CN111135850A - Application of three-dimensional ordered macroporous carbon nitride supported palladium catalyst in catalytic hydrogenation of styrene unsaturated copolymer - Google Patents
Application of three-dimensional ordered macroporous carbon nitride supported palladium catalyst in catalytic hydrogenation of styrene unsaturated copolymer Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 19
- 229920001577 copolymer Polymers 0.000 title claims abstract description 17
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002077 nanosphere Substances 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005345 coagulation Methods 0.000 claims description 11
- 230000015271 coagulation Effects 0.000 claims description 11
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- 238000000926 separation method Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- NASVITFAUKYCPM-UHFFFAOYSA-N ethanol;tetraethyl silicate Chemical compound CCO.CCO[Si](OCC)(OCC)OCC NASVITFAUKYCPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 12
- 229920002521 macromolecule Polymers 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 60
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 31
- 229920003048 styrene butadiene rubber Polymers 0.000 description 21
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 21
- 239000002174 Styrene-butadiene Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 11
- 239000002638 heterogeneous catalyst Substances 0.000 description 9
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- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
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- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 3
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- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 3
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- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention discloses an application of a three-dimensional ordered macroporous carbon nitride supported palladium catalyst in catalytic hydrogenation of styrene unsaturated copolymer, which is core-shell structure SiO with three-dimensional ordered mesopores2Preparing three-dimensional ordered macroporous carbon nitride (3DOM g-C) by using nanospheres as a template and cyanamide as a precursor through a thermal condensation auxiliary colloidal crystal template method3N4) Then Pd/3DOM g-C is prepared by taking the mesoporous silica as a carrier through a chemical reduction method3N4The supported catalyst has a three-dimensional porous structure which is orderly arranged, and a macroporous cavity is spherical, so that the defect of diffusion limitation of polymer macromolecules in microporous and mesoporous channels can be overcome.
Description
Technical Field
The invention belongs to the field of catalyst preparation and the field of heterogeneous hydrogenation of styrene unsaturated polymers, and particularly relates to application of a three-dimensional ordered macroporous supported catalyst in heterogeneous catalytic hydrogenation of styrene unsaturated copolymers SBR and SBS.
Background
Styrene unsaturated copolymers such as SBS (styrene-butadiene-styrene block copolymer) and SBR (styrene butadiene rubber) have very active chemical properties due to the existence of unsaturated double bonds, and have poor resistance to oxygen, ozone and ultraviolet degradation, so that the service performance of the styrene unsaturated copolymers is limited to a certain extent, and the common method for modification is hydrogenation.
SEBS and HSBR are hydrogenated products which are widely applied at present. SEBS is saturated SBS, or hydrogenated SBS, and is prepared through selective catalytic hydrogenation of unsaturated carbon-carbon double bond and retaining benzene ring. The hydrogenated SEBS not only has thermoplasticity of non-hydrogenated unsaturated polymers, but also can show the flowing property of the softened resin under the condition of high temperature, and has high elasticity of rubber at normal temperature. Compared with SBS, SEBS has good heat resistance, stability and good processability, is widely used for producing high-grade elastomers, adhesives, lubricating oil tackifiers, filling fillers and sheathing materials of high-grade cables and wires, and can be used for manufacturing various soft contact materials such as handles, stationery, toys, handles of sports equipment, automobile sealing strips and the like, and is called as 'gold rubber' due to excellent performance and wide application. HSBR is prepared by selective catalytic hydrogenation of unsaturated carbon-carbon double bonds with SBR and retention of benzene ring. After hydrogenation modification, the HSBR has excellent temperature resistance, weather resistance, oxygen resistance, heat resistance and aging resistance and good tensile property, prolongs the service life of the HSBR polymer, and is widely applied to production of high-grade elastomers, plastic modification, adhesives, lubricating oil viscosity index improvers, fillers of wires and cables and the like.
The prior art for preparing hydrogenated products HSBR and SEBS by styrene unsaturated copolymers SBS and SBR mainly comprises the following steps: non-catalytic hydrogenation and solution hydrogenation (including homogeneous catalytic hydrogenation and heterogeneous catalytic hydrogenation). The non-catalytic hydrogenation is to carry out reduction hydrogenation on double bonds by using azo generated in situ by using Tosylhydrazide (TSH) as a hydride precursor, and needs to be carried out under a high-temperature condition, and the TSH is expensive in price, so that the production cost is overhigh, and the application of the TSH in industry is limited. The homogeneous catalytic hydrogenation process occupies the dominant position in the preparation of the hydrogenated product of the styrene unsaturated copolymer at present, but the homogeneous catalyst has large dosage, poor stability and difficult separation of the catalyst from the hydrogenated product, and the catalyst remained in the hydrogenated product can cause degradation and aging of the hydrogenated product, so the recovery of the catalyst in the homogeneous hydrogenation process is a challenge at present. In a heterogeneous catalytic hydrogenation reaction system, the catalyst and the polymer glue solution are two phases, the problem of separating and recycling the catalyst can be well solved through simple filtration or centrifugation, the residue of noble metal in the polymer can be effectively avoided, and the method has good industrial application prospect.
Jen-Ray Chang and Shi-Ming Huang in 1998 (J R C, Huang S M. Pd/Al)2O3Catalysts for Selective Hydrogenation of Polystyrene-block-polybutadiene-block-polystyrene Thermoplastic Elastomers[J]. Industrial&Engineering chemistry Research, 1998, 37(4):1220-2O3Is a heterogeneous catalyst for SBS hydrogenation, and the results show that: the hydrogenation speed is increased along with the increase of the reaction temperature and the Pd loading capacity, but the selectivity is also deteriorated, namely, the double bonds of the PB segment are reduced, the benzene rings on the PS segment are also greatly hydrogenated, and the SBS polymer macromolecules are easily subjected to Al2O3Limitation of pore diffusion of the carrier. In recent years, researchers have conducted extensive research on three-dimensional macroporous materials, the three-dimensional ordered macroporous materials have the advantages of being orderly and orderly in pore passage arrangement, single in pore diameter, orderly in pore structure in a three-dimensional space, strong in thermal stability of the pore structure and the like, and the defect that micro-pores and mesoporous materials are difficult to enable macromolecules to enter a cavity is overcome; the surface of the pores can be properly modified, which is beneficial to the catalytic conversion of macromolecules, is easy to load metal active components, and can be widely used in the fields of macromolecule catalysis, macromolecule filtration, catalyst carriers, electrode materials and the like. However, up to now there has not been a three-dimensionally ordered macroporous carbon nitride (3DOM g-C)3N4) Is a report related to the application of the carrier in the hydrogenation reaction of polymer macromolecules. Therefore, the invention prepares Pd/3DOM g-C with high activity3N4The heterogeneous catalyst has very important significance and use value for the use of the supported catalyst in the production of hydrogenation products HSBR and SEBS with high added values.
Disclosure of Invention
In order to solve the technical problem, the invention provides high-activity Pd/3DOM g-C3N4The supported catalyst is applied to heterogeneous catalytic hydrogenation of styrene unsaturated copolymers SBS and SBR.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of three-dimensional ordered macroporous carbon nitride supported palladium catalyst in catalytic hydrogenation of styrene unsaturated copolymer is characterized by firstly synthesizing SiO with three-dimensional ordered mesopore core-shell structure2Nanospheres, and preparation by thermal condensation assisted colloidal crystal template methodTo three-dimensionally ordered macroporous carbon nitride (3DOM g-C)3N4) (ii) a Then with 3DOM g-C3N4As a carrier, loading active metal Pd on the carrier by a chemical reduction method to obtain Pd/3DOM g-C3N4Wherein the loading amount of the active metal Pd is 0.1-10 wt%, preferably 0.5-5 wt%.
The specific preparation method of the three-dimensional ordered macroporous carbon nitride supported palladium catalyst comprises the following steps:
one, core-shell structure SiO with three-dimensional ordered mesopores2Preparing nanospheres:
a) dispersing tetraethyl orthosilicate (TEOS) in ethanol according to the volume ratio of 1:3-1:10 to obtain a solution A; the volume ratio is preferably 1:4-1: 6;
b) mixing and stirring ethanol, deionized water and 25-28wt% ammonia water solution uniformly according to the volume ratio of 50 (10-25) to (1.5-15) to obtain solution B; the volume ratio is preferably 50 (18-22) to (8-12);
c) dissolving polyvinylpyrrolidone (PVP) in an amount of 0.04 g/mL in tetraethyl orthosilicate-ethanol solution prepared according to a volume ratio of 1 (2-10) to obtain solution C; the volume ratio is preferably 1: 4-8;
d) rapidly adding the solution A into the solution B at the stirring speed of 300-1200 rpm, and stirring for 2.5 h at the temperature of 20-60 ℃ to obtain a mixed solution D; the stirring speed is preferably 600-1000 rpm, and the temperature is preferably 30-50 ℃;
e) adding the solution C into the mixed solution D, continuously stirring for reaction for 2h, standing at room temperature overnight, washing a white solid obtained after centrifugation at 1000-class 10000 r/min with deionized water and ethanol, drying at 60 ℃ for 12h in a vacuum oven, transferring to a crucible, calcining for 6 h in a 700 ℃ muffle furnace to obtain the core-shell structure SiO with the three-dimensional ordered mesopore with the diameter of 150-class 1000 nm2Nanospheres; the centrifugal rotation speed is preferably 5000-;
two, 3DOM g-C3N4The preparation of (1):
1) the obtained SiO with a core-shell structure2Soaking the nanospheres in 1 mol/L hydrochloric acid solution, performing ultrasonic treatment for 10min, and drying at 60 ℃ for 12 h;
2) according to SiO2Weighing a certain amount of cyanamide solid according to the mass ratio of the nanospheres to the cyanamide of 1:1-1:6, melting the solid in a water bath kettle at 50 ℃, and adding the molten solid into the treated SiO with the core-shell structure2Soaking the nanospheres in water at 60 ℃ for 12h, stirring at 60 ℃ for 6 h, evaporating to dryness at 80-100 ℃, and grinding the dried solid to obtain a solid A; SiO 22The mass ratio of the nanospheres to the cyanamide is preferably 1:2-1: 4;
3) placing the solid A in a muffle furnace or a tubular furnace, heating at the speed of 2.3 ℃/min, then calcining at the high temperature of 500-550 ℃ for 2-4 h, and cooling to room temperature to obtain a yellow solid B; the calcination temperature is preferably 520-550 ℃, and the calcination time is preferably 4 h;
4) dissolving solid B in 10vol% HF solution or 4M NH4HF2Stirring the solution for 24-48 h, then carrying out suction filtration, washing filter residues to be neutral by using deionized water, and then placing the filter residues in a 60 ℃ drying oven for drying for 12h to obtain carbon nitride with a three-dimensional ordered macroporous structure; the stirring time is preferably 24 h;
thirdly, loading of active metal:
3DOM g-C according to the mass-to-volume ratio of 1:50-300 g/mL3N4Ultrasonically dispersing in deionized water, and slowly adding 0.5-5 mol/L PdCl under stirring2Hydrochloric acid solution, stirring at 30 deg.C for 30-60 min, adjusting pH to 9-12 with 1 mol/L NaOH solution, and adding excessive NaBH dropwise under rapid stirring4Solution of Pd2+Reduction to Pd0After the addition, the reaction is continued for 1 to 5 hours, and then the Pd/3DOM g-C is obtained by suction filtration, water washing, ethanol washing and vacuum drying at 60 DEG C3N4；3DOM g-C3N4The mass ratio of the PdCl to the deionized water is preferably 1:100-200, PdCl2The concentration of the hydrochloric acid solution is preferably 1-2 mol/L, and the continuous reaction time is preferably 2-3 h.
The application method of the three-dimensional ordered macroporous carbon nitride supported palladium catalyst in the catalytic hydrogenation of the styrene unsaturated copolymer comprises the following steps: dissolving styrene unsaturated copolymer SBS or SBR in organic solvent to prepare glue solution with certain concentration, then placing the glue solution in a high-pressure reaction kettle, adding a certain amount of load type catalyst Pd/3DOM g-C3N4Stirring uniformly, and reacting for 0.5-15 h at 30-200 ℃ and 0.1-10 MPa hydrogen pressure; and after the reaction is finished, carrying out centrifugal separation on the reaction liquid, carrying out coagulation on the supernatant in ethanol to obtain a hydrogenated product, and using the recovered supported catalyst for the next hydrogenation reaction.
Wherein the mass ratio of the organic solvent to the styrene unsaturated copolymer is 100-10:1, preferably 80: 0.5-2. The organic solvent is one or more of n-heptane, n-octane, toluene, benzene, cyclohexane, dichloromethane and chloroform. Preferably, the organic solvent is n-heptane, n-octane, toluene or cyclohexane.
The mass ratio of the supported catalyst to the styrene unsaturated copolymer is 0.1-2:1, preferably 0.5-1.2: 1.
The hydrogenation reaction condition of SBS is 50-200 deg.C (preferably 100-160 deg.C), 0.1-10 MPa (preferably 1-4 MPa) hydrogen pressure, reaction time is 0.5-15 h (preferably 4-10 h); the hydrogenation reaction conditions of SBR are 30-80 deg.C (preferably 30-60 deg.C) and 0.5-6 MPa (preferably 0.5-4 MPa) hydrogen pressure, and the reaction is carried out for 0.58 h (preferably 1.5-6 h).
The invention has the beneficial effects that:
(1) the invention relates to three-dimensional ordered macroporous carbon nitride (3DOM g-C)3N4) The pore size of the macropores can be adjusted by controlling the particle size of the silica nanosphere template. The macroporous cavity is spherical, the diameter of the macroporous cavity is 200-1000 nm, and the macroporous cavity has a higher specific surface area.
(2) The supported catalyst prepared by the invention has the following characteristics: 1) the problem of diffusion of polymer macromolecules in micropores and mesoporous channels is solved; 2) the N-rich electronic characteristic of the catalyst enables the binding force between the carrier and the active component Pd nano-particles to be stronger, the active component particles are small, the dispersion is uniform, the stability is strong, and the agglomeration is not easy during the reaction; 3) 3DOM g-C3N4The pi-pi interaction between the carrier and the SBR and SBS polymer molecules enables polymer macromolecules to be more accessible to the active components; 4) the catalyst is easy to recover.
(3) The invention provides Pd/3DOM g-C3N4High catalytic activity, and its application in unsaturated styrene copolymerThe heterogeneous solution of the polymer SBS and SBR is hydrogenated, when the load of the Pd nano-particles is 1.0%, the hydrogenation degree of SBS can reach 98%, the hydrogenation degree of SBR can reach 90%, and the selectivity of both is 100%.
Drawings
FIG. 1 is 3DOM g-C prepared in example 13N4SEM image of (d).
FIG. 2 is 3DOM g-C prepared in example 13N4A TEM image of (a).
FIG. 3 shows g-C obtained in comparative example 1, comparative example 2 and example 13N4N of the vector2Adsorption-desorption isotherm diagram.
FIG. 4 is a comparison graph of IR spectra of SEBS and SBS obtained from example 1, comparative example 1 and comparative example 2.
FIG. 5 is a comparison graph of the IR spectra of HSBR and SBR obtained in example 11, comparative example 1 and comparative example 2.
Detailed Description
The following examples will describe the present invention more fully for the purpose of better understanding the technical features, objects and advantages of the present invention, but should not be construed as limiting the operable scope of the present invention.
In the embodiment, the SEM is the appearance obtained by the observation of a scanning electron microscope of a Phenom ProX tungsten filament in the Netherlands; TEM images were obtained by a field emission transmission electron microscope model Tecnai G2F 20, produced by FEI corporation, USA; n is a radical of2The adsorption-desorption isotherm diagram was obtained from a fully automatic adsorption apparatus model ASAP 2460, manufactured by mcirometrics, usa; the IR spectrum was obtained from an FTIR spectrometer model NICOLET is 50.
Example 1
Dispersing 10 mL of tetraethyl orthosilicate (TEOS) in 50 mL of ethanol to obtain a solution A; mixing and stirring 50 mL of ethanol, 20 mL of deionized water and 10 mL of 25-28wt% ammonia water solution uniformly, and controlling the stirring speed to be 1100 rpm to obtain a solution B; rapidly adding the solution A into the solution B in a water bath at 40 ℃, keeping 1100 rpm and stirring for 1 min, then reducing the rotation speed to 600rpm, and continuing to react for 2.5 h to obtain the uniformly dispersed core SiO2A mixed solution of solids; this will contain 1 mL TEOS, 5 mL ethanol, and 0.Dropwise adding a mixed solution of 2 g of PVP into the solution under vigorous stirring, continuously stirring at 40 ℃ for reaction for 2h, standing at room temperature overnight, washing a white solid obtained after centrifugation with deionized water and ethanol, drying at 60 ℃ for 12h in a vacuum oven, transferring to a crucible, calcining in a muffle furnace at 700 ℃ for 6 h to obtain the core-shell structure SiO with the three-dimensional ordered mesopores2Nanospheres.
1 g of the resulting core-shell SiO2Soaking the nanospheres in 10 mL of 1 mol/L hydrochloric acid solution, performing ultrasonic treatment for 10min, and drying at 60 ℃ for 12 h; weighing 2 g of cyanamide solid, melting in a water bath kettle at 50 ℃, and then dropwise adding the solid to the treated SiO with the core-shell structure2Soaking nanosphere in water at 60 deg.C for 12 hr, stirring at 60 deg.C for 6 hr, evaporating in 80 deg.C oil bath to dryness, grinding the obtained white solid, calcining at 550 deg.C for 4 hr, cooling to room temperature to obtain yellow solid, dissolving in 10vol% HF solution, stirring for 24 hr to remove SiO2Filtering after a template is formed, washing filter residues to be neutral by deionized water, and drying in an oven at 60 ℃ for 12h to obtain 3DOM g-C3N4Having a specific surface area of 21 m2·g-1。
1.0 g of 3DOM g-C3N4Dispersing in 100 mL of deionized water, and performing ultrasonic dispersion for 0.5 h; PdCl dissolved in 1 mol/L HCl is slowly added with stirring2Stirring the solution at 30 ℃ for 30 min, adjusting the pH value to 10 by using 1 mol/L NaOH solution, and dropwise adding excessive NaBH under rapid stirring4After the solution is added, the reaction is continued for 3 hours, and then the dispersion liquid is filtered, washed by water and ethanol and dried in vacuum at 60 ℃ to obtain the heterogeneous catalyst Pd/3DOMg-C with the loading of 1.0 wt%3N4。
1 g SBS was dissolved in 80 g cyclohexane and 1 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 140 ℃, the hydrogen pressure is 3.0MPa, and the reaction time is 6.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 2
The catalyst synthesis procedure was the same as in example 1.2 g SBS was dissolved in 80 g cyclohexane and 1 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 140 ℃, the hydrogen pressure is 3.0MPa, and the reaction time is 6.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 3
The catalyst synthesis procedure was the same as in example 1. 3 g SBS was dissolved in 80 g cyclohexane and 1 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 140 ℃, the hydrogen pressure is 3.0MPa, and the reaction time is 6.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 4
The catalyst synthesis procedure was the same as in example 1. 1 g SBS was dissolved in 80 g cyclohexane and 0.5 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 140 ℃, the hydrogen pressure is 3.0MPa, and the reaction time is 6.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 5
The catalyst synthesis procedure was the same as in example 1. 1 g SBS was dissolved in 80 g cyclohexane and 1 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 60 ℃, the hydrogen pressure is 3.0MPa, and the reaction time is 6.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 6
The catalyst synthesis procedure was the same as in example 1. 1 g SBS was dissolved in 80 g cyclohexane and 1 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: temperature 100 ℃ and hydrogen pressure3.0MPa and 6.0 h of reaction time. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 7
The catalyst synthesis procedure was the same as in example 1. 1 g SBS was dissolved in 80 g cyclohexane and 1 g catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 100 ℃, the hydrogen pressure is 1.0MPa, and the reaction time is 6.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product SEBS, and the hydrogenation degree is listed in Table 1.
Example 8
A heterogeneous catalyst Pd/3DOM g-C having a loading of 0.3 wt% was prepared according to the synthetic procedure of example 13N4。
The hydrogenation method and reaction conditions in example 1 were followed, and the catalyst was used to catalyze SBS hydrogenation to prepare SEBS, the degree of hydrogenation being shown in Table 1.
Example 9
A heterogeneous catalyst Pd/3DOM g-C having a loading of 0.5% by weight was prepared according to the synthetic procedure of example 13N4。
The hydrogenation method and reaction conditions in example 1 were followed, and the catalyst was used to catalyze SBS hydrogenation to prepare SEBS, the degree of hydrogenation being shown in Table 1.
Example 10
A heterogeneous catalyst Pd/3DOM g-C having a loading of 2.0 wt% was prepared according to the synthetic procedure of example 13N4。
The hydrogenation method and reaction conditions in example 1 were followed, and the catalyst was used to catalyze SBS hydrogenation to prepare SEBS, the degree of hydrogenation being shown in Table 1.
Example 11
The catalyst synthesis procedure was the same as in example 1. 1 g of SBR was dissolved in 80 g of cyclohexane and 1 g of the catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 60 ℃, the hydrogen pressure is 1.0MPa, and the reaction time is 2.5 h. After the reaction is finished, centrifugally separating, and adding ethanol into the glue solutionThe product HSBR was obtained by coagulation and the degree of hydrogenation is shown in Table 2.
Example 12
The catalyst synthesis procedure was the same as in example 1. 1 g of SBR was dissolved in 80 g of cyclohexane and 1 g of the catalyst Pd/3DOM g-C was added3N4And carrying out catalytic hydrogenation reaction in a high-pressure reaction kettle. The reaction conditions are as follows: the temperature is 60 ℃, the hydrogen pressure is 1.0MPa, and the reaction time is 4.0 h. After the reaction is finished, centrifugal separation is carried out, ethanol is added into the glue solution for coagulation to obtain a product HSBR, and the hydrogenation degree is listed in Table 2.
Example 13
A heterogeneous catalyst Pd/3DOM g-C having a loading of 0.3 wt% was prepared according to the synthetic procedure of example 13N4。
HSBR was prepared by hydrogenation of SBR catalyzed by this catalyst according to the hydrogenation method and reaction conditions of example 1, and the degree of hydrogenation is shown in Table 2.
Example 14
A heterogeneous catalyst Pd/3DOM g-C having a loading of 0.5% by weight was prepared according to the synthetic procedure of example 13N4。
HSBR was prepared by hydrogenation of SBR catalyzed by this catalyst according to the hydrogenation method and reaction conditions of example 1, and the degree of hydrogenation is shown in Table 2.
Example 15
A heterogeneous catalyst Pd/3DOM g-C having a loading of 2.0 wt% was prepared according to the synthetic procedure of example 13N4。
HSBR was prepared by hydrogenation of SBR catalyzed by this catalyst according to the hydrogenation method and reaction conditions of example 1, and the degree of hydrogenation is shown in Table 2.
Comparative example 1
Weighing a certain amount of ground cyanamide in a crucible with a cover, putting the crucible in a muffle furnace, calcining the crucible for 4 hours at 550 ℃, and cooling to room temperature to obtain graphite-phase carbon nitride g-C3N4Having a specific surface area of 7.1 m2·g-1. Pd/g-C was prepared by the same loading method and conditions as in example 13N4Catalyst for comparison with example 1.
The hydrogenation method and reaction conditions in example 1 are followed to catalyze SBS hydrogenation to prepare SEBS. The degree of hydrogenation is listed in table 1; HSBR was prepared by catalytic SBR hydrogenation according to the hydrogenation method and reaction conditions in example 11. The degree of hydrogenation is listed in table 2.
Comparative example 2
Respectively weighing 2.5 g of cyanamide solid and 6.25 g of 40% silica gel solution, and dissolving the solid cyanamide in 50%oAnd C, placing the mixture in a water bath for a period of time to melt the mixture, dropwise adding the mixture into the silica gel solution, stirring the mixture at room temperature for 1 hour, moving the mixture into an oil bath at 90 ℃, and continuously stirring the mixture until the water is evaporated to dryness. Grinding the obtained white solid, transferring to a crucible, putting into a muffle furnace, calcining at 550 ℃ for 4 h, cooling to room temperature, and dissolving the obtained yellow powder into 100 mL of 4M NH4HF2Stirring the solution for 48 hours to remove SiO2And (5) template. Finally, carrying out suction filtration, washing the obtained product with deionized water to be neutral, and drying the obtained product to obtain the mesoporous carbon nitride M-g-C3N4Having a specific surface area of 6.6 m2·g-1. Pd/g-C was prepared by the same loading method and conditions as in example 13N4Catalyst for comparison with example 1.
The hydrogenation method and reaction conditions in example 1 are followed to catalyze SBS hydrogenation to prepare SEBS. The degree of hydrogenation is listed in table 1; HSBR was prepared by catalytic SBR hydrogenation according to the hydrogenation method and reaction conditions in example 11. The degree of hydrogenation is listed in table 2.
FIGS. 1 and 2 are 3DOM g-C obtained in example 1, respectively3N4SEM and TEM images of (a). From the figure, it can be seen that the three-dimensional ordered porous structure with large area and regular arrangement has spherical pores which are connected with each other, are about 600 nm directly and are close to SiO2Particle size of the nanospheres.
FIG. 3 shows g-C obtained in comparative example 1, comparative example 2 and example 13N4N of (A)2Adsorption-desorption isotherm diagram. As can be seen from the figure, the specific surface area of the carrier is enhanced by the constructed three-dimensional ordered macroporous structure, so that more active sites can be exposed, the contact between reactant molecules and the active sites is favorably improved, and the catalytic reaction activity is further improved.
FIG. 4 is a comparison graph of IR spectra of SEBS and SBS obtained in example 1, comparative example 1 and comparative example 2, and FIG. 5 is a comparison graph of IR spectra of HSBR and SBR obtained in example 11, comparative example 1 and comparative example 2, and the degree of hydrogenation is obtained by using the intensity of absorption peaks of the IR spectra. As shown, the hydrogenation products SEBS with different degrees of hydrogenation are at 700 cm-1The absorption peak intensity of benzene ring is not changed and is at 820-900 cm-1There is no absorption peak of cyclohexyl between them, which indicates that the benzene ring is not hydrogenated, i.e. the selectivity is 100%. 970 and 910 cm-1The absorption peaks at (A) and (B) were 1, 4-double bond group and 1, 2-double bond group, 910 and 970 cm in example 1-1The characteristic absorption peaks of (A) are all basically disappeared, which shows that the double bonds in the polybutadiene block are basically completely hydrogenated, 970 cm and 910 cm in comparative example 1 and comparative example 2-1The absorption peak intensity of (A) is reduced, but the reduction amplitude is much smaller than that of example 1, which indicates that the hydrogenation degree is lower. Meanwhile, the hydrogen concentration is 723 cm after hydrogenation-1Appearance of a new peak belonging to- [ CH ]2]n- (wherein n)>4) The structure is a newly appeared structure after C = C in a molecular chain is subjected to hydrogenation saturation.
TABLE 1 degree of hydrogenation and Selectivity of SBS
TABLE 2 SBR hydrogenation degree and Selectivity
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. The application of the three-dimensional ordered macroporous carbon nitride supported palladium catalyst in the catalytic hydrogenation of styrene unsaturated copolymers is characterized in that: firstly synthesizing the SiO with a three-dimensional ordered mesopore core-shell structure2Nanospheres are prepared by a thermal condensation assisted colloidal crystal template method3DOM g-C3N4(ii) a Then 3DOM g-C3N4The active metal Pd is loaded on the carrier by a chemical reduction method to obtain the catalyst Pd/3DOM g-C3N4。
2. Use according to claim 1, characterized in that: core-shell structure SiO with three-dimensional ordered mesopores2The specific preparation method of the nanosphere comprises the following steps:
a) dispersing tetraethyl orthosilicate in ethanol according to the volume ratio of 1:3-1:10 to obtain a solution A;
b) mixing and stirring ethanol, deionized water and 25-28wt% ammonia water solution uniformly according to the volume ratio of 50 (10-25) to (1.5-15) to obtain solution B;
c) dissolving polyvinylpyrrolidone in an amount of 0.04 g/mL in tetraethyl orthosilicate-ethanol solution prepared according to a volume ratio of 1 (2-10) to obtain a solution C;
d) rapidly adding the solution A into the solution B at the stirring speed of 300-1200 rpm, and stirring for 2.5 h at the temperature of 20-60 ℃ to obtain a mixed solution D;
e) adding the solution C into the mixed solution D, continuously stirring for reacting for 2h, standing overnight at room temperature, centrifuging to obtain a white solid, washing with deionized water and ethanol, drying at 60 ℃ for 12h, and calcining at 700 ℃ for 6 h to obtain the core-shell structure SiO2Nanospheres;
the obtained SiO with a core-shell structure2The diameter of the nanosphere is 150-1000 nm.
3. Use according to claim 1, characterized in that: 3DOM g-C3N4The specific preparation method comprises the following steps:
1) the SiO with a three-dimensional ordered mesopore core-shell structure2Soaking the nanospheres in 1 mol/L hydrochloric acid solution, performing ultrasonic treatment for 10min, and drying at 60 ℃ for 12 h;
2) after cyanamide is melted, the cyanamide is added into the treated SiO with the core-shell structure according to the mass ratio of 1:1-6:12Soaking in nanosphere at 60 deg.C for 12 hr, stirring at 60 deg.C for 6 hr, evaporating at 80-100 deg.C, and dryingGrinding the dried solid to obtain a solid A;
3) placing the solid A in a muffle furnace or a tubular furnace, calcining at the high temperature of 500-550 ℃ for 2-4 h, and cooling to room temperature to obtain a yellow solid B;
4) dissolving solid B in 10vol% HF solution or 4M NH4HF2And stirring the solution for 24-48 h, then carrying out suction filtration, washing filter residues to be neutral by using deionized water, and drying the filter residues at 60 ℃ for 12h to obtain the carbon nitride with the three-dimensional ordered macroporous structure.
4. Use according to claim 1, characterized in that: adopting a chemical reduction method to carry 3DOM g-C3N4The method comprises the following steps of: mixing 3DOM g-C3N4Ultrasonically dispersing in deionized water, adding 0.5-5 mol/L PdCl2Hydrochloric acid solution, stirring for 30-60 min, adjusting pH to 9-12 with 1 mol/L NaOH solution, adding NaBH4The solution is reduced, and then is filtered, washed by water, washed by ethanol and dried in vacuum to obtain Pd/3DOM g-C3N4。
5. Use according to claim 4, characterized in that: the loading amount of the active metal Pd is 0.1-10 wt%.
6. Use according to claim 1, characterized in that: dissolving styrene unsaturated copolymer in organic solvent to prepare glue solution, then placing the glue solution in a high-pressure reaction kettle, adding three-dimensional ordered macroporous carbon nitride supported palladium catalyst, and reacting for 0.5-15 h at 30-200 ℃ and 0.1-10 MPa hydrogen pressure; and after the reaction is finished, carrying out centrifugal separation on the reaction liquid, and carrying out coagulation on the supernatant in ethanol to obtain a hydrogenated product.
7. Use according to claim 6, characterized in that: the organic solvent is one or more of n-heptane, n-octane, toluene, benzene, cyclohexane, dichloromethane and trichloromethane;
the mass ratio of the three-dimensional ordered macroporous carbon nitride supported palladium catalyst to the styrene unsaturated copolymer is 0.1-2: 1.
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Application publication date: 20200512 |