CN109336758A - A method of hexafluoropropylene oxide oligomer is prepared using high activity emulsion layer - Google Patents
A method of hexafluoropropylene oxide oligomer is prepared using high activity emulsion layer Download PDFInfo
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- CN109336758A CN109336758A CN201811337247.7A CN201811337247A CN109336758A CN 109336758 A CN109336758 A CN 109336758A CN 201811337247 A CN201811337247 A CN 201811337247A CN 109336758 A CN109336758 A CN 109336758A
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- hexafluoropropylene oxide
- emulsion layer
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- passed
- kettle
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- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000839 emulsion Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 241000143437 Aciculosporium take Species 0.000 claims abstract 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000001265 acyl fluorides Chemical group 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- 238000013517 stratification Methods 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004427 diamine group Chemical group 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000006071 cream Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000007812 deficiency Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 24
- 150000004985 diamines Chemical group 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 150000002170 ethers Chemical class 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000539 dimer Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NHEOWFLLFDKMDU-UHFFFAOYSA-N C1C(C)O1.[F] Chemical compound C1C(C)O1.[F] NHEOWFLLFDKMDU-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods using high activity emulsion layer preparation hexafluoropropylene oxide oligomer, a. take a certain amount of high activity emulsion layer in solvent in reaction kettle in proportion, 10~40 DEG C of temperature of control, 0.5~1h is stirred, nitrogen is constantly passed through in whipping process and drives the hydrogen fluoride that air and emulsion layer generate in kettle away；B. hexafluoropropylene oxide monomer is passed through with certain rate, the mass ratio of emulsion layer and hexafluoropropylene oxide monomer is 1:2~50, and hexafluoropropylene oxide monomer is passed through rate control in 50~800sccm；C. after the reaction was completed, continue 1~2h of stirring, make in kettle for reaction hexafluoropropylene oxide fully reacting；D. 0.5h is stood, from bottom discharge.The present invention overcomes the prior art moisture absorption, side reactions to generate, and the deficiency being not easily recycled.
Description
Present patent application is that " a kind of high activity emulsion layer catalyst and hexafluoropropylene oxide are oligomeric for invention and created name
The applying date of the divisional application of the preparation method of object ", original application is on November 7th, 2016, and application No. is 2016109719245.
Technical field
The present invention relates to the preparation methods of fluorine Chemical Engineering Technology more particularly to hexafluoropropylene oxide oligomer.
Background technique
Hexafluoropropylene oxide oligomer is the important intermediate of material circle, only contains tri- kinds of elements of C, F, O in molecule, in heat
Stability, inoxidizability, mechanical stability, radiation resistance, anticorrosive property etc. are excellent in.
Dimerization of hexafluoropropene oxide body, is used to prepare perfluoropropylvinylether (PPVE), it is important fluorine-containing list
Body, a small amount of PPVE are added in tetrafluoroethylene polymerization, can prepare soluble poly tetrafluoroethene (PFA), this polytetrafluoroethylene (PTFE)
The characteristic of original tetrafluoroethene is not only remained, while overcoming the deficiency of polytetrafluoroethylene (PTFE), can be molded or extrusion molding.
Hexafluoropropylene oxide tripolymer and the tetramer have good biodegradability, it is expected to contain as environmental-friendly
The new varieties of fluorinated surfactant can be used as novel fluorocarbon surfactant after modifying its end, with " three is high by two
Hate " special performance.It is widely used in washing all conglomeraties such as adjustment, cosmetics, food, rubber, plastics, photosensitive material, ink.
More description is prepared with about hexafluoropropylene oxide oligomer at present.Heinrich L et al. is German special
Sharp DE2026669 is described using acetonitrile as solvent, and for AgNO3 as catalyst, HFPO dimer yield reaches 86%, but
Catalyst is done using silver nitrate, there is light sensitivity, stability is poor.German patent DE 2924385 describe done using acetonitrile it is molten
Agent, CuCl/CuCl2/ acrylonitrile system is as catalyst system, also available dimer, but this method is unfortunately adopted
With the acrylonitrile catalyst system for having carcinogenic suspicion, operational safety is relatively low.
Japan Patent JP62195345 and JP6312952 are described using CsF etc. as catalyst, in proton polar solvent
In, dry environment is needed, and CsF is expensive since catalyst CsF easily absorbs water with raw material HFPO preparation dimer,
Cause product cost higher.
Hexafluoropropylene oxide two is described in the Chinese patent CN1044092A of German's Gu Entexi lattice door moral application
Polymerizing preparation method: carrying out the preparation reaction of dimer in the presence of one or more polar aprotic solvent catalyst neutralisation systems,
The catalyst system is a kind of metal salt and tertiary diamine composition of transition metal in the periodic table of elements, and wherein metal salt is preferably
CuCl, CuCl2, CoCl2, ZnCl2 etc., the defect using this catalyst are to be easy for the elements such as Cl to be introduced into target product,
And the preparation method, mainly to prepare based on dimer, yield is between 80%~90%.
One kind is described in the Chinese patent CN10341199A of Wilfried Cruise et al. application by alkali metal fluosilicate
Compound, nitrile compound and ethers mix catalyst system, the method for preparing HFPO hexafluoropropylene oxide oligomer.In reaction temperature
Degree is can reach 80% or more for dimerization of hexafluoropropene oxide body acyl fluorides selectivity maximum under the conditions of as 5 DEG C~35 DEG C.
But the alkali metal fluoride in the catalyst system is solid, is in non-homogeneous phase in solvent, and metal fluoride is easy to inhale
Moisture knot block and go bad, be not easily recycled and reuse, therefore be unfavorable for environmental protection.
Described in Chinese patent CN1044090A using to proton have inert polar solvent, tertiary diamine, protonation and
The catalyst system of object composition, proton compound are preferred: water, methanol, ethylene glycol, ammonia or diethylamine.The advantages of invention is logical
Cross addition proton additive, the deviation short chain oligomer for the property of can choose, especially dimer.Shortcoming is exactly that matter is added
After sub- compound, by-product generation is had.
Summary of the invention
Hexafluoropropylene oxide is prepared using high activity emulsion layer the technical problem to be solved by the invention is to provide a kind of
The method of oligomer overcomes the moisture absorption in current hexafluoropropylene oxide oligomer preparation process, side reaction to generate and be not easily recycled
It is insufficient.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A method of hexafluoropropylene oxide oligomer is prepared using high activity emulsion layer, is included the following steps:
A. it takes a certain amount of high activity emulsion layer in solvent in reaction kettle in proportion, controls 10~40 DEG C of temperature, stirring
0.5~1h is constantly passed through nitrogen in whipping process and drives the hydrogen fluoride that air and emulsion layer generate in kettle away；
B. hexafluoropropylene oxide monomer is passed through with certain rate, monomer is passed through rate volume flow counter device meter
Amount, is passed through quality and is measured with precision electronic balance, wherein and the mass ratio of emulsion layer and hexafluoropropylene oxide monomer is 1:2~50,
Hexafluoropropylene oxide monomer is passed through rate control in 50~800sccm；
C. after the reaction was completed, continue 1~2h of stirring, make in kettle for reaction hexafluoropropylene oxide fully reacting；
D. 0.5h is stood, from bottom discharge；The stratification in separatory funnel, upper layer are solvent, and middle layer is emulsion layer,
Lower layer's transparency liquid, the transparency liquid are hexafluoropropylene oxide oligomer, and structural formula is as follows:
N=0~5 in structural formula；
Wherein, the preparation method of high activity emulsion layer includes the following steps:
(1) polar non-proton organic solvent, tertiary diamine, triethylamine and acyl fluorides are added at one time in reaction kettle in proportion,
Logical nitrogen simultaneously stirs, and temperature in the kettle is stablized the triethylamine, tertiary diamine and acyl between 5~40 DEG C with cooling circulating water
The mass ratio of fluorine is 1~10:10~100:50~400, and the polar non-proton organic solvent, tertiary diamine, triethylamine are adding
It all needs to remove water by 3A or 4A molecular sieve or sodium or calcium hydride before entering reaction kettle；；
(2) 2~6h is stirred, layering is then allowed to stand, intermediate cream colour chromatograph is exactly the high activity emulsification being prepared after layering
Layer.
Preferably, the mass ratio of the emulsion layer and hexafluoropropylene oxide monomer is 1:2~30, the Hexafluoropropylene third
Alkane monomer is passed through rate control in 100~500sccm.
Preferably, the solvent uses diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
Preferably, the hexafluoropropylene oxide monomer carries out removal of impurities processing before the reaction, used method be by
Hexafluoropropylene oxide monomer passes sequentially through in several concatenated stainless steel drying towers, in stainless steel drying tower place molecular sieve,
Calcium oxide and activated alumina, and after dry, make the water content of hexafluoropropylene oxide monomer lower than 20ppm.
Preferably, the acyl fluorides includes perfluoro-propionyl fluoride or perfluor -2- methyl -3- oxa- hexanoyl fluorine.
Preferably, the general formula of the tertiary diamine is R1R2N-R-NR3R4, R is one and has 1 to 12 carbon original in general formula
Non-branched or branch the saturation or unsaturated aliphatic alkyl of son, R1 and R4 are mutually indepedent and for 1 to 12 carbon atom
Aliphatic or alicyclic saturation or unsaturated alkyl.
The technical solution adopted by the present invention, the catalysis using the emulsion layer of high activity as hexafluoropropylene oxide oligomerisation reaction
Agent, the emulsion layer are the organic salt that acyl fluorides and tertiary diamine are formed, and density is greater than solvent, so after completion of the reaction, emulsion layer position
Below solvent, avoids and contacted with air, and have a small amount of acyl fluorides or free F in solvent layer-, can with it is a small amount of in air
Reaction of moisture forms hydrofluoric acid, further avoids the emulsion layer moisture absorption；Secondly acyl fluorides and tertiary diamine form emulsion layer catalyst, into
- 2, hexafluoropropylene oxide carbon is attacked, Rf-CF is formed3CF2CF2O-, the anion can further attack hexafluoropropylene oxide, due to
Rf-CF3CF2CF2O-It is unstable, it is easy to slough F-, acyl fluorides is formed, no other impurities participate in reaction, therefore without side reaction.Therefore,
The deficiencies of overcoming the prior art moisture absorption, side reaction generation, and being not easily recycled.
In addition, the high activity emulsion layer density is about 1.2~1.5g/ml, and it is in homogeneous phase, it during the reaction can be more preferable
Ground is contacted with hexafluoropropylene oxide (HFPO), therefore the high conversion rate of hexafluoropropylene oxide is up to 95% or more.
In addition, dissolution very little of the catalyst in product phase, long service life can be reused, drop by separation
Low product cost, and be conducive to environmental protection.The operation is simple, and production can carry out at normal temperatures and pressures, meets industry
Production.
Specific embodiment
A kind of preparation method of high activity emulsion layer catalyst, includes the following steps:
(1) polar non-proton organic solvent, tertiary diamine, triethylamine and acyl fluorides are added at one time in reaction kettle in proportion,
Logical nitrogen simultaneously stirs, and is stablized temperature in the kettle between 5~40 DEG C with cooling circulating water；
Wherein, the mass ratio of triethylamine, tertiary diamine and acyl fluorides is 1~10:10~100:50~400；2~6h is stirred, so
Stratification afterwards, intermediate cream colour chromatograph is exactly the emulsion layer prepared after layering.
Wherein, the acyl fluorides includes perfluoro-propionyl fluoride or perfluor -2- methyl -3- oxa- hexanoyl fluorine.The tertiary diamine
General formula is R1R2N-R-NR3R4, R is non-branched or branch the saturation or unsaturation for having 1 to 12 carbon atom in general formula
Aliphatic hydrocarbyl, R1 and R4 are mutually indepedent and are aliphatic or alicyclic saturation or unsaturated alkyl with 1 to 12 carbon atom.
The aliphatic tertiary diamine compound that tetraalkyl replaces includes: N, N, N ', N ' ,-tetramethyl methylene diamine, N, N, N ', N ' ,-tetra-
Methyl ethylenediamine, N, N, N ', N ', -4-methyl-diaminopropane, N, N, N ', N ',-tetraethyl methylene diamine, N, N, N ', N ', -
Tetraethylethylenediamine, N, N, N ', N ' ,-tetrapropyl ethylenediamine etc., preferably N, N, N ', N ' ,-tetramethylethylenediamine.
The polar non-proton organic solvent, tertiary diamine, triethylamine are all needed before keying in reaction kettle by 3A or 4A points
Son sieve or sodium or calcium hydride water removal.The polar non-proton organic solvent is ethers, alkylamide, at least one in nitrile
Kind.Preferably, the mass ratio of the triethylamine, tertiary diamine and acyl fluorides is 1~3:20:80~100~250.
Firstly, the additional amount of organic solvent, which has reaction, centainly to be influenced, according to the test done it is found that reducing organic molten
Agent, the trend of the oriented long-chain polymer transfer of polymer；Increase organic solvent, then what the yield of underlying polymer was reduced becomes
Gesture has small part is oligomeric to be dissolved in solvent, so that yield declines.From the point of view of the result of test, the body of catalyst and organic solvent
Product ratio is about in 1:1~10.
Secondly, triethylamine, tertiary diamine and acyl fluorides are influential, especially tertiary diamine, emulsification on the preparation of emulsion layer
The yield of layer increases with the increase of tertiary diamine, and certainly while increasing emulsion layer, the amount that acyl fluorides is added should be no less than uncle two
2 to 5 times of amine.Second, a small amount of triethylamine also wants certain influence to the preparation of emulsion layer, according to the experiment done, when adding
It is excessive to enter triethylamine, then occurs without emulsion layer；Triethylamine is not added, then generates the yield of emulsion layer three second a small amount of less than addition
The yield of emulsion layer obtained by amine.
Below by embodiment, present invention is described.It is necessarily pointed out that following embodiment is served only for pair
The present invention further illustrates, should not be understood as limiting the scope of the invention, professional and technical personnel in the field is according to this
Some nonessential modifications and adaptations that the content of invention is made, still fall within protection scope of the present invention.
The preparation example of high activity emulsion layer catalyst
150ml diethylene glycol dimethyl ether, 60g tetramethylethylenediamine and 1.0g triethylamine are added in stainless steel cauldron,
It is continuously added into perfluoro-propionyl fluoride under nitrogen atmosphere protection and is stirred continuously, it will be warm in the kettle in reaction process using cooling circulating water
Degree maintains 25 DEG C or so.After perfluoro-propionyl fluoride 200g is added, reaction stops, and continues 1~2h of stirring, stands 0.5h, from anti-
Kettle bottom discharge is answered, the stratification in separatory funnel, the emulsion layer that lower layer's ecru lotion is prepared needed for being.
High activity emulsion layer catalyst obtained goes to prepare the preparation method of fluorine propylene oxide oligomer in aforementioned manners, packet
Include following steps:
A. it takes a certain amount of high activity emulsion layer in solvent in reaction kettle in proportion, controls 10~40 DEG C of temperature, stirring
0.5~1h is constantly passed through nitrogen in whipping process and drives the hydrogen fluoride that air and emulsion layer generate in kettle away；
B. hexafluoropropylene oxide monomer is passed through with certain rate, monomer is passed through rate volume flow counter device meter
Amount, is passed through quality and is measured with precision electronic balance, wherein and the mass ratio of emulsion layer and hexafluoropropylene oxide monomer is 1:2~50,
Hexafluoropropylene oxide monomer is passed through rate control in 50~800sccm；
C. after the reaction was completed, continue 1~2h of stirring, make in kettle for reaction hexafluoropropylene oxide fully reacting；
D. 0.5h is stood, from bottom discharge；The stratification in separatory funnel, upper layer are solvent, and middle layer is emulsion layer,
Lower layer's transparency liquid, the transparency liquid are hexafluoropropylene oxide oligomer, and structural formula is as follows:
N=0~5 in structural formula.
Wherein, it is preferred that the emulsion layer catalyst and the mass ratio of hexafluoropropylene oxide are 1:2~30, the hexafluoro
Propylene oxide monomer is passed through rate control in 100~500sccm.The polar non-proton organic solvent can be ethers, alkane
Base amides, one of nitrile.
In hexafluoropropylene oxide polymerization process, when temperature is excessively high, that is, when temperature is more than 40 DEG C, hexafluoropropylene oxide exists
Under the action of catalyst be easy isomerization formed perfluoro-propionyl fluoride, it is easy to just reaction kettle is full of, cause the reaction mainly with
Based on perfluoro-propionyl fluoride gas, it cannot get hexafluoropropylene oxide polymer.When temperature is lower than 10 DEG C, the polymer of the reaction with
Be biased to long-chain four are poly-, based on the polymer of the five poly- and higher degree of polymerization, and obtained common hexafluoropropylene oxide two
Poly-, trimerization is less.
For being passed through the determination of hexafluoropropylene oxide monomer reaction parameter:
Firstly, just having started hexafluoropropylene oxide in hexafluoropropylene oxide polymerization and being isomerizated into perfluoro-propionyl fluoride, and had one
The phase buffer of section.If emulsion layer is quantitative, the hexafluoropropylene oxide being passed through is less, then the polymer reacted is less or does not have
There is polymer generation；When the hexafluoropropylene oxide being passed through is excessive, with the progress of reaction, catalyst can be inactivated slowly, and reaction is lived
Property reduce, cause part hexafluoropropylene oxide not react and waste.
Secondly the rate that is passed through of hexafluoropropylene oxide should be appropriate, i.e. control is between 50~800ml/min, if being added six
Fluorine propylene oxide is too fast, then the rate of the perfluoro-propionyl fluoride generated is greater than rate of polymerization, causes perfluoro-propionyl fluoride gas full of anti-
It answers kettle and terminates reaction, hexafluoropropylene oxide rate is too slow if being added, so that the rate for generating perfluoro-propionyl fluoride is less than polymerization speed
Rate, therefore the reaction time can be extended, while with the progress of reaction, resulting polymers are biased to the polymer of long-chain, and non-dimeric
Based on body, tripolymer.
Wherein, ethers includes diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, five ethylene glycol two
Methyl ether, tetrahydrofuran and crown ether etc..The alkylamide includes N, N-dimethylformamide, N, N-dimethyl acetamide
Deng.The nitrile includes acetonitrile, propionitrile, adiponitrile, adiponitrile etc..It is excellent in above-described polar non-proton organic solvent
Select the diethylene glycol dimethyl ether in ethers.Solvent is not the key that influence the polymerization reaction, the selection for solvent, in hexafluoro ring
In the ring-opening polymerization of Ethylene Oxide, the influence of solvent shows dissolubility or mixing to catalyst, monomer and polymer
Property.In addition, also needing to consider whether solvent is toxic, if inflammable and explosive, if environmental protection, and come from economic angle etc. factor
Select solvent.Mainly there are ethers, alkylamide, nitrile for the polar non-proton organic solvent of the reaction.Alkylamide,
Nitrile organic solvent has toxicity, and inflammable, has greater environmental impacts；And ethers toxicity is smaller, and it is more environmentally friendly, to catalyst, list
The dissolubility of body is preferable, so selecting ethers for the solvent of the reaction, and can be used for polarity organic reaction in ethers,AnionIt is poly-
It closes, in the solvent of coordinated ionic polymerization reaction, it is most commonly seen with diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
The hexafluoropropylene oxide carries out removal of impurities processing before the reaction, used method be by hexafluoropropylene oxide according to
It is secondary by the way that molecular sieve, calcium oxide and active oxygen are placed in stainless steel drying tower respectively in several concatenated stainless steel drying towers
Change aluminium, and after dry, makes the water content of hexafluoropropylene oxide monomer lower than 20ppm.This is because the hexafluoro in industry
Containing there are many impurity in propylene oxide gas, the impurity such as moisture, hydrofluoric acid and Hexafluoro acetone therein can be such that carboanion polymerize
It terminates, significant impact is generated to polymerization, therefore must first carry out purifying pretreatment to unstrpped gas before the polymerization.It is not purified
Unstrpped gas in, micro-water content 1000~2000ppm, HF mass content be 0.15%~0.20%, the matter of Hexafluoro acetone
Measuring content is about 1%.It is dry that molecular sieve, calcium oxide, the self-control stainless steel of aluminium oxide scarvenger are respectively provided in 3 500mL that connect
Dry tower is purified, and each material mass of loading is all 400g.Under room temperature, it is passed through hexafluoropropylene oxide, gas flow rate is
400mL/min, detects the content of micro- water in tower gas, hydrofluoric acid, Hexafluoro acetone, and detection makes Hexafluoropropylene as the result is shown
The water content of oxide monomer is lower than 20ppm, and HF mass content is less than 0.1%, and the mass content of Hexafluoro acetone is about 0.3%,
After purifying by purification column, impurity content is significantly reduced, and especially contains micro- water.
Embodiment 1
The emulsion layer of 150ml diethylene glycol dimethyl ether and 50.0g is rapidly added in dry stainless steel cauldron, leads to height
Pure nitrogen gas drives the white cigarette that air and emulsion layer generate in kettle away.And 1h or so is stirred under nitrogen atmosphere protection, discharge nitrogen in kettle
Make initial pressure 0 in reaction kettle, HFPO is passed through reaction kettle with the rate of 200sccm and is reacted, will using cooling circulating water
Temperature in the kettle in reaction process is to maintain 25 DEG C or so.After being passed through the HFPO of 250g, stopping is passed through HFPO, and reaction stops
Only, continue to stir 1h, stand 0.5h, discharge from reactor bottom, the stratification in separatory funnel, upper layer is solvent, intermediate
Layer is emulsion layer, and lower layer is that transparency liquid is hexafluoropropylene oxide oligomer, obtains crude product 249.7g, yield 99.88%.
It takes sample segment to carry out gas chromatographic analysis, obtains following result:
| N=0 | N=1 | N=2 | N=3 | Other |
| 48.26% | 35.91% | 6.91% | 0.94% | 7.98% |
Embodiment 2
The emulsion layer of 150ml solvent used in embodiment 1 and 50g is rapidly added dry stainless steel cauldron
In, it is passed through high pure nitrogen, drives the white cigarette that air and emulsion layer generate in kettle away.And 1h or so is stirred under nitrogen atmosphere protection, it releases
Putting nitrogen in kettle makes initial pressure 0 in reaction kettle, and HFPO is passed through reaction kettle with the rate of 200sccm and is reacted, and utilization is cold
But the temperature in the kettle in reaction process is maintained 25 DEG C or so by recirculated water.After being passed through the HFPO of 250g, stopping is passed through HFPO,
Reaction stops, and continues to stir 1h, stands 0.5h, discharges from reactor bottom, the stratification in separatory funnel, lower layer's transparent liquid
Body is hexafluoropropylene oxide oligomer, obtains crude product 248.8g, yield 99.52%.Sample segment is taken to carry out gas-chromatography
Analysis, obtains following result:
| N=0 | N=1 | N=2 | N=3 | Other |
| 46.54% | 36.90% | 8.87% | 1.13% | 6.55% |
Embodiment 3
Emulsion layer used in embodiment 1 is mixed with 150ml diethylene glycol dimethyl ether, is rapidly added dry stainless
In steel reaction kettle, it is passed through high pure nitrogen, drives the white cigarette that air and emulsion layer generate in kettle away.And 1h is stirred under nitrogen atmosphere protection
Left and right, discharging nitrogen in kettle makes initial pressure 0 in reaction kettle, and HFPO is passed through reaction kettle with the rate of 200sccm and is reacted,
The temperature in the kettle in reaction process is maintained 25 DEG C or so using cooling circulating water.After being passed through the HFPO of 250g, stop logical
Entering HFPO, reaction stops, and continue to stir 1h, stand 0.5h, discharges from reactor bottom, the stratification in separatory funnel, under
Layer transparency liquid is hexafluoropropylene oxide oligomer, obtains crude product 245.1g, yield 98.04%.Sample segment is taken to carry out
Gas chromatographic analysis obtains following result:
| N=0 | N=1 | N=2 | N=3 | Other |
| 23.25% | 44.29% | 25.35% | 5.19% | 1.92% |
Claims (6)
1. a kind of method using high activity emulsion layer preparation hexafluoropropylene oxide oligomer, it is characterised in that including walking as follows
It is rapid:
A. take a certain amount of high activity emulsion layer in solvent in reaction kettle in proportion, 10~40 DEG C of temperature of control, stirring 0.5~
1h is constantly passed through nitrogen in whipping process and drives the hydrogen fluoride that air and emulsion layer generate in kettle away；
B. hexafluoropropylene oxide monomer is passed through with certain rate, monomer is passed through the metering of rate volume flow counter device, leads to
Enter quality to be measured with precision electronic balance, wherein the mass ratio of emulsion layer and hexafluoropropylene oxide monomer is 1:2~50, hexafluoro
Propylene oxide monomer is passed through rate control in 50~800sccm；
C. after the reaction was completed, continue 1~2h of stirring, make in kettle for reaction hexafluoropropylene oxide fully reacting；
D. 0.5h is stood, from bottom discharge；The stratification in separatory funnel, upper layer are solvent, and middle layer is emulsion layer, lower layer
Transparency liquid, the transparency liquid are hexafluoropropylene oxide oligomer, and structural formula is as follows:
N=0~5 in structural formula；
Wherein, the preparation method of high activity emulsion layer includes the following steps:
(1) polar non-proton organic solvent, tertiary diamine, triethylamine and acyl fluorides are added at one time in reaction kettle in proportion, lead to nitrogen
Gas simultaneously stirs, and stablized temperature in the kettle between 5~40 DEG C with cooling circulating water, the triethylamine, tertiary diamine and acyl fluorides
Mass ratio is 1~10:10~100:50~400, and the polar non-proton organic solvent, tertiary diamine, triethylamine are being added instead
It all needs to remove water by 3A or 4A molecular sieve or sodium or calcium hydride before answering kettle；
(2) 2~6h is stirred, layering is then allowed to stand, intermediate cream colour chromatograph is exactly the high activity emulsion layer being prepared after layering.
2. it is according to claim 1 preparation hexafluoropropylene oxide oligomer method, it is characterised in that: the emulsion layer with
The mass ratio of hexafluoropropylene oxide monomer is 1:2~30, the hexafluoropropylene oxide monomer be passed through rate control 100~
500sccm。
3. the method for preparation hexafluoropropylene oxide oligomer according to claim 1, it is characterised in that: the solvent uses
Diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
4. the method for preparation hexafluoropropylene oxide oligomer according to claim 1, it is characterised in that: the hexafluoro ring
Ethylene Oxide monomer carries out removal of impurities processing before the reaction, and used method is that hexafluoropropylene oxide monomer is passed sequentially through several
In concatenated stainless steel drying tower, molecular sieve, calcium oxide and activated alumina are placed in stainless steel drying tower, and by drying
Afterwards, make the water content of hexafluoropropylene oxide monomer lower than 20ppm.
5. the method for preparation hexafluoropropylene oxide oligomer according to claim 1, it is characterised in that: the acyl fluorides packet
Include perfluoro-propionyl fluoride or perfluor -2- methyl -3- oxa- hexanoyl fluorine.
6. the method for preparation hexafluoropropylene oxide oligomer according to claim 1, it is characterised in that: the tertiary diamine
General formula is R1R2N-R-NR3R4, R is non-branched or branch the saturation or unsaturation for having 1 to 12 carbon atom in general formula
Aliphatic hydrocarbyl, R1 and R4 are mutually indepedent and are aliphatic or alicyclic saturation or unsaturated alkyl with 1 to 12 carbon atom.
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| EP0378767A1 (en) * | 1989-01-14 | 1990-07-25 | Hoechst Aktiengesellschaft | Method for the oligomerisation of hexafluoropropene oxide |
| EP0503294A2 (en) * | 1991-02-14 | 1992-09-16 | Hoechst Aktiengesellschaft | Process for preparing perfluorpolyetheracrylfluorides |
| CN104513390A (en) * | 2013-12-24 | 2015-04-15 | 东莞市长安东阳光铝业研发有限公司 | Method for preparing hexafluoropropylene oxide oligomer |
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| CN1034199A (en) * | 1987-11-07 | 1989-07-26 | 赫彻斯特股份公司 | The production method of perfluoro-carbonyl fluoride |
| EP0378767A1 (en) * | 1989-01-14 | 1990-07-25 | Hoechst Aktiengesellschaft | Method for the oligomerisation of hexafluoropropene oxide |
| CN1044090A (en) * | 1989-01-14 | 1990-07-25 | 赫彻斯特股份公司 | The oligomerization process of Propylene oxide hexafluoride |
| EP0503294A2 (en) * | 1991-02-14 | 1992-09-16 | Hoechst Aktiengesellschaft | Process for preparing perfluorpolyetheracrylfluorides |
| CN104513390A (en) * | 2013-12-24 | 2015-04-15 | 东莞市长安东阳光铝业研发有限公司 | Method for preparing hexafluoropropylene oxide oligomer |
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| CN112500259A (en) * | 2020-12-14 | 2021-03-16 | 常熟三爱富中昊化工新材料有限公司 | Preparation method of heptafluoropropane |
| CN112500259B (en) * | 2020-12-14 | 2023-09-22 | 常熟三爱富中昊化工新材料有限公司 | Process for the preparation of heptafluoropropane |
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