WO2013007103A1 - 一种有机骨架多孔固体酸的应用 - Google Patents
一种有机骨架多孔固体酸的应用 Download PDFInfo
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- WO2013007103A1 WO2013007103A1 PCT/CN2012/000938 CN2012000938W WO2013007103A1 WO 2013007103 A1 WO2013007103 A1 WO 2013007103A1 CN 2012000938 W CN2012000938 W CN 2012000938W WO 2013007103 A1 WO2013007103 A1 WO 2013007103A1
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- Prior art keywords
- solid acid
- porous solid
- polydivinylbenzene
- catalyst
- acid according
- Prior art date
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- 239000011973 solid acid Substances 0.000 title claims abstract description 24
- 239000013384 organic framework Substances 0.000 title claims abstract 4
- 229920000779 poly(divinylbenzene) Polymers 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005917 acylation reaction Methods 0.000 claims abstract description 4
- 238000007872 degassing Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 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 abstract 6
- 238000001704 evaporation Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006277 sulfonation reaction Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 5
- -1 1,2-dichloroethane oxime Chemical class 0.000 claims description 2
- JKNZUZCGFROMAZ-UHFFFAOYSA-L [Ag+2].[O-]S([O-])(=O)=O Chemical compound [Ag+2].[O-]S([O-])(=O)=O JKNZUZCGFROMAZ-UHFFFAOYSA-L 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000367 silver sulfate Inorganic materials 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011175 product filtration Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- C08F112/00—Homopolymers 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
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F112/36—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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- 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
- B01J31/10—Ion-exchange resins sulfonated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the invention relates to the use of an organic backbone porous solid acid.
- the traditional acid catalysts are zeolite molecular sieves, sulfurized metal oxides, acid functionalized mesoporous materials, Heteropolyacids, etc., but such as: hydrophilic framework structure, pore size limitation of zeolite materials, etc. affect the general application of inorganic solid acid materials.
- the pure organic skeleton solid acid material has been more and more widely studied due to its unique framework hydrophobic property, simple and convenient functionalization process, and good catalytic performance.
- a strong acidic cation exchange resin is disclosed, the skeleton of which is a copolymer of divinylbenzene and styrene, and the reactive functional group is a sulfonate, as a novel organic
- the skeleton solid acid material, hydrophobic framework structure and high acid center content make the material widely used in acid catalytic reaction and ion exchange, including esterification, transesterification and etherification, and achieved good results.
- Zto/. 2008, 25 ⁇ 205. has been industrialized. It occupies a very important position in industrial applications. However, its low ratio of 3 ⁇ 4 area, lack of pore structure, and poor stability of the skeleton structure limit its wide application.
- the object of the present invention is to provide an organic skeleton porous solid acid application, which utilizes ft porous polydivinylbenzene as a material, and utilizes its good swelling property to obtain an organic skeleton solid acid by sulfonation reaction for catalyzing esterification and acyl group.
- the catalyst for the reaction has high crosslinking degree, high stability, large specific surface area and abundant pore structure compared with the conventional resin.
- the method for synthesizing the organic skeleton porous solid acid of the present invention is: (1) Add 2 g of divinylbenzene (DVB) monomer to a mixed solvent containing 0.03 - 0. p5 g of butyl phthalate and 10-20 ml of tetrahydrofuran, 1-2 ml of water, 3 ⁇ 4 under normal temperature and pressure After stirring for >3 hours, 75-150 ° C hydrothermal treatment for 1-2 days, take out, open the lid, and evaporate the dry solvent at room temperature to obtain a high specific surface area, rich in mesoporous structure of polydivinylbenzene (PPVB);
- DVB divinylbenzene
- sample name is divided into two parts: PDVB stands for mesoporous polydivinylbenzene, and "-S0 3 H” stands for mesoporous polydivinylbenzene material after sulfonate functionalization.
- the mesoporous polydivinyl ⁇ material is synthesized by using tetrahydrofuran and water as a mixed solvent.
- the chlorosulfonate is selected as a solvent, and the concentrated sulfuric acid is a sulfonating reagent for sulfonation reaction.
- Table 1 shows the catalytic activity of the material in the catalytic esterification and acylation reactions. It can be seen that the material exhibits a good catalytic activity for a variety of acid-catalyzed reactions. The conversion rates are as follows: 62.5, 72.5, 89.4, 61.8 %; In the catalytic esterification reaction, the activity of recycling 5 times decreased by 11.3, indicating that the material has good regenerative capacity and anti-toxicity.
- the sulfonic acid functionalized mesoporous polydivinylbenzene of the present invention has a large specific ratio product
- the sulfonated mesoporous polydivinylbenzene material of the present invention has a high sulfonic acid content (2.45 mmol/g).
- the sulfonic acid functionalized mesoporous polydivinylbenzene of the present invention has a stable bone structure (575 ° C) and a stable acid center (305 ° C) o
- the sulfonic acid functionalized mesoporous polydivinylbenzene of the present invention exhibits good catalytic activity and regenerating performance in the catalytic esterification reaction, and the activity is reduced by 11.3% after 5 cycles of recycling.
- the invention is characterized in that a polydivinylbenzene material having a rich mesoporous structure is synthesized by a solvothermal method, the specific surface area is 600-700 m 2 /g, the average pore diameter is 15-23 nm, and the pore volume is 0.7-1.4 ml/g. .
- the materials for most organic solvents include: benzene and its homologues, alkanes, alcohols, etc. have very good swelling properties, using this feature, combined with the material rich I pore structure and large specific surface area, by first swelling after sulfonation The successful synthesis of the new synthetic route I has a new stable, high-efficiency organic skeleton solid acid material.
- the sulfonated material maintains a large specific surface area and a rich pore structure.
- the content of sulfonate after sulfonation is 2.0 ⁇ 3.5 mmol/g.
- the hydrogen ion exchange capacity is 2.2 to 3.7 mmol/g.
- the specific surface area is 280-500 m 2 /g.
- Table 1 shows the catalytic activity of synthetic sulfonated materials in esterification and acylation reactions.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
一种有机骨架多孔固体酸的应用，用作催化酯化和酰基化反应的催化剂，其制备过程为：将二乙烯基苯单体加入到含偶氮二异丁腈、四氢呋喃和水的混合溶剂中，常温常压下水热处理，室温挥发干溶剂，得到聚二乙烯基苯；研磨成200目粉末，氮气条件下脱气处理；然后加入1,1',2-三氯乙垸中进行溶胀；取1,1',2-三氯乙垸，浓硫酸混合均匀，加入硫酸银为催化剂，加入溶胀后的聚二乙烯基苯，磺化，过滤，二氧六环洗涤，水洗至中性，干燥，用稀硫酸活化，水洗至中性，干燥。该催化剂具有较高的催化活性。
Description
- -种有机骨架多孔固体酸的应用
技术领域
本发明涉及一种有机骨架多孔固体酸的应用。
背景技术
随着化学工业的发展， 固体酸催化剂得到广泛应用，尤其是在石油化 工和精细化工领域起着举足轻重的作用，传统的酸催化剂有沸石分子筛， 硫化金属氧化物， 酸功能化的介孔材料， 杂多酸等， 但其 点如： 亲水 骨架结构， 沸石材料的孔径限制等影响了无机固体酸材料的 泛应用。 与传统无机骨架的酸催化剂相比， 纯有机骨架固体酸材料以其独特的骨 架疏水性能， 简单而方便的功能化过程， 较好的催化性能而受到越来越 广泛的研究。
美国专利： B01J31/10;B01J47/00;C07C37/20等公布了一 #强酸性阳 离子交换树脂， 其骨架是二乙烯基苯和苯乙烯共聚物， 活性官能团为磺 酸根， 作为一种新型的有机骨架固体酸材料， 疏水性的骨架结构和高的 酸中心含量使得该材料广泛应用于酸催化反应和离子交换等领域， 包括 酯化， 酯交换， 醚化， 取得了很好的效果 C/. zto/. 2008， 25^ 205.)， 现 已被工业化。 在工业应用中占有非常重要的位置。 但其低比 ¾面积， 匮 乏的孔结构， 稳定性较差的骨架结构限制其广泛应用。
发明内容
本发明的目的是提供一种有机骨架多孔固体酸的应用，采 ft多孔聚二 乙烯基苯为材料， 利用其良好的溶胀性能， 通过磺化反应取得有机骨架 固体酸用于催化酯化和酰基化反应的催化剂， 与传统的树脂相比交联度 高， 稳定性高， 具有大的比表面积和丰富的孔结构。
本发明所述的有机骨架多孔固体酸的合成方法是：
( 1 ) 将 2 g 二乙烯基苯 （DVB ) 单体加入到含 0.03— 0.p5 g 偶 异丁睛和 10-20毫升四氢呋喃， 1-2毫升水的混合溶剂中， ¾温常压下搅 拌>3小时后， 75-150摄氏度水热处理 1-2天后取出， 开盖， 室温挥发干 溶剂， 得到高比表面积， 丰富介孔结构的聚二乙烯基苯（PPVB);
(2)将 2— 3 g聚二乙烯基苯（PDVB)研磨成 200目粉末， 100-150。C 氮气条件下脱气处理 10 h;
(3 ) 将 2.0 g聚二乙烯基苯（PDVB)块加入 30毫升 1,1，,2-三氯乙垸， PDVB材料迅速发生溶胀， PDVB很快炸裂成小块， 同时伴随体积迅速 胀大；
(4)取 30毫升 1，1，，2-三氯乙烷， 70 mL， 质量浓度 98%的浓硫酸混 合均匀， 加入 0.2 g硫酸银为催化剂， 搅拌均匀后， 加入进过 （3 ) 处理 的聚二乙烯基苯（PDVB), 强力搅拌， 温度升高到 90 °C磺化 12 h， 结 束反应， 产物过滤， 二氧六环洗涤， 水洗至中性， 80 °C干燥， 用 0.1 M 稀硫酸活化 4小时后大量水洗到中性， 干燥， 待用。
具体实施方式
说明本发明中具有高效稳定结构， 高比表面积， 高磺酸 j根含量的新 型固体酸材料的合成方法。
实施例中， 样品命名分为两部分： PDVB代表介孔聚二 I乙烯基苯， "-S03H"代表磺酸根功能化后的介孔聚二乙烯基苯材料。
实施例 1:
首先以四氢呋喃和水为混合溶剂来合成介孔聚二乙烯基 Φ材料，即为
PDVBo
将 2 g DVB单体加入到含 0.03—0.05 g偶氮二异丁睛和 10-20毫升四 氢呋喃， 1-2毫升水的混合溶剂中， 常温常压下搅拌>3小时后， 75-150
摄氏度水热处理 1-2天后取出， 开盖， 室温挥发干溶剂， 即 i可得到高比 表面积， 丰富介孔结构的聚二乙烯基苯材料 (PDVB)。
实施例 2:
选择二氯甲垸为溶剂， 浓硫酸为磺化试剂进行磺化反应。
(1)将 2— 3 g PDVB研磨成超细粉末， 100-150 °C氮气条件下脱气处理 10 h;
(2)溶胀过程： 将 2.0 g PDVB块加入过量的溶剂中， PDVB 才料迅速发 生溶胀， PDVB很快炸裂成小块， 同时伴随体积迅速胀大。
(3)取 30 mL二氯甲烷， 70 mL浓硫酸混合均匀， 加入 0.2 g硫酸银为催 化剂， 搅拌均匀后， 加入上述 PDVB， 强力搅拌， 温度升高 I到 90 °C磺 化 12 h， 结束反应， 产物过滤， 二氧六环洗涤， 水洗至中性， 80 °C干 燥， 用 0.1 M洗硫酸活化 4小时后大量水洗到中性， 干燥， 寺用。
实施例 3:
催化性能评价及其与传统催化材料的对比
乙酸和环己醇的酯化反应条件： 0.2 g催化剂， 11.5 mL环己醇， 17.5 mL冰醋酸混合均勾后 100 °C反应 5 h结束， 十二烷为内标。
正己酸和乙醇的酯化反应条件： 0.3 g催化剂， 6.26 mL id己酸， 11.67 mL乙醇混合均匀后 80 °C反应 5 h结束， 十二烷为内标。
十二酸和乙醇的酯化反应条件： 0.15 g催化剂， 4 mmol†二酸， 50 mmol乙醇混合均匀后 70。C反应 5 h结束， 十二烷为内标。
付克酰基化反应： 0.3 g催化剂， 5.5 mL苯甲醚， 0.71 mL|乙酰氯混合 均匀后 60 °C反应 5 h结束， 十二垸为内标。
附表 1给出了材料在催化酯化和酰基化反应中的催化活 可以看出 该材料对多种酸催化反应表现出了良好的催化活性反应转化率依次为：
62.5, 72.5, 89.4, 61.8 %; 在催化酯化反应中，循环利用 5次 活性降低了 11.3 , 表明该材料具有较好的再生能力和抗毒化能力。
工业实用性
本发明的磺酸功能化的介孔聚二乙烯基苯具有大的比表 ^积
(523m2/g)。
本发明的磺化的介孔聚二乙烯基苯材料具有较高的磺酸 含量 (2.45 mmol/g)。
本发明的磺酸功能化的介孔聚二乙烯基苯具有稳定的骨 结构 (575 °C)和稳定的酸中心 (305 °C)o
本发明磺酸功能化的介孔聚二乙烯基苯在催化酯化反应 付克酰基 化反应中表现出了良好的催化活性和再生性能， 循环利用 5次后活性降 低了 11.3 %。
本发明的特点是通过溶剂热的方法合成具有丰富介孔结构的聚二乙 烯基苯材料， 比表面积为 600— 700m2/g， 平均孔径为 15— 23nm， 孔容 为 0.7-1.4 ml/g。 材料对大部分有机溶剂包括： 苯及其同系物， 烷烃， 醇 等具有非常好的溶胀性能， 利用这个特点， 结合该材料丰富 I的孔结构和 大的比表面积， 通过先溶胀后磺化的新合成路线成功的合成 I了新型的稳 定， 高效有机骨架固体酸材料， 同时磺化后材料保持着大比 I表面积和丰 富孔结构， 磺化后磺酸根量含量为 2.0〜3.5 mmol/g， 氢离子交换容量为 2.2〜3.7 mmol/g。 比表面积为 280—500m2/g。 与上述专利技术相比本发 明的固体酸具有独特的骨架疏水性能， 简单而方便的功能化过程， 较好 的催化性能和再生功能
表 1是合成磺化材料在酯化反应和酰基化反应中的催化活性
表 1
Catalyst 乙酸环己醇酯 正己酸乙醇酯 十二酸乙醇酯化 苯甲醚乙酰氯酰基化
化 化
选择 转化率 选择 转化率 选择性 转化率 选择性 对位产 选择性 邻位产 转化 ^ 性 (%) 性 (%) (%) (%) 物 （％) 物 (%)
(%) (%) (%)
PDVB- S03H -100 62.5 〜議 72.5 〜100 89.4 97.5 2.5 61.8 a -100 50.4
PDVB-SO3H b -100 55.4
PDVB-SQ3H c
a 0.2 g催化剂 0.1 g催化剂。
c 0.2 g催化剂在催化乙酸环己醇酯化反应中被循环利用四次。
d乙酸环己醇酯化反应。
e 正己酸和乙醇酯化反应。
Claims
1.一种有机骨架多孔固体酸的应用，其特征在于： 用于 化酯化和酰 基化反应的催化剂， 催化剂的合成方法如下：
( 1 ) 将二乙烯基苯单体加入到偶氮二异丁睛和四氢呋 ， 水的混合 溶剂中， 常温常压下搅拌>3小时后， 水热处理 1-2天后取 ， 开盖， 室 温挥发干溶剂， 得到具有介孔结构的聚二乙烯基苯；
(2 ) 将聚二乙烯基苯研磨成 200目粉末， 氮气条件下脱,处理 10 h;
(3 )将聚二乙烯基苯块加入 1，1，,2-三氯乙烷中，聚二乙 ^基苯块迅速 发生溶胀， 炸裂成小块， 同时伴随体积迅速胀大；
(4) 取 1，1，,2-三氯乙垸， 浓硫酸混合均匀， 加入硫酸银 催化剂， 搅拌均匀后， 加入经过（3 )处理的聚二乙烯基苯， 强力搅 ^， 温度升高
J
到磺化 12 h， 结束反应， 产物过滤， 用二氧六环洗涤， 水 至中性， 80 °C干燥， 用 0.1 M稀硫酸活化 4小时后大量水洗到中性， 燥。
2.根据权利要求 1所述的有机骨架多孔固体酸的应用，其 j寺征在于： 步骤（1 )将 2 g二乙烯基苯单体加入到偶氮二异丁睛和四 ^呋喃、水的 混合溶剂中。
3. 根据权利要求 1所述的有机骨架多孔固体酸的应用，其½征在于： 步骤（1 )将二乙烯基苯单体加入到含 0.03— 0.05 g偶氮二异十 ！睛和 10-20 毫升四氢呋喃、 1-2毫升水的混合溶剂中。
4. 根据权利要求 1所述的有机骨架多孔固体酸的应用,其 征在于： 步骤 （1 ) 水热处理温度 75-150摄氏度。
5. 根据权利要求 1所述的有机骨架多孔固体酸的应用，帛特征在于: 步骤 （2 ) 聚二乙烯基苯为 2— 3 g。
6. 根据权利要求 1所述的有机骨架多孔固体酸的应用，其特征在于:
步骤 （2 ) 氮气条件下脱气处理温度 100-150 °C。
7. 根据权利要求 1所述的有机骨架多孔固体酸的应用， 特征在于： 步骤 （3 ) 将 2.0 g聚二乙烯基苯块加入 30毫升 1，1，，2-三氯 烷中。
8. 根据权利要求 1所述的有机骨架多孔固体酸的应用， 特征在于： 步骤（4 )取 30 毫升 1，1，，2-三氯乙烷， 70 mL浓硫酸混合均匀， 加入 0.2 g硫酸银为催化剂。
9. 根据权利要求 1所述的有机骨架多孔固体酸的应用， 特征在于： 步骤 （4) 磺化温度 90。C。
10. 根据权利要求 1所述的有机骨架多孔固体酸的应用， ^特征在于: 步骤 （4) 磺化时间 12 h。
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| WO2018123536A1 (ja) * | 2016-12-28 | 2018-07-05 | シャープ株式会社 | 光照射器及び光遮蔽部材 |
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