CN1230252C - Catalyst for synthesizing methyl phenyl varbonate by using ester exchange process - Google Patents
Catalyst for synthesizing methyl phenyl varbonate by using ester exchange process Download PDFInfo
- Publication number
- CN1230252C CN1230252C CN 01128938 CN01128938A CN1230252C CN 1230252 C CN1230252 C CN 1230252C CN 01128938 CN01128938 CN 01128938 CN 01128938 A CN01128938 A CN 01128938A CN 1230252 C CN1230252 C CN 1230252C
- Authority
- CN
- China
- Prior art keywords
- organic
- phenol
- methyl phenyl
- catalyst
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 6
- 125000003944 tolyl group Chemical group 0.000 title claims description 3
- 125000004185 ester group Chemical group 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 150000002148 esters Chemical group 0.000 claims abstract description 3
- -1 tetramethyl ester Chemical class 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 11
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract 2
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 abstract 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NHZZUJIRMHDTKR-UHFFFAOYSA-N carbonic acid;toluene Chemical compound OC(O)=O.CC1=CC=CC=C1 NHZZUJIRMHDTKR-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a compound catalyst for synthesizing methyl phenyl carbonate by ester exchange reactions of dimethyl carbonate and phenol, which is compounded by organic tin, organic titanium and organic amine according to a certain molar ratio. The present invention is characterized in that the molar ratio of the organic tin, the organic titanium and the organic amine is 1: (0.2 to 2): (0.001 to 0.5), and proper reaction conditions comprise normal pressure, 150 to 200 DEG C of temperature and 6 to 30 hours of time. The molar ratio of the dimethyl carbonate and the phynol is 1: (0.025 to 2), the molar ratio of the phynol and the catalyst is 0.001 to 0.05, the conversion rate of the phynol is from 15% to 50%, and the selectivity of the methyl phenyl carbonate is more than 90%.
Description
Technical field
The present invention is about a kind of composite catalyst of methylcarbonate and phenol ester permutoid reaction synthesis of methyl phenyl carbonic ether, and this composite catalyst is to be formed by certain mol proportion is composite by organotin, organic titanium and organic amine compound.
Background technology
The methyl phenyl carbonate ester is mainly used in and dihydroxyphenyl propane transesterify polycarbonate synthesis (JP070766207), also can be used for lithium-ion battery electrolytes and gasoline antiknock.Methyl benzol carbonate also can further generate diphenyl carbonate and methylcarbonate with phenol ester exchange synthesizing diphenyl carbonate or self disproportionation.Methylcarbonate and phenol ester permutoid reaction are a kind of cleaner Production in Chemical Industry technology.This technology is compared with traditional chloromethyl ester methyl esters method (JP08283205), has advantages such as quality product height, three-waste free pollution, production cost be low.(gas chemical industries such as Sun Bi Xiu; 1992,17 (4) 21～24) with the transesterification reaction of organotin, organic titanium and the mixture of the two methylcarbonate that has been catalyst research and phenol, its main purpose is a diphenyl carbonate synthesis.Japanese Patent JP09169704 and JP09110805 are catalyzer with metatitanic acid four phenyl esters and Dibutyltin oxide respectively, and what obtain is the mixture of methyl benzol carbonate and diphenyl carbonate, and the separation of this mixture is difficulty very.
Summary of the invention
The objective of the invention is synthesis of methyl phenyl carbonic ether with a kind of composite catalyst highly selective.This catalyzer is that organotin, organic titanium and organic amine compound are composited, and be characterized in that their mol ratios in catalyzer are organotin: organic titanium: organic amine is 1: 0.2～2: 0.001～0.5; Used organo-tin compound is Dibutyltin oxide, tetrabutyl tin, dibutyl tin dilaurate etc.; Organic titanic compound is metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate, tetrabutyl titanate, metatitanic acid four phenyl esters etc.; Organic amine compound is trolamine, N, N-two ylmethyl aniline, Tributylamine, trioctylamine, dipyridyl, phenanthroline etc.
The composite catalyst that the present invention uses is used for methylcarbonate and phenol ester permutoid reaction synthesis of methyl phenyl carbonic ether, and the processing condition that are fit under normal pressure are: temperature of reaction is 150～200 ℃; Methylcarbonate and phenol mol ratio are 1: 0.025～2; Phenol and catalyst molar ratio are 1: 0.001～0.05; Reaction times is 6～30 hours.In time steam the methyl alcohol of generation and the azeotrope of methylcarbonate in reaction process.The reaction product gc analysis.
Embodiment
Embodiment 1
In the 100ml round-bottomed flask of agitator, feed hopper and fractional column is housed, add methylcarbonate 0.5mol, phenol 0.25mol, composite catalyst 0.005mol is heated to 175 ℃, reacts 10 hours.The mol ratio of used composite catalyst is (C
4H
9)
2SnO: Ti (OC
4H
9)
4: trolamine is 1: 1: 0.01.Through gas chromatographic analysis, phenol conversion is 45%, and generating product methyl benzol carbonate selectivity is 99%.
Embodiment 2
Used composite catalyst mol ratio is (C
4H
9)
2SnO: Ti (OC
3H
7)
4: trolamine is 1: 1: 0.02, and all the other conditions are with embodiment 1.Through gas chromatographic analysis, phenol conversion 35%, MPC selectivity 98%.
Embodiment 3
Used composite catalyst mol ratio is (C
4H
9)
2SnO: Ti (OCH
3)
4: trolamine is 1: 0.8: 0.03, and all the other conditions are with embodiment 1.Phenol conversion 20%, MPC selectivity 95%.
Embodiment 4
Used composite catalyst mol ratio is: (C
4H
9)
4Sn: Ti (OC
4H
9)
4: trioctylamine is 1: 1: 0.01, and all the other conditions are with embodiment 1, phenol conversion 15%, MPC selectivity 90%.
Claims (2)
1, a kind of catalyzer of synthesizing methyl phenyl varbonate by using ester exchange process, it is characterized in that using a kind of composite catalyst in methylcarbonate and phenol ester exchange procedure, this catalyzer is to be composited by certain molar ratio by organotin, organic titanium and organic amine; Used organo-tin compound is Dibutyltin oxide, tetrabutyl tin or dibutyl tin dilaurate; Organic titanic compound is metatitanic acid tetramethyl ester, tetraethyl titanate, titanium isopropylate, tetrabutyl titanate or metatitanic acid four phenyl esters; Organic amine compound is trolamine, N.N-xylidine, Tributylamine, trioctylamine, dipyridyl or phenanthroline, and the mol ratio of organotin, organic titanium and organic amine is an organotin: organic titanium: organic amine is 1: 0.2～2: 0.001～0.5.
2, a kind of method of synthesis of methyl phenyl carbonic ether is characterized in that: with methylcarbonate and phenol is raw material, is that catalyzer carries out transesterification reaction with the catalyzer of claim 1; Wherein the mol ratio of methylcarbonate and phenol is 1: 0.025～2; Phenol and catalyst molar ratio are 1: 0.001～0.05; Temperature of reaction is 150～200 ℃, and the reaction times is 6～30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01128938 CN1230252C (en) | 2001-10-09 | 2001-10-09 | Catalyst for synthesizing methyl phenyl varbonate by using ester exchange process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01128938 CN1230252C (en) | 2001-10-09 | 2001-10-09 | Catalyst for synthesizing methyl phenyl varbonate by using ester exchange process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1411909A CN1411909A (en) | 2003-04-23 |
| CN1230252C true CN1230252C (en) | 2005-12-07 |
Family
ID=4668747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01128938 Expired - Lifetime CN1230252C (en) | 2001-10-09 | 2001-10-09 | Catalyst for synthesizing methyl phenyl varbonate by using ester exchange process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1230252C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423476B (en) * | 2004-12-30 | 2013-03-20 | 中国科学院成都有机化学有限公司 | Method for synthesizing diphenyl carbonate by transesterification |
| CN110339858B (en) * | 2019-07-17 | 2020-10-16 | 河南科技学院 | Bi for synthesizing methyl phenyl carbonate2O3-PbO-SBA-15 catalyst, preparation method and application |
-
2001
- 2001-10-09 CN CN 01128938 patent/CN1230252C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1411909A (en) | 2003-04-23 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHENGDU ORGANIC CHEMICALS CO., LTD., CHINESE ACADE Free format text: FORMER OWNER: CHENGDU ORGANIC CHEMISTY INST., CHINESE ACADEMY OF SCIENCES Effective date: 20150113 Owner name: AOKE CHEMICAL YANGZHOU CO., LTD. Effective date: 20150113 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150113 Address after: 610041 Chengdu South Road, Sichuan, No. four, No. nine Patentee after: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Patentee after: Oxiranchem (Yangzhou) Co., Ltd. Address before: 610041 Chengdu South Road, Sichuan, No. four, No. nine Patentee before: Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences |
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| CP01 | Change in the name or title of a patent holder |
Address after: 610041 Chengdu South Road, Sichuan, No. four, No. nine Co-patentee after: Jiangsu oxiranchem Co., Ltd. Patentee after: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Address before: 610041 Chengdu South Road, Sichuan, No. four, No. nine Co-patentee before: Oxiranchem (Yangzhou) Co., Ltd. Patentee before: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences |
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| CP01 | Change in the name or title of a patent holder | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051207 |
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| CX01 | Expiry of patent term |