CN1736600A - Dialkyl containing stannum compound catalyst for synthesizing aryl carbonate by ester exchange - Google Patents
Dialkyl containing stannum compound catalyst for synthesizing aryl carbonate by ester exchange Download PDFInfo
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- CN1736600A CN1736600A CN 200510021339 CN200510021339A CN1736600A CN 1736600 A CN1736600 A CN 1736600A CN 200510021339 CN200510021339 CN 200510021339 CN 200510021339 A CN200510021339 A CN 200510021339A CN 1736600 A CN1736600 A CN 1736600A
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- carbonate
- oac
- catalyst
- dialkyl
- hydroxy compound
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a tin dialkyl contained composite catalyst used for synthesizing single- aryl carbonic ester and dual- aryl carbonic ester with dual- alkyl carbonic ester and single- aryl hydroxy compound by ester exchange. The tin dialkyl contained composite catalyst comprises the compounds having following structures and at least one of metallic compounds: with the catalyst, in a condition of: the molar ratio of dual- alkyl carbonic ester to single- aryl hydroxy compound being among 1: 0.25- 4, the molar ratio of single- aryl hydroxy compound to catalyst among 1: 0.0005- 0.1, the ester exchange temperature 120- 220Deg. C, and the reaction pressure of ester exchange 0.1- 0.5MPa, the yield- high and selectivity- high production can be prepared.
Description
Technical field
The present invention relates to a kind of be used for dialkyl carbonate (as dimethyl carbonate) and single aromatic hydroxy compound (as phenol) ester exchange carbonate synthesis list aryl ester (as methyl benzol carbonate), diaryl carbonate (as diphenyl carbonate) contain the dialkyl tin composite catalyst.
Background technology
Diaryl carbonate (particularly diphenyl carbonate) is a kind of important organic intermediate, not only is used for synthetic medicine, agricultural chemicals and other products, and is the important intermediate of preparation Merlon, has very high industrial value.The synthetic method of diaryl carbonate mainly contains three kinds of methods such as phosgenation, ester-interchange method and single aromatic hydroxy compound oxidative carbonylation method.Problem just progressively is eliminated phosgenation because raw material severe toxicity, environmental pollution be serious etc.; Single aromatic hydroxy compound oxidative carbonylation method combined coefficient is not high, and the catalyst costliness.Ester-interchange method adopts a kind of single aromatic hydroxy compound (for example phenol, methylphenol, xylenol etc.) and a kind of dialkyl carbonate (as dimethyl carbonate, diethyl carbonate) to carry out ester exchange reaction and generates diaryl carbonate.This method is a kind of eco-friendly method, and it has avoided employed harmful substance in the traditional handicraft, as phosgene, METHYLENE CHLORIDE etc.
JP 8188558, and EP 0780361, and JP 10032361 has introduced a class titanium, tin organic compound catalyst.As butyl titanate [Ti (OC
4H
9)
4], Dibutyltin oxide [n-Bu
2SnO], metatitanic acid four phenyl esters [Ti (OPh)
4] etc.Such catalyst performance height, target product productive rate can reach more than 50%, but catalyst and product separate difficulty of recovery.
Chinese patent CN 1411909 discloses a kind of composite catalyst that is used for ester exchange synthesis of methyl phenyl carbonic ester and preparation method thereof.This catalyst is to be formed by certain mol proportion is composite by organotin, organic titanium and organic amine.The mol ratio that is characterized in three kinds of components is: 1: 0.2～2: 0.001～0.5.Reaction temperature is 150～200 ℃, and reaction pressure is a normal pressure, and the time is 6～30 hours.Phenol conversion is 15～50%, methyl benzol carbonate selectivity＞90%.This kind catalyst combines the advantage of organotin and organic titanium catalyst, adds organic amine on this basis, makes catalyst activity, selectivity higher.
Chinese patent CN1036951 has introduced a class organo-tin compound and a metal compound as catalyst.The organo-tin compound catalyst is SnO and/or XR
2SnOSnR
2(X and Y can be identical, also can be different for Y.They represent OH, SCN etc. separately); Metallic compound is the compound that is selected from any element in Sc, Cr, Mo, W, Mn, Au, Ga, In, Bi, Te and the blue lanthanide series.But these activity of such catalysts are low, and the total recovery of methyl benzol carbonate and diphenyl carbonate is lower than 20%.
US4554110 has reported a kind of tin compound of polymerization, and its molecular formula is as follows:
Wherein R, R1 represent alkyl.When such catalyst is used for ester exchange reaction, only under long reaction time (〉=24 hours) condition, could obtain high diphenyl carbonate yield.
US4552704 has reported RSn (O) OH catalyzed carbon acid dialkyl ester and aromatic hydroxy compound synthesizing aryl alkyl carbonate and diaryl carbonate, but only has single RSn (O) OH to make catalyst.
Summary of the invention
The dialkyl tin composite catalyst that contains of the present invention is made of at least a in the compound metallizing thing with following array structure.
R wherein
1C for replacement or non-replacement
1～C
12Alkyl, alkoxyl, the replacement or the aromatic radical of non-replacement, fragrant oxygen base.Substituent R
1Specifically can be: any one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, cyclopenta, cyclohexyl, phenyl, benzyl, the methoxyl group.
Metallic compound is main group, the oxide of subgroup metal, halide, acetate, carbonate, sulfate; Specifically can be: the oxide of lanthanide series metal, halide, acetate, carbonate, sulfate, CuX (X=F, Cl, Br, I), Cu
2O, CuSO
4, CuBr
2, CuCl
2, Cu (OAc)
2, CuCO
3, CuO, ZnO, ZnCl
2, Zn (OAc)
2, ZnCO
3, ZnSO
4, TiO
2, TiOCl
2, TiOSO
4, V
2O
5, VOCl
2, VOSO
4, Cr
2O
3, CrCl
3, Cr (OAc)
3, Cr
2(SO
4)
3, MnO, MnO
2, MnCl
2, MnSO
4, FeO, Fe
2O
3, FeCl
2, FeCl
3, FeSO
4, Fe
2(SO
4)
3, CoO, CoCl
2, Co (OAc)
2, CoSO
4, NiO, Ni (OAc)
2, NiSO
4, ZrO
2, ZrOCl
2, ZrOSO
4, Nb
2O
5, MoO
3, WO
3, Al
2O
3, AlCl
3, Al
2(SO
4)
3, Al (OAc)
3, MgO, PbO, Pb
3O
4, Pb (OAc)
2, PbCO
3, PbSO
4, PbCl
2, SnO
2, SnCl
2, SnCl
4In any one.
Catalyst of the present invention, its ester exchange reaction formula that is suitable for is as follows:
The general equation formula is:
(1), the R in (2), (3) formula and the general equation formula
2Represent in the following group any one or multiple: H, CH
3, CH
3CH
2, NO
2, F, Cl, Br, CN, R
3OR
3, R
4Represent C
1～10Alkyl, specifically can be: any one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, the decyl.
The process conditions that catalyst system therefor of the present invention is fit to are: the mol ratio of dialkyl carbonate and single aromatic hydroxy compound is 1: 0.25～4, and the mol ratio of single aromatic hydroxy compound and catalyst is 1: 0.0005～0.1.120～220 ℃ of transesterification reaction temperature, ester exchange reaction pressure 0.1～0.5MPa.In the course of reaction, the low-carbon alcohols of by-product and dialkyl carbonate form azeotropic mixture, in time separate with rectifying column.The product gc analysis.
The specific embodiment
About method of the present invention, be illustrated with following example, but the present invention never is subjected to the restriction of these examples.
[embodiment 1] adds 0.3mol phenol, the Dibutyltin oxide of 0.00542mol and the cuprous bromide of 0.00542mol in the 100ml reactor of being furnished with agitator, rectifying column, condenser, charge pump under nitrogen protection.After reacting liquid temperature rises to 180 ℃, begin to add dimethyl carbonate.0.15mol dimethyl carbonate in 3h, add, continue reaction 5h then.The azeotropic mixture that timely separating by-products methyl alcohol of course of reaction and dimethyl carbonate form.The conversion ratio of dimethyl carbonate is 50.8%, and the productive rate of methyl benzol carbonate (MPC) is 32.3%, and the productive rate of diphenyl carbonate (DPC) is 18.5%.
[embodiment 2] add 0.3mol phenol, the Dibutyltin oxide of 0.00542mol and the stannous chloride of 0.00542mol in the 100ml reactor of being furnished with agitator, rectifying column, condenser, charge pump under nitrogen protection.After reacting liquid temperature rises to 180 ℃, begin to add diethyl carbonate.0.15mol diethyl carbonate adds in 3h, continues reaction 5h then.The azeotropic mixture that timely separating by-products ethanol of course of reaction and diethyl carbonate form.The conversion ratio of diethyl carbonate is 55.2%, and the productive rate of ethylphenyl carbonic ester is 39.7%, and the productive rate of diphenyl carbonate is 14.5%, and the yield of phenetole is 1.0%.
The composite catalyst that is made of equimolar Dibutyltin oxide and cupric oxide of [embodiment 3] p-nitrophenol 1mol, dimethyl carbonate 3mol, 0.01mol joins in the reactor.205 ℃～220 ℃ of reaction temperatures, reaction gauge pressure 2.5kgf/cm
2, reaction time 8h.The conversion ratio of p-nitrophenol is 44.6%, and the productive rate of p-nitrophenyl methyl carbonic is 34.3%, and the productive rate of NSC 1730 is 10.3%.
Claims (7)
- An ester-interchange method carbonate synthesis list aryl ester (as methyl benzol carbonate), diaryl carbonate (as diphenyl carbonate) contain the dialkyl tin composite catalyst, be characterized in dialkyl carbonate (as dimethyl carbonate) and single aromatic hydroxy compound (as phenol) course of reaction, using.
- 2. according to claim 1, contain the dialkyl tin composite catalyst by at least a composition the in the compound metallizing thing with following array structure.
- 3. according to claim 1 and 2, it is characterized in that described substituent R 1Specifically can be: any one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, cyclopenta, cyclohexyl, phenyl, the benzyl.
- 4. according to claim 1 and 2, it is characterized in that described metallic compound is any one in the oxide, halide, acetate, carbonate, sulfate of main group, subgroup metal; Specifically can be: the oxide of lanthanide series metal, halide, acetate, carbonate, sulfate, CuX (X=F, Cl, Br, I), Cu 2O, CuSO 4, CuBr 2, CuCl 2, Cu (OAc) 2, CuCO 3, CuO, ZnO, ZnCl 2, Zn (OAc) 2, ZnCO 3, ZnSO 4, TiO 2, TiOCl 2, TiOSO 4, V 2O 5, VOCl 2, VOSO 4, Cr 2O 3, CrCl 3, Cr (OAc) 3, Cr 2(SO 4) 3, MnO, MnO 2, MnCl 2, MnSO 4, FeO, Fe 2O 3, FeCl 2, FeCl 3, FeSO 4, Fe 2(SO 4) 3, CoO, CoCl 2, Co (OAc) 2, CoSO 4, NiO, Ni (OAc) 2, NiSO 4, ZrO 2, ZrOCl 2, ZrOSO 4, Nb 2O 5, MoO 3, WO 3, Al 2O 3, AlCl 3, Al 2(SO 4) 3, Al (OAc) 3, MgO, PbO, Pb 3O 4, Pb (OAc) 2, PbCO 3, PbSO 4, PbCl 2, SnO 2, SnCl 2, SnCl 4In any one.
- 5. according to claim 1, it is characterized in that described single aromatic hydroxy compound has following structure:Substituent R 2Specifically can be: H, CH 3, CH 3CH 2, NO 2, F, Cl, Br, CN, R 3Among the O any one; R wherein 3Specifically can be: any one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, the decyl.
- 6. according to claim 1, it is characterized in that described dialkyl carbonate has following structure:
Substituent R 4Be C 1～10Alkyl, specifically can be: any one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, the decyl. - 7. according to claim 1,2 and 3, the service condition that it is characterized in that catalyst is: the mol ratio of dialkyl carbonate and single aromatic hydroxy compound is 1: 0.25～4, the mol ratio of single aromatic hydroxy compound and catalyst is 1: 0.0005～0.1,120～220 ℃ of transesterification reaction temperature, ester exchange reaction pressure 0.1～0.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510021339 CN1736600A (en) | 2005-07-28 | 2005-07-28 | Dialkyl containing stannum compound catalyst for synthesizing aryl carbonate by ester exchange |
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|---|---|---|---|
| CN 200510021339 CN1736600A (en) | 2005-07-28 | 2005-07-28 | Dialkyl containing stannum compound catalyst for synthesizing aryl carbonate by ester exchange |
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| CN1736600A true CN1736600A (en) | 2006-02-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464852C (en) * | 2006-04-30 | 2009-03-04 | 中国科学院成都有机化学有限公司 | Organic stannum sulfonate catalyst for exchange reaction of methyl carbonate and phenol ester |
| CN103664626A (en) * | 2012-09-14 | 2014-03-26 | 中国科学院兰州化学物理研究所 | Method for synthesizing diphenyl carbonate through ester exchange |
-
2005
- 2005-07-28 CN CN 200510021339 patent/CN1736600A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464852C (en) * | 2006-04-30 | 2009-03-04 | 中国科学院成都有机化学有限公司 | Organic stannum sulfonate catalyst for exchange reaction of methyl carbonate and phenol ester |
| CN103664626A (en) * | 2012-09-14 | 2014-03-26 | 中国科学院兰州化学物理研究所 | Method for synthesizing diphenyl carbonate through ester exchange |
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