CN111804342A - 担载型金属离子液体催化剂的制备方法及其所得产品和应用 - Google Patents
担载型金属离子液体催化剂的制备方法及其所得产品和应用 Download PDFInfo
- Publication number
- CN111804342A CN111804342A CN202010937816.2A CN202010937816A CN111804342A CN 111804342 A CN111804342 A CN 111804342A CN 202010937816 A CN202010937816 A CN 202010937816A CN 111804342 A CN111804342 A CN 111804342A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polymer microspheres
- porous polymer
- auxiliary agent
- supported metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 title claims description 10
- 229910021645 metal ion Inorganic materials 0.000 title claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 45
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 imidazole compound Chemical class 0.000 claims abstract description 29
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000003944 halohydrins Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 150000003440 styrenes Chemical class 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 8
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 235000010981 methylcellulose Nutrition 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims 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 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 238000005406 washing Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000010992 reflux Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YAQLSKVCTLCIIE-UHFFFAOYSA-N 2-bromobutyric acid Chemical compound CCC(Br)C(O)=O YAQLSKVCTLCIIE-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- QSECPQCFCWVBKM-UHFFFAOYSA-N 2-iodoethanol Chemical compound OCCI QSECPQCFCWVBKM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- DHXNZYCXMFBMHE-UHFFFAOYSA-N 3-bromopropanoic acid Chemical compound OC(=O)CCBr DHXNZYCXMFBMHE-UHFFFAOYSA-N 0.000 description 1
- SIJLYRDVTMMSIP-UHFFFAOYSA-N 4-Bromo-1-butanol Chemical compound OCCCCBr SIJLYRDVTMMSIP-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了担载型金属离子液体催化剂的制备方法及其所得产品和应用,属于催化剂制备技术领域。所述方法包括:1)将苯乙烯、二乙烯基苯或二乙烯基苯的衍生物与含不饱和烯基的咪唑类化合物聚合,得到多孔聚合物微球;2)将多孔聚合物微球采用卤代烷、卤代醇或卤代羧酸进行改性,得到接枝多孔聚合物微球;3)将接枝多孔聚合物微球与卤化锌和甲苯混合加热,得到担载型金属离子液体催化剂。本发明制备得到的催化剂活性高,反应后催化剂易于分离,可重复使用,且制备工艺简单、成本低。
Description
技术领域
本发明涉及催化剂制备技术领域,具体涉及担载型金属离子液体催化剂的制备方法及其所得产品和应用。
背景技术
碳酸丙烯酯是一种性能优良的溶剂和精细化工中间体,广泛应用于电解液、医药、农药合成等领域,是有机化工潜在的基础原料。工业上采用环氧丙烷、二氧化碳和催化剂进行环加成反应制备得到。催化剂按形态分为均相和非均相两大类。均相催化剂大多是用路易斯酸金属和路易斯碱组成的二元催化体系,其中路易斯酸金属包括碱/碱土金属卤化物、过渡金属盐、金属配合物,路易斯碱包括有机碱、季铵盐、季鏻盐、离子液体等。均相催化剂的催化效果较好,但存在难分离、活性组分易流失、对水敏感等缺点。非均相催化剂通常是指分子筛、金属氧化物、离子交换树脂等,但其催化活性比较低,需要高温高压。
目前离子液体类催化剂是研究的热点,主要是将咪唑类嫁接到其他载体上,如聚苯乙烯树脂、壳聚糖、羧甲基纤维素、SiO2等。专利CN104549513B公开了一种固体催化剂,以聚苯乙烯微球负载烷基咪唑、锌盐、乌洛托品为活性组分,但需使用酚醛树脂作为粘接成型剂,影响其催化活性;专利CN102728402B合成了一种介孔氧化硅泡沫材料固载离子液体催化剂,但催化体系活性不高,且合成工艺涉及水热反应,较为复杂。
发明内容
本发明针对上述背景技术中催化剂存在产物难分离、催化活性低的技术问题,本发明提供了一种担载型金属离子液体催化剂的制备方法及其所得产品和应用,制备得到的催化剂活性高,反应后催化剂易于分离,可重复使用,且制备工艺简单、成本低。
为了解决上述技术问题,本发明提供了一种担载型金属离子液体催化剂的制备方法,包括如下步骤:
1)将苯乙烯、二乙烯基苯或二乙烯基苯的衍生物与含不饱和烯基的咪唑类化合物聚合,得到多孔聚合物微球;
2)将所述步骤1)的多孔聚合物微球采用卤代烷、卤代醇或卤代羧酸进行改性,得到接枝多孔聚合物微球;
3)将所述步骤2)的接枝多孔聚合物微球与卤化锌和甲苯混合加热,得到担载型金属离子液体催化剂。
优选的,所述步骤1)中含不饱和烯基的咪唑类化合物包括N-乙烯基咪唑、N-烯丙基咪唑及其衍生物。
优选的,所述步骤1)中的聚合包括如下步骤:
a.将单体、引发剂和助剂一混合,得到有机溶剂;
所述单体包括苯乙烯、二乙烯基苯或二乙烯基苯的衍生物和含不饱和烯基的咪唑类化合物;
所述引发剂包括过氧化苯甲酰、偶氮二异丁腈、过氧化月桂酰和异丙苯过氧化氢中的一种或几种;
所述助剂一包括甲苯、苯和二甲苯中的一种或几种;
b.将所述步骤a中的有机溶剂与助剂二的水溶液混合加热,得到多孔聚合物微球;
所述助剂二包括聚乙烯醇、明胶、淀粉和甲基纤维素中的一种或几种。
优选的,所述步骤a中助剂一、引发剂和单体的质量比为(1~3):(0.005~0.02):1。
优选的,所述有机溶剂与助剂二的水溶液的质量比为3~8:1;所述助剂二的水溶液中助剂的质量浓度为0.2%~4%。
优选的,所述步骤2)中改性时的反应温度为70~80℃,时间为20~28h。
优选的,所述步骤3)中卤化锌与含不饱和烯基的咪唑类化合物的摩尔比为1:(2~10)。
优选的,所述步骤3)中卤化锌包括氯化锌、溴化锌或碘化锌中的一种或几种。
本发明提供了一种担载型金属离子液体催化剂,由上述任意一项所述方法制备得到。
本发明提供了一种上述方案所述的担载型金属离子液体催化剂在制备碳酸丙烯酯中的应用。
本发明相较于现有技术取得了以下技术效果:
本发明使用含不饱和烯基的咪唑类化合物与苯乙烯、二乙烯基苯或其衍生物进行聚合,得到多孔聚合物微球,可直接将咪唑催化位点引入非均相催化剂骨架,其含量可以通过更改单体比例进行调控,催化活性组分负载量大,催化活性高。
本发明使用卤代烷、卤代醇、卤代羧酸,对咪唑环进行改性,并与金属卤化物形成配合物,从而形成金属离子液体接枝的微孔聚合物,是一种非均相催化剂,克服了均相催化剂难分离的缺点。
具体实施方式
本发明提供了一种担载型金属离子液体催化剂的制备方法,包括如下步骤:
1)将苯乙烯、二乙烯基苯或二乙烯基苯的衍生物与含不饱和烯基的咪唑类化合物聚合,得到多孔聚合物微球;
2)将所述步骤1)的多孔聚合物微球采用卤代烷、卤代醇或卤代羧酸进行改性,得到接枝多孔聚合物微球;
3)将所述步骤2)的接枝多孔聚合物微球与卤化锌和甲苯混合加热,得到担载型金属离子液体催化剂。
本发明将苯乙烯、二乙烯基苯或二乙烯基苯的衍生物与含不饱和烯基的咪唑类化合物聚合,得到多孔聚合物微球。在本发明中,所述含不饱和烯基的咪唑类化合物优选为N-乙烯基咪唑、N-烯丙基咪唑及其衍生物,更优选为N-乙烯基咪唑。在本发明中,所述苯乙烯、二乙烯基苯或二乙烯基苯的衍生物与含不饱和烯基的咪唑类化合物的摩尔比优选为1:(0.5~1)。
在本发明中,所述聚合优选包括如下步骤:
a.将单体、引发剂和助剂一混合,得到有机溶剂;
所述单体包括苯乙烯、二乙烯基苯或二乙烯基苯的衍生物和含不饱和烯基的咪唑类化合物;
所述引发剂包括过氧化苯甲酰、偶氮二异丁腈、过氧化月桂酰和异丙苯过氧化氢中的一种或几种;
所述助剂一包括甲苯、苯和二甲苯中的一种或几种;
b.将所述步骤a中的有机溶剂与助剂二的水溶液混合加热,得到多孔聚合物微球;
所述助剂二包括聚乙烯醇、明胶、淀粉和甲基纤维素中的一种或几种。
在本发明中,优选将单体、引发剂和助剂一混合,得到有机溶剂。在本发明中,所述单体优选包括苯乙烯、二乙烯基苯或二乙烯基苯的衍生物和含不饱和烯基的咪唑类化合物;所述引发剂优选包括过氧化苯甲酰、偶氮二异丁腈、过氧化月桂酰和异丙苯过氧化氢中的一种或几种;所述助剂一包括甲苯、苯和二甲苯中的一种或几种。在本发明中,所述助剂一、引发剂和单体的质量比优选为(1~3): (0.005~0.02):1,更优选为2:0.01:1。
得到有机溶剂后,本发明优选将所述机溶剂与助剂二的水溶液混合加热,得到多孔聚合物微球。在本发明中,所述助剂二优选包括聚乙烯醇、明胶、淀粉和甲基纤维素中的一种或几种。所述助剂二的水溶液中助剂二的质量浓度优选为0.2%~4%,更优选为0.5%~3%,最优选为1%~2%。在本发明中,所述有机溶剂与助剂二的水溶液的质量比优选为(3~8):1,更优选为5:1。在本发明中,所述加热的温度优选为70~110℃,更优选为80℃;加热的时间优选为2~8h,更优选为6h。
本发明使用含不饱和烯基的咪唑类化合物与苯乙烯、二乙烯基苯或其衍生物进行聚合,得到多孔聚合物微球,可直接将咪唑催化位点引入非均相催化剂骨架,而且含量可以通过更改单体比例进行调控,催化活性组分负载量大。
得到多孔聚合物微球后,本发明将所述多孔聚合物微球采用卤代烷、卤代醇或卤代羧酸进行改性,得到接枝多孔聚合物微球。在本发明中,在采用卤代烷、卤代醇或卤代羧酸进行改性前,本发明优选对得到的多孔聚合物微球依次进行洗涤、干燥。在本发明中,所述洗涤的方式优选为依次采用水和甲醇进行洗涤。所述干燥的方式优选为真空干燥。所述真空干燥的温度优选为40℃。
在本发明中,所述卤代烷优选包括溴乙烷、1-溴己烷、1-溴辛烷、1-溴丁烷、1-氯丁烷和1-碘丁烷中的一种或几种;所述卤代醇优选包括氯乙醇、溴乙醇、碘乙醇、4-溴丁醇和3-溴丙醇中的一种或几种;所述卤代羧酸优选包括2-溴丁酸、3-溴丙酸、2-溴丙酸、溴乙酸和氯乙酸中的一种或几种。在本发明中,所述卤代烷、卤代醇或卤代羧酸与含不饱和烯基的咪唑类化合物的摩尔比为1:(1~2)。
在本发明中,采用卤代烷、卤代醇或卤代羧酸进行改性时,优选将多孔聚合物微球溶解在甲苯溶剂中后再进行改性。在本发明中,所述改性时的反应温度优选为70~80℃,更优选为75℃;时间优选为20~28h,更优选为24h。
得到接枝多孔聚合物微球后,本发明将所述接枝多孔聚合物微球与卤化锌和甲苯混合加热,得到担载型金属离子液体催化剂。在本发明中,将接枝多孔聚合物微球与卤化锌和溶剂混合前优选对所述接枝多孔聚合物微球依次进行洗涤、干燥。在本发明中,所述洗涤的方式优选为采用乙酸乙酯进行洗涤。所述干燥的方式优选为真空干燥。所述真空干燥的温度优选为65℃。
在本发明中,所述卤化锌优选为氯化锌、溴化锌或碘化锌中的一种或几种。所述卤化锌与含不饱和烯基的咪唑类化合物的摩尔比优选为1:(2~10),更优选为1:6。在本发明中,所述甲苯作为溶剂,以使卤化锌和接枝多孔聚合物微球溶解在其中进行改性。
在本发明中,所述加热的温度优选为40~90℃,更优选为60℃;所述加热的时间优选为6~24h,更优选为20h。
本发明使用卤代烷、卤代醇、卤代羧酸,对咪唑环进行改性,并与金属卤化物形成配合物,从而形成金属离子液体接枝的微孔聚合物,是一种非均相催化剂,克服了均相催化剂难分离的缺点。
得到担载型金属离子液体催化剂,本发明优选对所述担载型金属离子液体催化剂依次进行洗涤和旋蒸,得到干燥的担载型金属离子液体催化剂。在本发明中,所述洗涤的方式优选为采用乙酸乙酯进行洗涤。所述旋蒸优选采用真空旋转蒸发仪进行。所述旋蒸时的温度优选为50℃。
本发明提供了一种担载型金属离子液体催化剂,由上述任意一项所述方法制备得到。
本发明提供了一种上述方案所述的担载型金属离子液体催化剂在制备碳酸丙烯酯中的应用。所述制备碳酸丙烯酯时,采用环氧丙烷和二氧化碳为原料,以本发明提供的担载型金属离子液体催化剂进行催化制备得到。
为了进一步说明本发明,下面结合实施例对本发明提供的技术方案进行详细地描述,但不能将它们理解为对本发明保护范围的限定。
实施例1
在装有机械搅拌器、回流冷凝管、搅拌装置和氮气阀门的四口圆底烧瓶反应器中,装入20mL含有2wt%明胶的水溶液。将含有34.64g甲苯、14.12gN-乙烯基咪唑、19.53g二乙烯基苯和0.49g偶氮二异丁腈的有机溶剂,加入到上述水溶液中,升温至80℃,反应6h,反应后用水和甲醇依次洗涤,并在40℃下真空干燥,得到干燥后的多孔聚合物微球。将干燥后的多孔聚合物微球分散在50mL的甲苯溶剂中,加入0.15mol的溴乙醇,于75℃下回流反应24h,用乙酸乙酯清洗3次,然后在65℃下真空中干燥,得到干燥后的接枝多孔聚合物微球。将干燥后的接枝多孔聚合物微球重新分散于50mL的甲苯溶剂中,加入75 mmol的ZnBr2,于60℃下回流反应24h,之后用乙酸乙酯进行多次洗涤,洗涤后再用真空旋转蒸发仪在50℃进行旋蒸,除去其中的乙酸乙酯和大部分水,得到催化剂1。
实施例2
在装有机械搅拌器、回流冷凝管、搅拌装置和氮气阀门的四口圆底烧瓶反应器中,装入20 mL含有0.5wt%聚乙烯醇的水溶液。将含有90 g甲苯(助剂一)、22.59 gN-乙烯基咪唑(单体)、12.50 g苯乙烯(单体)和0.18g过氧化苯甲酰(引发剂)的有机溶剂,加入到上述水溶液中,升温至110℃,反应2h。反应后用水和甲醇依次洗涤,并在40℃下真空干燥,得到干燥后的多孔聚合物微球。将干燥后的多孔聚合物微球分散在50mL的甲苯溶剂中,加入0.2mol的1-溴丁烷,于80℃下回流反应20h,用乙酸乙酯清洗3次,然后在65℃下真空中干燥,得到干燥后的接枝多孔聚合物微球。将干燥后的接枝多孔聚合物微球重新分散于50mL的甲苯溶剂中,加入24mmol的ZnCl2,于60℃下回流反应24h,之后用乙酸乙酯进行多次洗涤,洗涤后再用真空旋转蒸发仪在50℃进行旋蒸,除去其中的乙酸乙酯和大部分水,得到催化剂2。
实施例3
在装有机械搅拌器、回流冷凝管、搅拌装置和氮气阀门的四口圆底烧瓶反应器中,装入10 mL含有0.2wt%甲基纤维素的水溶液。将含有30 g甲苯(助剂一)、14.12 gN-乙烯基咪唑(单体)、9.76 g二乙烯基苯(单体)和0.44 g过氧化月桂酰(引发剂)的有机溶剂,加入到上述水溶液中,升温至70℃,反应8h。反应后用水和甲醇依次洗涤,并在40℃下真空干燥,得到干燥后的多孔聚合物微球。将干燥后的多孔聚合物微球分散在50mL的甲苯溶剂中,加入0.1mol的2-溴丁酸,于70℃下回流反应28h,用乙酸乙酯清洗3次,然后在65℃下真空中干燥,得到干燥后的接枝多孔聚合物微球。将干燥后的接枝多孔聚合物微球重新分散于50mL的甲苯溶剂中,加入30mmol的ZnI2,于40℃下回流反应20h,之后用乙酸乙酯进行多次洗涤,洗涤后再用真空旋转蒸发仪在50℃进行旋蒸,除去其中的乙酸乙酯和大部分水,得到催化剂3。
实施例4
在装有机械搅拌器、回流冷凝管、搅拌装置和氮气阀门的四口圆底烧瓶反应器中,装入7 mL含有4wt%甲基纤维素的水溶液。将含有30 g甲苯(助剂一)、14.12 gN-乙烯基咪唑(单体)、9.76 g二乙烯基苯(单体)和0.44 g过氧化月桂酰(引发剂)的有机溶剂,加入到上述水溶液中,升温至70℃,反应8h。反应后用水和甲醇依次洗涤,并在40℃下真空干燥,得到干燥后的多孔聚合物微球。将干燥后的多孔聚合物微球分散在50mL的甲苯溶剂中,加入0.1mol的2-溴丁酸,于70℃下回流反应28h,用乙酸乙酯清洗3次,然后在65℃下真空中干燥,得到干燥后的接枝多孔聚合物微球。将干燥后的接枝多孔聚合物微球重新分散于50mL的甲苯溶剂中,加入30mmol的ZnI2,于40℃下回流反应20h,之后用乙酸乙酯进行多次洗涤,洗涤后再用真空旋转蒸发仪在50℃进行旋蒸,除去其中的乙酸乙酯和大部分水,得到催化剂4。
实施例5
在250mL配置有磁力搅拌器和自动温度控制系统的不锈钢反应器内加入0.5mol的PO(环氧丙烷),加入500mg催化剂,通入CO2气体,保持一定压力(具体压力如表1所示),反应1h,具体催化效果如表1所示。
采用联苯作为内标物,进行催化后产物的气相色谱分析,其中:
收率(%)=(产物中碳酸丙烯酯的质量/理论环氧丙烷全部转化为碳酸丙烯酯的质量)*100%
选择性(%)=(产物中碳酸丙烯酯的质量/催化后产物的总质量)*100%
表1 催化效果
由表1可以看出,本发明制备得到的催化剂,克服了传统均相催化剂难分离的问题,同时具有较高的催化活性和选择性。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.担载型金属离子液体催化剂的制备方法,其特征在于,包括如下步骤:
1)将苯乙烯、二乙烯基苯或二乙烯基苯的衍生物与含不饱和烯基的咪唑类化合物聚合,得到多孔聚合物微球;
2)将所述步骤1)的多孔聚合物微球采用卤代烷、卤代醇或卤代羧酸进行改性,得到接枝多孔聚合物微球;
3)将所述步骤2)的接枝多孔聚合物微球与卤化锌和甲苯混合加热,得到担载型金属离子液体催化剂。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤1)中含不饱和烯基的咪唑类化合物包括N-乙烯基咪唑、N-烯丙基咪唑及其衍生物。
3.根据权利要求1所述的制备方法,其特征在于,所述步骤1)中的聚合包括如下步骤:
a.将单体、引发剂和助剂一混合,得到有机溶剂;
所述单体包括苯乙烯、二乙烯基苯或二乙烯基苯的衍生物和含不饱和烯基的咪唑类化合物;
所述引发剂包括过氧化苯甲酰、偶氮二异丁腈、过氧化月桂酰和异丙苯过氧化氢中的一种或几种;
所述助剂一包括甲苯、苯和二甲苯中的一种或几种;
b.将所述步骤a中的有机溶剂与助剂二的水溶液混合加热,得到聚合物微球;
所述助剂二包括聚乙烯醇、明胶、淀粉和甲基纤维素中的一种或几种。
4.根据权利要求3所述的制备方法,其特征在于,所述步骤a中助剂一、引发剂和单体的质量比为(1~3):(0.005~0.02):1。
5.根据权利要求3所述的制备方法,其特征在于,所述有机溶剂与助剂二的水溶液的质量比为(3~8):1;所述助剂二的水溶液中助剂的质量浓度为0.2%~4%。
6.根据权利要求1所述的制备方法,其特征在于,所述步骤2)中改性时的反应温度为70~80℃,时间为20~28h。
7.根据权利要求1所述的制备方法,其特征在于,所述步骤3)中卤化锌与含不饱和烯基的咪唑类化合物的摩尔比为1:(2~10)。
8.根据权利要求1所述的制备方法,其特征在于,所述步骤3)中卤化锌包括氯化锌、溴化锌或碘化锌中的一种或几种。
9.一种担载型金属离子液体催化剂,其特征在于,由权利要求1~8任意一项所述方法制备得到。
10.权利要求9所述的担载型金属离子液体催化剂在制备碳酸丙烯酯中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010937816.2A CN111804342A (zh) | 2020-09-09 | 2020-09-09 | 担载型金属离子液体催化剂的制备方法及其所得产品和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010937816.2A CN111804342A (zh) | 2020-09-09 | 2020-09-09 | 担载型金属离子液体催化剂的制备方法及其所得产品和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111804342A true CN111804342A (zh) | 2020-10-23 |
Family
ID=72860181
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010937816.2A Pending CN111804342A (zh) | 2020-09-09 | 2020-09-09 | 担载型金属离子液体催化剂的制备方法及其所得产品和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111804342A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114369080A (zh) * | 2022-01-19 | 2022-04-19 | 凯瑞环保科技股份有限公司 | 一种合成碳酸乙烯酯或碳酸丙烯酯的装置及方法 |
CN114367311A (zh) * | 2022-01-14 | 2022-04-19 | 北京化工大学 | 一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法及应用 |
CN114797978A (zh) * | 2022-05-07 | 2022-07-29 | 南京工业大学 | 羧基化三嗪聚离子液体催化剂及其制备方法和应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101280042A (zh) * | 2007-04-03 | 2008-10-08 | 中国科学院化学研究所 | 一种负载有离子液体的聚合物及其制备方法与应用 |
CN102049301A (zh) * | 2010-11-03 | 2011-05-11 | 华东理工大学 | 一种高效离子液体交聚苯乙烯负载钯催化剂及其应用 |
EP1954793B2 (en) * | 2005-12-02 | 2012-11-21 | Unilever PLC | Laundry composition |
CN104549513A (zh) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | 一种co2与环氧丙烷制备碳酸丙烯酯的催化剂的制备方法 |
CN105503811A (zh) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | 制备碳酸乙烯酯的方法 |
CN108579807A (zh) * | 2018-05-21 | 2018-09-28 | 江苏棋成化工有限公司 | 一种交联聚合酸性离子液体烷基化催化剂及其制备方法 |
-
2020
- 2020-09-09 CN CN202010937816.2A patent/CN111804342A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1954793B2 (en) * | 2005-12-02 | 2012-11-21 | Unilever PLC | Laundry composition |
CN101280042A (zh) * | 2007-04-03 | 2008-10-08 | 中国科学院化学研究所 | 一种负载有离子液体的聚合物及其制备方法与应用 |
CN102049301A (zh) * | 2010-11-03 | 2011-05-11 | 华东理工大学 | 一种高效离子液体交聚苯乙烯负载钯催化剂及其应用 |
CN104549513A (zh) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | 一种co2与环氧丙烷制备碳酸丙烯酯的催化剂的制备方法 |
CN105503811A (zh) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | 制备碳酸乙烯酯的方法 |
CN108579807A (zh) * | 2018-05-21 | 2018-09-28 | 江苏棋成化工有限公司 | 一种交联聚合酸性离子液体烷基化催化剂及其制备方法 |
Non-Patent Citations (3)
Title |
---|
LINA HAN ET AL.: ""Porous polymer bead-supported ionic liquids for the synthesis of cyclic carbonate from CO2 and epoxide"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
LIYING GUO ET AL.: ""Immobilizing Polyether Imidazole Ionic Liquids on ZSM-5 Zeolite for the Catalytic Synthesis of Propylene Carbonate from Carbon Dioxide"", 《MOLECULES》 * |
YE XIE ET AL.: ""CO2 Cycloaddition Reactions Catalyzed by an Ionic Liquid Grafted onto a Highly Cross-Linked Polymer Matrix"", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114367311A (zh) * | 2022-01-14 | 2022-04-19 | 北京化工大学 | 一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法及应用 |
CN114369080A (zh) * | 2022-01-19 | 2022-04-19 | 凯瑞环保科技股份有限公司 | 一种合成碳酸乙烯酯或碳酸丙烯酯的装置及方法 |
CN114369080B (zh) * | 2022-01-19 | 2024-03-29 | 凯瑞环保科技股份有限公司 | 一种合成碳酸乙烯酯或碳酸丙烯酯的装置及方法 |
CN114797978A (zh) * | 2022-05-07 | 2022-07-29 | 南京工业大学 | 羧基化三嗪聚离子液体催化剂及其制备方法和应用 |
CN114797978B (zh) * | 2022-05-07 | 2023-09-26 | 南京工业大学 | 羧基化三嗪聚离子液体催化剂及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111804342A (zh) | 担载型金属离子液体催化剂的制备方法及其所得产品和应用 | |
Sels et al. | Use of WO42-on layered double hydroxides for mild oxidative bromination and bromide-assisted epoxidation with H2O2 | |
CN112341394B (zh) | 一种氢键供体功能化的聚合离子液体催化制备环状碳酸酯的方法 | |
WO2011063500A1 (en) | Process for preparing furfural from xylose | |
CN105503811B (zh) | 制备碳酸乙烯酯的方法 | |
CN108558598B (zh) | 一种酸性溶胀聚离子液体催化环己酯类化合物水解反应制备环己醇的方法 | |
CN109574807B (zh) | 环氧烷烃催化水合制乙二醇的方法 | |
CN109569717B (zh) | 离子交换树脂及用途 | |
CN108579807B (zh) | 一种交联聚合酸性离子液体烷基化催化剂及其制备方法 | |
CN111072601B (zh) | 一种5-羟甲基糠醛制备2,5-呋喃二甲醛的方法 | |
CN112619705B (zh) | 环氧烷烃加成反应催化剂及其应用 | |
CN114560964B (zh) | 一种羧基功能化聚离子液体的合成方法及其应用 | |
CN111454205B (zh) | 一种连续非溶剂法催化氧化合成吡啶类-n-氧化物的方法 | |
CN109574793B (zh) | 环氧烷烃水合制乙二醇的方法 | |
CN114989408A (zh) | 一种二氧化碳/环氧化合物共聚用固相催化剂及其制备方法 | |
CN109575162B (zh) | 离子交换树脂和用途 | |
CN109575292B (zh) | 离子交换树脂及其用途 | |
CN109590029B (zh) | 离子交换树脂和其用途 | |
CN114433228A (zh) | 一种核壳型聚合离子液体催化合成环状碳酸酯的方法 | |
CN105085187B (zh) | 碳酸乙烯酯水解制备乙二醇的方法 | |
CN114433229B (zh) | 一种用于制备碳酸亚烷酯的催化剂及其制备方法和应用 | |
CN115591580B (zh) | 一种二氧化碳环加成反应多位点催化剂及其制备方法与应用 | |
CN114920878B (zh) | 用于甘油酯交换的碱基功能化聚离子液体催化剂及其制备方法、应用 | |
CN105272822B (zh) | 用于碳酸乙烯酯水解制备乙二醇的方法 | |
CN105503520B (zh) | 碳酸乙烯酯水解制备乙二醇的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201023 |