CN107930690B - Superfine fibrous polymer immobilized catalyst and preparation method and application thereof - Google Patents
Superfine fibrous polymer immobilized catalyst and preparation method and application thereof Download PDFInfo
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- CN107930690B CN107930690B CN201711008651.5A CN201711008651A CN107930690B CN 107930690 B CN107930690 B CN 107930690B CN 201711008651 A CN201711008651 A CN 201711008651A CN 107930690 B CN107930690 B CN 107930690B
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- itaconic acid
- fibrous polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 239000003622 immobilized catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 57
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000000835 fiber Substances 0.000 claims abstract description 45
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 78
- -1 imidazole compound Chemical class 0.000 claims description 59
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 19
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000013067 intermediate product Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 claims description 2
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001410 Microfiber Polymers 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 229930091371 Fructose Natural products 0.000 description 20
- 239000005715 Fructose Substances 0.000 description 20
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 20
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000012528 membrane Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 9
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 9
- 229940040102 levulinic acid Drugs 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 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 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
Abstract
The invention discloses a preparation method of a superfine fibrous polymer immobilized catalyst, which takes functional ion grafted itaconic acid-based polyurethane as a raw material, prepares superfine fiber by an electrostatic spinning process, and obtains the superfine fibrous polymer immobilized catalyst after crosslinking; the diameter of the superfine fiber is 0.01-4 mu m, and the length of the superfine fiber is 2-150 mm. The invention provides a preparation method of a superfine fibrous polymer immobilized catalyst, which prepares a polymer immobilized catalyst integrating three functions of strong catalysis, high surface activity and easy separation, and synchronously solves the problems of difficult catalyst recovery and larger equipment corrosivity; the polymer supported catalyst can be used in saccharide conversion reaction.
Description
Technical Field
The invention belongs to the field of preparation of catalysts, and particularly relates to a superfine fibrous polymer immobilized catalyst, and a preparation method and application thereof.
Background
The biomass resource has the characteristics of large yield, wide distribution, reproducibility, low cost and the like, is used as a basic raw material of the polymer material technical industry, and can endow the material with the advantages of greenness, low cost, reproducibility and the like. However, the processing inertness of biomass resources is high, and it is difficult to directly process the biomass resources into high-performance polymer materials by using the conventional method of converting mechanical and physical into main means, thereby restricting the development of biomass in the material technology industry. In recent years, with the introduction of chemical conversion thinking, the disassembly and recombination of biomass raw materials are implemented on a molecular scale, so that the limitation and influence of the processing inertia of biomass on a conventional processing method can be greatly avoided, and conditions are created for successfully realizing the preparation of high-performance high polymer materials from biomass. From biomass, a great amount of saccharides such as glucose, fructose and the like which can be obtained by extraction and dissociation can be used as a technical route for the preferential conversion of biomass to high-performance high polymer materials by further preparing active chemical raw materials such as 5-hydroxymethylfurfural, levulinic acid, furandicarboxylic acid and the like through catalytic conversion.
Currently, the catalytic conversion preparation of active chemical raw materials such as 5-hydroxymethylfurfural and levulinic acid by taking monosaccharides such as glucose and fructose as raw materials receives wide attention. Inorganic acid (such as H) is mostly used as the catalyst2SO4、H3PO4Etc.), metal chlorides, organic acids (e.g., formic acid, acetic acid), etc. Although inorganic acid-based homogeneous catalysts exhibit high catalytic efficiency in the reaction, such catalysts are not easily recycled and are highly corrosive to equipment in the reaction.
Liquid ionic catalysts developed in recent years have the advantages of good thermal stability, chemical stability, organic matter solubility and the like. By using the catalyst in catalytic conversion, the corrosion to equipment is effectively avoided while the high catalytic efficiency is maintained, but the separation and recovery are still quite difficult due to the excessively strong solubility of the catalyst.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a superfine fibrous polymer immobilized catalyst, which prepares a polymer immobilized catalyst integrating three functions of strong catalysis, high surface activity and easy separation, and synchronously solves the problems of difficult catalyst recovery and high equipment corrosivity; the polymer supported catalyst can be used in saccharide conversion reaction.
The specific technical scheme is as follows:
a preparation method of a superfine fibrous polymer immobilized catalyst is characterized in that functional ion grafted itaconic acid-based polyurethane is used as a raw material, superfine fibers are prepared by an electrostatic spinning process, and the superfine fibrous polymer immobilized catalyst is obtained after crosslinking;
the structural general formula of the functional ion-grafted itaconic acid-based polyurethane is shown as the following formula (I):
in the formula, R1Is selected from C1～C4Alkyl groups of (a);
R2＝CzH2z，z＝0～10；
x is 0-20, y is 0-30, and x and y are not 0 at the same time;
m＝5～50，n＝10～150；
the diameter of the superfine fiber is 0.01-4 mu m, and the length of the superfine fiber is 2-150 mm.
In the attached drawings of the specification, the structural formula is shown as attached figure 1, so that the structure of the electronic device can be further observed conveniently.
In order to give full play to the advantages of ionic catalysis, improve the separation capacity of the ionic catalysis and the product and lay the foundation for the design and preparation of a catalyst core component, the invention provides the preparation method of the superfine fibrous polymer immobilized catalyst, which combines the design and preparation of functional materials with the special processing means of electrostatic spinning: firstly, active ion catalytic sites are immobilized on an itaconic acid-based polyurethane main chain, then the functional ion grafted itaconic acid-based polyurethane is prepared into superfine fibers through electrostatic spinning, and finally the superfine fibrous polymer immobilized catalyst is obtained through photo-crosslinking.
Preferably, the preparation process of the functional ion-grafted itaconic acid-based polyurethane comprises the following steps:
step 1: mixing dibromoneopentyl glycol with an imidazole compound, heating to 110-150 ℃, reacting completely, washing, and drying to obtain an intermediate product A;
the molar ratio of the dibromoneopentyl glycol to the imidazole compound is 1: 2-10;
the imidazole compound comprises imidazole or imidazole derivatives, and the imidazole derivatives are selected from at least one of 1-butylimidazole, 1-propylimidazole, 1-ethylimidazole and 1-methylimidazole;
step 2: mixing the intermediate product A prepared in the step 1 with ammonium hexafluorophosphate, and carrying out ion exchange reaction at room temperature to obtain an intermediate product B;
the molar ratio of the intermediate product A to ammonium hexafluorophosphate is 1: 2-10;
and step 3: the functional ion-grafted itaconic acid-based polyurethane is obtained by using itaconic acid-based polyester prepolymer, the intermediate product B prepared in the step 2, dihydric alcohol and isophorone diisocyanate as main raw materials and performing reaction and activation;
the molar ratio of the itaconic acid-based polyester prepolymer to the intermediate product B to the dihydric alcohol to the isophorone diisocyanate is (1-5) to (1-3) to (2-12) to (4-20).
In the step 1, only dibromoneopentyl glycol and an imidazole compound are used as raw materials, and no solvent is added, so that the preparation method greatly shortens the reaction time and improves the yield.
In step 2, the crude product after the ion exchange reaction is subjected to post-treatment such as washing, drying and the like to obtain an intermediate product B.
In step 3, the main raw materials include itaconic acid-based polyester prepolymer, intermediate product B, dihydric alcohol and isophorone diisocyanate, and besides the main raw materials, the main raw materials also include solvent, catalyst and other raw materials.
Preferably, the step 3 specifically comprises:
firstly, mixing an itaconic acid-based polyester prepolymer, isophorone diisocyanate and toluene to obtain a mixed solution I, adding the mixed solution I into a reaction kettle, adding a catalyst into the reaction kettle, and heating to 55-75 ℃ to react for 4-8 hours under the atmosphere of nitrogen; mixing the intermediate product B, dihydric alcohol and N, N-dimethylformamide to obtain a mixed solution II, adding the mixed solution II into a reaction kettle, adding a catalyst into the reaction kettle again, heating to 70-100 ℃, reacting for 16-24 hours, and performing post-treatment to obtain the functional ion-grafted itaconic acid-based polyurethane;
in the mixed liquid I, the mass concentration of the itaconic acid-based polyester prepolymer is 10-40%, and the mass concentration of the isophorone diisocyanate is 2-10%;
in the mixed solution II, the mass concentration of the intermediate product B is 3-30%, and the mass concentration of the dihydric alcohol is 1-10%.
The dihydric alcohol can be common varieties, such as ethylene glycol, propylene glycol, butanediol and the like.
The catalyst is selected from common catalyst varieties in the field of polyurethane synthesis, such as dibutyltin dilaurate, stannous octoate, triethylene diamine, bis- (dimethylaminoethyl) ether, carboxylate-1-methyl-4- (2-dimethylaminoethyl) piperazine of tertiary amine, tertiary amine-boride and the like.
The itaconic acid based polyester prepolymer is obtained by condensation of itaconic acid containing carbon-carbon double bond and dihydric alcohol, and the specific preparation process can refer to (Xue W W, Zhang L S, Chen H Z, et al. Synthesis of polyurethane crosslinking carbon-carbon double bonds to preparation of functionalized oligomers [ J ]. Polymer Chemistry 2015,6(20):3858 + 3864).
In the invention, itaconic acid is selected as an initial raw material to prepare itaconic acid-based polyurethane, and active ion catalytic sites (imidazole cations and hexafluorophosphate anions) are immobilized on the main chain of the itaconic acid-based polyurethane in the synthesis process, because the polyurethane is easily dissolved in an organic solvent, and the solvent resistance of the polyurethane can be improved after ultraviolet light-initiated crosslinking by introducing the itaconic acid.
Preferably, the preparation method of the ultrafine fibrous polymer immobilized catalyst comprises the following steps:
the method comprises the following steps: preparation of spinning solution
Mixing functional ion-grafted itaconic acid-based polyurethane with a solvent to prepare a spinning solution;
the solvent is at least one selected from N, N-dimethylformamide, tetrahydrofuran, toluene and acetone;
step two: preparation of superfine fiber
Injecting the spinning solution prepared in the first step into an injector, and performing electrostatic spinning at a voltage of 5-30 kV to obtain superfine fibers;
step three: ultra-fine fiber photocrosslinking
And (2) mixing a photoinitiator with water to prepare a photoinitiator solution, soaking the superfine fibers prepared in the step two in the photoinitiator solution, taking out the superfine fibers, irradiating by ultraviolet light to perform illumination crosslinking, and performing post-treatment to obtain the superfine fibrous polymer immobilized catalyst.
In the first step, preferably, the solvent is selected from a mixed solvent of N, N-dimethylformamide and tetrahydrofuran, and the mixed solvent has good fiberizability; further preferably, the volume ratio of the N, N-dimethylformamide to the tetrahydrofuran is 0.25-4: 1;
in the spinning solution, the mass percentage concentration of the functional ion-grafted itaconic acid-based polyurethane is 35-60%.
Preferably, in the second step, the electrostatic spinning is performed at a voltage of 12-20 kV, the feeding speed of the spinning solution is 0.1-0.3 mL/h, and the receiving distance is 10-20 cm.
The photoinitiator is selected from at least one of α -hydroxyphenyl ketone, thioxanthone and derivatives thereof, benzil derivatives, alkyl thiosulfate ester salts, polycyclic aromatic hydrocarbon derivatives, acyl phosphine oxide and acyl phosphonate, azo compounds and water-soluble inorganic salts;
the concentration of the photoinitiator solution is 1.5-4 wt%;
the soaking time is 30-180 min.
Preferably, in the third step, the time of ultraviolet irradiation is 15-60 min;
the post-treatment comprises washing and drying.
The invention also discloses the superfine fibrous polymer immobilized catalyst prepared by the method and application thereof in catalyzing saccharide dehydration reaction.
The saccharide dehydration reaction takes glucose or fructose as a raw material, and products obtained by the dehydration reaction comprise 5-hydroxymethylfurfural, levulinic acid and furandicarboxylic acid.
Compared with the prior art, the invention has the following beneficial effects:
firstly, active ion catalytic sites are immobilized on an itaconic acid-based polyurethane main chain, then the functional ion grafted itaconic acid-based polyurethane is prepared into superfine fibers through electrostatic spinning, and finally the superfine fibers are subjected to photo-crosslinking to obtain the superfine fibrous polymer immobilized catalyst. In the superfine fibrous solid-supported catalyst, the fiber diameter is evenly distributed at 0.01-4 μm, the fiber length is distributed at 2-150 mm, the surface area is larger, and the catalytic efficiency is improved. The preparation process can improve the later processing applicability and durability of the catalyst while improving the catalytic conversion efficiency.
The superfine fibrous polymer immobilized catalyst prepared by the method has the advantages of good stability, simple recovery, repeated use, large specific surface area and the like, can be used for catalyzing saccharide dehydration reaction, can ensure that the fructose conversion rate reaches over 80 percent by taking the fructose dehydration reaction as an example, and can be repeatedly used for multiple times, and the obtained active chemical raw material product mainly contains 5-hydroxymethylfurfural and levulinic acid. Moreover, the catalytic efficiency of the catalyst can be popularized to other organic molecule conversion fields.
Drawings
FIG. 1 is a general structural formula of a functional ion-grafted itaconic acid-based polyurethane according to the present invention;
FIG. 2 is a NMR spectrum of the functional ion-grafted itaconate-based polyurethane prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1
15g of dibromoneopentyl glycol and 18.5g of 1-butylimidazole are weighed respectively and then added into a reaction kettle with a magnetic stirring device, a thermometer and a condenser tube. And (3) heating to 150 ℃ to initiate the reaction, stopping the reaction after 5 hours of reaction, cooling to room temperature, washing, filtering, and drying at 80 ℃ for 12 hours to obtain the dibutyl imidazole neopentyl glycol bromide salt.
10g of dibutyl imidazole neopentyl glycol bromide salt and 8.11g of ammonium hexafluorophosphate are weighed, dissolved in 20ml of deionized water and put into a reaction kettle with magnetic stirring. After 5 hours of reaction at room temperature, washing and filtering are carried out, and vacuum drying is carried out for 10 hours at the temperature of 80 ℃ to obtain the dibutyl imidazole neopentyl glycol hexafluorophosphate.
4g of itaconic acid-based polyester, 1.7878g of dibutyl imidazole neopentyl glycol hexafluorophosphate, 0.5028g of 1, 4-butanediol and 2.5403g of isophorone diisocyanate were weighed out respectively. First, itaconic acid-based polyester and isophorone diisocyanate were mixed into 20g of toluene, and then added into a reaction kettle, and 0.0026g of dibutyltin dilaurate as a catalyst was added dropwise. After the air in the autoclave was purged with nitrogen, the mechanical stirring was turned on and the temperature was raised to 65 ℃. After 4 hours of reaction, the dibutyl imidazole neopentyl glycol hexafluorophosphate and the dihydric alcohol are dissolved in 20g N N-dimethylformamide, slowly dropped into the reaction kettle, added with 0.002g of catalyst dibutyltin dilaurate again, heated to 80 ℃ for 24 hours of reaction, and cooled to room temperature. Dropping the solution into a large amount of deionized water to obtain floccule, and repeatedly washing with deionized water. And drying at room temperature for 12 hours, dissolving in a proper amount of tetrahydrofuran, placing the solution in a polytetrafluoroethylene mold to form a film, drying at room temperature for 12 hours, and placing in a vacuum oven to dry to obtain the functional ion-grafted itaconic acid-based polyurethane.
The nuclear magnetic resonance hydrogen spectrum of the functional ion-grafted itaconic acid-based polyurethane is shown in figure 2.
Measuring 0.9mL of N, N-dimethylformamide and 0.6mL of tetrahydrofuran to prepare a mixed solvent, and then measuring 1g of functional ion grafted itaconic acid-based polyurethane, and dissolving in the mixed solvent to prepare a spinning solution.
The spinning solution was filled into a 5mL plastic syringe with a metal needle having a diameter of 0.7-0.8 mm. Electrostatic spinning voltage is 18kV, spinning solution feeding speed is 0.2mL/h, a rotary drum covered with aluminum foil is used as a receiver, receiving distance is 15cm, and after 7 hours of spinning, the superfine fiber membrane can be obtained by airing at room temperature.
Soaking the obtained superfine fiber membrane in 2 wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure2959) water solution for 30 minutes, irradiating for 60 minutes by using ultraviolet light, washing by using a large amount of deionized water after the reaction is finished, and drying in a vacuum drying oven to obtain the superfine fibrous polymer immobilized catalyst.
The polymer immobilized catalyst has fiber diameter of 0.1-0.5 micron and fiber length of 4-10 mm.
The superfine fibrous polymer immobilized catalyst prepared in the embodiment is used for fructose conversion reaction, and the process conditions are as follows:
1g of a 5 wt% fructose/dimethyl sulfoxide solution and 0.3g of a microfine fibrous polymer-supported catalyst were put into a 10mL test tube and reacted at 120 ℃ for 5 minutes.
Tests show that the conversion rate of fructose is 84%, and the products are 5-hydroxymethylfurfural, levulinic acid and furandicarboxylic acid.
Example 2
Weighing 15g of dibromoneopentyl glycol and 20g of 1-methylimidazole respectively, and adding the weighed materials into a reaction kettle with a magnetic stirring device, a thermometer and a condenser tube. And (3) heating to 120 ℃ to initiate the reaction, stopping the reaction after 8 hours of reaction, cooling to room temperature, washing and filtering, and drying at 80 ℃ for 10 hours to obtain the dibutyl imidazole neopentyl glycol bromide salt.
10g of dimethyl imidazole neopentyl glycol bromide salt and 12g of ammonium hexafluorophosphate are weighed, dissolved in 10ml of deionized water and put into a reaction kettle with magnetic stirring. Reacting for 6 hours at room temperature, washing, filtering, and drying for 5 hours at 80 ℃ in vacuum to obtain the dibutyl imidazole neopentyl glycol hexafluorophosphate.
7.5g of itaconic acid based polyester, 2.7648g of dimethyl imidazole neopentyl glycol hexafluorophosphate, 0.8950g of 1, 4-butanediol and 4.3957g of isophorone diisocyanate were weighed out respectively. First, itaconic acid based polyester and isophorone diisocyanate were mixed into 15g of toluene, added to a reaction kettle, and 0.004g of dibutyltin dilaurate as a catalyst was added dropwise. After the air in the autoclave was purged with nitrogen, the mechanical stirring was turned on and the temperature was raised to 65 ℃. After 4 hours of reaction, the dimethyl imidazole neopentyl glycol hexafluorophosphate and the dihydric alcohol are dissolved in 25g N, N-dimethylformamide, slowly dropped into the reaction kettle, added with 0.002g of catalyst dibutyltin dilaurate again, heated to 80 ℃ for 24 hours of reaction, and cooled to room temperature. Dropping the solution into a large amount of deionized water to obtain floccule, and repeatedly washing with deionized water. And drying at room temperature for 12 hours, dissolving in a proper amount of tetrahydrofuran, placing the solution in a polytetrafluoroethylene mold to form a film, drying at room temperature for 12 hours, and placing in a vacuum oven to dry to obtain the functional ion-grafted itaconic acid-based polyurethane.
Measuring 1mL of N, N-dimethylformamide and 1.5mL of tetrahydrofuran to prepare a mixed solvent, and then measuring 1.8g of functional ion grafted itaconic acid-based polyurethane, dissolving in the mixed solvent to prepare a spinning solution.
And (3) filling the spinning solution into a 5mL plastic syringe with a metal needle head with the diameter of 0.7-0.8 mm. Electrostatic spinning voltage is 15kV, spinning solution feeding speed is 0.3mL/h, a rotary drum covered with aluminum foil is used as a receiver, receiving distance is 15cm, spinning is carried out for 8 hours, and then the superfine fiber membrane can be obtained by airing at room temperature.
Soaking the obtained superfine fiber membrane in 2 wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure2959) water solution for 60 minutes, irradiating for 30 minutes by using ultraviolet light, washing by using a large amount of deionized water after the reaction is finished, and drying in a vacuum drying oven to obtain the superfine fibrous polymer immobilized catalyst.
The diameter of the polymer immobilized catalyst fiber is 0.3-0.8 μm, and the fiber length is 6-34 mm.
The superfine fibrous polymer immobilized catalyst prepared in the embodiment is used for fructose conversion reaction, and the process conditions are as follows:
1g of a 5 wt% fructose/dimethyl sulfoxide solution and 0.4g of a microfine fibrous polymer-supported catalyst were put into a 10mL test tube and reacted at 120 ℃ for 5 minutes.
Tests show that the conversion rate of fructose is 86%, and the products are 5-hydroxymethylfurfural, levulinic acid and furandicarboxylic acid.
Example 3
20g of dibromoneopentyl glycol and 35g of 1-methylimidazole are respectively weighed and then added into a reaction kettle with a magnetic stirring device, a thermometer and a condenser tube. And (3) heating to 140 ℃ to initiate the reaction, stopping the reaction after 7 hours of reaction, cooling to room temperature, washing, filtering, and drying at 80 ℃ to obtain the dibutyl imidazole neopentyl glycol bromide salt.
Weighing 10g of dimethyl imidazole neopentyl glycol bromide salt and 16g of ammonium hexafluorophosphate, and putting into a reaction kettle with magnetic stirring. Reacting for 6 hours at room temperature, washing, filtering, and drying in vacuum at 80 ℃ to obtain the dibutyl imidazole neopentyl glycol hexafluorophosphate.
6g of itaconic acid-based polyester, 5.0564g of dimethyl imidazole neopentyl glycol hexafluorophosphate, 0.3600g of 1, 4-butanediol and 4.3958g of isophorone diisocyanate were weighed out respectively. First, itaconic acid based polyester and isophorone diisocyanate were mixed into 25g of toluene, added to a reaction kettle, and 0.003g of dibutyltin dilaurate as a catalyst was added dropwise. After the air in the autoclave was purged with nitrogen, the mechanical stirring was turned on and the temperature was raised to 65 ℃. After 4 hours of reaction, the dimethyl imidazole neopentyl glycol hexafluorophosphate and the dihydric alcohol are dissolved in 15g N, N-dimethylformamide, slowly dropped into the reaction kettle, added with 0.008g of catalyst dibutyltin dilaurate again, heated to 80 ℃ for 24 hours of reaction, and cooled to room temperature. Dropping the solution into a large amount of deionized water to obtain floccule, and repeatedly washing with deionized water. And drying at room temperature for 12 hours, dissolving in a proper amount of tetrahydrofuran, placing the solution in a polytetrafluoroethylene mold to form a film, drying at room temperature for 12 hours, and placing in a vacuum oven to dry to obtain the functional ion-grafted itaconic acid-based polyurethane.
Measuring 0.5mL of N, N-dimethylformamide and 1.5mL of tetrahydrofuran to prepare a mixed solvent, and then measuring 1.5g of functional ion grafted itaconic acid-based polyurethane, dissolving in the mixed solvent to prepare a spinning solution.
And (3) filling the spinning solution into a 5mL plastic syringe with a metal needle head with the diameter of 0.7-0.8 mm. Electrostatic spinning voltage is 20kV, spinning solution feeding speed is 0.12mL/h, a rotary drum covered with aluminum foil is used as a receiver, receiving distance is 15cm, spinning is carried out for 8 hours, and then the superfine fiber membrane can be obtained by airing at room temperature.
Soaking the obtained superfine fiber membrane in 2 wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure2959) water solution for 45 minutes, irradiating the superfine fiber membrane for 45 minutes by using ultraviolet light, washing the superfine fiber membrane by using a large amount of deionized water after the reaction is finished, and drying the superfine fiber membrane in a vacuum drying oven to obtain the superfine fiber-shaped polymer immobilized catalyst.
The diameter of the polymer immobilized catalyst fiber is 0.05-0.6 μm, and the fiber length is 15-42 mm.
The superfine fibrous polymer immobilized catalyst prepared in the embodiment is used for fructose conversion reaction, and the process conditions are as follows:
1g of a 5 wt% fructose/dimethyl sulfoxide solution and 0.35g of a microfine fibrous polymer-supported catalyst were put into a 10mL test tube and reacted at 120 ℃ for 5 minutes.
Tests show that the fructose conversion rate is 81%, and the products are 5-hydroxymethyl furfural, levulinic acid and furandicarboxylic acid.
Example 4
20g of dibromoneopentyl glycol and 35g of 1-methylimidazole are respectively weighed and then added into a reaction kettle with a magnetic stirring device, a thermometer and a condenser tube. And (3) heating to 140 ℃ to initiate the reaction, stopping the reaction after 7 hours of reaction, cooling to room temperature, washing, filtering, and drying at 80 ℃ for 15 hours to obtain the dibutyl imidazole neopentyl glycol bromide salt.
Weighing 10g of dimethyl imidazole neopentyl glycol bromide salt and 16g of ammonium hexafluorophosphate, and putting into a reaction kettle with magnetic stirring. Reacting at room temperature for 6 hours, washing, filtering, and drying at 80 ℃ for 8 hours in vacuum to obtain the dibutyl imidazole neopentyl glycol hexafluorophosphate.
6g of itaconic acid-based polyester, 5.0564g of dimethyl imidazole neopentyl glycol hexafluorophosphate, 0.3600g of 1, 4-butanediol and 4.3958g of isophorone diisocyanate were weighed out respectively. First, itaconic acid based polyester and isophorone diisocyanate were mixed into 18g of toluene, added to a reaction kettle, and 0.003g of dibutyltin dilaurate as a catalyst was added dropwise. After the air in the autoclave was purged with nitrogen, the mechanical stirring was turned on and the temperature was raised to 65 ℃. After 4 hours of reaction, the dimethyl imidazole neopentyl glycol hexafluorophosphate and the dihydric alcohol are dissolved in 13g N, N-dimethylformamide, slowly dropped into the reaction kettle, added with 0.001g of catalyst dibutyltin dilaurate again, heated to 80 ℃ for 24 hours of reaction, and cooled to room temperature. Dropping the solution into a large amount of deionized water to obtain floccule, and repeatedly washing with deionized water. And drying at room temperature for 12 hours, dissolving in a proper amount of tetrahydrofuran, placing the solution in a polytetrafluoroethylene mold to form a film, drying at room temperature for 12 hours, and placing in a vacuum oven to dry to obtain the functional ion-grafted itaconic acid-based polyurethane.
Measuring 0.5mL of N, N-dimethylformamide and 1.5mL of tetrahydrofuran to prepare a mixed solvent, and then measuring 1.5g of functional ion grafted itaconic acid-based polyurethane, dissolving in the mixed solvent to prepare a spinning solution.
And (3) filling the spinning solution into a 5mL plastic syringe with a metal needle head with the diameter of 0.7-0.8 mm. Electrostatic spinning voltage is 12kV, spinning solution feeding speed is 0.24mL/h, a rotary drum covered with aluminum foil is used as a receiver, receiving distance is 12cm, spinning is carried out for 8 hours, and then the superfine fiber membrane can be obtained by airing at room temperature.
Soaking the obtained fiber membrane in 2 wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure2959) water solution for 60 minutes, irradiating for 15 minutes by using ultraviolet light, washing by using a large amount of deionized water after the reaction is finished, and drying in a vacuum drying oven to obtain the superfine fibrous polymer immobilized catalyst.
The diameter of the polymer immobilized catalyst fiber is 0.7-3 μm, and the fiber length is 23-86 mm.
The superfine fibrous polymer immobilized catalyst prepared in the embodiment is used for fructose conversion reaction, and the process conditions are as follows:
1g of a 5 wt% fructose/dimethyl sulfoxide solution and 0.5g of a microfine fibrous polymer-supported catalyst were put into a 10mL test tube and reacted at 120 ℃ for 5 minutes.
Tests show that the fructose conversion rate is 82%, and the products are 5-hydroxymethylfurfural, levulinic acid and furandicarboxylic acid.
Example 5
20g of dibromoneopentyl glycol and 40g of 1-butylimidazole are respectively weighed and then added into a reaction kettle with a magnetic stirring device, a thermometer and a condenser tube. And (3) heating to 145 ℃ to initiate the reaction, stopping the reaction after 5.5 hours of reaction, cooling to room temperature, washing and filtering, and drying at 80 ℃ for 14 hours to obtain the dibutyl imidazole neopentyl glycol bromide salt.
Weighing 15g of dibutyl imidazole neopentyl glycol bromide salt and 30g of ammonium hexafluorophosphate, and putting into a reaction kettle with magnetic stirring. After 5 hours of reaction at room temperature, washing and filtering are carried out, and vacuum drying is carried out for 24 hours at the temperature of 80 ℃ to obtain the dibutyl imidazole neopentyl glycol hexafluorophosphate.
15g of itaconic acid-based polyester, 7.5643g of dibutyl imidazole neopentyl glycol hexafluorophosphate, 1.3349g of 1, 4-butanediol and 8.7915g of isophorone diisocyanate were weighed out respectively. First, itaconic acid based polyester and isophorone diisocyanate were mixed into 30g of toluene, and then added into a reaction kettle, and 0.01g of dibutyltin dilaurate as a catalyst was added dropwise. After the air in the autoclave was purged with nitrogen, the mechanical stirring was turned on and the temperature was raised to 65 ℃. After reacting for 4 hours, dissolving the dibutyl imidazole neopentyl glycol hexafluorophosphate and the dihydric alcohol in N, N-dimethylformamide, slowly dropping into the reaction kettle, adding 3 drops of catalyst dibutyltin dilaurate again, heating to 80 ℃ for reacting for 24 hours, and cooling to room temperature. Dropping the solution into a large amount of deionized water to obtain floccule, and repeatedly washing with deionized water. And drying at room temperature for 12 hours, dissolving in a proper amount of tetrahydrofuran, placing the solution in a polytetrafluoroethylene mold to form a film, drying at room temperature for 12 hours, and placing in a vacuum oven to dry to obtain the functional ion-grafted itaconic acid-based polyurethane.
Weighing 4mL of N, N-dimethylformamide and 1mL of tetrahydrofuran to prepare a mixed solvent, weighing 4g of functional ion grafted itaconic acid-based polyurethane, and dissolving in the mixed solvent to prepare a spinning solution.
And (3) filling the spinning solution into a 5mL plastic syringe with a metal needle head with the diameter of 0.7-0.8 mm. Electrostatic spinning voltage is 17kV, spinning solution feeding speed is 0.2mL/h, a rotary drum covered with aluminum foil is used as a receiver, receiving distance is 12cm, spinning is carried out for 8 hours, and then the superfine fiber membrane can be obtained by airing at room temperature.
Soaking the obtained fiber membrane in 2 wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure2959) water solution for 60 minutes, irradiating for 30 minutes by using ultraviolet light, washing by using a large amount of deionized water after the reaction is finished, and drying in a vacuum drying oven to obtain the superfine fibrous polymer immobilized catalyst.
The diameter of the polymer immobilized catalyst fiber is 0.2-0.7 μm, and the fiber length is 15-25 mm.
The superfine fibrous polymer immobilized catalyst prepared in the embodiment is used for fructose conversion reaction, and the process conditions are as follows:
1g of a 5 wt% fructose/dimethyl sulfoxide solution and 0.25g of a microfine fibrous polymer-supported catalyst were put into a 10mL test tube and reacted at 120 ℃ for 5 minutes.
Tests show that the fructose conversion rate is 81%, and the products are 5-hydroxymethyl furfural, levulinic acid and furandicarboxylic acid.
Claims (10)
1. A preparation method of a superfine fibrous polymer immobilized catalyst is characterized in that functional ion grafted itaconic acid-based polyurethane is used as a raw material, superfine fibers are prepared by an electrostatic spinning process, and the superfine fibrous polymer immobilized catalyst is obtained after crosslinking;
the structural general formula of the functional ion-grafted itaconic acid-based polyurethane is shown as the following formula (I):
in the formula, R1Is selected from C1～C4Alkyl groups of (a);
R2＝CzH2z，z＝0～10；
x is 0-20, y is 0-30, and x and y are not 0 at the same time;
m＝5～50，n＝10～150；
the diameter of the superfine fiber is 0.01-4 mu m, and the length of the superfine fiber is 2-150 mm.
2. The preparation method of the ultrafine fibrous polymer supported catalyst according to claim 1, wherein the functional ion-grafted itaconic acid-based polyurethane is prepared by the following process:
step 1: mixing dibromoneopentyl glycol with an imidazole compound, heating to 110-150 ℃, reacting completely, washing, and drying to obtain an intermediate product A;
the molar ratio of the dibromoneopentyl glycol to the imidazole compound is 1: 2-10;
the imidazole compound comprises imidazole or imidazole derivatives, and the imidazole derivatives are selected from at least one of 1-butylimidazole, 1-propylimidazole, 1-ethylimidazole and 1-methylimidazole;
step 2: mixing the intermediate product A prepared in the step 1 with ammonium hexafluorophosphate, and carrying out ion exchange reaction at room temperature to obtain an intermediate product B;
the molar ratio of the intermediate product A to ammonium hexafluorophosphate is 1: 2-10;
and step 3: the functional ion-grafted itaconic acid-based polyurethane is obtained by using itaconic acid-based polyester prepolymer, the intermediate product B prepared in the step 2, dihydric alcohol and isophorone diisocyanate as main raw materials and performing reaction and activation;
the molar ratio of the itaconic acid-based polyester prepolymer to the intermediate product B to the dihydric alcohol to the isophorone diisocyanate is (1-5) to (1-3) to (2-12) to (4-20).
3. The method for preparing the ultrafine fibrous polymer-supported catalyst according to claim 2, wherein the step 3 specifically comprises:
firstly, mixing an itaconic acid-based polyester prepolymer, isophorone diisocyanate and toluene to obtain a mixed solution I, adding the mixed solution I into a reaction kettle, adding a catalyst into the reaction kettle, and heating to 55-75 ℃ to react for 4-8 hours under the atmosphere of nitrogen; mixing the intermediate product B, dihydric alcohol and N, N-dimethylformamide to obtain a mixed solution II, adding the mixed solution II into a reaction kettle, adding the catalyst into the reaction kettle again, heating to 70-100 ℃, reacting for 16-24 hours, and performing post-treatment to obtain the functional ion-grafted itaconic acid-based polyurethane;
the catalyst is any one or more of dibutyltin dilaurate, stannous octoate, triethylene diamine, bis- (dimethylaminoethyl) ether, carboxylate-1-methyl-4- (2-dimethylaminoethyl) piperazine of tertiary amine and tertiary amine-boride;
in the mixed liquid I, the mass concentration of the itaconic acid-based polyester prepolymer is 10-40%, and the mass concentration of the isophorone diisocyanate is 2-10%;
in the mixed solution II, the mass concentration of the intermediate product B is 3-30%, and the mass concentration of the dihydric alcohol is 1-10%.
4. The method for preparing the ultrafine fibrous polymer-supported catalyst according to claim 1, comprising:
the method comprises the following steps: preparation of spinning solution
Mixing functional ion-grafted itaconic acid-based polyurethane with a solvent to prepare a spinning solution;
the solvent is at least one selected from N, N-dimethylformamide, tetrahydrofuran, toluene and acetone;
step two: preparation of superfine fiber
Injecting the spinning solution prepared in the first step into an injector, and performing electrostatic spinning at a voltage of 5-30 kV to obtain superfine fibers;
step three: ultra-fine fiber photocrosslinking
And (2) mixing a photoinitiator with water to prepare a photoinitiator solution, soaking the superfine fibers prepared in the step two in the photoinitiator solution, taking out the superfine fibers, irradiating by ultraviolet light to perform illumination crosslinking, and performing post-treatment to obtain the superfine fibrous polymer immobilized catalyst.
5. The method for preparing the ultrafine fibrous polymer-supported catalyst according to claim 4, wherein in the step one, the solvent is selected from a mixed solvent of N, N-dimethylformamide and tetrahydrofuran, and the volume ratio of N, N-dimethylformamide to tetrahydrofuran is 0.25-4: 1;
in the spinning solution, the mass percentage concentration of the functional ion-grafted itaconic acid-based polyurethane is 35-60%.
6. The method for preparing the ultrafine fibrous polymer-supported catalyst according to claim 4, wherein in the second step, the electrostatic spinning is performed at a voltage of 12 to 20kV, the feeding speed of the spinning solution is 0.1 to 0.3mL/h, and the receiving distance is 10 to 20 cm.
7. The method for preparing the ultrafine fibrous polymer supported catalyst according to claim 4, wherein in step three, the photoinitiator is at least one selected from α -hydroxyphenyl ketone, thioxanthone and its derivatives, benzil derivatives, alkyl thiosulfate salts, polycyclic aromatic hydrocarbon derivatives, acyl phosphine oxide and acyl phosphonate, azo compounds, and water-soluble inorganic salts;
the concentration of the photoinitiator solution is 1.5-4 wt%;
the soaking time is 30-180 min.
8. The method for preparing the ultrafine fibrous polymer-supported catalyst according to claim 4, wherein in the third step, the time for irradiating the ultraviolet light is 15 to 60 min;
the post-treatment comprises washing and drying.
9. An ultrafine fibrous polymer-supported catalyst prepared by the method according to any one of claims 1 to 8.
10. The use of the ultrafine fibrous polymer-supported catalyst according to claim 9 for catalyzing a dehydration reaction of saccharides.
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| CN101891876A (en) * | 2010-07-23 | 2010-11-24 | 浙江大学 | Imidazole salt type cationic polyurethane and preparation method thereof |
| CN102718945A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid-based epoxy resin composition and method for preparing cured substance |
| CN105542651A (en) * | 2015-12-30 | 2016-05-04 | 中物功能材料研究院有限公司 | Polyurethane acrylate dispersion and preparation method thereof, and ultraviolet-curing conducting paint and preparation method thereof |
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| CN101891876A (en) * | 2010-07-23 | 2010-11-24 | 浙江大学 | Imidazole salt type cationic polyurethane and preparation method thereof |
| CN102718945A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid-based epoxy resin composition and method for preparing cured substance |
| CN105542651A (en) * | 2015-12-30 | 2016-05-04 | 中物功能材料研究院有限公司 | Polyurethane acrylate dispersion and preparation method thereof, and ultraviolet-curing conducting paint and preparation method thereof |
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