CN115722238B - Method for synthesizing olefin monomer by catalytic conversion of biomass glycosyl compound and preparation of reversible cured liquid rubber - Google Patents
Method for synthesizing olefin monomer by catalytic conversion of biomass glycosyl compound and preparation of reversible cured liquid rubber Download PDFInfo
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- CN115722238B CN115722238B CN202211445882.3A CN202211445882A CN115722238B CN 115722238 B CN115722238 B CN 115722238B CN 202211445882 A CN202211445882 A CN 202211445882A CN 115722238 B CN115722238 B CN 115722238B
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- catalyst
- nitrate
- cerium
- hap
- acid
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 101
- 239000000178 monomer Substances 0.000 title claims abstract description 88
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 47
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 45
- 229920001971 elastomer Polymers 0.000 title abstract description 63
- 239000007788 liquid Substances 0.000 title abstract description 63
- 239000005060 rubber Substances 0.000 title abstract description 63
- 239000002028 Biomass Substances 0.000 title abstract description 23
- 230000003197 catalytic effect Effects 0.000 title abstract description 18
- 230000002441 reversible effect Effects 0.000 title abstract description 13
- 150000002340 glycosyl compounds Chemical class 0.000 title abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 164
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 115
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 98
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052684 Cerium Inorganic materials 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000006104 solid solution Substances 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 34
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 29
- -1 furyl butadiene Chemical compound 0.000 claims description 29
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 29
- 229910052746 lanthanum Inorganic materials 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910002482 Cu–Ni Inorganic materials 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 229910017816 Cu—Co Inorganic materials 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- YGGXZTQSGNFKPJ-UHFFFAOYSA-N methyl 2-naphthalen-1-ylacetate Chemical compound C1=CC=C2C(CC(=O)OC)=CC=CC2=C1 YGGXZTQSGNFKPJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 60
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 239000007859 condensation product Substances 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 7
- 238000005698 Diels-Alder reaction Methods 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 73
- 239000011701 zinc Substances 0.000 description 72
- 239000011777 magnesium Substances 0.000 description 67
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 62
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 58
- 230000001276 controlling effect Effects 0.000 description 48
- 239000002585 base Substances 0.000 description 42
- 229910019142 PO4 Inorganic materials 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 32
- 239000002904 solvent Substances 0.000 description 31
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 30
- USWLXMQMWKPZQX-UHFFFAOYSA-N 2-buta-1,3-dienylfuran Chemical compound C=CC=CC1=CC=CO1 USWLXMQMWKPZQX-UHFFFAOYSA-N 0.000 description 29
- 229960002089 ferrous chloride Drugs 0.000 description 29
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 24
- LJBTWTBUIINKRU-UHFFFAOYSA-K cerium(3+);triperchlorate Chemical compound [Ce+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LJBTWTBUIINKRU-UHFFFAOYSA-K 0.000 description 20
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 19
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 17
- 239000011609 ammonium molybdate Substances 0.000 description 17
- 235000018660 ammonium molybdate Nutrition 0.000 description 17
- 229940010552 ammonium molybdate Drugs 0.000 description 17
- 239000011790 ferrous sulphate Substances 0.000 description 17
- 235000003891 ferrous sulphate Nutrition 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 17
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 16
- 238000000227 grinding Methods 0.000 description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 15
- 229910000024 caesium carbonate Inorganic materials 0.000 description 15
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 15
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 15
- 239000011736 potassium bicarbonate Substances 0.000 description 15
- 235000015497 potassium bicarbonate Nutrition 0.000 description 15
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 15
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 15
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 description 14
- 235000017550 sodium carbonate Nutrition 0.000 description 14
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 13
- 239000011592 zinc chloride Substances 0.000 description 13
- 235000005074 zinc chloride Nutrition 0.000 description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 12
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 12
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- 235000011181 potassium carbonates Nutrition 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 229910000365 copper sulfate Inorganic materials 0.000 description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 10
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 10
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 9
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- LVNQQSHCPFQTBO-UHFFFAOYSA-N 1-(furan-2-yl)but-3-en-2-one Chemical compound C=CC(=O)CC1=CC=CO1 LVNQQSHCPFQTBO-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 8
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 description 7
- 229960001763 zinc sulfate Drugs 0.000 description 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 6
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 229940045803 cuprous chloride Drugs 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 229940049953 phenylacetate Drugs 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 5
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- OXUBOOPFXQOMBI-UHFFFAOYSA-N ethyl 2-bromo-2-phenylpropanoate Chemical compound CCOC(=O)C(C)(Br)C1=CC=CC=C1 OXUBOOPFXQOMBI-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 5
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 5
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 5
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 5
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 4
- 150000002402 hexoses Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 241001538234 Nala Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000005194 ethylbenzenes Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229940040102 levulinic acid Drugs 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002972 pentoses Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical group CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention provides an application of a catalyst in synthesizing olefin monomers; the catalyst comprises a Cu-based active metal-acid-base catalyst; the general formula of the Cu-based active metal-acid-base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4. The Cu-based active metal-acid-base catalyst designed by the invention is used after furfural is condensed with acetone, can realize one-step hydrogenation-deoxidation of a condensation product of furyl-3-butene-2-one to generate furyl-3-butadiene, and has higher yield. The invention also provides a method for synthesizing olefin monomer by catalytic conversion of biomass glycosyl compound and a method for preparing reversible curing liquid rubber, wherein a controllable free radical initiation system is adopted to realize self polymerization of furan-based butadiene and copolymerization of furan-based butadiene to prepare liquid rubber, and the method is based on Diels-Alder reaction of furan to realize reversible curing.
Description
Technical Field
The invention belongs to the technical field of biomass-based green polymer synthesis, relates to application of a catalyst in synthesizing an olefin monomer, a synthesis method of the olefin monomer and a preparation method of liquid rubber, and particularly relates to application of the catalyst in synthesizing the olefin monomer, a method for synthesizing the olefin monomer by catalytic conversion of a biomass glycosyl compound and preparation of reversible solidified liquid rubber.
Background
The biomass-based chemicals in the future are planned to account for 25% of the total chemicals in China, however, the substitution rate is less than 5% at present, and therefore, the development of a new technology for the fine and deep processing of biomass resources is important. Cellulose and hemicellulose are widely present in agricultural waste such as straw, corncob, etc. The straw contains 39-47% of cellulose, 27-38% of hemicellulose and the balance of ash and lignin. The cellulose is formed by polymerizing hexose through beta-1, 4-glycosidic bond, and the hemicellulose is composed of pentose and hexose, wherein the pentose is catalyzed and dehydrated/enzymatically hydrolyzed to generate furfural, levulinic acid and other platform compounds, and the hexose is converted into 5-hydroxymethylfurfural, levulinic acid and the like. At present, based on the research on the hydrolysis mechanism of the straw, the hydrolysis degree is controlled, the accurate control of the product can be realized, the hexose is converted into levulinic acid through 5-hydroxymethyl furfural, and the pentose is dehydrated to generate furfural. The production of furfural from corncob has been industrialized, and furfural is produced by xylose dehydration, and the production of furfural by hydrolyzing corncob with concentrated sulfuric acid is industrially performed (yield >25 ten thousand tons/year).
Biomass resources such as straw, corncob and the like have huge yield, short growth cycle and low cost and are easy to obtain, and the catalytic conversion of the furfural serving as an important platform compound for acidolysis of the biomass such as straw, corncob and the like is a key for realizing high-value utilization of biomass resources. The furfural can be used for producing furfuryl alcohol, 2-methyltetrahydrofuran, pentanediol and other chemicals, the furfural is condensed with acetone, and aviation oil, polymers and the like can be produced by deep processing. However, the catalytic activity of the corresponding reaction process disclosed in the prior art is still lower, and the yield is still to be improved.
Therefore, based on the condensation of furfural and acetone, how to design and develop a catalyst with high activity is always the focus of research in the industry, and how to better utilize a biomass platform compound, namely furfural, to continuously develop a novel technology for the fine and deep processing of furfural, so that the preparation of special chemical products with high added value is significant for promoting the development of biomass-based chemicals, and is one of the focus of attention of a plurality of prospective researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an application of a catalyst in synthesizing an olefin monomer, a method for synthesizing an olefin monomer, and a method for preparing liquid rubber, in particular a method for synthesizing an olefin monomer by catalytic conversion of a biomass glycosyl compound. The invention provides a method for preparing reversibly solidified liquid rubber by condensing furfural and acetone, and then realizing one-step hydrogenation-deoxidation of furyl-3-butene-2-ketone to generate furyl-3-butadiene. Meanwhile, the reaction condition is mild, the operation is simple, and the method has the prospect of large-scale synthesis.
The invention provides an application of a catalyst in synthesizing olefin monomers;
The catalyst comprises a Cu-based active metal-acid-base catalyst;
The general formula of the Cu-based active metal-acid-base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4;
Wherein M is Cu-Ni and/or Cu-Co;
HAP is hydroxyapatite;
Z is a cerium-based solid solution;
a is one or more of La, ce, pr, nd and Gd;
B is one or more of Mo, zr, zn, W and V;
x＝0.7～1.4，y＝0.02～0.3。
preferably, the olefin monomer comprises a furan-based olefin monomer;
the cerium-based solid solution includes a cerium-based binary solid solution;
in the cerium-based binary solid solution, the atomic ratio of metal to cerium is (0.5-1.2): 1, a step of;
the synthetic raw materials comprise furfural and acetone.
Preferably, the olefin monomer comprises furanyl butadiene;
the cerium-based solid solution includes one or more of LaCe, prCe, moCe, zrCe and ZnCe;
in the M.HAP, the loading of M is 2-15 wt%;
The mass ratio of M.HAP to Z, M.HAP to A xByPO4 and the mass ratio of M.HAP to (Z+A xByPO4) are independently selected from (0.5-3): 1.
Preferably, the catalyst further comprises M 1·(Znx1-Aly1 Mg) catalyst;
Wherein M 1 is one or more of Na, K, cs, la, ce, pr and Nd;
x1＝0.02～1.2，y1＝0.2～4；
the loading amount of the M 1 is 5-25 wt%;
The synthesis is specifically two-stage synthesis;
The M 1·(Znx1-Aly1 Mg) catalyst is a catalyst for one-stage synthesis;
the Cu-based active metal-acid-base catalyst is a catalyst for two-stage synthesis;
the first stage synthesis is a condensation reaction;
the two-stage synthesis is hydrodeoxygenation reaction.
Preferably, the preparation process of the Cu-based active metal-acid-base catalyst comprises the following steps:
Roasting hydroxyapatite, placing the hydroxyapatite in an M source solution, and roasting again after the exchange-adsorption-deposition process to obtain M.HAP;
Regulating the pH value of the mixed solution of the cerium source and the other metal source in the cerium-based solid solution to obtain a precipitate, and performing heat treatment to obtain the cerium-based solid solution;
Regulating the pH value of the mixed solution of the rare earth metal soluble compound and the transition metal soluble compound to obtain a precipitate, drying, carrying out stepped temperature rise ball milling with a phosphoric acid solution, and continuously roasting to obtain A xByPO4;
mixing the M.HAP obtained in the step with cerium-based solid solution and/or A xByPO4 again to obtain a Cu-based active metal-acid-base catalyst;
The preparation process of the M 1·(Znx1-Aly1 Mg) catalyst comprises the following steps:
a) Ball milling a Zn source, an Al source, an Mg source and water to obtain powder, and roasting to obtain Zn x1-Aly1 Mg;
b) Adding Zn x1-Aly1 Mg obtained in the steps into soluble M 1 source aqueous solution, standing, and roasting again to obtain the M 1·(Znx1-Aly1 Mg) catalyst.
The invention provides a method for synthesizing an olefin monomer, which comprises the following steps:
1) Carrying out condensation reaction on furfural and acetone, M 1·(Znx1-Aly1 Mg) catalyst in a mixed solvent to obtain furyl-3-butene-2-ketone;
2) Under the action of Cu-based active metal-acid-base catalyst and under the condition of hydrogen, the furyl-3-butene-2-ketone obtained in the steps is subjected to hydrodeoxygenation reaction to obtain the furyl butadiene.
Preferably, the molar ratio of the acetone to the furfural is (1-12): 1, a step of;
the mixed solvent comprises a mixed solvent of methanol and water;
The mass ratio of the mixed solvent to the reactant is (5-15): 1, a step of;
The mass ratio of the M 1·(Znx1-Aly1 Mg) catalyst to the reactant is 1-5 wt%;
the temperature of the condensation reaction is 60-160 ℃;
The time of the condensation reaction is 2-12 h.
Preferably, the hydrodeoxygenation reaction mode is a fixed bed reaction;
the temperature of the hydrodeoxygenation reaction is 180-280 ℃;
the reaction pressure of the hydrodeoxygenation reaction is 0.01-0.5 Mpa;
The flow rate of the hydrogen is 0-100 ml/min;
the feeding speed of the furyl-3-butene-2-ketone is 0.2-0.8 ml/min.
The invention also provides a preparation method of the liquid rubber, which comprises the following steps:
Mixing a catalyst system, a monomer and a solvent, and then performing solution polymerization reaction to obtain liquid rubber;
The monomer includes an olefin-type monomer and butadiene, or, an olefin-type monomer;
The olefin monomer comprises the olefin monomer in the application of any one of the technical schemes or the olefin monomer prepared by the preparation method of any one of the technical schemes.
Preferably, the catalyst system comprises one or more of methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, ethyl 2-bromo-2-phenylpropionate/Cu, ethyl 2-bromo-2-p-phenylacetate/Cu, or haloethylbenzene/cuprous halide/bipyridine, or triphenylchloromethane, trifluoroacetic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, and hydrogen peroxide/ferrous chloride;
The solvent comprises one or more of N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, tertiary butanol, dimethyl sulfoxide and N, N-dimethylformamide;
The molar ratio of the olefin monomer to butadiene is (0.1-0.6): 1, a step of;
After the mixing, the concentration of the monomer is 1.0-3.5 mol/L;
After the mixing, the concentration of the catalyst is 2-20 mmol/L;
the temperature of the solution polymerization reaction is 40-90 ℃;
the time of the solution polymerization reaction is 0.5-5 h;
the molecular weight of the obtained liquid rubber is 2000-6000 g/mol;
the liquid rubber includes a reversible-curing liquid rubber.
The invention provides an application of a catalyst in synthesizing olefin monomers; the catalyst comprises a Cu-based active metal-acid-base catalyst; the general formula of the Cu-based active metal-acid-base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4; wherein M is Cu-Ni and/or Cu-Co; HAP is hydroxyapatite; z is a cerium-based solid solution; a is one or more of La, ce, pr, nd and Gd; b is one or more of Mo, zr, zn, W and V; x=0.7 to 1.4, and y=0.02 to 0.3. Compared with the prior art, the invention particularly designs the Cu-based active metal-acid-base catalyst with specific structure and composition, which can realize one-step hydrogenation-deoxidation of a condensation product furyl-3-butene-2-one to generate furyl-3-butadiene after the condensation product of furfural and acetone is condensed in the synthesis process of the furfural-based olefin monomer. The two-stage reaction provided by the invention has good catalyst activity, the condensation product of furfural and acetone has higher yield, the two-stage reaction can realize the one-step hydrogenation-deoxidation process of the condensation product, and the two-stage reaction has higher yield, simple process and strong controllability. The invention also provides a method for synthesizing the olefin monomer by catalytic conversion of the corresponding biomass glycosyl compound, and further provides a method for preparing the reversibly solidified liquid rubber by using the method, which has the advantages of mild reaction conditions, simple operation and large-scale synthesis prospect.
The invention provides a synthetic method of olefin monomer and a preparation process of functional liquid rubber, which comprises the steps of firstly adopting a heterogeneous catalyst to condense furfural and acetone to prepare furyl-3-butene-2-ketone; then adopting a Cu-based metal-acid-base multifunctional catalyst to synthesize the furyl butadiene monomer by one-step hydrogenation-deoxidation of the furyl-3-butene-2-one. The invention also discloses a method for preparing the liquid rubber by polymerizing in the solution and adopting a controllable free radical initiation system to realize self polymerization of the furyl butadiene and copolymerization of the furyl butadiene and the butadiene, and the method is based on Diels-Alder reaction of furan to realize reversible curing.
Experimental results show that biomass-based furfural can be effectively converted into furyl butadiene by the method provided by the invention, catalytic conversion is realized in one step, the process is simple, the catalyst efficiency is high, and the obtained furyl butadiene is used for synthesizing novel liquid rubber.
Drawings
FIG. 1 is a schematic diagram of a reaction process for synthesizing an olefin monomer by catalytic conversion of a biomass glycosyl compound and converting the olefin monomer into a reversible curing liquid rubber;
FIG. 2 is an external view of a liquid rubber prepared according to the present invention;
FIG. 3 is a GPC chart of the liquid rubber prepared in example 1 of the present invention;
FIG. 4 is an H-NMR chart of a liquid rubber prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs the purity requirements conventional in the art of synthesizing analytically pure or furanyl olefin monomers.
All raw materials and processes of the invention, the brands or abbreviations of which belong to the conventional brands or abbreviations in the field of the related application are clear and definite, and according to the brands, abbreviations and the corresponding application, the raw materials and processes can be purchased from the market or prepared by the conventional method or realized by adopting the corresponding equipment.
The invention provides an application of a catalyst in synthesizing olefin monomers;
The catalyst comprises a Cu-based active metal-acid-base catalyst;
The general formula of the Cu-based active metal-acid-base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4;
Wherein M is Cu-Ni and/or Cu-Co;
HAP is hydroxyapatite;
Z is a cerium-based solid solution;
a is one or more of La, ce, pr, nd and Gd;
B is one or more of Mo, zr, zn, W and V;
x＝0.7～1.4，y＝0.02～0.3。
In the invention, the general formula of the Cu-based active metal-acid base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4;
wherein M is Cu-Ni and/or Cu-Co, and can be Cu-Ni or Cu-Co.
In the present invention, a is one or more of La, ce, pr, nd and Gd, which may be La, ce, pr, nd or Gd.
In the present invention, B is one or more of Mo, zr, zn, W and V, which may be Mo, zr, zn, W or V.
In the present invention, x=0.7 to 1.4 may be 0.8 to 1.3, preferably 0.9 to 1.2, and more preferably 1.0 to 1.1.
In the present invention, y=0.02 to 0.3, may be 0.2 to 0.28, and preferably 0.22 to 0.26.
In the present invention, the olefin-based monomer preferably includes a furyl olefin-based monomer.
In the present invention, the cerium-based solid solution preferably includes a cerium-based binary solid solution.
In the present invention, in the cerium-based binary solid solution, the atomic ratio of metal to cerium is preferably (0.5 to 1.2): 1, more preferably (0.6 to 1.1): 1, more preferably (0.7 to 1.0): 1, more preferably (0.8 to 0.9): 1.
In the present invention, the synthetic raw materials preferably include furfural and acetone. In particular, the starting material is preferably a starting material.
In the present invention, the olefin-based monomer preferably includes furanyl butadiene.
In the present invention, the cerium-based solid solution preferably includes one or more of LaCe, prCe, moCe, zrCe and ZnCe, more preferably LaCe, prCe, moCe, zrCe or ZnCe.
In the present invention, the loading amount of M in the m·hap is preferably 2wt% to 15wt%, more preferably 5wt% to 12wt%, and still more preferably 8wt% to 9wt%.
In the present invention, the mass ratio of m.hap to Z, M.hap to a xByPO4 and the mass ratio of m.hap to (z+a xByPO4) are each independently preferably selected from (0.5 to 3): 1, or (0.8-2.5): 1, or (1-2): 1.
In the present invention, the catalyst also preferably includes M 1·(Znx1-Aly1 Mg) catalyst.
In the present invention, among them, M 1 is preferably one or more of Na, K, cs, la, ce, pr and Nd, more preferably Na, K or Cs, and alkali metal and rare earth elements. Specifically, the number of M 1 may be one or more, where M1 is one, M 1 is Na, K or Cs, and where M 1 is one or more, at least one is Na, K or Cs. That is, M 1 is preferably one or more of Na, K, and Cs, or a combination of one or more of Na, K, and Cs with one or more of La, ce, pr, and Nd.
In the present invention, x1=0.02 to 1.2, more preferably 0.2 to 1.0, and still more preferably 0.4 to 0.8.
In the present invention, y1=0.2 to 4, more preferably 0.5 to 3.0, and still more preferably 1.0 to 2.0.
In the present invention, the loading amount of the M 1 is preferably 5wt% to 25wt%, more preferably 9wt% to 21wt%, and still more preferably 13wt% to 17wt%.
In the present invention, the synthesis is specifically preferably a two-stage synthesis.
In the present invention, the M 1·(Znx1-Aly1 Mg) catalyst is preferably a catalyst for one-stage synthesis.
In the present invention, the Cu-based active metal-acid base catalyst is preferably a catalyst for two-stage synthesis.
In the present invention, the one-stage synthesis is preferably a condensation reaction.
In the present invention, the two-stage synthesis is preferably a hydrodeoxygenation reaction.
In the present invention, in the preparation of the catalyst, the various raw material sources are preferably soluble raw material sources.
In the present invention, the preparation process of the Cu-based active metal-acid base catalyst preferably includes the steps of:
Roasting hydroxyapatite, placing the hydroxyapatite in an M source solution, and roasting again after the exchange-adsorption-deposition process to obtain M.HAP;
Regulating the pH value of the mixed solution of the cerium source and the other metal source in the cerium-based solid solution to obtain a precipitate, and performing heat treatment to obtain the cerium-based solid solution;
Regulating the pH value of the mixed solution of the rare earth metal soluble compound and the transition metal soluble compound to obtain a precipitate, drying, carrying out stepped temperature rise ball milling with a phosphoric acid solution, and continuously roasting to obtain A xByPO4;
And mixing the M.HAP obtained in the step with cerium-based solid solution and/or A xByPO4 again to obtain the Cu-based active metal-acid-base catalyst.
The invention is to bake the hydroxyapatite, then place it in M source solution, after exchanging-adsorbing-depositing process, bake it again, get M.HAP.
In the present invention, the temperature of the hydroxyapatite is preferably 800 to 1500 ℃, more preferably 900 to 1400 ℃, more preferably 1000 to 1300 ℃, more preferably 1100 to 1200 ℃.
In the present invention, the time for firing the hydroxyapatite is preferably 2 to 8 hours, more preferably 3 to 7 hours, and still more preferably 4 to 6 hours.
In the present invention, the M source preferably includes a copper source and a nickel source or a cobalt source.
In the present invention, the copper source preferably includes one or more of copper nitrate, copper chloride, cuprous chloride, copper sulfate and copper oxalate, more preferably copper nitrate, copper chloride, cuprous chloride, copper sulfate or copper oxalate.
In the present invention, the nickel source preferably includes one or more of nickel nitrate, nickel chloride and nickel sulfate, more preferably nickel nitrate, nickel chloride or nickel sulfate.
In the present invention, the cobalt source preferably includes one or more of cobalt nitrate, cobalt chloride and cobalt sulfate, more preferably cobalt nitrate, cobalt chloride or cobalt sulfate.
In the present invention, the M ion concentration in the M source solution is preferably 0.02 to 1.2g/ml, more preferably 0.2 to 1.0g/ml, and still more preferably 0.4 to 0.8g/ml.
In the present invention, the pH of the system during the exchange-adsorption-deposition process is preferably 5 to 8, more preferably 5.5 to 7.5, and still more preferably 6 to 7.
In the present invention, the time of the exchange-adsorption-deposition process is preferably 2 to 24 hours, more preferably 5 to 20 hours, and still more preferably 9 to 16 hours.
In the present invention, the temperature of the re-firing is preferably 600 to 1300 ℃, more preferably 700 to 1200 ℃, still more preferably 800 to 1100 ℃, still more preferably 900 to 1000 ℃.
In the present invention, the time for the re-baking is preferably 2 to 8 hours, more preferably 3 to 7 hours, and still more preferably 4 to 6 hours.
In the present invention, the m·hap is preferably subjected to a reduction treatment before use.
In the present invention, the reduction treatment is preferably performed in a hydrogen atmosphere.
In the present invention, the temperature of the reduction treatment is preferably 150 to 300 ℃, more preferably 180 to 270 ℃, and still more preferably 210 to 240 ℃.
In the present invention, the time of the reduction treatment is preferably 1 to 8 hours, more preferably 2 to 7 hours, still more preferably 3 to 6 hours, and still more preferably 4 to 5 hours.
The invention adjusts the pH value of the mixed solution of the cerium source and the other metal source in the cerium-based solid solution to obtain precipitate, and then the precipitate is subjected to heat treatment to obtain the cerium-based solid solution.
In the present invention, the cerium source preferably includes cerium nitrate and/or cerium ammonium nitrate, more preferably cerium nitrate or cerium ammonium nitrate.
In the present invention, the other metal source preferably includes one or more of lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc chloride, and zinc nitrate, more preferably lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc chloride, or zinc nitrate.
In the present invention, the atomic ratio of cerium to another metal is preferably (0.2 to 1.5): 1, more preferably (0.5 to 1.2): 1, more preferably (0.8 to 0.9): 1.
In the present invention, the pH is preferably 8 to 10, more preferably 8.4 to 9.6, and still more preferably 8.8 to 9.2.
In the present invention, the temperature of the heat treatment is preferably 400 to 600 ℃, more preferably 440 to 560 ℃, and still more preferably 480 to 520 ℃.
In the present invention, the time of the heat treatment is preferably 3 to 8 hours, more preferably 4 to 7 hours, and still more preferably 5 to 6 hours.
The invention mixes rare earth metal soluble compound and transition metal soluble compound, the obtained mixed solution adjusts pH value to obtain precipitate, after drying, the precipitate and phosphoric acid solution are subjected to step heating ball milling, and then roasting is continued to obtain A xByPO4.
In the present invention, the rare earth metal-soluble compound preferably includes one or more of lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, cerium ammonium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate, and gadolinium nitrate, more preferably lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, cerium ammonium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate, or gadolinium nitrate.
In the present invention, the transition metal soluble compound preferably includes one or more of ammonium molybdate, molybdenum chloride, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper chloride, copper sulfate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, tungsten chloride, ammonium metavanadate, vanadium trichloride, and vanadium oxychloride, more preferably ammonium molybdate, molybdenum chloride, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper chloride, copper sulfate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, tungsten chloride, ammonium metavanadate, vanadium trichloride, or vanadium oxychloride.
In the present invention, the total concentration of the metal compounds in the mixed solution is preferably 10 to 80g/L, more preferably 25 to 65g/L, and still more preferably 40 to 50g/L.
In the present invention, the temperature of the mixing is preferably 50 to 80 ℃, more preferably 55 to 75 ℃, still more preferably 60 to 70 ℃.
In the present invention, the pH is preferably 8 to 10, more preferably 8.4 to 9.6, and still more preferably 8.8 to 9.2.
In the present invention, the temperature of the drying is preferably 50 to 80 ℃, more preferably 55 to 75 ℃, and still more preferably 60 to 70 ℃.
In the present invention, the drying time is preferably 3 to 10 hours, more preferably 4.5 to 8.5 hours, and still more preferably 6 to 7 hours.
In the present invention, the concentration of the phosphoric acid solution is preferably 3 to 30g/L, more preferably 8 to 25g/L, and still more preferably 13 to 20g/L.
In the invention, the start-stop temperature of the step-heating ball milling is preferably 15-200 ℃, more preferably 50-160 ℃, and even more preferably 90-120 ℃.
In the invention, the temperature rising rate of the step-heated ball mill is preferably 1-20 ℃, more preferably 5-16 ℃, and even more preferably 9-12 ℃.
In the present invention, the residence time of the step is preferably 0.5 to 3.5 hours, more preferably 1.0 to 3.0 hours, and still more preferably 1.5 to 2.5 hours.
In the present invention, the temperature at which the firing is continued is preferably 400 to 600 ℃, more preferably 440 to 560 ℃, and still more preferably 480 to 520 ℃.
In the present invention, the time for continuing the calcination is preferably 3 to 10 hours, more preferably 4.5 to 8.5 hours, and still more preferably 6 to 7 hours.
Finally, mixing the M & HAP obtained in the steps with cerium-based solid solution and/or A xByPO4 again to obtain the Cu-based active metal-acid-base catalyst.
In the present invention, the manner of mixing again preferably includes ball-milling mixing.
In the present invention, the preparation process of the M 1·(Znx1-Aly1 Mg) catalyst preferably includes the steps of:
a) Ball milling a Zn source, an Al source, an Mg source and water to obtain powder, and roasting to obtain Zn x1-Aly1 Mg;
b) And adding Zn x1-Aly1 Mg obtained in the steps into the soluble M 1 source aqueous solution, standing, and roasting again to obtain the M 1·Znx1-Aly1 Mg catalyst.
Firstly, ball milling a Zn source, an Al source, an Mg source and water to obtain powder, and roasting to obtain Zn x1-Aly1 Mg.
In the present invention, the Zn source preferably includes zinc nitrate.
In the present invention, the Al source preferably includes aluminum nitrate.
In the present invention, the Mg source preferably includes magnesium nitrate.
In the present invention, the molar ratio of Al to Mg is preferably (0.2 to 4): 1, more preferably (0.5 to 3): 1, more preferably (1 to 2): 1.
In the present invention, the molar ratio of Zn to Mg is preferably (0.02 to 1.2): 1, more preferably (0.2 to 1.0): 1, more preferably (0.4 to 0.8): 1.
In the present invention, the Zn source, al source and Mg source are preferably mixed-milled prior to ball milling.
In the present invention, the temperature of the calcination in the step a) is preferably 400 to 700 ℃, more preferably 450 to 650 ℃, and still more preferably 500 to 600 ℃.
In the present invention, the time of the calcination in the step a) is preferably 3 to 8 hours, more preferably 4 to 7 hours, and still more preferably 5 to 6 hours.
Finally, adding Zn x1-Aly1 Mg obtained in the steps into a soluble M 1 source aqueous solution, standing, and roasting again to obtain the M 1·Znx1-Aly1 Mg catalyst, namely M 1·(Znx1-Aly1 Mg).
In the present invention, the soluble M 1 source preferably includes one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, cerium ammonium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium chloride, and neodymium nitrate, more preferably sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, cerium ammonium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium chloride, or neodymium nitrate.
In the present invention, the time for the standing is preferably 4 to 12 hours, more preferably 5.5 to 10.5 hours, and still more preferably 7 to 9 hours.
In the present invention, in the step b), the temperature of the re-firing is preferably 400 to 700 ℃, more preferably 450 to 650 ℃, and still more preferably 500 to 600 ℃.
In the present invention, the time for the re-firing in the step b) is preferably 3 to 8 hours, more preferably 4 to 7 hours, and still more preferably 5 to 6 hours.
The invention provides a method for synthesizing an olefin monomer, which comprises the following steps:
1) Carrying out condensation reaction on furfural and acetone, M 1·(Znx1-Aly1 Mg) catalyst in a mixed solvent to obtain furyl-3-butene-2-ketone;
2) Under the action of Cu-based active metal-acid-base catalyst and under the condition of hydrogen, the furyl-3-butene-2-ketone obtained in the steps is subjected to hydrodeoxygenation reaction to obtain the furyl butadiene.
The invention firstly carries out condensation reaction on furfural and acetone, M 1·(Znx1-Aly1 Mg) catalyst in a mixed solvent to obtain furyl-3-butene-2-ketone. Specifically, the furyl-3-buten-2-one is 4- (2-furyl) -3-buten-2-one.
In the present invention, the molar ratio of the acetone to the furfural is preferably (1 to 12): 1, more preferably (3 to 10): 1, more preferably (5 to 8): 1.
In the present invention, the mixed solvent preferably includes a mixed solvent of methanol and water.
In the invention, the mass ratio of the mixed solvent to the reactant is preferably (5-15): 1, more preferably (7 to 13): 1, more preferably (9 to 11): 1.
In the present invention, the mass ratio of the M 1·(Znx1-Aly1 Mg) catalyst to the reactant is preferably 1wt% to 5wt%, more preferably 1.5wt% to 4.5wt%, still more preferably 2wt% to 4wt%, and still more preferably 2.5wt% to 3.5wt%.
In the present invention, the temperature of the condensation reaction is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, and still more preferably 100 to 120 ℃.
In the present invention, the time of the condensation reaction is preferably 2 to 12 hours, more preferably 4 to 10 hours, and still more preferably 6 to 8 hours.
Under the action of Cu-based active metal-acid-base catalyst, the invention carries out hydrodeoxygenation reaction on the furyl-3-butene-2-ketone obtained in the steps under the condition of hydrogen to obtain the furyl butadiene.
In the present invention, the reaction mode of the hydrodeoxygenation reaction is preferably a fixed bed reaction.
In the present invention, the hydrodeoxygenation reaction temperature is preferably 180 to 280 ℃, more preferably 200 to 260 ℃, and still more preferably 220 to 240 ℃.
In the present invention, the reaction pressure of the hydrodeoxygenation reaction is preferably 0.01 to 0.5Mpa, more preferably 0.1 to 0.4Mpa, and still more preferably 0.2 to 0.3Mpa.
In the present invention, the flow rate of the hydrogen gas is preferably 0 to 100ml/min, more preferably 20 to 80ml/min, and still more preferably 40 to 60ml/min.
In the present invention, the feed rate of the furyl-3-buten-2-one is preferably 0.2 to 0.8ml/min, more preferably 0.3 to 0.7ml/min, still more preferably 0.4 to 0.6ml/min.
The invention is a complete and refined integral technical proposal, better improves the reaction efficiency and the reaction stability of preparing the olefin monomer and the property of the product olefin monomer, further improves the performance of the synthesized liquid rubber, and the synthesis method of the olefin monomer specifically and preferably comprises the following steps:
The preparation method for synthesizing an olefin monomer by catalytic conversion of biomass glycosyl compounds comprises the following steps:
(1) Preparing furyl-3-butene-2-ketone by condensing furfural and acetone;
(2) Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
Specifically, the furfuraldehyde is condensed with acetone to prepare furyl-3-butene-2-ketone:
adding furfural and acetone into a reaction kettle by adopting a catalyst M.Zn x-Aly Mg (M is one or more of Na, K, cs, la, ce, pr, nd, x=0.02-1.2 and y=0.2-4), controlling the molar ratio of the acetone to the furfural to be 1-12, adding water and methanol as solvents (volume ratio is 1:1), and controlling the mass ratio of the solvents to the reactants to be 5-15: 1, adding a catalyst (the mass is 1-5 wt% of the reactant), the reaction temperature is 60-160 ℃, the reaction time is 2-12 h, extracting the product by using methylene dichloride, and removing the solvent to obtain the product.
Specifically, the M.Zn x-Aly Mg catalyst is one or more of Na, K, cs, la, ce, pr, nd, wherein M is sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate and the like, and Al, zn and Mg are aluminum nitrate, zinc nitrate and magnesium nitrate.
Specifically, the preparation method of the catalyst comprises the following steps:
(1) Taking aluminum nitrate, zinc nitrate and magnesium nitrate in a mortar according to the metering ratio Al/Mg=0.2-4 and Zn/Mg=0.02-1.2, grinding for 30min, transferring to ball milling, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, drying in a 100 ℃ oven for 4-10 h, and roasting at 400-700 ℃ for 3-8 h to obtain Zn x-Aly Mg;
(2) Dissolving one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate and the like in water, adding one or more of lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate and the like (whether two or one or more of them is necessary), stirring uniformly, adding Zn x-Aly Mg powder, standing for 4-12 h, stirring in an oil bath at 80 ℃ to remove water, drying in an oven at 100 ℃ for 5h and roasting at 400-700 ℃ for 3-8 h to obtain the catalyst M.Zn x-Aly Mg, wherein the loading amount of M is 5-25 wt%.
Specifically, the furyl-3-buten-2-one hydrodeoxygenation synthesizes furyl butadiene:
The method is characterized in that a metal-acid-base multifunctional catalyst is adopted, a one-step method is realized to convert carbonyl into hydroxyl and dehydrate on a fixed bed reactor, and activation and side reaction of furan rings and exocyclic C=C are inhibited; the reaction temperature is 180-280 ℃, the hydrogen flow rate is 10-100 ml/min, the reaction pressure is 0-0.3 MPa, the feeding rate is 0.2-0.8 ml/min, and the outlet of the reactor adopts an ice bath cold trap to collect the product.
Specifically, the metal-acid-base multifunctional catalyst consists of a copper-based active metal part and an acid-base part, wherein the copper-based active metal part is copper-based hydroxyapatite (M.HAP), M is Cu-Ni or Cu-Co, and the loading amount of M is 2-15 wt%; the acid-base part is cerium-based solid solution LaCe, prCe, moCe, zrCe, znCe or rare earth phosphate (A xByPO4), A is one of La, ce, pr, nd, gd and the like, the atomic ratio x of the acid-base part to P is 0.7-1.4, B is one of Mo, zr, zn, W, V and the like, and the atomic ratio y of the acid-base part to P is 0.02-0.3.
And (3) respectively preparing a copper-based active metal part and an acid-base part, and uniformly mixing the two parts by adopting ball milling to obtain the metal-acid-base multifunctional catalyst.
Specifically, the preparation process of the copper-based hydroxyapatite (M.HAP) comprises the following steps:
(1) The adopted hydroxyapatite is used as a commodity, and is roasted for 2 to 8 hours at the temperature of 800 to 1500 ℃ before being used;
(2) Adding Cu, ni, co-containing solution for exchange-adsorption-deposition for 2-24 hr with ion concentration of 0.02-1.2 g/ml, and the Cu, ni, co are copper nitrate, copper chloride, copper sulfate, copper oxalate, nickel nitrate, nickel chloride, nickel sulfate, cobalt nitrate, cobalt chloride, cobalt sulfate, etc.;
(3) Adjusting the pH value of the system to be between 5 and 8, drying the system for 3 to 8 hours at the temperature of 100 ℃ after filtering, roasting the system for 2 to 8 hours at the temperature of 600 to 1300 ℃ to obtain the modified hydroxyapatite catalyst M and HAP, and reducing the modified hydroxyapatite catalyst M and HAP in hydrogen for 1 to 8 hours at the temperature of 150 to 300 ℃ before use.
Specifically, the preparation process of the cerium-based solid solution comprises the following steps:
(1) Preparing a Ce solution, adding La, pr, mo, zr, zn, and controlling the atomic ratio of La/Ce, pr/Ce, mo/Ce, zr/Ce and Zn/Ce to be 0.2-1.5, wherein Ce and La, pr, mo, zr, zn are from cerium nitrate, ammonium cerium nitrate, lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc chloride, zinc nitrate and the like;
(2) After stirring evenly, the pH=8-10 of the system is slowly adjusted by ammonia water to form precipitate, the precipitate is filtered, washed to be neutral by water, dried for 10h at 100 ℃, and baked for 3-8 h at 400-600 ℃.
Specifically, the preparation process of the rare earth phosphate (A xByPO4) comprises the following steps:
(1) Dissolving a soluble compound containing La, ce, pr, nd, gd and other rare earth metals in water, wherein La, ce, pr, nd, gd is prepared from lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate, gadolinium nitrate and the like; adding Mo, zr, cu, zn, W, V or other soluble compounds, mo, zr, cu, zn, W, V or other substances from ammonium molybdate, molybdenum chloride, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper chloride, copper sulfate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, tungsten chloride, ammonium metavanadate, vanadium trichloride, vanadium oxychloride or the like; controlling the total concentration of the metal compounds in the solution to be 10-80 g/L;
(2) Stirring and mixing at 50-80 ℃, regulating the pH value to 8-10, filtering out precipitate, and drying at 50-80 ℃ for 3-10 hours;
(3) Adding 3-30 g/L phosphoric acid solution, adopting a temperature programming-ball milling mode, controlling the temperature programming to be between room temperature and 200 ℃, the temperature programming rate to be between 1 and 20 ℃ and the residence time to be between 0.5 and 3.5 hours; roasting for 3-10 hours at 400-600 ℃ to obtain A xByPO4.
The invention provides a preparation method of liquid rubber, which comprises the following steps:
And mixing the catalyst system, the monomer and the solvent, and then performing solution polymerization reaction to obtain the liquid rubber.
In the present invention, the monomer preferably includes an olefin-type monomer and butadiene, or an olefin-type monomer.
In the present invention, the olefin-type monomer preferably includes the olefin-type monomer for use according to any one of the above-mentioned aspects or the olefin-type monomer produced by the production method according to any one of the above-mentioned aspects.
In the present invention, the catalyst system preferably comprises one or more of methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, ethyl 2-bromo-2-phenylpropionate/Cu, or ethyl 2-bromo-2-p-phenylacetate/Cu, or halogenated ethylbenzene/halogenated cuprous/bipyridine, or triphenylchloromethane, trifluoroacetic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, and hydrogen peroxide/ferrous chloride, more preferably methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, ethyl 2-bromo-2-p-phenylacetate/Cu, or halogenated ethylbenzene/halogenated cuprous/bipyridine, or triphenylchloromethane, trifluoro methane, ammonium persulfate/ferrous sulfate, potassium persulfate/ferrous chloride, ferrous persulfate/ferric sulfate, ferrous chloride/ferrous chloride, ferrous persulfate/ferrous chloride, or ferrous persulfate/ferrous chloride.
In the present invention, the solvent preferably includes one or more of N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, t-butanol, dimethyl sulfoxide, and N, N-dimethylformamide, more preferably N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, t-butanol, dimethyl sulfoxide, or N, N-dimethylformamide.
In the present invention, the molar ratio of the olefin monomer to butadiene is preferably (0.1 to 0.6): 1, more preferably (0.2 to 0.5): 1, more preferably (0.3 to 0.4): 1.
In the present invention, the concentration of the monomer after the mixing is preferably 1.0 to 3.5mol/L, more preferably 1.5 to 3.0mol/L, and still more preferably 2.0 to 2.5mol/L.
In the present invention, the concentration of the catalyst after the mixing is preferably 2 to 20mmol/L, more preferably 6 to 16mmol/L, and still more preferably 10 to 12mmol/L.
In the present invention, the temperature of the solution polymerization reaction is preferably 40 to 90 ℃, more preferably 50 to 80 ℃, and still more preferably 60 to 70 ℃.
In the present invention, the time of the solution polymerization is preferably 0.5 to 5 hours, more preferably 1.5 to 4 hours, and still more preferably 2.5 to 3 hours.
In the present invention, the molecular weight of the liquid rubber obtained is preferably 2000 to 6000g/mol, more preferably 2500 to 5500g/mol, still more preferably 3000 to 5000g/mol, still more preferably 3500 to 4500g/mol.
In the present invention, the liquid rubber preferably includes a curable reversible liquid rubber.
The invention relates to a complete and refined integral technical scheme, which better improves the reaction efficiency and the reaction stability of synthetic liquid rubber and further improves the performance of the synthetic liquid rubber, and the preparation method of the liquid rubber specifically and preferably comprises the following steps:
preparation of liquid rubber from furanyl butadiene monomer:
Polymerizing in the solution to realize self-polymerization of furan-based butadiene and copolymerization of furan-based butadiene and butadiene, thus obtaining the liquid rubber.
Specifically, the molecular weight of the obtained liquid rubber is 2000-6000 g/mol, and the curing reversibility is realized based on Diels-Alder reaction of furan.
Specifically, the solvent is N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, tert-butanol, dimethyl sulfoxide, N-dimethylformamide, etc.
Specifically, the catalyst system is 2-bromopropionic acid methyl ester/tris [2- (dimethylamino) ethyl ] amine/Cu, 2-bromo-2-phenylacetic acid ethyl ester/Cu, 2-bromo-2-p-phenylacetic acid ethyl ester/Cu, or halogenated ethylbenzene/halogenated cuprous/bipyridine, or triphenylchloromethane, trifluoro formic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/mercaptan, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, and the like.
Specifically, before polymerization, the furanyl butadiene monomer is purified, the purity is more than 99.5 percent, the furanyl butadiene monomer is added into a mechanical stirring reaction kettle, the reaction temperature is controlled to be 40-90 ℃, the reaction time is controlled to be 0.5-5 h, the monomer concentration is controlled to be 1.0-3.5 mol/l, the catalyst concentration is controlled to be 2-20 mmol/l, and the molar ratio of furanyl butadiene to butadiene is controlled to be 0.1-0.6.
Further, the method comprises the steps of,
The invention provides an olefin monomer synthesized by catalytic conversion of biomass glycosyl compounds, which is used for preparing reversibly solidified liquid rubber by condensing furfural and acetone to realize one-step hydrogenation-deoxidation of furyl-3-butene-2-ketone to generate furyl-3-butadiene, and specifically comprises the following steps:
1. furfural is condensed with acetone to prepare furyl-3-buten-2-one.
The furfurol and acetone are condensed to prepare furyl-3-butene-2-ketone, a catalyst M.Zn x-Aly Mg (M is one or more of Na, K, cs, la, ce, pr, nd, x=0.02-1.2, preferably 0.04-1.16, y=0.2-4, preferably 0.25-3.5) is adopted, the furol and the acetone are added into a reaction kettle, and the molar ratio of the acetone to the furol is controlled to be 1-12, preferably 2-11; adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 5-15: 1, preferably from 6 to 14:1, adding a catalyst (the mass is 1-5 wt% of the reactant, preferably 1.3-4.6 wt%) at a reaction temperature of 60-160 ℃, preferably 65-155 ℃ for 2-12 hours, preferably 3-10 hours, extracting the product by using methylene dichloride, and removing the solvent to obtain the product.
Specifically, the m·zn x-Aly Mg catalyst, M is one or more of Na, K, cs, la, ce, pr, nd, preferably one or two of Na, K, cs, la, ce, pr, nd, is derived from sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate, and the like, and is preferably sodium carbonate, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, cerium nitrate, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, neodymium chloride, neodymium nitrate, and the like; al, zn and Mg are from aluminum nitrate, zinc nitrate and magnesium nitrate. The preparation method of the catalyst comprises the following steps:
(1) According to the metering ratio Al/Mg=0.2-4, preferably 0.25-3.5; zn/Mg=0.02 to 1.2, preferably 0.04 to 1.16; grinding aluminum nitrate, zinc nitrate and magnesium nitrate in a mortar for 30min, transferring to ball milling, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, and drying in a 100 ℃ oven for 4-10 h, preferably 5-9 h; roasting for 3-8 h at 400-700 ℃, preferably for 4-7 h at 420-650 ℃; obtaining Zn x-Aly Mg;
(2) Dissolving one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, etc. in water, preferably one or two of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, etc.; adding one or more of lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate and the like, preferably one or two of lanthanum nitrate, cerium nitrate, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, neodymium chloride, neodymium nitrate and the like; uniformly stirring, adding Zn x-Aly Mg powder, and standing for 4-12 h, preferably 5-11 h; stirring in an oil bath at 80 ℃ until water is removed, drying in a baking oven at 100 ℃ for 5h, and roasting at 400-700 ℃ for 3-8 h, preferably at 420-650 ℃ for 4-7 h; the catalyst M.Zn x-Aly Mg is obtained, and the loading of M is 5 to 25wt%, preferably 8 to 23wt%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
The furyl-3-butene-2-ketone hydrodeoxygenation is adopted to synthesize furyl butadiene, a metal-acid-base multifunctional catalyst is adopted, and on a fixed bed reactor, a one-step method is realized to convert carbonyl into hydroxyl and dehydrate, and activation and side reaction of furan rings and exocyclic C=C are inhibited; the reaction temperature is 180-280 ℃, preferably 185-270 ℃; the flow rate of the hydrogen is 10-100 ml/min, preferably 15-90 ml/min; the reaction pressure is 0-0.3 MPa, preferably 0-0.28 MPa; the feed rate is 0.2 to 0.8ml/min, preferably 0.26 to 0.74ml/min; the reactor outlet was ice-bath cold trap to collect the product.
Specifically, the metal-acid-base multifunctional catalyst consists of a copper-based active metal part and an acid-base part, wherein the copper-based active metal part is copper-based hydroxyapatite (M.HAP), M is Cu-Ni or Cu-Co, and the loading amount of M is 2-15 wt%, preferably 4-14 wt%; the acid-base part is cerium-based solid solution LaCe, prCe, moCe, zrCe, znCe or rare earth phosphate (A xByPO4), A is one of La, ce, pr, nd, gd and the like, preferably one of La, ce, pr, nd, gd; x is 0.7 to 1.4, preferably 0.75 to 1.35; b is one of Mo, zr, zn, W, V, etc., preferably one of Mo, zr, zn, W, V, and y is 0.02 to 0.3, preferably 0.03 to 0.28. And (3) respectively preparing a copper-based active metal part and an acid-base part, and uniformly mixing the two parts by adopting ball milling to obtain the metal-acid-base multifunctional catalyst.
Specifically, the preparation process of the copper-based hydroxyapatite (M.HAP) comprises the following steps:
(1) The adopted hydroxyapatite is used as a commodity, and is roasted for 2 to 8 hours at 800 to 1500 ℃ before being used, preferably for 3 to 7 hours at 850 to 1400 ℃;
(2) Adding Cu, ni, co and other solution for exchange-adsorption-deposition for 2-24 hr, preferably 4-20 hr; the ion concentration is 0.02-1.2 g/ml, preferably 0.03-1.15 g/ml; cu, ni, co are derived from copper nitrate, copper chloride, cuprous chloride, copper sulfate, copper oxalate, nickel nitrate, nickel chloride, nickel sulfate, cobalt nitrate, cobalt chloride, cobalt sulfate, etc., preferably copper nitrate, copper chloride, copper oxalate, nickel nitrate, nickel sulfate, cobalt nitrate, cobalt chloride;
(3) Adjusting the pH value of the system to be between 5 and 8, and drying the system for 3 to 8 hours at the temperature of 100 ℃ after filtering, preferably for 3.5 to 7.5 hours; roasting for 2-8 h at 600-1300 ℃, preferably for 3-7 h at 650-1200 ℃; the modified hydroxyapatite catalyst M.HAP is obtained and reduced in hydrogen at 150-300 ℃ for 1-8 h, preferably 160-290 ℃ for 2-7 h before use.
Specifically, the preparation process of the cerium-based solid solution comprises the following steps:
(1) Preparing a Ce solution, adding La, pr, mo, zr, zn, and controlling the atomic ratio of La/Ce, pr/Ce, mo/Ce, zr/Ce and Zn/Ce to be 0.2-1.5, preferably 0.3-1.4; ce. La, pr, mo, zr, zn is derived from cerium nitrate, ceric ammonium nitrate, lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc chloride, zinc nitrate, etc., preferably cerium nitrate, ceric ammonium nitrate, lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc nitrate, etc.;
(2) After stirring evenly, the pH=8-10 of the system is slowly adjusted by ammonia water to form precipitate, the precipitate is filtered, washed to be neutral by water, dried for 10 hours at 100 ℃, roasted for 3-8 hours at 400-600 ℃, and roasted for 3.5-7.5 hours at 420-580 ℃ preferably.
Specifically, the preparation process of the rare earth phosphate (A xByPO4) comprises the following steps:
(1) Dissolving a soluble compound containing La, ce, pr, nd, gd or other rare earth metals in water, preferably La, ce, pr, nd, gd; lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate, gadolinium nitrate, etc., preferably lanthanum nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, neodymium chloride, neodymium nitrate, gadolinium nitrate; adding Mo, zr, cu, zn, W, V or other soluble compounds, preferably Mo, zr, cu, zn, W, V, from ammonium molybdate, molybdenum chloride, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper chloride, copper sulfate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, tungsten chloride, ammonium metavanadate, vanadium trichloride, vanadium oxychloride, etc., preferably ammonium molybdate, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, ammonium metavanadate, vanadium trichloride, vanadium oxychloride; controlling the total concentration of the metal compounds in the solution to be 10-80 g/L, preferably 15-75 g/L;
(2) Stirring and mixing at 50-80 ℃, preferably 55-75 ℃; adjusting the pH value to 8-10, filtering out the precipitate, drying at 50-80 ℃ for 3-10 h, preferably at 55-75 ℃ for 3.5-9.5 h;
(3) Adding 3-30 g/L phosphoric acid solution, preferably 5-26 g/L phosphoric acid solution, adopting a temperature programming-ball milling mode, controlling the temperature programming to be between room temperature and 200 ℃, and controlling the temperature programming rate to be between 1 and 20 ℃, preferably between 3 and 18 ℃; the residence time is 0.5 to 3.5 hours, preferably 0.8 to 3 hours; roasting for 3-10 h at 400-600 ℃, preferably for 3.5-9.5 h at 430-580 ℃ to obtain A xByPO4.
3. The furanyl butadiene monomer prepares the liquid rubber.
The furan-based butadiene monomer is used for preparing liquid rubber, and polymerization is carried out in a solution to realize the self-polymerization of furan-based butadiene and the copolymerization of furan-based butadiene and butadiene, wherein the molecular weight of the obtained liquid rubber is 2000-6000 g/mol, preferably 2500-5500 g/mol; the Diels-Alder reaction based on furan achieves reversible curing. The solvent is N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, tert-butanol, dimethyl sulfoxide, N-dimethylformamide, etc., preferably N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, tert-butanol, dimethyl sulfoxide, N-dimethylformamide.
Specifically, the catalyst system is methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, or haloethylbenzene/cuprous halide/bipyridine, or triphenylchloromethane, trifluoro-carboxylic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, and the like, preferably methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, ethyl 2-bromo-2-phenylpropionate/Cu, ethyl 2-bromo-2-p-phenylacetate/Cu, or bromoethylbenzene/cuprous bromide/bipyridine, or triphenylchloromethane, trifluoro-carboxylic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, potassium peroxide/ferrous chloride, ferric chloride, ferrous peroxide/ferrous chloride, silver peroxide/ferrous chloride, and the like.
Specifically, before the polymerization reaction, purifying the furanyl butadiene monomer, wherein the purity is more than 99.5%, adding the furanyl butadiene monomer into a mechanical stirring reaction kettle, and controlling the reaction temperature to be 40-90 ℃, preferably 45-85 ℃; the reaction time is 0.5 to 5 hours, preferably 0.8 to 4.5 hours; the monomer concentration is 1.0 to 3.5mol/l, preferably 1.2 to 3.3mol/l; the catalyst concentration is 2-20 mmol/l, preferably 4-18 mmol/l; the molar ratio of furanylbutadiene to butadiene is 0.1 to 0.6, preferably 0.15 to 0.55.
Still further, the method comprises the steps of,
1. Furfural is condensed with acetone to prepare furyl-3-buten-2-one.
The furfurol and acetone are condensed to prepare furyl-3-butene-2-ketone, a catalyst M.Zn x-Aly Mg (M is one or more of Na, K, cs, la, ce, pr, nd, x=0.02-1.2, preferably 0.04-1.16, more preferably 0.05-1.15, y=0.2-4, preferably 0.25-3.5, more preferably 0.28-3.2) is adopted, the furol and the acetone are added into a reaction kettle, and the molar ratio of the acetone to the furol is controlled to be 1-12, preferably 2-11, more preferably 3-10; adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 5-15: 1, preferably from 6 to 14:1, more preferably 7 to 13:1, a step of; adding a catalyst (the mass is 1-5 wt%, preferably 1.3-4.6 wt%, more preferably 1.5-4.5 wt% of the reactants), and the reaction temperature is 60-160 ℃, preferably 65-155 ℃ and preferably 70-150 ℃; the time is 2 to 12 hours, preferably 3 to 10 hours, more preferably 3.5 to 9 hours; the product is extracted by methylene dichloride, and the solvent is removed to obtain the product.
Specifically, the m·zn x-Aly Mg catalyst, M is one or more of Na, K, cs, la, ce, pr, nd, preferably one or two of Na, K, cs, la, ce, pr, nd, more preferably one or two of Na, K, cs, la, ce, pr; sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, etc., preferably sodium carbonate, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, cerium nitrate, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, more preferably sodium carbonate, potassium bicarbonate, cesium carbonate, lanthanum nitrate, cerium nitrate, ammonium cerium nitrate, praseodymium nitrate; al, zn and Mg are from aluminum nitrate, zinc nitrate and magnesium nitrate.
Specifically, the preparation method of the catalyst comprises the following steps:
(1) The ratio Al/mg=0.2 to 4, preferably 0.25 to 3.5, more preferably 0.28 to 3.2; zn/Mg=0.02 to 1.2, preferably 0.04 to 1.16, more preferably 0.05 to 1.15; taking aluminum nitrate, zinc nitrate and magnesium nitrate, grinding for 30min in a mortar, transferring to ball milling, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, and drying in a 100 ℃ oven for 4-10 h, preferably 5-9 h, more preferably 5.5-8.5 h; roasting at 400-700 deg.c for 3-8 hr, preferably 420-650 deg.c for 4-7 hr, and more preferably 450-620 deg.c for 4.5-6.5 hr; obtaining Zn x-Aly Mg;
(2) Dissolving one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate and the like in water, preferably one or two of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium oxalate, potassium bicarbonate, cesium carbonate and the like, more preferably sodium carbonate, potassium bicarbonate and cesium carbonate; adding one or more of lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ceric ammonium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate and the like, preferably one or two of lanthanum nitrate, cerium nitrate, ceric ammonium nitrate, cerium perchlorate, praseodymium nitrate, neodymium chloride, neodymium nitrate and the like, more preferably lanthanum nitrate, cerium nitrate, ceric ammonium nitrate and praseodymium nitrate; uniformly stirring, adding Zn x-Aly Mg powder, and standing for 4-12 h, preferably 5-11 h, more preferably 5.5-10 h; stirring in an oil bath at 80 ℃ until water is removed, drying in an oven at 100 ℃ for 5h, roasting at 400-700 ℃ for 3-8 h, preferably at 420-650 ℃ for 4-7 h, more preferably at 450-620 ℃ for 4.5-7 h; the catalyst M.Zn x-Aly Mg is obtained with a loading of 5 to 25wt%, preferably 8 to 23wt%, more preferably 9 to 21wt%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
The furyl-3-butene-2-ketone hydrodeoxygenation is adopted to synthesize furyl butadiene, a metal-acid-base multifunctional catalyst is adopted, and on a fixed bed reactor, a one-step method is realized to convert carbonyl into hydroxyl and dehydrate, and activation and side reaction of furan rings and exocyclic C=C are inhibited; the reaction temperature is 180-280 ℃, preferably 185-270 ℃, more preferably 190-265 ℃; the flow rate of the hydrogen is 10 to 100ml/min, preferably 15 to 90ml/min, more preferably 18 to 85ml/min; the reaction pressure is 0 to 0.3MPa, preferably 0 to 0.28MPa, more preferably 0 to 0.26MPa; the feed rate is 0.2 to 0.8ml/min, preferably 0.26 to 0.74ml/min, more preferably 0.28 to 0.72ml/min; the reactor outlet was ice-bath cold trap to collect the product.
Specifically, the metal-acid-base multifunctional catalyst consists of a copper-based active metal part and an acid-base part, wherein the copper-based active metal part is copper-based hydroxyapatite (M.HAP), M is Cu-Ni or Cu-Co, and the loading amount of M is 2-15 wt%, preferably 4-14 wt%, more preferably 5-13 wt%; the acid-base part is cerium-based solid solution LaCe, prCe, moCe, zrCe, znCe; or rare earth phosphate (a xByPO4), a being one of La, ce, pr, nd, gd and the like, preferably one of La, ce, pr, nd, gd, more preferably one of La, ce, pr, nd; x is 0.7 to 1.4, preferably 0.75 to 1.35, more preferably 0.78 to 1.32; b is one of Mo, zr, zn, W, V and the like, preferably one of Mo, zr, zn, W, V, more preferably one of Mo, zr, zn, W; y is 0.02 to 0.3, preferably 0.03 to 0.28, more preferably 0.04 to 0.26. And (3) respectively preparing a copper-based active metal part and an acid-base part, and uniformly mixing the two parts by adopting ball milling to obtain the metal-acid-base multifunctional catalyst.
Specifically, the preparation process of the copper-based hydroxyapatite (M.HAP) comprises the following steps:
(1) The adopted hydroxyapatite is taken as a commodity, and is roasted for 2 to 8 hours at 800 to 1500 ℃ before being used, preferably for 3 to 7 hours at 850 to 1400 ℃, and more preferably for 3.5 to 6.5 hours at 880 to 1380 ℃;
(2) Adding a solution containing Cu, ni, co and the like for 'exchange-adsorption-deposition' for 2 to 24 hours, preferably 4 to 20 hours, more preferably 5 to 18 hours; the ion concentration is 0.02 to 1.2g/ml, preferably 0.03 to 1.15g/ml, more preferably 0.04 to 1.13g/ml; cu, ni, co are derived from copper nitrate, copper chloride, cuprous chloride, copper sulfate, copper oxalate, nickel nitrate, nickel chloride, nickel sulfate, cobalt nitrate, cobalt chloride, cobalt sulfate, etc., preferably copper nitrate, copper chloride, copper oxalate, nickel nitrate, nickel sulfate, cobalt nitrate, cobalt chloride, more preferably copper nitrate, copper oxalate, nickel nitrate, nickel sulfate, cobalt nitrate;
(3) Adjusting the pH of the system to be between 5 and 8, and drying the system for 3 to 8 hours at the temperature of 100 ℃ after filtering, preferably for 3.5 to 7.5 hours, and more preferably for 4 to 7 hours; roasting for 2-8 h at 600-1300 ℃, preferably for 3-7 h at 650-1200 ℃, more preferably for 3.5-6.5 h at 700-1150 ℃; the modified hydroxyapatite catalyst M.HAP is obtained, and is reduced in hydrogen at 150-300 ℃ for 1-8 h, preferably in hydrogen at 160-290 ℃ for 2-7 h, more preferably in hydrogen at 165-285 ℃ for 2.5-6.5 h before use.
Specifically, the preparation process of the cerium-based solid solution comprises the following steps:
(1) Preparing a Ce solution, adding La, pr, mo, zr, zn, and controlling the atomic ratio of La/Ce, pr/Ce, mo/Ce, zr/Ce and Zn/Ce to be 0.2-1.5, preferably 0.3-1.4, more preferably 0.4-1.3; ce. La, pr, mo, zr, zn is derived from cerium nitrate, ammonium cerium nitrate, lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc chloride, zinc nitrate, etc., preferably cerium nitrate, ammonium cerium nitrate, lanthanum nitrate, praseodymium nitrate, ammonium molybdate, molybdenum chloride, zirconyl nitrate, zinc nitrate, more preferably cerium nitrate, ammonium cerium nitrate, lanthanum nitrate, praseodymium nitrate, ammonium molybdate, zirconyl nitrate, zinc nitrate;
(2) After stirring uniformly, slowly adjusting the pH=8-10 of the system by ammonia water to form precipitate, filtering, washing with water to neutrality, drying at 100 ℃ for 10h, roasting at 400-600 ℃ for 3-8 h, preferably at 420-580 ℃ for 3.5-7.5 h, and more preferably at 450-550 ℃ for 4-7 h.
Specifically, the preparation process of the rare earth phosphate (A xByPO4) comprises the following steps:
(1) Dissolving a La, ce, pr, nd, gd-containing soluble compound of a rare earth metal in water, preferably La, ce, pr, nd, gd, more preferably La, ce, pr, nd; lanthanum nitrate, lanthanum chloride, cerium nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, praseodymium chloride, neodymium nitrate, etc., preferably lanthanum nitrate, cerium chloride, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, neodymium chloride, neodymium nitrate, more preferably lanthanum nitrate, cerium nitrate, ammonium cerium nitrate, cerium perchlorate, praseodymium nitrate, neodymium nitrate; the soluble compound containing Mo, zr, cu, zn, W, V or the like, preferably Mo, zr, cu, zn, W, V, more preferably Mo, zr, cu, zn, W, is added, and is derived from ammonium molybdate, molybdenum chloride, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper chloride, copper sulfate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, tungsten chloride, preferably ammonium molybdate, phosphomolybdic acid, zirconium nitrate, zirconyl nitrate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, phosphotungstic acid, ammonium tungstate, more preferably ammonium molybdate, zirconium nitrate, zirconyl nitrate, copper acetate, zinc nitrate, zinc chloride, phosphotungstic acid, ammonium tungstate; controlling the total concentration of the metal compounds in the solution to be 10-80 g/L, preferably 15-75 g/L, more preferably 20-70 g/L;
(2) Stirring and mixing at 50-80 ℃, preferably at 55-75 ℃, more preferably at 60-70 ℃; adjusting the pH to 8-10, filtering out the precipitate, drying at 50-80 ℃ for 3-10 h, preferably at 55-75 ℃ for 3.5-9.5 h, more preferably at 60-70 ℃ for 4-8 h;
(3) Adding 3-30 g/L phosphoric acid solution, preferably 5-26 g/L, more preferably 8-24 g/L; adopting a temperature programming-ball milling mode, controlling the temperature programming to be between room temperature and 200 ℃, and controlling the temperature programming rate to be between 1 and 20 ℃, preferably between 3 and 18 ℃, and more preferably between 5 and 15 ℃; the residence time is 0.5 to 3.5 hours, preferably 0.8 to 3 hours, more preferably 1 to 3 hours; roasting for 3-10 h at 400-600 ℃, preferably for 3.5-9.5 h at 430-580 ℃, more preferably for 4-9 h at 450-550 ℃; a xByPO4 is obtained.
3. The furanyl butadiene monomer prepares the liquid rubber.
The furan-based butadiene monomer is used for preparing liquid rubber, and polymerization is carried out in a solution to realize the self-polymerization of furan-based butadiene and the copolymerization of furan-based butadiene and butadiene, wherein the molecular weight of the obtained liquid rubber is 2000-6000 g/mol, preferably 2500-5500 g/mol, more preferably 2600-5400 g/mol; the Diels-Alder reaction based on furan achieves reversible curing. The solvent is N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, t-butanol, dimethyl sulfoxide, N-dimethylformamide, etc., preferably N-hexane, cyclohexane, toluene, diethyl ether, tetrahydrofuran, methanol, t-butanol, dimethyl sulfoxide, N-dimethylformamide, more preferably N-hexane, toluene, diethyl ether, tetrahydrofuran, t-butanol, dimethyl sulfoxide, N-dimethylformamide.
Specifically, the catalyst system is methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, or haloethylbenzene/cuprous halide/bipyridine, or triphenylchloromethane, trifluoro-carboxylic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, and the like, preferably methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, ethyl 2-bromo-2-phenylpropionate/Cu, ethyl 2-bromo-2-p-phenylacetate/Cu, or bromoethylbenzene/cuprous bromide/bipyridine, or triphenylchloromethane, trifluoro-carboxylic acid, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, potassium peroxide/ferrous chloride, ferric chloride, ferrous peroxide/ferrous chloride, silver peroxide/ferrous chloride, and the like. More preferably methyl 2-bromopropionate/tris [2- (dimethylamino) ethyl ] amine/Cu, ethyl 2-bromo-2-phenylacetate/Cu, ethyl 2-bromo-2-phenylpropionate/Cu, ethyl 2-bromo-2-p-phenylacetate/Cu, or bromoethylbenzene/cuprous bromide/bipyridine, or trifluoroacetic acid, ammonium persulfate/ferrous sulfate, potassium persulfate/silver nitrate, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride.
Specifically, the furanyl butadiene monomer is purified before polymerization, the purity is more than 99.5 percent, and the furanyl butadiene monomer is added into a mechanical stirring reaction kettle, and the reaction temperature is controlled to be 40-90 ℃, preferably 45-85 ℃, more preferably 50-80 ℃; the reaction time is 0.5 to 5 hours, preferably 0.8 to 4.5 hours, more preferably 1 to 4 hours; the monomer concentration is 1.0 to 3.5mol/l, preferably 1.2 to 3.3mol/l, more preferably 1.4 to 3.1mol/l; the catalyst concentration is2 to 20mmol/l, preferably 4 to 18mmol/l, more preferably 5 to 16mmol/l; the molar ratio of furanylbutadiene to butadiene is 0.1 to 0.6, preferably 0.15 to 0.55, more preferably 0.18 to 0.52.
The invention provides a synthesis method of an olefin monomer and preparation of functional liquid rubber, which specifically comprises the following steps: firstly, adopting heterogeneous catalyst M.Zn x-Aly Mg (M is one or more of Na, K, cs, la, ce, pr, nd, x=0.02-1.2, y=0.2-4) to condense furfural and acetone to prepare furyl-3-butene-2-ketone; then, on a fixed bed, adopting a Cu-based metal-acid base multifunctional catalyst (M.HAP/cerium-based solid solution/A xByPO4; HAP is hydroxyapatite; M is Cu-Ni or Cu-Co; A is La, ce, pr, nd or Gd, x=0.7-1.4, B is Mo, zr, zn, W or V, y=0.02-0.3, cerium-based solid solution is LaCe, prCe, moCe, zrCe or ZnCe, and the atomic ratio is 0.2-1.5), and synthesizing furyl-3-butene-2-one into furyl butadiene through one-step hydrogenation-deoxidation; finally, polymerizing in the solution, and adopting a controllable free radical initiation system to realize self-polymerization of the furanyl butadiene and copolymerization of the furanyl butadiene and the butadiene to prepare the liquid rubber.
Referring to fig. 1, fig. 1 is a schematic diagram of a reaction process of synthesizing an olefin monomer by catalytic conversion of a biomass glycosyl compound and converting the olefin monomer into a reversible curing liquid rubber.
Referring to fig. 2, fig. 2 is an external view of the liquid rubber prepared according to the present invention.
The invention provides application of the catalyst in synthesizing olefin monomers, a method for synthesizing the olefin monomers by catalytic conversion of biomass glycosyl compounds and preparation of reversible curing liquid rubber. The Cu-based active metal-acid-base catalyst with specific structure and composition is specially designed, and can realize one-step hydrogenation-deoxidation of a condensation product furyl-3-butene-2-one to generate furyl-3-butadiene after the condensation of furfural and acetone in the synthesis process of the furfural-based olefin monomer. The two-stage reaction provided by the invention has good catalyst activity, the condensation product of furfural and acetone has higher yield, the two-stage reaction can realize the one-step hydrogenation-deoxidation process of the condensation product, and the two-stage reaction has higher yield, simple process and strong controllability. The invention also provides a method for synthesizing the olefin monomer by catalytic conversion of the corresponding biomass glycosyl compound, and further provides a method for preparing the reversibly solidified liquid rubber by using the method, which has the advantages of mild reaction conditions, simple operation and large-scale synthesis prospect.
The invention provides a synthetic method of olefin monomer and a preparation process of functional liquid rubber, which comprises the steps of firstly adopting a heterogeneous catalyst to condense furfural and acetone to prepare furyl-3-butene-2-ketone; then adopting a Cu-based metal-acid-base multifunctional catalyst to synthesize the furyl butadiene monomer by one-step hydrogenation-deoxidation of the furyl-3-butene-2-one. The invention also discloses a method for preparing the liquid rubber by polymerizing in the solution and adopting a controllable free radical initiation system to realize self polymerization of the furyl butadiene and copolymerization of the furyl butadiene and the butadiene, and the method is based on Diels-Alder reaction of furan to realize reversible curing.
Experimental results show that biomass-based furfural can be effectively converted into furyl butadiene by the method provided by the invention, catalytic conversion is realized in one step, the process is simple, the catalyst efficiency is high, and the obtained furyl butadiene is used for synthesizing novel liquid rubber.
For further explanation of the present invention, the application of the catalyst provided in the present invention to the synthesis of olefin-type monomers, the synthesis method of olefin-type monomers and the preparation method of liquid rubber will be described in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
1. Preparation of furyl-3-butene-2-one by condensing furfural with acetone
Preparation of catalyst NaCe.Zn 0.8-Al0.8 Mg: according to the metering ratio Al/Mg=0.8 and Zn/Mg=0.8, taking aluminum nitrate, zinc nitrate and magnesium nitrate, grinding for 30min, transferring to ball milling, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, drying in a 100 ℃ oven for 6h, and roasting at 500 ℃ for 5h to obtain Zn 0.8-Al0.8 Mg. Adding Zn 0.8-Al0.8 Mg into sodium bicarbonate and cerium nitrate solution, controlling the loading amount of NaCe (atomic ratio 1:5) to be 15wt%, uniformly stirring, standing for 8h, stirring in an oil bath at 80 ℃ to remove water, drying in an oven at 100 ℃ for 5h, and roasting at 500 ℃ for 5h to obtain the catalyst NaCe.Zn 0.8-Al0.8 Mg.
Adding furfural and acetone into a reaction kettle, controlling the molar ratio of the acetone to the furfural to be 8, adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 7:1, adding a catalyst NaCe.Zn 0.8-Al0.8 Mg (the mass is 2.5wt% of the reactant), wherein the reaction temperature is 100 ℃, the time is 4 hours, extracting the product by using methylene dichloride, and removing the solvent to obtain the product with the yield of 78%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
Preparing a catalyst Cu-Ni-HAP: 20g of purchased hydroxyapatite is taken and baked for 5 hours at 950 ℃, the loading of Cu-Ni is controlled to be 12wt% (the atomic ratio is 1:1), copper nitrate and nickel chloride solution (the ion concentration is 0.7 g/ml) are added, the 'exchange-adsorption-deposition' is carried out for 16 hours, the pH value of the system is regulated to be 7, the system is dried for 6 hours at 100 ℃ after filtration, the catalyst is baked for 5 hours at 950 ℃, and the catalyst Cu-Ni-HAP is obtained and is reduced for 2 hours in hydrogen at 200 ℃ before use.
Solid solution La/Ce preparation: preparing ammonium ceric nitrate and lanthanum nitrate solution according to the La/Ce atomic ratio of 0.8, stirring uniformly, slowly adjusting the pH=9 of the system by ammonia water to form precipitate, filtering, washing to be neutral, drying at 100 ℃ for 10h, and roasting at 50 ℃ for 5h.
Mixing Cu-Ni-HAP and La/Ce according to the mass ratio of 2:1, adopting ball milling and mixing uniformly, taking 0.5g and loading into a fixed bed reactor, introducing furyl-3-butene-2-ketone into the reactor at the rate of 0.4ml/min, controlling the reaction temperature to be 230 ℃, controlling the hydrogen flow rate to be 60ml/min, controlling the reaction pressure to be 0.2MPa, and collecting the product at the outlet of the reactor by adopting an ice bath cold trap, wherein the yield is 78%.
3. The furanyl butadiene monomer prepares the liquid rubber.
Adding a furan-based butadiene monomer with purity of more than 99.5% into a mechanical stirring reaction kettle, adding toluene, introducing butadiene, adjusting the mole ratio of the furan-based butadiene to the butadiene to be 0.3, adjusting the monomer concentration to be 3mol/l, adding a catalyst system of 2-bromopropionic acid methyl ester/tris [2- (dimethylamino) ethyl ] amine/Cu, controlling the catalyst concentration to be 12mmol/l, and reacting for 2 hours at 55 ℃, wherein the molecular weight of the obtained liquid rubber is 5800g/mol.
Referring to fig. 3, fig. 3 is a GPC diagram of the liquid rubber prepared in example 1 of the present invention.
Referring to FIG. 4, FIG. 4 is an H-NMR chart of the liquid rubber prepared in example 1 of the present invention.
Example 2
1. Furfural is condensed with acetone to prepare furyl-3-buten-2-one.
Preparation of catalyst cs·zn 0.65-Al2.5 Mg: taking aluminum nitrate, zinc nitrate and magnesium nitrate in a mortar according to a metering ratio Al/Mg=2.5 and Zn/Mg=0.65, grinding for 30min, transferring to a ball mill, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, drying in a 100 ℃ oven for 8h, and roasting at 460 ℃ for 4h to obtain Zn 0.65-Al2.5 Mg; adding Zn 0.65-Al2.5 Mg into cesium carbonate solution, controlling the loading amount of Cs to be 6wt%, stirring uniformly, standing for 8h, stirring in an oil bath at 80 ℃ until water is removed, drying in an oven at 100 ℃ for 5h, and roasting at 550 ℃ for 5h to obtain the catalyst Cs.Zn 0.65-Al2.5 Mg.
Adding furfural and acetone into a reaction kettle, controlling the molar ratio of the acetone to the furfural to be 5, adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 8:1, adding a catalyst (the mass is 3wt% of the reactant), wherein the reaction temperature is 110 ℃, the reaction time is 3 hours, and the product is extracted by methylene dichloride and the solvent is removed to obtain the product with the yield of 82%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
Preparing a catalyst Cu-Co-HAP: 20g of purchased hydroxyapatite is taken and baked for 6 hours at 850 ℃, the loading of Cu-Co is controlled to be 8wt% (the atomic ratio is 1:1), copper sulfate and cobalt nitrate solution (the ion concentration is 0.88 g/ml) are added, the 'exchange-adsorption-deposition' is carried out for 10 hours, the pH value of the system is regulated to be 7, the system is dried for 5 hours at 100 ℃ after filtration, the catalyst Cu-Co-HAP is obtained after baking for 6 hours at 850 ℃, and the catalyst is reduced for 3 hours in hydrogen at 240 ℃ before use.
Catalyst La 0.9Zn0.23PO4 preparation: according to the metering ratio of La/P=0.9 and Zn/P=0.23, dissolving lanthanum nitrate in water, adding zinc nitrate, and controlling the total concentration of metal compounds in the solution to be 55g/L; stirring and mixing at 60 ℃, adjusting the pH to 9, filtering out precipitate, drying at 60 ℃ for 6 hours, adding a phosphoric acid solution with the concentration of 24g/L, adopting a temperature programming-ball milling mode, controlling the temperature programming to be between room temperature and 200 ℃, controlling the temperature programming rate to be 10 ℃/min, staying at 100 ℃ for 2.5 hours, and staying at 200 ℃ for 2.5 hours; roasting for 5 hours at 500 ℃ to obtain La 0.9Zn0.23PO4.
Mixing Cu-Co-HAP and La 0.9Zn0.23PO4 according to the mass ratio of 3:1, adopting ball milling to mix uniformly, taking 0.5g to fill into a fixed bed reactor, introducing furyl-3-butene-2-ketone into the reactor at the rate of 0.5ml/min, controlling the reaction temperature to be 200 ℃, controlling the hydrogen flow rate to be 80ml/min, controlling the reaction pressure to be 0.3MPa, and adopting an ice bath cold trap to collect the product at the outlet of the reactor, wherein the yield is 77%.
3. The furanyl butadiene monomer prepares the liquid rubber.
Adding furan-based butadiene monomer with purity of more than 99.5% into a mechanical stirring reaction kettle, adding n-hexane, controlling the monomer concentration to be 1.0-3.5 mol/l, adding a catalyst system trifluoro formic acid, controlling the catalyst concentration to be 14mmol/l, and reacting for 1.5h at 70 ℃, wherein the molecular weight of the obtained liquid rubber is 2400g/mol.
Example 3
1. Furfural is condensed with acetone to prepare furyl-3-buten-2-one.
Preparing a catalyst KPr, zn 1.0-Al3 Mg: taking aluminum nitrate, zinc nitrate and magnesium nitrate in a mortar according to a metering ratio Al/Mg=3 and Zn/Mg=1.0, grinding for 30min, transferring to ball milling, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, drying in a 100 ℃ oven for 5h, and roasting at 620 ℃ for 6h to obtain Zn 1.0-Al3 Mg; adding Zn 1.0-Al3 Mg into a potassium oxalate and praseodymium chloride solution, controlling the carrying capacity of KPr (atomic ratio is 1:1) to be 15wt%, stirring uniformly, standing for 10h, stirring in an oil bath at 80 ℃ until water is removed, drying in an oven at 100 ℃ for 5h, and roasting at 520 ℃ for 7h to obtain the catalyst KPr & Zn 1.0-Al3 Mg.
Adding furfural and acetone into a reaction kettle, controlling the molar ratio of the acetone to the furfural to be 4, adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 6:1, adding a catalyst (the mass is 4wt% of the reactant), wherein the reaction temperature is 85 ℃, the reaction time is 4 hours, and the product is extracted by methylene dichloride and the solvent is removed to obtain the product with the yield of 71%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
Preparing a catalyst Cu-Ni-HAP: 20g of purchased hydroxyapatite is taken and baked for 3 hours at 1200 ℃, the loading of Cu-Ni (the atomic ratio is 3:1) is controlled to be 13wt%, cuprous chloride and nickel chloride solution (the ion concentration is 0.9 g/ml) are added, the 'exchange-adsorption-deposition' is carried out for 8 hours, the pH=7 of the system is regulated, the system is dried for 4 hours at 100 ℃ after filtration, the catalyst is baked for 3 hours at 1200 ℃, and the catalyst Cu-Ni-HAP is obtained and is reduced for 5 hours in hydrogen at 220 ℃ before use.
Solid solution preparation: preparing cerium nitrate and zirconium oxynitrate solution according to the atomic ratio of Zr/Ce of 0.6, stirring uniformly, slowly adjusting the pH=9 of the system by ammonia water to form precipitate, filtering, washing to be neutral, drying at 100 ℃ for 10h, and roasting at 550 ℃ for 6h.
The mass ratio is 2:1, mixing Cu-Ni-HAP and Zr/Ce, adopting ball milling and mixing uniformly, taking 0.5g and loading into a fixed bed reactor, introducing furyl-3-butene-2-one into the reactor at the rate of 0.45ml/min, controlling the reaction temperature to be 230 ℃, controlling the hydrogen flow rate to be 55ml/min, controlling the reaction pressure to be 0.2MPa, and collecting the product at the outlet of the reactor by adopting an ice bath cold trap, wherein the yield is 64%.
3. The furanyl butadiene monomer prepares the liquid rubber.
Adding a furan-based butadiene monomer with purity of more than 99.5% into a mechanical stirring reaction kettle, adding tertiary butanol, adjusting the monomer concentration to 2.8mol/l, adding a catalytic system of hydrogen peroxide/ferrous sulfate, controlling the catalyst concentration to 10mmol/l, and reacting for 2.5h at 75 ℃, wherein the molecular weight of the obtained liquid rubber is 3200g/mol.
Example 4
1. Furfural is condensed with acetone to prepare furyl-3-buten-2-one.
Preparation of catalyst NaLa. Zn 0.2-Al3.5 Mg: taking aluminum nitrate, zinc nitrate and magnesium nitrate in a mortar according to a metering ratio Al/Mg=3.5 and Zn/Mg=0.2, grinding for 30min, transferring to a ball mill, adding water with the mass being one fourth of the solid mass, slowly grinding to be in a powder shape, drying in a 100 ℃ oven for 5h, and roasting at 600 ℃ for 5h to obtain Zn 0.2-Al3.5 Mg; adding Zn 0.2-Al3.5 Mg into sodium bicarbonate and lanthanum chloride (the atomic ratio is 1:1), dissolving in water, controlling the carrying amount of NaLa to be 18wt%, stirring uniformly, standing for 6h, stirring in an oil bath at 80 ℃ until water is removed, drying in an oven at 100 ℃ for 5h, and roasting at 530 ℃ for 7h to obtain the catalyst NaLa.Zn 0.2-Al3.5 Mg.
Adding furfural and acetone into a reaction kettle, controlling the molar ratio of the acetone to the furfural to be 8, adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 13:1, adding a catalyst (the mass is 4wt% of the reactant), wherein the reaction temperature is 110 ℃, the reaction time is 4 hours, and the product is extracted by methylene dichloride and the solvent is removed to obtain the product with the yield of 82%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
Preparing a catalyst Cu-Ni-HAP: 20g of purchased hydroxyapatite is taken and baked for 5 hours at 950 ℃, the loading of Cu-Ni is controlled to be 12wt% (the atomic ratio is 2:1), copper nitrate and nickel chloride solution (the ion concentration is 0.8 g/ml) are added, the 'exchange-adsorption-deposition' is carried out for 12 hours, the pH value of the system is regulated to be 7, the system is dried for 5 hours at 100 ℃ after filtration, the catalyst is baked for 5 hours at 950 ℃, and the catalyst Cu-Ni-HAP is obtained and is reduced for 5 hours in hydrogen at 200 ℃ before use.
Preparation of a catalyst Nd 1.2V0.26PO4: according to the metering ratio Nd/P=1.2 and V/P=0.26, neodymium nitrate is dissolved in water, ammonium metavanadate is added, and the total concentration of metal compounds in the solution is controlled to be 35g/L; stirring and mixing at 65 ℃, regulating the pH to 9, filtering out precipitate, drying at 65 ℃ for 8 hours, adding a phosphoric acid solution with the concentration of 15g/L, adopting a temperature programming-ball milling mode, controlling the temperature programming to be between room temperature and 200 ℃, controlling the temperature programming rate to be 15 ℃/min, staying at 100 ℃ for 2.5 hours, and staying at 200 ℃ for 1.5 hours; roasting at 560 ℃ for 6 hours to obtain Nd 1.2V0.26PO4.
The mass ratio is 2:1, mixing Cu-Ni-HAP and Nd 1.2V0.26PO4, adopting ball milling and mixing uniformly, taking 0.5g and loading into a fixed bed reactor, controlling the reaction temperature to 255 ℃ and the hydrogen flow rate to 50ml/min at the rate of 0.38ml/min, adopting an ice bath cold trap to collect the product at the outlet of the reactor, and the yield is 75%.
3. The furanyl butadiene monomer prepares the liquid rubber.
Adding a furan-based butadiene monomer with purity of more than 99.5% into a mechanical stirring reaction kettle, adding toluene, introducing butadiene, adjusting the mol ratio of the furan-based butadiene to the butadiene to be 0.4, adjusting the monomer concentration to be 2mol/l, adding a catalyst system to be 2-bromo-2-p-phenyl ethyl acetate/Cu, controlling the catalyst concentration to be 18mmol/l, and reacting for 3 hours at 65 ℃, wherein the molecular weight of the obtained liquid rubber is 4300g/mol.
Example 5
1. Furfural is condensed with acetone to prepare furyl-3-buten-2-one.
Preparing a catalyst KPr, zn 0.24-Al2.2 Mg: taking aluminum nitrate, zinc nitrate and magnesium nitrate in a mortar according to a metering ratio Al/Mg=2.2 and Zn/Mg=0.24, grinding for 30min, transferring to a ball mill, adding water with the mass being one fourth of the solid mass, slowly grinding to be powder, drying in a 100 ℃ oven for 8h, and roasting at 620 ℃ for 6h to obtain Zn 0.24-Al2.2 Mg; adding Zn 0.24-Al2.2 Mg into a solution of potassium bicarbonate and praseodymium chloride (the atomic ratio is 2:1), controlling the carrying capacity of KPr to be 14wt%, uniformly stirring, standing for 8 hours, then stirring in an oil bath at 80 ℃ until water is removed, drying in an oven at 100 ℃ for 5 hours, and roasting at 630 ℃ for 4 hours to obtain the catalyst KPr & Zn 0.24-Al2.2 Mg.
Adding furfural and acetone into a reaction kettle, controlling the molar ratio of the acetone to the furfural to be 6, adding water and methanol as solvents (volume ratio is 1:1), wherein the mass ratio of the solvents to the reactants is 8:1, adding a catalyst (the mass is 3wt% of the reactant), wherein the reaction temperature is 95 ℃ and the reaction time is 5 hours, extracting the product by using methylene dichloride, and removing the solvent to obtain the product with the yield of 69%.
2. Furanyl-3-buten-2-one hydrodeoxygenation to synthesize furanyl butadiene.
Preparing a catalyst Cu-Co-HAP: 20g of purchased hydroxyapatite is taken and baked for 3 hours at 1200 ℃, the loading of Cu-Ni (the atomic ratio is 2:1) is controlled to be 10wt%, cuprous chloride and cobalt nitrate solution (the ion concentration is 0.75 g/ml) are added, the 'exchange-adsorption-deposition' is carried out for 8 hours, the pH=7 of the system is regulated, the system is dried for 4 hours at 100 ℃ after filtration, the catalyst is baked for 3 hours at 1050 ℃, and the catalyst Cu-Co-HAP is obtained and is reduced for 5 hours in hydrogen at 200 ℃ before use.
Solid solution preparation: preparing cerium nitrate and ammonium molybdate solution according to the atomic ratio of Mo/Ce of 0.2-1.5, stirring uniformly, slowly adjusting the pH=9 of the system by ammonia water to form precipitate, filtering, washing to neutrality, drying at 100 ℃ for 10h, and roasting at 450 ℃ for 6h.
The mass ratio is 3:1, mixing Cu-Co-HAP and Mo/Ce, adopting ball milling and mixing uniformly, taking 0.5g and loading into a fixed bed reactor, introducing furyl-3-butene-2-one into the reactor at the rate of 0.5ml/min, controlling the reaction temperature to 240 ℃, controlling the hydrogen flow rate to 55ml/min, controlling the reaction pressure to 0.2MPa, and collecting the product at the outlet of the reactor by adopting an ice bath cold trap, wherein the yield is 75%.
3. The furanyl butadiene monomer prepares the liquid rubber.
Adding a furan-based butadiene monomer with purity of more than 99.5% into a mechanical stirring reaction kettle, adding tertiary butanol, adjusting the monomer concentration to 3.2mol/l, adding a catalyst system of bromoethylbenzene/cuprous bromide/bipyridine, controlling the catalyst concentration to 12mmol/l, and reacting for 3 hours at 85 ℃, wherein the molecular weight of the obtained liquid rubber is 5100g/mol.
The use of the catalyst provided in the present invention in the synthesis of olefin-type monomers, a method for the catalytic conversion of biomass sugar-based compounds to olefin-type monomers, and the preparation of reversible-curable liquid rubbers are described in detail hereinabove, with specific examples being set forth in order to facilitate an understanding of the process of the present invention and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The application of the catalyst in synthesizing olefin monomers;
The catalyst comprises a Cu-based active metal-acid-base catalyst;
The general formula of the Cu-based active metal-acid-base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4;
Wherein M is Cu-Ni and/or Cu-Co;
HAP is hydroxyapatite;
Z is a cerium-based solid solution;
the cerium-based solid solution includes a cerium-based binary solid solution;
a is one or more of La, ce, pr, nd and Gd;
B is one or more of Mo, zr, zn, W and V;
x=0.7~1.4，y=0.02~0.3；
the synthetic raw materials comprise furfural and acetone;
The olefin monomer comprises furyl butadiene;
The synthesis is specifically two-stage synthesis;
the first stage synthesis is a condensation reaction;
The second-stage synthesis is hydrodeoxygenation reaction;
the Cu-based active metal-acid-base catalyst is a catalyst for two-stage synthesis.
2. The use according to claim 1, wherein the atomic ratio of metal to cerium in the cerium-based binary solid solution is (0.5-1.2): 1.
3. The use according to claim 1, wherein the cerium-based solid solution comprises one or more of LaCe, prCe, moCe, zrCe and ZnCe;
In the M and HAP, the loading amount of M is 2-15 wt%;
The mass ratio of M.HAP to Z, M.HAP to A xByPO4 and the mass ratio of M.HAP to (Z+A xByPO4) are respectively and independently selected from (0.5-3): 1.
4. The use according to claim 1, wherein the catalyst further comprises M 1·（Znx1-Aly1 Mg) catalyst;
Wherein M 1 is one or more of Na, K, cs, la, ce, pr and Nd;
x1=0.02~1.2，y1=0.2~4；
The loading amount of the M 1 is 5-25 wt%;
the M 1·（Znx1-Aly1 Mg) catalyst is a catalyst for one-stage synthesis.
5. The use according to claim 1, wherein the preparation process of the Cu-based active metal-acid base catalyst comprises the steps of:
Roasting hydroxyapatite, placing the hydroxyapatite in an M source solution, and roasting again after the exchange-adsorption-deposition process to obtain M.HAP;
Regulating the pH value of the mixed solution of the cerium source and the other metal source in the cerium-based solid solution to obtain a precipitate, and performing heat treatment to obtain the cerium-based solid solution;
Regulating the pH value of the mixed solution of the rare earth metal soluble compound and the transition metal soluble compound to obtain a precipitate, drying, carrying out stepped temperature rise ball milling with a phosphoric acid solution, and continuously roasting to obtain A xByPO4;
mixing the M.HAP obtained in the step with cerium-based solid solution and/or A xByPO4 again to obtain a Cu-based active metal-acid-base catalyst;
the preparation process of the M 1·（Znx1-Aly1 Mg) catalyst comprises the following steps:
a) Ball milling a Zn source, an Al source, an Mg source and water to obtain powder, and roasting to obtain Zn x1-Aly1 Mg;
b) Adding Zn x1-Aly1 Mg obtained in the steps into soluble M 1 source aqueous solution, standing, and roasting again to obtain the M 1·（Znx1-Aly1 Mg) catalyst.
6. A method for synthesizing an olefin monomer, comprising the steps of:
1) Carrying out condensation reaction on furfural and acetone, M 1·（Znx1-Aly1 Mg) catalyst in a mixed solvent to obtain furyl-3-butene-2-ketone;
m 1·（Znx1-Aly1 Mg), M 1 is one or more of Na, K, cs, la, ce, pr and Nd;
x1=0.02~1.2，y1=0.2~4；
2) Under the action of a Cu-based active metal-acid-base catalyst, under the condition of hydrogen, carrying out hydrodeoxygenation reaction on the furyl-3-butene-2-ketone obtained in the steps to obtain furyl butadiene;
The general formula of the Cu-based active metal-acid-base catalyst is M.HAP/Z, M.HAP/A xByPO4 or M.HAP/Z/A xByPO4;
Wherein M is Cu-Ni and/or Cu-Co;
HAP is hydroxyapatite;
Z is a cerium-based solid solution;
the cerium-based solid solution includes a cerium-based binary solid solution;
a is one or more of La, ce, pr, nd and Gd;
B is one or more of Mo, zr, zn, W and V;
x=0.7~1.4，y=0.02~0.3。
7. the synthesis method according to claim 6, wherein the molar ratio of acetone to furfural is (1-12): 1, a step of;
the mixed solvent comprises a mixed solvent of methanol and water;
the mass ratio of the mixed solvent to the reactant is (5-15): 1.
8. The synthesis method according to claim 6, wherein the mass ratio of the M 1·（Znx1-Aly1 Mg) catalyst to the reactant is 1wt% to 5wt%;
the temperature of the condensation reaction is 60-160 ℃;
The time of the condensation reaction is 2-12 hours.
9. The synthetic method according to claim 6, wherein the hydrodeoxygenation reaction is carried out in a fixed bed manner;
The temperature of the hydrodeoxygenation reaction is 180-280 ℃;
The reaction pressure of the hydrodeoxygenation reaction is 0.01-0.5 mpa.
10. The synthesis method according to claim 6, wherein the flow rate of the hydrogen gas is 0-100 ml/min;
The feeding speed of the furyl-3-butene-2-ketone is 0.2-0.8 ml/min.
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