CN110894185A - Preparation method of diphenyl carbonate compound - Google Patents
Preparation method of diphenyl carbonate compound Download PDFInfo
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- CN110894185A CN110894185A CN201811057931.XA CN201811057931A CN110894185A CN 110894185 A CN110894185 A CN 110894185A CN 201811057931 A CN201811057931 A CN 201811057931A CN 110894185 A CN110894185 A CN 110894185A
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- -1 diphenyl carbonate compound Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 37
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002148 esters Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 28
- 150000003609 titanium compounds Chemical class 0.000 claims description 27
- 229920006395 saturated elastomer Polymers 0.000 claims description 20
- 238000005809 transesterification reaction Methods 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000012662 bulk polymerization Methods 0.000 claims description 5
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- GGTXHXCWAIAERM-UHFFFAOYSA-N ClC(CCC[Ti])(Cl)Cl Chemical compound ClC(CCC[Ti])(Cl)Cl GGTXHXCWAIAERM-UHFFFAOYSA-N 0.000 claims description 2
- NYNSEMTYAHXLBA-UHFFFAOYSA-N ClC(Cl)(Cl)CCO[Ti] Chemical compound ClC(Cl)(Cl)CCO[Ti] NYNSEMTYAHXLBA-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GHRBKUMCCNCPKK-UHFFFAOYSA-N cyclohexanolate;titanium(4+) Chemical compound [Ti+4].[O-]C1CCCCC1.[O-]C1CCCCC1.[O-]C1CCCCC1.[O-]C1CCCCC1 GHRBKUMCCNCPKK-UHFFFAOYSA-N 0.000 claims description 2
- DAKRXZUXJUPCOF-UHFFFAOYSA-N diethyl(dihydroxy)silane Chemical compound CC[Si](O)(O)CC DAKRXZUXJUPCOF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical compound C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 claims description 2
- MNLMLEWXCMFNFO-UHFFFAOYSA-K ethanol;trichlorotitanium Chemical compound CCO.Cl[Ti](Cl)Cl MNLMLEWXCMFNFO-UHFFFAOYSA-K 0.000 claims description 2
- OLDJJINSZWUKCD-UHFFFAOYSA-N hydroxy-propoxy-dipropylsilane Chemical compound CCCO[Si](O)(CCC)CCC OLDJJINSZWUKCD-UHFFFAOYSA-N 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 claims description 2
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 claims description 2
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 6
- 238000001577 simple distillation Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VHZZVMHWADQDDI-UHFFFAOYSA-M 10-methoxy-2-methyl-11ah-pyrido[4,3-c]carbazol-2-ium;iodide Chemical compound [I-].C1=C[N+](C)=CC2=C3C4C=C(OC)C=CC4=NC3=CC=C21 VHZZVMHWADQDDI-UHFFFAOYSA-M 0.000 description 1
- AZRZBCASYOBNKQ-UHFFFAOYSA-N 6-chloro-3,5-diaminopyrazine-3-carboxamide Chemical compound CN(C)C(N)=NC(=O)C1=NC(Cl)=C(N)N=C1N AZRZBCASYOBNKQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- KPZUWETZTXCDED-UHFFFAOYSA-N [V].[Cu] Chemical compound [V].[Cu] KPZUWETZTXCDED-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- BSNASBXELXDWSZ-UHFFFAOYSA-N dihydroxy(dipropyl)silane Chemical compound CCC[Si](O)(O)CCC BSNASBXELXDWSZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- ULDITJUIBRUBND-UHFFFAOYSA-N hydroxy-phenoxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)OC1=CC=CC=C1 ULDITJUIBRUBND-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FRSRGACXHCLBTC-UHFFFAOYSA-N methyl n-(3,5-dichlorophenyl)carbamate Chemical compound COC(=O)NC1=CC(Cl)=CC(Cl)=C1 FRSRGACXHCLBTC-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- 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
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
- B01J31/127—Silicones or siloxanes or comprising such units the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of diphenyl carbonate synthesis, and discloses a preparation method of diphenyl carbonate compounds, which comprises the following steps: in the presence of a catalyst represented by the formula (1-1) or the formula (1-2), carrying out an ester exchange reaction between a phenol compound represented by the formula (II) and a carbonic acid diester compound represented by the formula (III); r1、R2And R3Is selected from C1‑C14Aliphatic hydrocarbon group, C3‑C14Cycloalkyl radical, C6‑C14Aryl radical, C7‑C14Alkylaryl group, C7‑C14Aralkyl or C10‑C14A fused ring aryl group; x is halogen. The method has the advantages of high catalytic activity, high selectivity and good stability. (H)‑[O‑Si‑(R1)2]n‑O)x1‑Ti‑(OR3)y1X(4‑x1‑y1)Formula (1-1) [ Si (R)2)xO]x2‑Ti‑(OR3)y2X(4‑x2‑y2)Formula (1-2)
Description
Technical Field
The invention relates to the field of synthesis of diphenyl carbonate compounds, in particular to a preparation method of a diphenyl carbonate compound.
Background
Diphenyl carbonate is an important chemical intermediate, and can replace toxic phosgene to carry out melt transesterification with bisphenol A to produce polycarbonate. At present, diphenyl carbonate is prepared by an oxidation carbonylation method, and because a catalyst is expensive and reaction selectivity is low, industrial application is not seen. The ester exchange method is the only green synthetic route of diphenyl carbonate which is industrially applied. The ester exchange method for preparing diphenyl carbonate uses a green organic intermediate dimethyl carbonate to react with phenol, and the reaction has small equilibrium constant and complex reaction process, so that a catalyst with high activity and high stability needs to be researched.
The diphenyl carbonate prepared by the transesterification method of dimethyl carbonate and phenol mostly uses homogeneous catalysts with higher activity, wherein the organic tin catalysts and the organic titanium catalysts have better catalytic activity and good reproducibility. Deshmukh et al (Deshmukh K M, Qureshi Z S, Dhake K P, et al catalysis Communications, 2011, 12 (3): 207-211) use dibutyltin oxide in combination with ionic liquid, and research shows that the acidic ionic liquid is used as a cocatalyst to significantly improve the catalytic performance, and the phenol conversion rate reaches 39% without anisole generation. The catalytic bulletin, 2001, 15 (4): 21-24, uses titanate catalyst for the ester exchange reaction of phenol and dimethyl carbonate, the reaction time is 8h, and the conversion rate of phenol is 23.8%. In CN1411909A, Wangchun et al used organotin, organotitanium and organic amine compound catalyst to achieve the conversion rate of 45% phenol and the selectivity of 99% methyl phenyl carbonate. However, the titanate catalyst is sensitive to moisture in the air, and brings a series of problems for using and storing the catalyst, drying raw materials and the like.
In a heterogeneous catalyst system, a composite oxide, a molecular sieve carrier loaded active species or heteropoly acid and the like are mostly used as catalysts, but the problems of poor catalytic activity, low ester exchange selectivity, expensive carrier, complex preparation process, poor reproducibility and the like exist. In CN1803282A, wangong et al used a catalyst of vanadium-copper bimetallic oxide type, and the total yield of diphenyl carbonate and methyl phenyl carbonate was low, only 30%, and the total selectivity was also only 96%. In CN102050740A, the carbon nano tube loaded titanium dioxide is used as a catalyst for ester exchange reaction, and the conversion rate of phenol reaches 49%.
Disclosure of Invention
The invention provides a preparation method of diphenyl carbonate compound aiming at the current situation that the catalyst used for preparing diphenyl carbonate compound has poor stability in air and large catalyst dosage, and aiming at the current situation that the conversion rate and selectivity of phenol are low in the current preparation method of diphenyl carbonate compound, the catalyst used in the method has high catalytic activity and high selectivity, and can stably exist in air, and the catalyst can reduce the catalyst dosage in the using process, thus being beneficial to reducing the product cost and simplifying the subsequent catalyst separation process.
In order to achieve the above object, one aspect of the present invention provides a method for preparing diphenyl carbonate compounds represented by formula (i), the method comprising: in the presence of a catalyst, carrying out an ester exchange reaction between a phenol compound shown as a formula (II) and a carbonic diester compound shown as a formula (III);
wherein the catalyst has a structural formula shown in a formula (1-1) or a formula (1-2);
(H-[O-Si-(R1)2]n-O)x1-Ti-(OR3)y1X(4-x1-y1)formula (1-1)
[Si(R2)xO]x2-Ti-(OR3)y2X(4-x2-y2)Formula (1-2)
Wherein each R is1、R2And R3Each independently selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4); x is halogen;
in the formula (1-1), each R1And each R3Equal to or different from each other, n is an integer greater than 0, x1 is an integer from 0 to 3, y1 is an integer from 1 to 2, and the sum of x1 and y1 is less than or equal to 4;
in the formula (1-2), each R2And each R3The same or different from each other, x is 2 or 3, x2 is an integer of 1 to 4, y2 is an integer of 0 to 3, and the sum of x2 and y2 is 4 or less;
wherein R is hydrogen or C1-C4R' and R "are each independently methyl or ethyl.
Preferably, the preparation method of the catalyst comprises the following steps: contacting a silicon compound and a titanium compound to carry out polymerization reaction to obtain a catalyst for preparing diphenyl carbonate compounds shown in a formula (1-1) or a formula (1-2);
wherein the silicon compound has a structure represented by formula (2-1), or a structure represented by formula (2-2), wherein the structure represented by formula (2-2) is a polymer having a structure represented by formula (2-1),
OH-[Si(R1)2-O]n-H formula (2-1)
Si(R2)x(OH)4-xFormula (2-2)
Each R1And R2Each independently selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4);
x is an integer from 2 to 3, n is an integer greater than 0, and each R1And R2Are the same or different from each other;
wherein the titanium compound has a structure represented by formula (3),
Ti(OR3)yX4-yformula (3)
Each R3Selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4); x is halogen;
y is an integer of 0 to 4, each R3The same or different from each other.
The invention has the following characteristics:
1. the titanium silicon organic metal compound catalyst in the method uses cheap and safe raw materials, the preparation scheme is simple, and the used organic solvent can be recycled during solution polymerization, so that the cost is reduced, and the pollution problem is avoided.
2. The titanium-silicon organic metal compound catalyst in the method has the characteristics of high stability in air, high catalytic reaction and the like, the conversion rate of phenol can reach more than 60 percent at most under the condition of liquid phase reaction, and the total selectivity can reach more than 99.8 percent at most.
3. Compared with the titanium silicon organic metal compound catalyst in the method of the invention, the conversion rate of phenol can be improved by 5-10% under the condition of the same catalyst usage amount, the selectivity of byproducts is reduced, and the production cost is reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows the formula (1-2) [ Si (R) according to the present invention2)xO]x2-Ti-(OR3)y2X(4-x2-y2)An infrared spectrum of a compound of the structure shown.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of diphenyl carbonate compounds shown as a formula (I), which comprises the following steps: in the presence of a catalyst, carrying out an ester exchange reaction between a phenol compound shown as a formula (II) and a carbonic diester compound shown as a formula (III);
wherein the catalyst has a structural formula shown in a formula (1-1) or a formula (1-2);
(H-[O-Si-(R1)2]n-O)x1-Ti-(OR3)y1X(4-x1-y1)formula (1-1)
[Si(R2)xO]x2-Ti-(OR3)y2X(4-x2-y2)Formula (1-2)
Wherein each R is1、R2And R3Each independently selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4); x is halogen;
in the formula (1-1), each R1And each R3Equal to or different from each other, n is an integer greater than 0, x1 is an integer from 0 to 3, y1 is an integer from 1 to 2, and the sum of x1 and y1 is less than or equal to 4;
in the formula (1-2), each R2And each R3The same or different from each other, x is 2 or 3, x2 is an integer of 1 to 4, y2 is an integer of 0 to 3, and the sum of x2 and y2 is 4 or less;
wherein R is hydrogen or C1-C4R' and R "are each independently methyl or ethyl.
Preferably, each R is1、R2And R3Each independently selected from linear or branched, saturated or unsaturated C1-C8Aliphatic hydrocarbon group of (2)3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
Further preferably, each R is1、R2And R3Each independently selected from linear or branched saturated or unsaturated C1-C4More preferably a straight or branched saturated C1-C4Alkyl of (e.g. C)1Alkyl of (C)2Alkyl of (C)3Alkyl of (C)4Including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl;
each R1、R2And R3Each independently selected from C3-C6Cycloalkyl of, e.g. C3Cycloalkyl of, C4Cycloalkyl of, C5Cycloalkyl of, C6Cycloalkyl groups of (a), including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
each R1、R2And R3Each independently selected from C6-C8Aryl of, e.g. C6Aryl (phenyl) of (C)7Aryl of (C)8Aryl of (a);
each R1、R2And R3Each independently selected from C7-C9Alkylaryl of, e.g. C7Alkylaryl of, C8Alkylaryl of, C9The alkylaryl group of (a) may be, but is not limited to, tolyl, ethylphenyl, n-butylphenyl, isobutylphenyl;
each R1、R2And R3Each independently selected from C7-C9Aralkyl, e.g. C7Aralkyl of (2), C8Aralkyl of (2), C9The aralkyl group of (a) may be, but is not limited to, benzyl, phenethyl, phenyl n-butyl, phenyl isobutyl.
According to the present invention, in formula (1-1), n may be 2 to 900, for example, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900.
According to the present invention, in the formula (1-1), x1 may be 0, 1, 2, 3.
According to the present invention, in the formula (1-1), y1 may be 1 or 2.
According to the present invention, in the formula (1-2), x2 may be 1, 2, 3, 4.
According to the present invention, y2 may be 0, 1, 2, 3.
According to the invention, X may be bromine, chlorine or iodine, more preferably chlorine.
According to a preferred embodiment of the present invention, the method for preparing the catalyst as described above comprises: contacting a silicon compound and a titanium compound to carry out polymerization reaction to obtain a catalyst for preparing diphenyl carbonate compounds shown in a formula (1-1) or a formula (1-2);
wherein the silicon compound has a structure represented by formula (2-1), or a structure represented by formula (2-2), wherein the structure represented by formula (2-2) is a polymer having a structure represented by formula (2-1),
OH-[Si(R1)2-O]n-H formula (2-1)
Si(R2)x(OH)4-xFormula (2-2)
Each R1And R2Each independently selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4);
x is an integer from 2 to 3, n is an integer greater than 0, and each R1And R2Are the same or different from each other;
wherein the titanium compound has a structure represented by formula (3),
Ti(OR3)yX4-yformula (3)
Each R3Selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4); x is halogen;
y is an integer of 0 to 4, each R3The same or different from each other.
According to the invention, in the silicon compound, preferably, each R is1And R2Each independently selected from linear or branched, saturated or unsaturated C1-C8Aliphatic hydrocarbon group of (2)3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
Further preferably, eachR is1And R2Each independently of the others, linear or branched, saturated or unsaturated C1-C4More preferably a straight or branched saturated C1-C4Alkyl of (e.g. C)1Alkyl of (C)2Alkyl of (C)3Alkyl of (C)4Including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl;
each R1And R2Each independently C3-C6Cycloalkyl of, e.g. C3Cycloalkyl of, C4Cycloalkyl of, C5Cycloalkyl of, C6Cycloalkyl groups of (a), including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
each R1And R2Each independently selected from C6-C8Aryl of, e.g. C6Aryl (phenyl) of (C)7Aryl of (C)8Aryl of (a);
each R1And R2Each independently selected from C7-C9Alkylaryl of, e.g. C7Alkylaryl of, C8Alkylaryl of, C9The alkylaryl group of (a) may be, but is not limited to, tolyl, ethylphenyl, n-butylphenyl, isobutylphenyl;
each R1And R2Each independently selected from C7-C9Aralkyl, e.g. C7Aralkyl of (2), C8Aralkyl of (2), C9The aralkyl group of (a) may be, but is not limited to, benzyl, phenethyl, phenyl n-butyl, phenyl isobutyl.
According to the present invention, the polymer having a structure represented by formula (2) is preferably an oligomer having a degree of polymerization (i.e., n) of 2 to 900, for example, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900. The term "degree of polymerization" is an index for measuring the molecular size of a polymer, and is based on the number of repeating units, i.e., the average of the number of repeating units contained in a polymer macromolecular chain.
According to a preferred embodiment of the invention, the silicon compound is selected from at least one of dimethylsilanediol, trimethylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanediol, dipropylsilanediol, diphenylsilanediol, triphenylsilaniol and hydroxyl-terminated polydimethylsiloxane, preferably triphenylsilanediol and/or diphenylsilanediol.
According to the invention, in the titanium compound, preferably, each R3Selected from linear or branched, saturated or unsaturated C1-C8Aliphatic hydrocarbon group of (2)3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
Further preferably, each R is3Selected from linear or branched saturated or unsaturated C1-C4More preferably a straight or branched saturated C1-C4Alkyl of (e.g. C)1Alkyl of (C)2Alkyl of (C)3Alkyl of (C)4Including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl;
each R3Is selected from C3-C6Cycloalkyl of, e.g. C3Cycloalkyl of, C4Cycloalkyl of, C5Cycloalkyl of, C6Cycloalkyl groups of (a), including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
each R3Is selected from C6-C8Aryl of, e.g. C6Aryl (phenyl) of (C)7Aryl of (C)8Aryl of (a);
each R3Is selected from C7-C9Alkylaryl of, e.g. C7Alkylaryl of, C8Alkylaryl of, C9The alkylaryl group of (a) may be, but is not limited to, tolyl, ethylphenyl, n-butylphenyl, isobutylphenyl;
each R3Is selected fromC7-C9Aralkyl, e.g. C7Aralkyl of (2), C8Aralkyl of (2), C9The aralkyl group of (a) may be, but is not limited to, benzyl, phenethyl, phenyl n-butyl, phenyl isobutyl.
According to the invention, in formula (3), y may be 0, 1, 2, 3, 4.
According to a preferred embodiment of the present invention, the titanium compound is at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetracyclohexyloxy titanium, tetraphenyl titanate, titanium tetrachloride, trichloromethoxy titanium, trichloroethoxy titanium, trichloropropoxy titanium and trichloron-butyl titanium, preferably at least one selected from the group consisting of tetra-n-butyl titanate, tetraphenyl titanate and tetraisopropyl titanate.
According to the invention, the amount of titanium compound and silicon compound used in the polymerization reaction can be selected within a wide range, preferably such that the molar ratio of elemental titanium to elemental silicon is from 0.01 to 0.5:1, for example from 0.01:1, from 0.05:1, from 0.1:1, from 0.15:1, from 0.2:1, from 0.25:1, from 0.3:1, from 0.35:1, from 0.4:1, from 0.45:1, from 0.5:1, more preferably from 0.04 to 0.25: 1.
According to the present invention, the manner of the polymerization reaction is not particularly limited as long as the silicon compound and the titanium compound can be polymerized to produce the compound represented by formula (1), and the polymerization reaction may be solution polymerization performed in an organic solvent or bulk polymerization performed in a molten state.
When the polymerization reaction is a solution polymerization, the organic solvent may be at least one selected from the group consisting of benzene, toluene, xylene, cyclohexane, and n-hexane. Specifically, the titanium compound and the silicon compound can be respectively dissolved in an organic solvent, and then the solution containing the titanium compound and the solution containing the silicon compound are subjected to a contact reaction, wherein the temperature of the contact reaction can be 20-40 ℃, and the time can be 3-5 h. Under such reaction conditions, the silicon compound of the structure represented by formula (2-1) or formula (2-2) may undergo no or little polymerization reaction by itself. Wherein the concentration of the titanium compound in the solution containing the titanium compound may be 2 to 8% by weight, and the concentration of the silicon compound in the solution containing the silicon compound may be 15 to 20% by weight.
Preferably, the contact reaction is carried out under stirring conditions.
When the polymerization reaction is bulk polymerization, it is possible to carry out a contact reaction by separately heating the titanium compound and the silicon compound to a molten state and then subjecting the molten silicon compound and the titanium compound to a contact reaction. The reaction temperature may be selected from a wide range as long as it is possible to ensure that the titanium compound and the silicon compound are in a molten state, and the reaction time may be 3 to 5 hours.
According to a preferred embodiment of the present invention, in order to smoothly perform the reaction and to improve the yield of the catalyst, it is preferable to add the titanium compound to the silicon compound for the reaction, and it is more preferable to add the titanium compound dropwise to the silicon compound.
According to the present invention, after the reaction is completed, the method further comprises a step of purifying the obtained product containing the catalyst to remove substances introduced during the reaction, for example, a solvent introduced during the polymerization reaction, unreacted raw materials, and by-products generated during the reaction, for example, alcohols generated during the polymerization reaction. Wherein, the purification method can be vacuum distillation. Preferably, the pressure of the reduced pressure distillation is 10-15KPa, and the temperature is 50-60 ℃.
In the present invention, R is preferably hydrogen or methyl, and more preferably hydrogen; r 'and R' are methyl.
In the present invention, the amount of the catalyst used in the transesterification reaction can be selected within a wide range, but the inventors of the present invention have found that the amount of the catalyst used can be significantly reduced by using the catalyst provided by the present invention, as compared with the titanium-based catalyst of the prior art. Therefore, the catalyst is preferably used in an amount of 0.5 to 1.5mol, for example, 0.5mol, 0.6mol, 0.7mol, 0.8mol, 0.9mol, 1.0 mol, 1.1mol, 1.2mol, 1.3mol, 1.4mol, or 1.5mol, in terms of titanium element, based on 100mol of the phenol compound represented by the formula (II).
In the present invention, in order to further improve the selectivity of the diphenyl carbonate compound, the molar ratio of the amount of the carbonic acid diester compound represented by the formula (III) to the amount of the phenol compound represented by the formula (II) is from 0.1 to 5:1, preferably 1 to 4:1, more preferably 2 to 3.5: 1.
in the present invention, the transesterification reaction conditions may be those capable of existing transesterification reactions, and preferably, the transesterification reaction conditions include: the temperature is 63-200 ℃, the reaction time is 1-22h, and more preferably, the conditions of the ester exchange reaction comprise: the temperature is 130 ℃ and 180 ℃, and the reaction time is 9-11 h.
In the present invention, it is preferable to perform simple distillation or rectification simultaneously with the transesterification reaction. The generated alcohol compounds and the azeotrope thereof are removed by simple distillation or rectification.
In the invention, the temperature of the liquid in the reactor is changed along with the low volatile alcohol substance HOR1And/or HOR2The removal of the product increases and therefore, the present invention preferably employs a heating medium to provide thermal energy, and the "temperature" of the transesterification reaction refers to the "temperature of the heating medium of the reactor", for example, when the temperature of the heating medium is 100 ℃, it can be understood that the temperature of the transesterification reaction is 100 ℃.
In the present invention, the heat source required for controlling the reaction temperature of the reaction is not particularly limited, and may be any of various methods known to those skilled in the art, for example, in the present invention, the heating medium of the reactor may be a water bath or an oil bath, and the heat source may be obtained by steam or electric heating, respectively.
In the present invention, the mode of the transesterification reaction is not particularly limited, and for example, the transesterification reaction may be a continuous reaction or a batch reaction.
According to a preferred embodiment of the present invention, the preparation method comprises: the phenol compound represented by the formula (II) is first mixed with the catalyst, the resulting mixture is heated to a temperature required for the transesterification reaction, and then the carbonic acid diester compound represented by the formula (III) is mixed with the mixture.
According to another preferred embodiment of the present invention, the preparation method comprises: mixing the catalyst, the phenol compound represented by the formula (II) and the carbonic acid diester compound represented by the formula (III), heating the obtained mixture to the temperature required for the transesterification reaction, reacting for 3.5-5 hours, and then adding an entrainer into the reaction solution.
In the present invention, in order to improve the conversion rate of the reactant and the selectivity of the product, it is preferable that the entrainer is added to the reaction solution in 3 to 7 times, and the time interval between two consecutive additions is 1.5 to 2 hours.
In the present invention, the entrainer may be an entrainer which can be used conventionally in the transesterification reaction, and preferably, the entrainer is a carbonic acid diester compound represented by the formula (III).
In the present invention, it is preferred that the amount of the azeotropic agent to be added is 33 to 200mL per one mole of the phenol compound represented by the formula (II).
The catalyst in the invention is recyclable and reusable, therefore, preferably, the preparation method further comprises: and after the ester exchange reaction is finished, recovering the catalyst in the reaction product.
In the present invention, if a diphenyl carbonate compound represented by the formula (I) having a high purity is to be obtained, after the reaction is terminated, the reaction solution is subjected to post-treatment such as simple distillation or rectification to separate the diphenyl carbonate compound represented by the formula (I) from the mixture obtained after the reaction.
For example, when R is hydrogen, diphenyl carbonate (abbreviated as DPC) is contained in the diphenyl carbonate compound represented by the formula (I). A method for separating diphenyl carbonate (DPC) from a mixture obtained after a reaction, comprising: the catalyst, unreacted phenol, dimethyl carbonate, by-product anisole and a small amount of intermediate methyl phenyl carbonate in the mixture obtained from the reaction are removed from the mixture obtained from the reaction. In the present invention, it is preferable to remove volatile compounds such as methanol and anisole formed by the reaction and unreacted phenol from the reaction mixture by simple distillation or rectification, remove a small amount of the catalyst from the product by washing with water, filtration, or extraction, and finally remove a small amount of the intermediate product from the product by recrystallization to purify the diphenyl carbonate represented by the formula (I). The extraction and recrystallization methods may be conventional in the art and will not be described further herein.
The present invention will be described in detail below by way of examples.
Preparation examples 1 to 7
Illustrating the catalyst provided by the present invention and the preparation method thereof by solution polymerization
A solution A was prepared by selecting the silicon compound and the solvent in Table 1, and a solution B was prepared by selecting the titanium compound and the solvent in Table 1. And dropwise adding the solution B into the solution A at 30 ℃, and reacting for 3 hours under the condition of stirring.
And carrying out reduced pressure distillation under the pressure of 12KPa and the water bath temperature of 55 ℃, removing the solvent added into the reaction product, the generated alcohol substances and unreacted products, and obtaining solid transparent products, namely the catalysts TS-1 to TS-7.
A small amount of the catalyst prepared in preparation example 2 was taken and characterized by an infrared analysis method, wherein the results are shown in FIG. 1, from which it can be seen that the compound having the structure shown in formula (1-2) was successfully obtained in the present application.
Infrared spectroscopic characterization of the catalysts prepared in preparation examples 1 and 3 to 7 was carried out in the same manner, and it was revealed that the compounds represented by the formula (1-1) or (1-2) were successfully obtained in each preparation example. Of these, preparation 1, preparation 3 and preparation 6 gave compounds having a structure represented by formula (1-1), and preparation 4, preparation 5 and preparation 7 gave compounds having a structure represented by formula (1-2).
TABLE 1
Preparation examples 8 to 9
To illustrate the catalyst provided by the present invention and the preparation method thereof by bulk polymerization
The silicon compound was melted according to the selection of the silicon compound in Table 2 to obtain a silicon compound in a molten state, and then the titanium compound was melted according to the selection of the titanium compound in Table 2 to obtain a titanium compound in a molten state. Keeping the molten state, dripping the molten titanium compound into the molten silicon compound, and reacting for 3 hours under the condition of stirring.
After cooling to about 55 ℃, carrying out reduced pressure distillation under the pressure of 12KPa and the water bath temperature of 55 ℃, removing the solvent added in the reaction product, the generated alcohol substances and the unreacted product to obtain solid transparent products, and obtaining the catalysts TS-8 and TS-9 of the invention.
A small amount of the catalyst prepared in preparation examples 8-9 was taken and characterized by an infrared analysis method, and the results showed that compounds having a structure represented by formula (1-2) were obtained.
TABLE 2
| Preparation example | Titanium compound | Silicon compounds | Molar ratio of titanium to silicon |
| 8 | Tetra-n-butyl titanate | Diphenyl silanediol | 1：4 |
| 9 | Tetra-isopropyl titanate | Diphenyl silanediol | 1：4 |
Test example 1
The transesterification of dimethyl carbonate and phenol to diphenyl carbonate was carried out using the titanium silicon metal organic compound catalysts prepared in preparation examples 1 to 9, respectively, as a control catalyst DTS-1 (tetra-n-butyl titanate and triphenyl silanol mixed at a molar ratio of 1: 4), and as a control catalyst DTS-2 (tetra-n-butyl titanate), respectively, as follows:
into a 100mL three-necked round bottom flask equipped with a dropping funnel, a dispenser and a condenser were charged 74.90mmol of phenol and 0.749mmol of catalyst (in terms of Ti mol) under a nitrogen blanket. The oil bath contacting the flask was heated to 178 ℃ and the mixture of phenol and catalyst was stirred magnetically. 22.47mmol of dimethyl carbonate were added dropwise to the flask containing the above mixture for a reaction time of 9 hours, and the resulting methanol and its azeotrope were distilled off to a knockout and removed by a simple distillation method at the same time as the reaction. After the reaction, the catalyst was recovered. The azeotrope and the reaction solution of the main products methyl phenyl carbonate and diphenyl carbonate were analyzed by Agilent6890 gas chromatography, and the catalytic properties thereof are shown in Table 3.
Wherein, the simple distillation device is a 'knockout' with a condensing tube at the upper end, and the 'knockout' refers to a dean-Stark device with a piston switch at the bottom;
the analysis of the reactants and products was determined by gas chromatograph Agilent 6890; carrying out quantitative analysis on the reaction solution by using an external standard method;
the conversion rate of the reactant phenol compound and the selectivity of the product are calculated according to the following methods:
conversion of phenol (Z)Phenol and its preparation)：
Selectivity (S) to diphenyl carbonate productDPC)：
Selectivity (S) of product alkylphenyl carbonateMPC)：
In the above formula, the first and second carbon atoms are,
Mphenol and its preparation、MDPC、MMPC、MPhenylmethyl etherRespectively represent the molecular weights of phenol, diphenyl carbonate, methyl phenyl carbonate and anisole;
Cphenol and its preparation: represents the chromatographic mass concentration (g/L) of the unreacted phenol in the liquid phase product;
CDPC: represents the chromatographic mass concentration (g/L) of the product diphenyl carbonate in the liquid phase product;
CMPC: represents the chromatographic mass concentration (g/L) of the product methylphenyl carbonate in the liquid product;
Cphenylmethyl ether: represents the mass concentration (g/L) of the by-product anisole in the liquid phase product by chromatography.
TABLE 3
As can be seen from Table 3, the titanium silicon organometallic compound catalyst provided by the invention has higher catalytic activity for the reaction of preparing diphenyl carbonate by a transesterification method, the conversion rate of phenol can reach more than 60% at most under the condition of liquid phase reaction, and the total selectivity can reach 99.9% at most. Compared with tetrabutyl titanate, the catalyst can obviously improve the conversion rate of phenol under the condition of the same catalyst usage amount, thereby obtaining that the catalyst can reduce the usage amount of the catalyst under the condition of the same phenol conversion rate.
Test example 2
The titanium silicon metal organic compound catalysts prepared in the above preparation examples 1 to 9 were left in the air for 6 months, and then the catalytic performance was tested in the same manner as in test example 1, and the results showed that the catalytic performance was not substantially changed, indicating that the catalysts prepared in the present invention had good stability in the air.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A preparation method of diphenyl carbonate compounds shown as a formula (I) is characterized by comprising the following steps: in the presence of a catalyst, carrying out an ester exchange reaction between a phenol compound shown as a formula (II) and a carbonic diester compound shown as a formula (III);
wherein the catalyst has a structural formula shown in a formula (1-1) or a formula (1-2);
(H-[O-Si-(R1)2]n-O)x1-Ti-(OR3)y1X(4-x1-y1)formula (1-1)
[Si(R2)xO]x2-Ti-(OR3)y2X(4-x2-y2)Formula (1-2)
Wherein each R is1、R2And R3Each independently selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4); x is halogen;
in the formula (1-1), each R1And each R3Equal to or different from each other, n is an integer greater than 0, x1 is an integer from 0 to 3, y1 is an integer from 1 to 2, and the sum of x1 and y1 is less than or equal to 4;
in the formula (1-2), each R2And each R3The same or different from each other, x is 2 or 3, x2 is an integer of 1 to 4, y2 is an integer of 0 to 3, and the sum of x2 and y2 is 4 or less;
wherein R is hydrogen or C1-C4R' and R "are each independently methyl or ethyl.
2. The method of claim 1, wherein each R1、R2And R3Each independently selected from linear or branched, saturated or unsaturated C1-C8Aliphatic hydrocarbon group of (2)3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
3. The method of claim 1 or 2, wherein each R is1、R2And R3Each independently selected from linear or branched saturated or unsaturated C1-C4Alkyl of (C)3-C6Cycloalkyl of, C6-C8Aryl of (C)7-C9Alkylaryl and C of7-C9An aralkyl group of (2).
4. The method according to any one of claims 1 to 3, wherein the preparation method of the catalyst comprises: contacting a silicon compound and a titanium compound to carry out polymerization reaction to obtain a catalyst for preparing diphenyl carbonate compounds shown in a formula (1-1) or a formula (1-2);
wherein the silicon compound has a structure represented by formula (2-1), or a structure represented by formula (2-2), wherein the structure represented by formula (2-2) is a polymer having a structure represented by formula (2-1),
OH-[Si(R1)2-O]n-H formula (2-1)
Si(R2)x(OH)4-xFormula (2-2)
Each R1And R2Each independently selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4);
x is an integer from 2 to 3, n is an integer greater than 0, and each R1And R2Are the same or different from each other;
wherein the titanium compound has a structure represented by formula (3),
Ti(OR3)yX4-yformula (3)
Each R3Selected from linear or branched, saturated or unsaturated C1-C14Aliphatic hydrocarbon group of (2)3-C14Cycloalkyl of, C6-C14Aryl of (C)7-C14Alkylaryl of, C7-C14Aralkyl or C10-C14A condensed ring aryl group of (4); x is halogen;
y is an integer of 0 to 4, each R3The same or different from each other.
5. The method of claim 4, wherein the polymer is a polymer having a degree of polymerization of 2 to 900.
6. The method according to claim 4 or 5, wherein the silicon compound is selected from at least one of dimethylsilanediol, trimethylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanediol, dipropylsilicediol, diphenylsilanediol, triphenylsilanol, and hydroxyl-terminated polydimethylsiloxane.
7. The method according to claim 4 or 5, wherein the titanium compound is selected from at least one of tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetracyclohexyloxy titanium, tetraphenyl titanate, titanium tetrachloride, trichloromethoxy titanium, trichloroethoxy titanium, trichloropropoxy titanium, and trichloron-butyl titanium.
8. The process according to any one of claims 4 to 7, wherein the polymerization is a solution polymerization carried out in the presence of an organic solvent, the conditions of the polymerization comprising: the reaction temperature is 20-40 ℃, the reaction time is 3-5h, and the molar ratio of the titanium element to the silicon element is 0.01-0.5: 1;
preferably, the organic solvent is selected from at least one of benzene, toluene, xylene, cyclohexane and n-hexane.
9. The process according to any one of claims 4 to 7, wherein the polymerization reaction is a bulk polymerization, the conditions of the bulk polymerization comprising: and contacting the silicon compound and the titanium compound for 3-5h in a molten state, wherein the molar ratio of titanium element to silicon element is 0.01-0.5: 1.
10. The method of any of claims 4-9, wherein the method further comprises: the obtained catalyst was subjected to distillation under reduced pressure to purify the catalyst.
11. The process according to claim 1, wherein R is hydrogen or methyl, further preferably hydrogen; r 'and R' are methyl.
12. The process according to any one of claims 1 to 11, wherein the catalyst is used in an amount of 0.5 to 1.5mol in terms of titanium element relative to 100mol of the phenol compound represented by the formula (ii);
preferably, the molar ratio of the amount of the carbonic acid diester compound represented by the formula (III) to the amount of the phenol compound represented by the formula (II) is 0.1 to 5: 1.
13. the method of claim 1, wherein the conditions of the transesterification reaction comprise: the temperature is 63-200 ℃, and the reaction time is 9-11 h;
preferably, the distillation or rectification is carried out simultaneously with the transesterification reaction.
14. The method according to claim 1 or 13, wherein the method comprises: firstly, mixing a phenol compound shown as a formula (II) with the catalyst, heating the obtained mixture to the temperature required by the ester exchange reaction, and then mixing a carbonic diester compound shown as a formula (III) with the mixture; or,
the method comprises the following steps: mixing the catalyst, the phenol compound shown in the formula (II) and the carbonic diester compound shown in the formula (III), heating the obtained mixture to the temperature required by the ester exchange reaction, reacting for 3.5-5 hours, and adding an entrainer into the reaction liquid;
preferably, the entrainer is added into the reaction liquid for 3 to 7 times, and the time interval between two adjacent times of addition is 1.5 to 2 hours;
preferably, the entrainer is a carbonic acid diester compound represented by formula (III);
preferably, the amount of the azeotropic agent added per one mole of the phenol compound represented by the formula (II) is 33 to 200 mL.
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