CN113813996A - Methyl ethyl carbonate strongly-basic anion resin catalyst and preparation method thereof - Google Patents
Methyl ethyl carbonate strongly-basic anion resin catalyst and preparation method thereof Download PDFInfo
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- CN113813996A CN113813996A CN202111104627.8A CN202111104627A CN113813996A CN 113813996 A CN113813996 A CN 113813996A CN 202111104627 A CN202111104627 A CN 202111104627A CN 113813996 A CN113813996 A CN 113813996A
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- strongly basic
- quaternary ammonium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 150000001450 anions Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 17
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 27
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 61
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 11
- -1 ethyl methyl carbonate anion Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000007265 chloromethylation reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000002148 esters Chemical group 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 4
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 claims description 4
- DCBJCKDOZLTTDW-UHFFFAOYSA-N 5-chloropentan-1-ol Chemical compound OCCCCCCl DCBJCKDOZLTTDW-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012946 outsourcing Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic 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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- 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)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the technical field of catalyst synthesis, and provides a methyl ethyl carbonate strong base anion resin catalyst which is prepared from the following components: 80-120 parts of styrene, 1-20 parts of divinylbenzene, 10-50 parts of pore-foaming agent, 0.5-3 parts of benzoyl peroxide, 180-230 parts of polyvinyl alcohol solution, 10-30 parts of zinc chloride, 800-1300 parts of chloromethyl ether, 80-120 parts of DMF, and 280-330 parts of quaternary ammonium salt. The quaternary ammonium salt is prepared from trimethylamine and chloroalkanol, the catalyst is functionalized by the quaternary ammonium salt, ether bonds are introduced into the catalyst, the catalytic effect of the catalyst in the synthesis of methyl ethyl carbonate is obviously improved, the catalyst can be repeatedly used, the high catalytic effect is still maintained, and the service life is prolonged.
Description
Technical Field
The invention relates to a catalyst for synthesizing methyl ethyl carbonate and a preparation method thereof, in particular to a strongly basic anion resin catalyst for methyl ethyl carbonate and a preparation method thereof.
Background
Methyl ethyl carbonate is an important organic raw material, is used as asymmetric carbonate, is widely applied to aspects such as a plasticizer, a textile auxiliary agent, an organic synthetic intermediate, a medical component, a special spice and the like in plastic processing, and particularly is a solvent capable of improving the energy density and the discharge capacity of a lithium battery. The current industrial production process of methyl ethyl carbonate mainly comprises a phosgene method, an oxidative carbonylation method and an ester exchange method. Among them, the phosgene process is complicated, the raw material toxicity is strong, the operation cost is high, and it has been eliminated under the current safety situation. The oxidation and carbonylation method has high catalyst cost and operation cost and low benefit. The ester exchange method has the advantages of low toxicity of raw materials, low cost, simple operation process, easy subsequent separation and the like. Therefore, the preparation of methyl ethyl carbonate by the transesterification method is the direction of industrial production development.
The catalysts currently used in transesterification reactions are classified into homogeneous catalysts and heterogeneous catalysts. The former is mostly represented by alkali metal alcohol, the reaction conversion rate and the reaction speed are high, but the homogeneous catalyst is not easy to separate from the product, is difficult to recover and reuse, and has high production cost. The latter commonly used catalysts are mostly supported on SiO2、Al2O3Alkali metal or metal salt, metal oxide, or alkali metal molecular sieve, resin, etc. on the same carrierThe catalyst and the product are easy to separate and recover, but the catalyst has the problems of selectivity and low yield.
In patent CN1228358A, 16% KOH/KX molecular sieve is used as a catalyst, propylene carbonate and methanol are used as raw materials to synthesize DMC by ester exchange, the conversion rate of the propylene carbonate is 41%, and the yield of the DMC is 38.5%. Al is mentioned in both patent US20050080287A1 and patent US06207850B12O3And MgO, etc. have low selectivity and yield. The highest conversion rate of ethylene carbonate is 93.9 percent in the solid base catalyst consisting of calcium oxide and zirconium oxide prepared in the patent application CN 101003018A; the highest conversion rate of the propylene carbonate is 94.7 percent, but the reaction temperature is higher and is 120-140 ℃, and performance parameters such as selectivity of the catalyst are not mentioned.
Most of resin ester exchange catalysts are ion exchange resins with tertiary amine, quaternary amine, sulfonic acid and carboxylic acid functional groups, and according to the literature, the catalysts are not suitable for high-temperature reaction, and the functional groups are easy to fall off and the activity is reduced quickly.
Disclosure of Invention
The invention provides a methyl ethyl carbonate strongly basic anion resin catalyst and a preparation method thereof, the temperature resistance of the catalyst is enhanced by connecting an alkaline group with an ether bond, and the catalyst has the advantages of high activity, long reaction time, high repeated utilization rate and the like, and the conversion rate and the selectivity both reach over 95 percent.
The technical scheme of the invention is as follows:
the strongly basic ethyl methyl carbonate anion resin catalyst is prepared from the following components in parts by weight: 80-120 parts of styrene, 1-20 parts of divinylbenzene, 10-50 parts of pore-foaming agent, 0.5-3 parts of benzoyl peroxide, 180-230 parts of polyvinyl alcohol solution, 10-30 parts of zinc chloride, 800-1300 parts of chloromethyl ether, 80-120 parts of DMF, and 280-330 parts of quaternary ammonium salt;
the mass percentage concentration of the polyvinyl alcohol solution is 0.1-1%.
Further, the pore-foaming agent is one or two of 300# liquid wax and n-butanol.
Preferably, the pore-foaming agent is a mixture of 300# liquid wax and n-butanol in a mass ratio of 3-8: 1.
Further, the quaternary ammonium salt is HO (CH)2)nN+(CH3)3Cl-One or more of homologues, isomers thereof; and n is 2-5.
Further, n is 2.
Further, the preparation method of the quaternary ammonium salt comprises the following steps: in CaO-Al, aqueous trimethylamine solution and chloroalkanol2O3Under the action of catalyst, quaternary ammonium salt is obtained.
Further, the chloroalkanol is one or more of 2-chloroethanol, 3-chloropropanol, 4-chlorobutanol and 5-chloropentanol.
Still further, the chloroalkanol is 2-chloroethanol.
Furthermore, the mass percentage concentration of the trimethylamine aqueous solution is 20-40%.
Further, the molar ratio of the trimethylamine to the chloroalkanol is 1-5: 1.
Further, the chloroalkanol is reacted with CaO-Al2O3The mass ratio of the catalyst is 4-8: 1.
Further, the aqueous trimethylamine solution and the chloroalkanol are reacted in CaO-Al2O3Reacting for 5-8h at 60-80 ℃ under the action of a catalyst.
The invention also provides a preparation method of the methyl ethyl carbonate strongly-basic anion resin catalyst, which comprises the following steps:
(1) polymerization reaction: uniformly mixing styrene, divinylbenzene, a pore-forming agent and benzoyl peroxide, adding the mixture into a polyvinyl alcohol solution, reacting to obtain a macroporous white ball, removing the pore-forming agent, and drying for later use;
(2) chloromethylation reaction: reacting the macroporous white balls obtained in the step (1) with zinc chloride and chloromethyl ether to generate benzyl balls;
(3) quaternization reaction: and (3) adding DMF (dimethyl formamide) into the benzyl ball prepared in the step (2), adding quaternary ammonium salt, and adjusting the pH value to obtain the benzyl ball.
Further, after adding the polyvinyl alcohol solution in the step (1), reacting for 4-35h at 40-100 ℃.
Furthermore, after the polyvinyl alcohol solution is added in the step (1), the temperature is firstly increased to 70-90 ℃ for reaction for 10-15h, and then the temperature is increased to 90-100 ℃ for reaction for 10-15 h.
Preferably, after the polyvinyl alcohol solution is added in the step (1), the temperature is firstly increased to 80 ℃ for reaction for 12 hours, and then increased to 97 ℃ within 1 hour for reaction for 12 hours.
Further, the chloromethylation reaction in the step (2) is carried out under the condition that the temperature is increased to 30-50 ℃ and the reaction is carried out for 15-20h, and the chlorine content is controlled to be more than 18%.
Preferably, the chloromethylation reaction in the step (2) is carried out under the condition of raising the temperature to 42 ℃ for 18 hours.
Further, DMF and quaternary ammonium salt are added in the step (3), the pH value is adjusted to 12-14, the temperature is raised to 130-160 ℃, the temperature is kept for 4-50h, and deionized water is used for washing to be neutral, so that the methyl ethyl carbonate strongly basic anion resin catalyst is obtained.
Preferably, DMF and quaternary ammonium salt are added in the step (3), then NaOH is used for adjusting the pH value to 12-14, the temperature is raised to 135 ℃, and the temperature is kept for 10 hours.
The invention also provides the application of the strong-base anion resin catalyst for methyl ethyl carbonate or the strong-base anion resin catalyst for methyl ethyl carbonate prepared by the preparation method in the reaction of synthesizing methyl ethyl carbonate by ester exchange.
Further, the specific reaction for synthesizing the methyl ethyl carbonate by catalyzing the methyl ethyl carbonate strongly basic anion resin catalyst comprises the following steps: putting a methyl ethyl carbonate strongly-basic anion resin catalyst into a reactor or a reaction bed, and before reaction, mixing dimethyl carbonate and ethanol according to a mol ratio of 1.5: 1, the reaction temperature is 95 ℃, the normal pressure is realized, and the space velocity of the feeding volume is 1h < -1 >.
The working principle and the beneficial effects of the invention are as follows:
1. in the invention, quaternary ammonium salt self-made by the applicant is used in quaternization reaction, ether bond is introduced into strong alkali group in the catalyst, the use temperature of the resin is greatly improved, functional group in the prepared catalyst is not easy to fall off, the pollution to reactants and the generation of by-products are reduced, the service life of the resin is prolonged, and the production cost is reduced.
2. According to the invention, the mixture of No. 300 liquid wax and n-butanol is used as a pore-forming agent, so that the aperture of the prepared resin catalyst is controlled to be 15-20nm, the affinity of the catalyst to alkyl carbonate materials is obviously improved, the raw materials of the ester exchange reaction are easier to approach the active center, the reaction is easier to carry out, the reaction efficiency is improved, and the reaction conditions are reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
The following examples used the following apparatus and materials:
1. device for measuring the position of a moving object
A constant temperature water bath (0-100 ℃), an adjustable electric stirrer (0-2000r), a three-mouth bottle (2000ml), a plastic stirring paddle, a thermometer (0-150 ℃), a rubber stopper (No. 5), a constant temperature oil bath (0-300 ℃), and a 100ml graduated cylinder.
2. Main raw materials
Divinylbenzene, outsourcing technical grade; styrene, outsourcing technical grade; HO (CH)2)nN+(CH3)3Cl-(n-2-5) made by self; chloromethyl ether, outsourcing technical grade; 300# liquid wax, outsourcing technical grade; n-butanol, purchased technical grade; water, deionized water; dimethyl carbonate, outsourcing commercial grade; ethanol, purchased technical grade.
Example 1
A strongly basic anionic methyl ethyl carbonate resin catalyst is prepared through the following steps
(1) Preparation of quaternary ammonium salts
In a stirred reflux reactor, 225mL of a 30% aqueous trimethylamine solution, 56g of 2-chloroethanol, 10g of CaO-Al were put in2O3Heating the catalyst to 70 ℃ to react for 6 hours to obtain quaternary ammonium salt HO (CH)2)2N+(CH3)3Cl-. (the molar ratio of trimethylamine to 3-chloropropanol is 1.6:1)
HO(CH2)2Cl+Me3N→HO(CH2)2N+Me3Cl-
(2) Polymerisation reaction
In a reaction kettle, uniformly mixing 100 parts of styrene, 10 parts of 63.5% divinylbenzene, 40 parts of No. 300 liquid wax, 10 parts of n-butyl alcohol and 1 part of benzoyl peroxide, adding the mixture into 200 parts of 0.5% polyvinyl alcohol solution, adding the mixture, heating to 80 ℃ for reaction for 12 hours after feeding, heating to 97 ℃ within 1 hour, reacting for 12 hours to obtain a product which is a macroporous white ball, extracting a pore-forming agent, and drying for later use; wherein, the crosslinking degree of the polymerization reaction is controlled to be 5.8 percent;
(3) chloromethylation reaction
Putting 100 parts by weight of the macroporous white balls obtained in the step (1), 20 parts by weight of zinc chloride and 1000 parts by weight of 40% chloromethyl ether into a reaction kettle, feeding materials, heating to 42 ℃ for reacting for 18 hours, controlling the chlorine content to be more than 18%, and generating benzyl balls after the reaction is finished;
(4) quaternization reaction
Adding 100 parts by weight of benzyl balls prepared in the step (2) into a reaction kettle, adding 100 parts by weight of DMF (dimethyl formamide), and adding 300 parts by weight of HO (CH) prepared in the step (1)2)2N+(CH3)3Cl-Adjusting the pH value to 12 by NaOH, heating to 135 ℃ for reaction for 10h, and washing by deionized water to be neutral to obtain the strong base anion resin catalyst containing ether bonds.
Example 2
A strongly basic anionic methyl ethyl carbonate resin catalyst is prepared through the following steps
(1) Preparation of quaternary ammonium salts
In a stirred reflux reactor, 296mL of a 20% aqueous trimethylamine solution, 94g of 3-chloropropanol, 12g of CaO-Al were put in2O3Heating the catalyst to 60 ℃ to react for 8 hours to obtain quaternary ammonium salt HO (CH)2)3N+(CH3)3Cl-. (the molar ratio of trimethylamine to 3-chloropropanol is 1:1)
HO(CH2)3Cl+Me3N→HO(CH2)3N+Me3Cl-
(2) Polymerisation reaction
In a reaction kettle, uniformly mixing 80 parts of styrene, 1 part of 63.5% divinylbenzene, 16 parts of No. 300 liquid wax, 2 parts of n-butyl alcohol and 0.5 part of benzoyl peroxide, adding the mixture into 180 parts of 0.1% polyvinyl alcohol solution, adding the mixture, heating to 70 ℃ for reaction for 15 hours after feeding, heating to 90 ℃ within 1 hour, reacting for 15 hours to obtain a product which is a macroporous white ball, extracting a pore-forming agent, and drying for later use; wherein, the crosslinking degree of the polymerization reaction is controlled to be 0.8 percent;
(3) chloromethylation reaction
Putting 100 parts by weight of the macroporous white balls obtained in the step (1), 10 parts by weight of zinc chloride and 800 parts by weight of 40% chloromethyl ether into a reaction kettle, feeding materials, heating to 30 ℃ for reaction for 20 hours, controlling the chlorine content to be more than 18%, and generating benzyl balls after the reaction is finished;
(4) quaternization reaction
Adding 100 parts by weight of benzyl balls prepared in the step (2) into a reaction kettle, adding 80 parts by weight of DMF (dimethyl formamide), and adding 280 parts by weight of HO (CH) prepared in the step (1)2)3N+(CH3)3Cl-Adjusting the pH value to 14 by NaOH, heating to 130 ℃ for reaction for 50h, and washing to be neutral by deionized water to obtain the ether bond-containing strong base anion resin catalyst.
Example 3
A strongly basic anionic methyl ethyl carbonate resin catalyst is prepared through the following steps
(1) Preparation of quaternary ammonium salts
In the stirred reflux reactor, 223mL of 40% tris was chargedMethylamine aqueous solution, 54g 4-chlorobutanol, 13g CaO-Al2O3Heating the catalyst to 80 ℃ to react for 5 hours to obtain quaternary ammonium salt HO (CH)2)4N+(CH3)3Cl-. (molar ratio of trimethylamine to 4-chlorobutanol is 3:1)
HO(CH2)4Cl+Me3N→HO(CH2)4N+Me3Cl-
(2) Polymerisation reaction
In a reaction kettle, uniformly mixing 120 parts by weight of styrene, 20 parts by weight of 63.5% divinylbenzene, 30 parts by weight of No. 300 liquid wax, 10 parts by weight of n-butyl alcohol and 3 parts by weight of benzoyl peroxide, adding the mixture into 230 parts by weight of 1% polyvinyl alcohol solution, heating to 90 ℃ for reaction for 10 hours after feeding, heating to 100 ℃ within 1 hour, reacting for 15 hours to obtain a product which is a macroporous white ball, extracting a pore-forming agent completely, and drying for later use; wherein, the crosslinking degree of the polymerization reaction is controlled at 9 percent;
(3) chloromethylation reaction
Putting 100 parts by weight of the macroporous white balls obtained in the step (1), 30 parts by weight of zinc chloride and 1300 parts by weight of 40% chloromethyl ether into a reaction kettle, feeding materials, heating to 50 ℃ for reaction for 15 hours, controlling the chlorine content to be more than 18%, and generating benzyl balls after the reaction is finished;
(4) quaternization reaction
Adding 100 parts by weight of benzyl balls prepared in the step (2) into a reaction kettle, adding 120 parts by weight of DMF (dimethyl formamide), and adding 330 parts by weight of HO (CH) prepared in the step (1)2)4N+(CH3)3Cl-Adjusting the pH value to 13 by NaOH, heating to 135 ℃ for reaction for 10h, and washing by deionized water to be neutral to obtain the strong base anion resin catalyst containing ether bonds.
Example 4
A strongly basic anionic methyl ethyl carbonate resin catalyst is prepared through the following steps
(1) Preparation of quaternary ammonium salts
Into a stirred reflux reactor, 198mL of 30% aqueous trimethylamine solution, 62g of 5-chloropentanol, 10g of CaO-Al2O3Heating the catalyst to 70 ℃ to react for 6 hours to obtain quaternary ammonium salt HO (CH)2)5N+(CH3)3Cl-. (the molar ratio of trimethylamine to 5-chloropentanol is 2:1)
HO(CH2)5Cl+Me3N→HO(CH2)5N+Me3Cl-
(2) Polymerisation reaction
In a reaction kettle, uniformly mixing 110 parts of styrene, 15 parts of 63.5% divinylbenzene, 40 parts of No. 300 liquid wax, 10 parts of n-butyl alcohol and 2 parts of benzoyl peroxide, adding the mixture into 210 parts of 0.5% polyvinyl alcohol solution, adding the mixture, heating to 80 ℃ for reaction for 12 hours after feeding, heating to 97 ℃ within 1 hour, reacting for 12 hours to obtain a product which is a macroporous white ball, extracting a pore-forming agent, and drying for later use; wherein, the crosslinking degree of the polymerization reaction is controlled at 8 percent;
(3) chloromethylation reaction
Putting 100 parts by weight of the macroporous white balls obtained in the step (1), 25 parts by weight of zinc chloride and 1200 parts by weight of 40% chloromethyl ether into a reaction kettle, feeding materials, heating to 42 ℃ for reacting for 18 hours, controlling the chlorine content to be more than 18%, and generating benzyl balls after the reaction is finished;
(4) quaternization reaction
Adding 100 parts by weight of benzyl balls prepared in the step (2) into a reaction kettle, adding 110 parts by weight of DMF, and adding 320 parts by weight of HO (CH) prepared in the step (1)2)5N+(CH3)3Cl-Adjusting the pH value to 12 by NaOH, heating to 135 ℃ for reaction for 10h, and washing by deionized water to be neutral to obtain the strong base anion resin catalyst containing ether bonds.
Comparative example 1
Trimethylamine hydrochloride was used as the quaternizing agent, as in example 1.
Comparative example 2
The quaternizing agent is HO (CH)2)6N+(CH3)3Cl-The specific preparation method is as follows, and the rest is the same as in example 1.
In a stirred reflux reactor, 225mL of a 30% aqueous trimethylamine solution, 96g of 6-chlorohexanol, 17g of CaO-Al were put2O3Heating the catalyst to 70 ℃ to react for 6 hours to obtain quaternary ammonium salt HO (CH)2)6N+(CH3)3Cl-. (the molar ratio of trimethylamine to 6-chlorohexanol is 1.6:1)
HO(CH2)6Cl+Me3N→HO(CH2)6N+Me3Cl-
Comparative example 3
The porogen used was 40 parts of 300# liquid wax and 10 parts of isobutanol, as in example 1.
Comparative example 4
The pore-forming agent used was 50 parts of white oil and 10 parts of n-butanol, as in example 1.
Experimental example 1 evaluation of the use of different resin catalysts in the reaction of transesterification to synthesize ethyl methyl carbonate
The test samples were the resin catalysts prepared in examples 1 to 4 of the present invention and comparative examples 1 to 4.
Measuring 50ml of test sample catalyst by a measuring cylinder respectively, placing the test sample catalyst in a stainless steel reactor with the inner diameter of 20mm, and before reaction, adding dimethyl carbonate and ethanol according to the mol ratio of 1.5: 1, uniformly mixing, reacting at 95 ℃ under normal pressure, collecting samples 10min, 30min, 1h and 3h after feeding, measuring the content by adopting a gas phase, and calculating the yield. Continuous sample introduction, feeding volume airspeed of 1h-1And continuously running for 1000h to determine the conversion rate of the ethanol and the selectivity of the ethyl methyl carbonate, and the following table 1 shows.
TABLE 1 Effect of the use of different resin catalysts
As can be seen from the above table, in the reaction for synthesizing ethyl methyl carbonate, the resin catalyst sample prepared in each example of the present invention can achieve a yield of 87% or more in 2 hours, which is substantially the same as the yield in 3 hours, which indicates that the reaction is substantially completely performed in 2 hours; after the catalyst is continuously used for 1000 hours at the temperature of 95 ℃, the average conversion rate of ethanol is over 93 percent, and the average selectivity of methyl ethyl carbonate is over 97 percent, which shows that the temperature resistance of the resin catalyst is obviously improved, the stable catalytic function can be realized within 1000 hours, and the service life of the resin catalyst is obviously prolonged.
In the comparative example 1, trimethylamine hydrochloride is used as a quaternizing agent, strong alkali groups in the catalyst cannot be connected through ether bonds, the catalytic effect of the catalyst is reduced, the service life of the catalyst is prolonged, the yield is 59.2% in 2 hours of reaction, the yield is only 74% in 3 hours of reaction, the yield is obviously increased, and the reaction is performed for 2 hours to 3 hours; under the environment of 95 ℃, after the catalyst is continuously used for 1000 hours, the conversion rate of ethanol and the selectivity of ethyl methyl carbonate are reduced, which shows that the temperature resistance of the catalyst is reduced, and the catalytic function is obviously reduced.
Comparative example 2 quaternary ammonium salt is prepared by 6-chlorohexanol for quaternization, the efficiency of the final catalyst is also obviously reduced, the carbon chain of the 6-chlorohexanol is possibly too long, the steric hindrance of the prepared catalyst is increased, the catalyst is close to dimethyl carbonate and ethanol, and the reaction process is influenced.
Compared example 3 and comparative example 4 replace the composition of the pore-forming agent, so that the pore-forming effect of the resin catalyst is poor in the preparation process, the formed pore diameter is not uniform, the catalytic effect of the catalyst is finally influenced, the reaction can not be completely carried out in 3 hours, the effect of the catalyst in repeated use is poor, and the ethanol conversion rate and the methyl ethyl carbonate selectivity are reduced after the catalyst is continuously used for 1000 hours.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The strongly basic ethyl methyl carbonate anion resin catalyst is characterized by comprising the following components in parts by weight: 80-120 parts of styrene, 1-20 parts of divinylbenzene, 10-50 parts of pore-foaming agent, 0.5-3 parts of benzoyl peroxide, 180-230 parts of polyvinyl alcohol solution, 10-30 parts of zinc chloride, 800-1300 parts of chloromethyl ether, 80-120 parts of DMF, 280-330 parts of quaternary ammonium salt;
the mass percentage concentration of the polyvinyl alcohol solution is 0.1-1%.
2. The strongly basic ethyl methyl carbonate anion catalyst as claimed in claim 1, wherein the pore-forming agent is one or two of 300# liquid wax and n-butanol.
3. The strongly basic ethyl methyl carbonate anion catalyst of claim 1, wherein the quaternary ammonium salt is HO (CH)2)nN+(CH3)3Cl-One or more of homologues, isomers thereof; and n is 2-5.
4. The strongly basic ethyl methyl carbonate anion catalyst of claim 3, wherein the preparation of the quaternary ammonium salt comprises the steps of: in CaO-Al, aqueous trimethylamine solution and chloroalkanol2O3Under the action of catalyst, quaternary ammonium salt is obtained.
5. The strongly basic ethyl methyl carbonate anion catalyst of claim 4, wherein the chloroalkanol is one or more of 2-chloroethanol, 3-chloropropanol, 4-chlorobutanol, 5-chloropentanol.
6. A process for preparing a strongly basic ethyl methyl carbonate anion catalyst as claimed in any of claims 1 to 5, comprising the steps of:
(1) polymerization reaction: uniformly mixing styrene, divinylbenzene, a pore-forming agent and benzoyl peroxide, adding the mixture into a polyvinyl alcohol solution, reacting to obtain a macroporous white ball, removing the pore-forming agent, and drying for later use;
(2) chloromethylation reaction: reacting the macroporous white balls obtained in the step (1) with zinc chloride and chloromethyl ether to generate benzyl balls;
(3) quaternization reaction: and (3) adding DMF (dimethyl formamide) into the benzyl ball prepared in the step (2), adding quaternary ammonium salt, and adjusting the pH value to obtain the benzyl ball.
7. The method for preparing a strongly basic ethylene carbonate resin catalyst as claimed in claim 6, wherein the reaction is carried out at 40-100 ℃ for 4-35h after adding the polyvinyl alcohol solution in the step (1).
8. The method for preparing the strongly basic anion resin catalyst of methyl ethyl carbonate according to claim 6, wherein the chloromethylation reaction in the step (2) is carried out under the condition of raising the temperature to 30-50 ℃ and reacting for 15-20h, and the chlorine content is controlled to be more than 18%.
9. The method for preparing the strongly basic ethyl methyl carbonate anion catalyst as claimed in claim 6, wherein the pH value of the mixture obtained in the step (3) is adjusted to 12-14 after adding DMF and quaternary ammonium salt, the temperature is raised to 160 ℃ at 130 ℃, the temperature is kept for 4-50h, and the mixture is washed to be neutral by deionized water to obtain the strongly basic ethyl methyl carbonate anion catalyst.
10. Use of the strongly basic ethyl methyl carbonate anion catalyst according to any one of claims 1 to 5 or the strongly basic ethyl methyl carbonate anion catalyst prepared by the preparation method according to any one of claims 6 to 9 in the reaction of synthesizing ethyl methyl carbonate by ester exchange.
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