CN111701617B - Branched high-solid-content 4-dimethylaminopyridine catalyst and preparation method thereof - Google Patents
Branched high-solid-content 4-dimethylaminopyridine catalyst and preparation method thereof Download PDFInfo
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- CN111701617B CN111701617B CN202010491322.6A CN202010491322A CN111701617B CN 111701617 B CN111701617 B CN 111701617B CN 202010491322 A CN202010491322 A CN 202010491322A CN 111701617 B CN111701617 B CN 111701617B
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- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 92
- 239000010703 silicon Substances 0.000 claims abstract description 92
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 27
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- 238000007126 N-alkylation reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 10
- 239000006085 branching agent Substances 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 60
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- -1 poly-alkyl chloro-silicon Chemical compound 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 42
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 33
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 24
- 229930003427 Vitamin E Natural products 0.000 description 22
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 22
- 229940046009 vitamin E Drugs 0.000 description 22
- 235000019165 vitamin E Nutrition 0.000 description 22
- 239000011709 vitamin E Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000010168 coupling process Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 230000008878 coupling Effects 0.000 description 11
- 238000005859 coupling reaction Methods 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 229940078552 o-xylene Drugs 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 238000006640 acetylation reaction Methods 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- ZFAYZXMSTVMBLX-UHFFFAOYSA-J silicon(4+);tetrachloride Chemical compound [Si+4].[Cl-].[Cl-].[Cl-].[Cl-] ZFAYZXMSTVMBLX-UHFFFAOYSA-J 0.000 description 6
- 235000010356 sorbitol Nutrition 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000003622 immobilized catalyst Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 102000012498 secondary active transmembrane transporter activity proteins Human genes 0.000 description 2
- 108040003878 secondary active transmembrane transporter activity proteins Proteins 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012011 nucleophilic catalyst Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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Abstract
The invention discloses a branched high-solid-content 4-dimethylaminopyridine catalyst and a preparation method thereof, wherein a poly-alkyl-chloro-silicon-based carrier is obtained by performing an epoxy-alcohol addition reaction on a polyhydroxy-silicon-based carrier, and the branched high-solid-content 4-dimethylaminopyridine catalyst is prepared by performing an N-alkylation reaction on the poly-alkyl-chloro-silicon-based carrier and 4-methylaminopyridine in the presence of a reaction catalyst; the polyhydroxy silicon-based carrier is prepared by modifying the surface of a silicon-based carrier by using a silane coupling agent to obtain an epoxy silicon-based carrier, and then branching the epoxy end of the epoxy silicon-based carrier in dimethylformamide by using a branching agent; the method improves the hydroxyl content on the surface of the silicon-based carrier in a branching mode, so that the solid carrying capacity of the 4-dimethylamino pyridine on the branched silicon-based carrier is obviously improved, and the 4-dimethylamino pyridine is fixed on the silicon-based carrier in a covalent bonding mode, so the method has stable property, is easy to separate and has no 4-dimethylamino pyridine residue.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation, and particularly relates to a branched high-solid-content 4-dimethylaminopyridine catalyst and a preparation method thereof.
Background
DMAP (4-dimethylaminopyridine) is a super-nucleophilic catalyst, has the characteristics of good solubility, small using amount, high catalytic activity, mild reaction conditions and the like, and is widely used for synthesis of spices, dyes, pesticides, medicines, high molecular compounds and the like. Homogeneous DMAP is not easily separated from the product, is difficult to recycle, increases cost, affects product purity, and has subsequent problems of waste treatment and environmental pollution, and attempts to immobilize DMAP on chemically stable supports have been chosen to solve the above problems.
There are four currently reported methods for DMAP immobilization:
(1) physical adsorption, which utilizes inorganic porous materials, such as molecular sieves, diatomaceous earth, neutral aluminum oxide, activated carbon, and the like, to fix DMAP onto a solid surface by physical adsorption to achieve the loading of DMAP.
(2) The polymer combination method realizes the covalent combination immobilization of DMAP by carrying out N-alkylation on DMAP through halogenated olefin monomers or halogen-containing polymers.
(3) Silane coupling method. 4-methylamino pyridine is N-alkylated by a haloalkane silane coupling agent and is bonded to a silicon-based carrier through silane coupling.
(4) Improved silane coupling processes. Silanization is carried out on a silicon-based carrier by using a haloalkylsilane coupling agent to obtain a coupled carrier, and then N-alkylation reaction is carried out on the coupled carrier and 4-methylamino pyridine, or N-alkylation reaction is carried out on the 4-methylamino pyridine by using the haloalkylsilane coupling agent to obtain a silane coupling agent-DMAP intermediate, and then silane coupling is carried out on the silicon-based carrier by using the silane coupling agent to obtain the immobilized DMAP acylation catalyst.
DMAP immobilized by a physical adsorption method is not firm, and the supported catalyst is easy to fall off, so that the product is polluted, and the performance of the immobilized catalyst is reduced. The second and third immobilization processes require halogen-containing compounds to carry out N-alkylation on 4-methylaminopyridine, and severe dangerous substances such as NaH, N-butyllithium and the like are used as catalysts, so that the whole operation process is complex, the safety guarantee is low according to experimenters, and industrialization is difficult to realize.
The fourth method abandons the use of severe dangerous substances such as NaH, n-butyllithium and the like, but is limited by the hydroxyl content on the surface of the silicon-based carrier, and the prepared immobilized catalyst has less active molecules DMAP, so that the immobilized DMAP catalyst has lower catalytic activity, thereby influencing the reaction effect. In summary, the existing methods can realize the immobilization of the DMAP catalyst, but due to the limitation of the surface hydroxyl content of the adopted carrier, the prepared catalyst has low immobilization capacity and cannot meet the actual production requirements.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a branched high-solid-content 4-dimethylaminopyridine catalyst and a preparation method thereof, and solves the technical problems that the catalyst prepared by the preparation method in the prior art is low in catalytic activity and repeatability, so that the reaction effect is influenced, the solid content of the prepared catalyst is low, and the actual production requirement cannot be met.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a preparation method of a branched high-solid-content 4-dimethylamino pyridine catalyst comprises the steps of carrying out epoxy-alcohol addition reaction on a polyhydroxy silicon-based carrier to obtain a poly-alkyl-chloro-silicon-based carrier, and carrying out N-alkylation reaction on the poly-alkyl-chloro-silicon-based carrier and 4-methylamino pyridine in the presence of a reaction catalyst to prepare the branched high-solid-content 4-dimethylamino pyridine catalyst;
the polyhydroxy silicon-based carrier is prepared by modifying the surface of a silicon-based carrier by using a silane coupling agent to obtain an epoxy silicon-based carrier and branching the epoxy end of the epoxy silicon-based carrier in dimethylformamide by using a branching agent;
the reaction catalyst for the N-alkylation reaction is K2CO3、Na2CO3、KHCO3、NaHCO3、KI、KOH、NaOH、Ca(OH)2、C2H5ONa, triethylamine or pyridine.
The invention also comprises the following technical characteristics:
the preparation method comprises the following specific steps:
modifying the surface of a silicon-based carrier by using a silane coupling agent in an anhydrous solvent 1 to obtain an epoxy silicon-based carrier, and branching the epoxy group tail end of the epoxy silicon-based carrier in dimethylformamide by using a branching agent to obtain a polyhydroxy silicon-based carrier;
carrying out epoxy-alcohol addition reaction on the obtained polyhydroxy silicon-based carrier and epoxy chloropropane in dimethylformamide to obtain a polyalkyl chloride-based silicon-based carrier;
then 4-methylaminopyridine is fully dissolved in an anhydrous solvent 2 to obtain a solution, and the solution is dissolved in N2Carrying out N-alkylation reaction under protection: and sequentially adding a poly-alkyl chloro-silicon-based carrier and a reaction catalyst into the solution, stirring, separating out solids after the reaction is finished, and washing and drying to obtain the branched high-solid-supported 4-dimethylaminopyridine catalyst.
The silane coupling agent is silane such as gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560), gamma-aminopropyl triethoxy silane (KH-550) or gamma-chloropropyl triethoxy silane (KH-430).
The silicon-based carrier is a natural or artificially synthesized silicon-containing material.
The reaction branching agent is polyhydroxy compounds such as glycerol, xylitol, sorbitol and the like.
The reaction condition for preparing the silicon epoxide-based carrier is drying, condensing and refluxing for 18h at 95 ℃.
The reaction condition for preparing the polyhydroxy silicon-based carrier is that the polyhydroxy silicon-based carrier is reacted for 2-12 hours at the temperature of 30-70 ℃, and 50 mu L of boron trifluoride ethyl ether solution is added every 2 hours for catalysis.
The reaction conditions for preparing the polyalkyl chloride-based silicon carrier are that the reaction is carried out for 2-12 h at the temperature of 60 ℃, and 50 mu L of boron trifluoride ethyl ether solution is added every 2h for catalysis.
The addition amount of the reaction catalyst is 0.1-4.5 times of the molar mass of the 4-methylamino pyridine.
The stirring speed is 300-700 rpm, the temperature of the N-alkylation reaction is 90-140 ℃, and the reaction lasts for 1-25 h.
The anhydrous solvent 1 and the anhydrous solvent 2 are both aromatic hydrocarbons.
The branched high-solid-content 4-dimethylaminopyridine catalyst is prepared by the preparation method.
The invention has the beneficial effects that:
the invention provides a preparation method of a branched high-solid-content 4-dimethylaminopyridine catalyst. The hydroxyl content on the surface of the silicon-based carrier is improved in a branching mode, so that the solid loading capacity of the 4-dimethylamino pyridine on the branched silicon-based carrier is obviously improved.
The 4-dimethylamino pyridine is fixed on the silicon-based carrier in a covalent bonding mode, so that the catalyst is stable in property and easy to separate from a reaction system, and 4-dimethylamino pyridine residues are not left in a reaction product.
(III) the immobilization method is simple and convenient to operate, avoids the use of dangerous reagents, and is easy to realize large-scale production.
Drawings
FIG. 1 is a graph showing the results of experiments conducted in example 5 of the present invention and comparative example 1;
FIG. 2 is a graph showing the results of experiments conducted in example 1 and comparative example 2 of the present invention;
FIG. 3 is a graph showing the results of experiments conducted in example 5 of the present invention and comparative example 3
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims.
The kind of the silica-based carrier used in the present invention is not particularly limited, and natural or artificial silicon-containing substrates may be used, such as silica gel, glass, silica, diatomaceous earth, molecular sieves, montmorillonite, zeolite, etc.
The silane coupling agent used in the present invention is not particularly limited, and examples thereof include γ - (2, 3-epoxypropoxy) propyltrimethoxysilane (KH560), γ -aminopropyltriethoxysilane (KH-550), and γ -chloropropyltriethoxysilane (KH-430).
The N-alkylation reaction of DMAP is carried out in a solvent, the type of the solvent is not particularly limited, and the anhydrous solvent is only required to be capable of dissolving DMAP, has a boiling point higher than 80 ℃ and is stable under reaction conditions, such as toluene, xylene, o-xylene and the like.
The branching agent used in the present invention is not particularly limited, and examples thereof include glycerin, xylitol, and sorbitol.
The invention is used for promoting the reactionThe reaction catalyst is inorganic salt such as K, inorganic base, organic base, etc2CO3、Na2CO3、KHCO3、NaHCO3KI, etc., inorganic bases such as KOH, NaOH, Ca (OH)2Etc., organic bases such as triethylamine, pyridine, sodium ethoxide, etc., with KI, K2CO3The effect is optimal.
The preparation of the epoxysilicon-based carrier mentioned in the present invention can be carried out by referring to the conventional method since the silane coupling to the silicon-based carrier is not a subject of the present invention.
Example 1:
the embodiment provides a preparation method of a branched high-solid-content 4-dimethylaminopyridine catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of silica gel and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing and refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and drying at 50 ℃ in vacuum for 12h to obtain the silicon-based epoxy carrier.
Transferring the obtained epoxy silicon-based carrier into a three-neck flask containing 30mLDMF (dimethylformamide), fully stirring for 30min at room temperature, adding glycerol (30mmol,2.5mL), reacting at 50 ℃, reacting for 8h, adding 50 mu L boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and vacuum drying at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride-based silicon-based carrier.
4-methylaminopyridine (0.5mmol, 54mg) was dissolved in 5mL of o-xylene in a microreactor, and 200mg of the polyalkylchlorosilane-based carrier was added after sufficient dissolution, followed by addition of potassium iodide (0.5mmol, 83mg) and potassium carbonate (0), respectively.5mmol，69mg)，N2Under the protection condition, carrying out N-alkylation reaction at 130 ℃, stirring at 500rpm, reacting for 18h, respectively washing with absolute ethyl alcohol and deionized water, and vacuum drying at 50 ℃ for 12h to obtain the branched high-immobilized 4-dimethylaminopyridine catalyst with the loading of 1.9mmol (0.205g) of 4-methylaminopyridine per 1g of silicon-based carrier.
The catalyst is used for catalyzing the acetylation reaction of vitamin E and acetic anhydride, the reaction lasts for 12h, the conversion rate of the vitamin E reaches 92 percent, and the initial activity of the supported catalyst is 5.25 mmol/h.gCatalyst and process for preparing same。
Example 2
The embodiment provides a preparation method of a branched high-solid-supported DMAP catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of silica gel and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing and refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and drying at 50 ℃ in vacuum for 12h to obtain the silicon-based epoxy carrier.
Transferring the obtained silicon epoxide-based carrier into a three-neck flask containing 30mLDMF, fully stirring for 30min at room temperature, adding glycerol (30mmol,2.5mL), reacting at 50 ℃, reacting for 8h, adding 50 mu L boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride silicon-based carrier.
Adding 4-methylamino pyridine (0.5mmol, 54mg) into a micro reaction bottle, dissolving in 5mL o-xylene, adding 200mg of polyalkyl chloro silicon based carrier after full dissolution, then adding calcium hydroxide (0.6mmol, 45mg), N2Under the condition of protection, the method can be used,the N-alkylation reaction is carried out at 130 ℃, the stirring speed is 600rpm, the reaction is carried out for 18h, the reaction product is washed by absolute ethyl alcohol and deionized water respectively, the reaction product is dried in vacuum at 50 ℃ for 12h, and the loading capacity is 0.45mmol (0.154g) of 4-methylaminopyridine per 1g of silicon-based carrier. The catalyst is used for catalyzing the acetylation reaction of vitamin E and acetic anhydride, the reaction lasts for 12h, the conversion rate of the vitamin E reaches 69%, and the initial activity of the supported catalyst is 3.94 mmol/h.gCatalyst and process for preparing same。
Example 3
The embodiment provides a preparation method of a branched high-solid-supported DMAP catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of silica gel and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing and refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and drying at 50 ℃ in vacuum for 12h to obtain the silicon-based epoxy carrier.
Transferring the obtained silicon epoxide-based carrier into a three-neck flask containing 30mLDMF, fully stirring for 30min at room temperature, adding glycerol (30mmol,2.5mL), reacting at 50 ℃, reacting for 8h, adding 50 mu L boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride silicon-based carrier.
Adding 4-methylamino pyridine (0.5mmol, 54mg) into a micro reaction bottle, dissolving in 5mL o-xylene, adding 200mg of polyalkyl chloro silicon based carrier after full dissolution, then adding sodium hydroxide (0.6mmol, 24mg), N2Under the protection condition, carrying out N-alkylation reaction at 120 ℃, stirring at 500rpm, reacting for 18h, respectively washing with absolute ethyl alcohol and deionized water, vacuum drying at 50 ℃ for 12h,the loading was 0.4mmol (0.137g) of 4-methylaminopyridine per 1g of silica-based support. The catalyst is used for catalyzing the acetylation reaction of vitamin E and acetic anhydride, the reaction lasts for 12h, the conversion rate of the vitamin E reaches 62 percent, and the initial activity of the supported catalyst is 3.54 mmol/h.gCatalyst and process for preparing same。
Example 4
The embodiment provides a preparation method of a branched high-solid-supported DMAP catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of silica gel and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing and refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and drying at 50 ℃ in vacuum for 12h to obtain the silicon-based epoxy carrier.
Transferring the obtained silicon epoxide-based carrier into a three-neck flask containing 30mLDMF, fully stirring for 30min at room temperature, adding glycerol (30mmol,2.5mL), reacting at 50 ℃, reacting for 8h, adding 50 mu L boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride silicon-based carrier.
Adding 4-methylamino pyridine (0.5mmol, 54mg) into a micro reaction bottle, dissolving in 5mL o-xylene, adding 200mg of polyalkyl chloro silicon based carrier after full dissolution, then respectively adding potassium bicarbonate (0.6mmol, 60mg), N2Under the protection condition, carrying out N-alkylation reaction at 100 ℃, stirring at 500rpm, reacting for 18h, respectively washing with absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50 ℃ for 12h, wherein the loading amount is 0.5mmol (0.137g) of 4-methylaminopyridine per 1g of silicon-based carrier. The catalyst is used for catalyzing the acetylation reaction of vitamin E and acetic anhydride, the reaction lasts for 12hThe conversion rate of the biotin E reaches 62 percent, and the initial activity of the supported catalyst is 3.54 mmol/h.gCatalyst and process for preparing same。
Example 5
The embodiment provides a preparation method of a branched high-solid-content 4-dimethylaminopyridine catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of silica gel and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing and refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and drying at 50 ℃ in vacuum for 12h to obtain the silicon-based epoxy carrier.
Transferring the obtained epoxy silicon-based carrier into a three-neck flask containing 30mLDMF, fully stirring for 30min at room temperature, adding sorbitol (8mL, 30mmol), reacting at 50 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and vacuum drying at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride silicon-based carrier.
Adding 4-methylaminopyridine (0.8mmol, 86.5mg) into a micro reaction flask, dissolving in 5mL o-xylene, adding 200mg of polyalkylchlorosilane-based carrier after fully dissolving, and adding potassium iodide (1.2mmol, 199mg), potassium carbonate (1.6mmol, 221mg), and N2Under the protection condition, carrying out N-alkylation reaction at 130 ℃, stirring at 600rpm, reacting for 24h, washing with absolute ethyl alcohol and deionized water respectively, and vacuum-drying at 50 ℃ for 12h to obtain the branched high-immobilized 4-dimethylaminopyridine catalyst with the loading of 3.6mmol (0.39g) of 4-methylaminopyridine per 1g of silicon-based carrier.
The catalyst is used for catalyzing the acetylation reaction of vitamin E and acetic anhydride, the reaction lasts for 12hThe conversion rate of the element E reaches 91 percent, and the initial activity of the supported catalyst is 13.5 mmol/h.gCatalyst and process for preparing same。
Example 6
The embodiment provides a preparation method of a branched high-solid-content 4-dimethylaminopyridine catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of nano-silica and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing, refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and vacuum-drying at 50 ℃ for 12h to obtain the epoxy silicon-based carrier.
Transferring the obtained epoxy silicon-based carrier into a three-neck flask containing 30mLDMF, fully stirring for 30min at room temperature, adding sorbitol (8mL, 30mmol), reacting at 50 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and vacuum drying at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride silicon-based carrier.
Adding 4-methylaminopyridine (0.8mmo, 86.5mg) into a micro reaction flask, dissolving in 5mL o-xylene, adding 200mg of polyalkylchlorosilane-based carrier after fully dissolving, and adding potassium iodide (1.2mmol, 199mg), potassium carbonate (1.6mmol, 221mg), and N2Under the protection condition, carrying out N-alkylation reaction at 130 ℃, stirring at 600rpm, reacting for 24h, washing with absolute ethyl alcohol and deionized water respectively, and vacuum-drying at 50 ℃ for 12h to obtain the branched high-immobilized 4-dimethylaminopyridine catalyst with the loading of 3.32mmol (0.39g) of 4-methylaminopyridine per 1g of silicon-based carrier.
The catalyst is used for catalyzing the acetylation reaction of vitamin E and succinic anhydride, and the reaction12h, the conversion rate of the vitamin E reaches 93 percent, and the initial activity of the supported catalyst is 17.75 mmol/h.gCatalyst and process for preparing same。
Example 7
The embodiment provides a preparation method of a branched high-solid-content 4-dimethylaminopyridine catalyst, which comprises the following specific steps:
firstly, preparing a coupling silicon-based carrier: adding 2.5g of MCM-41 molecular sieve and 30mL of toluene into a 100mL reaction bottle, fully stirring at room temperature for 30min, adding KH-560(2.5mL and 15mmol), drying at 95 ℃, condensing, refluxing for 18h, centrifuging, washing the obtained solid with toluene and acetone respectively, and drying at 50 ℃ in vacuum for 12h to obtain the silicon epoxide-based carrier.
Transferring the obtained epoxy silicon-based carrier into a three-neck flask containing 30mLDMF, fully stirring for 30min at room temperature, adding sorbitol (8mL, 30mmol), reacting at 50 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and vacuum drying at 50 ℃ for 12h to obtain the polyhydroxy silicon-based carrier.
Transferring the obtained polyhydroxy silicon-based carrier into a three-neck flask containing 30mLDMF, stirring for 30min at room temperature, adding 2.5mL of epoxy chloropropane, reacting at 60 ℃, reacting for 8h, adding 50 mu L of boron trifluoride diethyl etherate solution every 2h for catalysis, centrifuging, washing the obtained solid with DMF, deionized water and acetone respectively, and drying in vacuum at 50 ℃ for 12h to obtain the polyalkyl chloride silicon-based carrier.
Adding 4-methylaminopyridine (0.8mmol, 86.5mg) into a micro reaction flask, dissolving in 5mL o-xylene, adding 200mg of polyalkylchlorosilane-based carrier after fully dissolving, and adding potassium iodide (1.2mmol, 199mg), potassium carbonate (1.6mmol, 221mg), and N2Under the protection condition, carrying out N-alkylation reaction at 130 ℃, stirring at 600rpm, reacting for 24h, washing with absolute ethyl alcohol and deionized water respectively, and vacuum-drying at 50 ℃ for 12h to obtain the branched high-immobilized 4-dimethylaminopyridine catalyst with the loading of 4.11mmol (0.39g) of 4-methylaminopyridine per 1g of silicon-based carrier.
The catalyst is used for catalyzing the acetylation reaction of vitamin E and succinic anhydrideThe reaction is carried out for 12 hours, the conversion rate of the vitamin E reaches 89 percent, and the initial activity of the supported catalyst is 12.75 mmol/h.gCatalyst and process for preparing same。
Comparative example 1:
into a 25mL reaction flask, 5mL of toluene was added, followed by vitamin E (0.5mmol, 215mg), the branched high-immobilized 4-dimethylaminopyridine catalyst prepared in example 5 (10.6mg), acetic anhydride (1.5mmol, 153mg), and N in that order2Under the protection condition, the reaction is carried out for 12h at 50 ℃, samples are taken every 2h and analyzed by TLC, and the conversion rate of the vitamin E reaches 91 percent. Then filtering and separating out the supported catalyst, washing with absolute ethyl alcohol and drying. Activity of the initially branched DMAP 13.5mmol/h gCatalyst and process for preparing sameAfter 20 times of recycling, the activity of the catalyst is still maintained above 90%, and no large activity loss is caused basically.
The acylation reaction is catalyzed by non-branched DMAP (which is carried out according to the method described in the background technology (4)) under the same reaction conditions, and when the dosage of the non-branched DMAP is 50mg, the conversion rate of the vitamin E reaches the maximum value of 79 percent; when the amount of branched DMAP was 10.6mg, which was about 1/5% of the amount of unbranched DMAP, the conversion of vitamin E was as high as 91%. By comparison, it is shown that branched DMAP can achieve better catalytic effect with lower dosage than non-branched DMAP.
The experimental results of this comparative example and example 5 are shown in fig. 1.
Comparative example 2:
the effect of the branched high-solid-supported DMAP catalyst is verified as follows:
into a 25mL reaction flask, 5mL of toluene was added, followed by sequentially adding vitamin E (0.5mmol, 215mg), the branched high-immobilized 4-dimethylaminopyridine catalyst prepared in example 1 (20mg), acetic anhydride (1.5mmol, 153mg), and N2Under the protection condition, the reaction is carried out for 12h at 50 ℃, samples are taken every 2h and analyzed by TLC, and the conversion rate of the vitamin E reaches 92 percent. Then filtering and separating out the supported catalyst, washing with absolute ethyl alcohol and drying. Activity of the initially branched DMAP 5.25mmol/h gCatalyst and process for preparing sameAfter 20 times of recycling, the activity of the catalyst is kept at 90 percentAbove, there is substantially no great loss of activity.
Free DMAP is used for catalyzing the acylation reaction under the same reaction condition, the conversion rate of the vitamin E is 98 percent, and the initial activity of the catalyst is 36 mmol/h.gCatalyst and process for preparing same. By contrast, supported DMAP catalysts have good reproducibility and stability, although their catalytic activity is reduced by their support.
The experimental results of this comparative example and example 1 are shown in fig. 2.
Comparative example 3:
into a 25mL reaction flask, 5mL of toluene was added, followed by vitamin E (0.5mmol, 215mg), the branched high-immobilized 4-dimethylaminopyridine catalyst prepared in example 5 (10.6mg), acetic anhydride (1.5mmol, 153mg), and N in that order2Under the protection condition, the reaction is carried out for 12h at 50 ℃, samples are taken every 2h and analyzed by TLC, and the conversion rate of the vitamin E reaches 91 percent. Then filtering and separating out the supported catalyst, washing with absolute ethyl alcohol and drying. Activity of the initially branched DMAP 13.5mmol/h gCatalyst and process for preparing sameAfter 20 times of recycling, the activity of the catalyst is still maintained above 90%, and no large activity loss is caused basically.
Free DMAP is used for catalyzing the acylation reaction under the same reaction condition, the conversion rate of the vitamin E is 98 percent, and the initial activity of the catalyst is 36 mmol/h.gCatalyst and process for preparing same. By contrast, supported DMAP catalysts have good reproducibility and stability, although their catalytic activity is reduced by their support.
The experimental results of this comparative example and example 5 are shown in fig. 3.
Claims (10)
1. A preparation method of a branched high-solid-content 4-dimethylaminopyridine catalyst is characterized in that a multi-alkyl chloride-based silicon-based carrier is obtained by performing an epoxy-alcohol addition reaction on a polyhydroxy silicon-based carrier, and the N-alkylation reaction is performed on the multi-alkyl chloride-based silicon-based carrier and 4-methylaminopyridine in the presence of a reaction catalyst to prepare the branched high-solid-content 4-dimethylaminopyridine catalyst;
the polyhydroxy silicon-based carrier is prepared by modifying the surface of a silicon-based carrier by using a silane coupling agent to obtain an epoxy silicon-based carrier and branching the epoxy end of the epoxy silicon-based carrier in dimethylformamide by using a branching agent;
the reaction catalyst for the N-alkylation reaction is K2CO3、Na2CO3、KHCO3、NaHCO3、KI、KOH、NaOH、Ca(OH)2、C2H5ONa, triethylamine or pyridine.
2. The preparation method according to claim 1, comprising the specific steps of:
modifying the surface of a silicon-based carrier by using a silane coupling agent in an anhydrous solvent 1 to obtain an epoxy silicon-based carrier, and branching the epoxy group tail end of the epoxy silicon-based carrier in dimethylformamide by using a branching agent to obtain a polyhydroxy silicon-based carrier;
carrying out epoxy-alcohol addition reaction on the obtained polyhydroxy silicon-based carrier and epoxy chloropropane in dimethylformamide to obtain a polyalkyl chloride-based silicon-based carrier;
then 4-methylaminopyridine is fully dissolved in an anhydrous solvent 2 to obtain a solution, and the solution is dissolved in N2Carrying out N-alkylation reaction under protection: and sequentially adding a poly-alkyl chloro-silicon-based carrier and a reaction catalyst into the solution, stirring, separating out solids after the reaction is finished, and washing and drying to obtain the branched high-solid-supported 4-dimethylaminopyridine catalyst.
3. The method of claim 2, wherein the silane coupling agent is γ - (2, 3-epoxypropoxy) propyltrimethoxysilane;
the silicon-based carrier is a natural or artificially synthesized silicon-containing material.
4. The method of claim 2, wherein the branching agent is glycerol, xylitol or sorbitol.
5. The method of claim 2, wherein the reaction conditions for preparing the silica-based carrier are dry condensation reflux at 95 ℃ for 18 h.
6. The preparation method of claim 2, wherein the reaction conditions for preparing the polyhydroxy silicon-based carrier are 30-70 ℃ for 2-12 h, and 50 μ L of boron trifluoride ethyl ether solution is added every 2h for catalysis.
7. The preparation method of claim 2, wherein the reaction conditions for preparing the polyalkylchlorosilane-based carrier are 60 ℃ for 2-12 h and 50 μ L of boron trifluoride ethyl ether solution is added every 2h for catalysis.
8. The preparation method according to claim 2, wherein the addition amount of the reaction catalyst is 0.1 to 4.5 times of the molar mass of the 4-methylaminopyridine, the stirring rate is 300 to 700rpm, the N-alkylation reaction temperature is 90 to 140 ℃, and the reaction is carried out for 1 to 25 hours.
9. The method according to claim 2, wherein the anhydrous solvent 1 and the anhydrous solvent 2 are both aromatic hydrocarbons.
10. The branched high-solid-content 4-dimethylaminopyridine catalyst is characterized by being prepared by the preparation method of any one of claims 1-9.
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