzonitrile.
8. a kind of any synthetic method of claim 1~7 is preparing fluoro phosphonitrile or derivatives thereof class battery electrolyte
In application.
9. a kind of any synthetic method of claim 1~7 is preparing answering in fluoro phosphonitrile or derivatives thereof class battery
With.
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| CN101648840B (en) * | 2009-06-16 | 2012-02-01 | 南京大学 | Application of fullerene used as catalyst for catalytic hydrogenation reaction of nitro group in nitroaromatic compounds under light irradiation |
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