CN1178212A - Preparation of diarylethanes - Google Patents
Preparation of diarylethanes Download PDFInfo
- Publication number
- CN1178212A CN1178212A CN 96113056 CN96113056A CN1178212A CN 1178212 A CN1178212 A CN 1178212A CN 96113056 CN96113056 CN 96113056 CN 96113056 A CN96113056 A CN 96113056A CN 1178212 A CN1178212 A CN 1178212A
- Authority
- CN
- China
- Prior art keywords
- under
- carry out
- diarylethane
- reflected
- vinylbenzene
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000002638 heterogeneous catalyst Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000012937 correction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- LVHFFCVSWIOHPR-UHFFFAOYSA-N O(O)O.C(C)[N+](CC)(CC)CC Chemical compound O(O)O.C(C)[N+](CC)(CC)CC LVHFFCVSWIOHPR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- -1 isobutyl- Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The aromatic of general formula II and the styrene of general formula III are used to react to prepare diarylethanes. The reaction is carried out batchwise or continuously in the liquid or supercritial phase at from 150 to 350 centi-grade and from 5-200 bar in presence of an acidic heterogeneous catalyst.
Description
The present invention relates to a kind of method for preparing diarylethane by aromatic hydrocarbons and vinylbenzene in reaction in the presence of the heterogeneous acid catalyst, under higher temperature and super-atmospheric pressure.
Disclose in the following document to react and prepared diarylethane by aromatic hydrocarbons and vinylbenzene or styrene derivatives: JP 63-238028 (1988), use Y shape to boil; Polymer Journal
12No.6 (1880), 407, use Nafion, Amberlyst 15 or CF
3SO
3H; And EP-A-421 340, use the L zeolite.Disclosed synthetic method only when using alkylated aromatic hydrocarbons, just obtain the productive rate of energy usefulness, but these productive rates all can not be satisfactory.When the aromatic hydrocarbons that uses is benzene, mainly generate cinnamic oligopolymer.
An object of the present invention is to overcome above-mentioned these shortcomings.
We find, this purpose can realize by a kind of aromatic hydrocarbons and the vinylbenzene of general formula III new improved method of reacting the diarylethane for preparing general formula I by general formula I I.
In the formula, R
1, R
2, R
3, R
4, R
5And R
6Respectively be hydrogen or C
1～C
8Alkyl,
In the formula, R
2, R
3, R
4, R
5And R
6Above-mentioned implication is arranged,
In the formula, R
1Above-mentioned implication is arranged, wherein be reflected in liquid phase or the supercritical phase, under 150～350 ℃, 5～200bar, in the presence of heterogeneous acid catalyst, intermittently carry out or carry out continuously.
Novel method can be carried out as follows:
The reaction of aromatic hydrocarbons II and vinylbenzene III can be in pressure-resistant equipment (as autoclave), in liquid phase or supercritical phase, intermittently carry out under the following conditions, or preferably carry out continuously: at 150～350 ℃, preferred 180～230 ℃, under preferred especially 190～220 ℃, with 5～200bar, preferred 10～130bar, particularly preferably under the autogenous pressure or than under beginning supercharging 1～50bar, in the presence of heterogeneous acid catalyst.So pressure must be enough high, so that make system remain liquid phase under reaction conditions, also can remain in the supercritical phase if desired.
New method for example can be carried out in continuous-stirring reactor or in the fixed-bed reactor.
Under the situation of in being reflected at fixed-bed reactor, carrying out, heterogeneous acid catalyst at first is molded and shaped form usually in fixed-bed reactor, reaction mixture is under violent back-mixing, pass through for several times fixed bed, fresh feed solution is measured, send into continuously in the cycle stock, remove the generation solution of equivalent simultaneously continuously.
Usually, the heterogeneous acid catalyst that is fit to is the strongly-acid large pore zeolite, 12 yuan of ring β zeolites, HY zeolite or mordenites.Usually, catalyzer can powder type be suspended in the reaction system and uses, or uses in fixed-bed reactor as moulded product.
The β zeolite is for example open in US-A3308069.They can consist of TEA by containing by tetraethyl ammonium oxyhydroxide, under 100～150 ℃
2O: SiO
2: Al
2O
3: Na
2O: H
2The gel crystallization of O obtains, wherein SiO
2/ Al
2O
3Ratio can be 10: 1 to 200: 1, Na
2O/TEAOH ratio can be 0 to 1: 1, TEAOH/SiO
2Ratio can be 0.1: 1 to 1: 1, and H
2O/TEAOH ratio can be 20: 1 to 75: 1.They have diameter is 6.5 * 5.6 and the three-dimension hole system of 12 yuan of 7.5 * 5.7_ ring macropores.
Usually, reaction is preferably carried out under the condition of only allowing low concentration of styrene.This point can be by using styrene solution or vinylbenzene being realized by measuring slowly to be added in the reaction system.For intermittently preparation, particularly preferred method comprises, at first be placed on aromatic hydrocarbons and the catalyzer that is suspended in wherein in the stirring tank together, in reaction process, vinylbenzene (or styrene solution) is enough dripped lentamente then, so that under lower concentration, between the cinnamic reaction vinylbenzene that is metered into, set up mobile equilibrium.Cinnamic Css should be no more than 3%, and preferred 0.1%, preferred especially 0.05%.
Diphenylethlene I can be obtained by base product.
In Compound I, II and III, R
1, R
2, R
3, R
4, R
5And R
6Following implication is arranged, and R
1Can be at the ortho position, a position or contraposition :-oxygen or-C
1～C
8Alkyl, preferred C
1～C
4Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, special preferable methyl or ethyl.
Compound I, II and III, wherein R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen simultaneously, promptly 1,2-diphenylethane, benzene and vinylbenzene are particularly preferred.
Diphenylethane is the important intermediate of preparation diphenylethlene, and diphenylethlene is as the comonomer of preparation plastics.By the diphenylethane catalytic dehydrogenation, can obtain the high yield diphenylethlene.
Embodiment
There is the gas chromatograph of 30m capillary column (DBS, 0.1 μ m) to be used for the analysis of following experiment.(temperature programming: 60 ℃ following 5 minutes, 10 ℃/minute were warmed up to 300 ℃, and 300 ℃ following 15 minutes).Make interior mark with toluene and carry out timing analysis.
Three kinds of dipolymers that generate (identifying with the GC/MS method) count following table together.Its correction factor is identical with diphenylethlene.The correction factor of the correction factor of benzene (not marking) and vinylbenzene and diphenylethane is measured by a series of concentration of target in the toluene.
Catalyst A
With the 100g β zeolite powder (ZEOCAT that obtains by Uetikon
_BETA; SiO
2=91%, Al
2O
3=7.8%, Na
2O=0.5%, K
2O=0.7%) with the NH of 1l 20%
4Cl solution stirred 2 hours down at 80 ℃, decant, with 500ml water washing 3 times, 110 ℃ dry 16 hours down, 500 ℃ of following roastings 3 hours.
Embodiment 1
The 2g catalyst A is at first put into the withstand voltage Glass Containers of 50ml with 30g benzene, under agitation the mixture of 10% vinylbenzene and the 90% benzene speed with 10ml/h is metered into then.
Long withstand voltage Glass tubing (diameter 1cm) settling section of the 20cm that catalyzer can settle therein is installed in the top of withstand voltage Glass Containers.Remain on 15bar with surplus valve with pressing in the container.The temperature of withstand voltage glass autoclave is 200 ℃.Discharge product with gc analysis, the result is compiled in table 1.
Table 1
| Operating time (h) | Vinylbenzene (%) | 1, the 1-diphenylethane | Transformation efficiency (%) | Productive rate (%) |
| ???6 | ????0.2 | ????7.08 | ????98 | ????---- |
| ???22 | ????0.13 | ????12.7 | ????98.7 | ????72.6 |
| ???90 | ????0.06 | ????16.7 | ????99.4 | ????95.4 |
| ???150 | ????0.05 | ????13.5 | ????99.5 | ????76.9 |
| ???200 | ????0.03 | ????14.2 | ????99.7 | ????81.3 |
| ???310 | ????0.03 | ????16.9 | ????99.7 | ????96.6 |
Embodiment 2
Carry out the experiment of similar embodiment 1, other adds 0.1% tert-butyl catechol as stablizer.The result is compiled in table 2.
Table 2
| Operating time (h) | Vinylbenzene (%) | 1, the 1-diphenylethane | Transformation efficiency (%) | Productive rate (%) |
| ????5 | ????0.02 | ????3.45 | ????99.8 | ????---- |
| ????21 | ????＜0.02 | ????12.0 | ????100 | ????68.6 |
| ????101 | ????0.04 | ????17.3 | ????99.6 | ????98.8 |
| ????149 | ????0.2 | ????17.4 | ????98 | ????98.9 |
| ????197 | ????1.17 | ????14.8 | ????88 | ????84.4 |
Embodiment 3
10g catalyzer and 100g benzene are at first put into three-necked flask, similar embodiment 1.Under normal pressure, be heated to after 80 ℃, the mixture of 10% vinylbenzene and the 90% benzene speed with 10ml/h is metered into.Rapid inactivation appears under such condition.The result is compiled in table 3.
Table 3
| Operating time (h) | Vinylbenzene (%) | 1, the 1-diphenylethane | Transformation efficiency (%) | Productive rate (%) |
| ????6 | ????＜0.01 | ????2.86 | ????100 | ????---- |
| ????22 | ????＜0.01 | ????13.5 | ????100 | ????77.0 |
| ????26 | ????0.06 | ????17.3 | ????99.4 | ????98.8 |
| ????30 | ????0.28 | ????13.7 | ????97.2 | ????78.2 |
| ????38 | ????1.04 | ????9.5 | ????89.6 | ????54.3 |
| ????54 | ????4.14 | ????3.24 | ????58.6 | ????18.5 |
| ????90 | ????8.74 | ????0.34 | ????12.6 | ????1.9 |
Catalyst B
With the 220g β zeolite powder (ZEOCAT that obtains by Uetikon
_BETA, SiO
2=91%, Al
2O
3=7.8%, Na
2O=0.5%, K
2O=0.7%) and 5%Walocel
_In kneader, mixed 45 minutes with 230g water.Then material modelling under 70bar is obtained the 2mm extrusion, 110 ℃ dry down, then at 500 ℃ of following roasting 16h.
The extrusion 3l 20%NH that 195g is such
4Cl solution is used the 10l water washing then 80 ℃ of following ion-exchanges 2 hours.After this carry out the ion-exchange second time, use 3l 20%NH equally
4Cl solution was 80 ℃ of ion-exchanges 2 hours.Then product is washed to there not being chlorine, 100 ℃ of dryings, 500 ℃ of roastings 5 hours.
Embodiment 4
With 10g β zeolite extrusion (catalyst B), at first put into the catalyzer basket of 50ml steel autoclave.With the 30ml benzene autoclave of packing into, and under agitation be heated to 250 ℃, the mixture continuous measurement with 10% vinylbenzene and 90% benzene adds then.By surplus valve reaction mixture is removed continuously.Surplus valve makes pressure remain on 50bar.Discharge product with gc analysis.The result is compiled in table 4.
Table 4
| Operating time (h) | Temperature (℃) | Inlet amount (g/h) | Vinylbenzene (%) | Diphenylethane (%) | Transformation efficiency (%) | Productive rate (%) |
| ????24 | ??250 | ????50 | ????0.02 | ????8.3 | ????99.8 | ????47 |
| ????48 | ??230 | ????50 | ????0.03 | ????12.7 | ????99.7 | ????72.6 |
| ????72 | ??230 | ????50 | ????0.03 | ????14.7 | ????99.7 | ????84 |
| ????96 | ??230 | ????50 | ????0.03 | ????13.5 | ????99.7 | ????77.3 |
| ????120 | ??230 | ????50 | ????0.04 | ????14.1 | ????99.6 | ????80.6 |
| ????144 | ??230 | ????50 | ????0.04 | ????14.2 | ????99.6 | ????81.1 |
| ????168 | ??230 | ????100 | ????0.09 | ????14.7 | ????99.1 | ????84 |
| ????192 | ??230 | ????200 | ????0.14 | ????15.8 | ????98.6 | ????90.2 |
| ????212 | ??230 | ????200 | ????1.78 | ????11.1 | ????82.2 | ????63.4 |
Claims (11)
1. the method for the diarylethane of a preparation formula I,
In the formula, the vinylbenzene prepared in reaction of the aromatic hydrocarbons of through type II and formula II wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen or C
1-C
3Alkyl,
In the formula, R
1, R
2, R
3, R
4, R
5And R
6Above-mentioned implication is arranged,
R in the formula
1Above-mentioned implication is arranged, be reflected in liquid phase or the supercritical phase, under 150～350 ℃, 5～200bar, in the presence of heterogeneous acid catalyst, intermittently carry out or carry out continuously.
2. according to the method for preparing diarylethane I of claim 1, wherein used heterogeneous acid catalyst is 12 yuan of rings of macropore zeolite.
3. according to the method for preparing diarylethane I of claim 1 or 2, wherein used heterogeneous acid catalyst is β zeolite, HY zeolite or mordenite.
4. according to each the method for preparing diarylethane I in the claim 1～3, wherein R
1, R
2, R
3, R
4, R
5And R
6All be hydrogen.
5. according to each the method for preparing diarylethane I in the claim 1～4, wherein be reflected under 180～230 ℃ and carry out.
6. according to each the method for preparing diarylethane I in the claim 1～5, wherein be reflected under 10～130bar and carry out.
7. according to the method for preparing diarylethane I of claim 1 or 2, wherein be reflected under the autogenous pressure or under supercharging 1～50bar and carry out.
8. according to each the method for preparing diarylethane I in the claim 1～7, wherein be reflected to be not more than under 3% the vinylbenzene Css and carry out.
9. according to each the method for preparing diarylethane I in the claim 1～8, wherein be reflected to be not more than under 0.1% the vinylbenzene Css and carry out.
10. according to each the method for preparing diarylethane I in the claim 1～9, wherein be reflected to be not more than under 0.05% the vinylbenzene Css and carry out.
11., wherein be reflected in the continuous mixing reactor or in fixed-bed reactor and carry out according to each the method for preparing diarylethane I in the claim 1～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96113056 CN1178212A (en) | 1996-09-27 | 1996-09-27 | Preparation of diarylethanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96113056 CN1178212A (en) | 1996-09-27 | 1996-09-27 | Preparation of diarylethanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1178212A true CN1178212A (en) | 1998-04-08 |
Family
ID=5121731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96113056 Pending CN1178212A (en) | 1996-09-27 | 1996-09-27 | Preparation of diarylethanes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1178212A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648841A (en) * | 2008-08-14 | 2010-02-17 | 新疆大学 | Method for catalytic synthesis of diaryl ethane |
| CN101898931A (en) * | 2009-05-25 | 2010-12-01 | 新疆大学 | Method for catalyzing and synthesizing diphenylethane with molecular sieves Al-MCM-41 |
| CN106349000A (en) * | 2015-07-17 | 2017-01-25 | 江苏中能化学有限公司 | 1-phenyl-1-(cyclohexyl methyl) base ethane isomer of heat conduction fluid and synthesis method of isomer |
| CN106673936A (en) * | 2016-12-14 | 2017-05-17 | 郑文亚 | Preparation method of bibenzyl |
| CN107266292A (en) * | 2017-07-24 | 2017-10-20 | 湖北阿泰克生物科技股份有限公司 | A kind of method for synthesizing Symwhite-337 |
-
1996
- 1996-09-27 CN CN 96113056 patent/CN1178212A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648841A (en) * | 2008-08-14 | 2010-02-17 | 新疆大学 | Method for catalytic synthesis of diaryl ethane |
| CN101898931A (en) * | 2009-05-25 | 2010-12-01 | 新疆大学 | Method for catalyzing and synthesizing diphenylethane with molecular sieves Al-MCM-41 |
| CN106349000A (en) * | 2015-07-17 | 2017-01-25 | 江苏中能化学有限公司 | 1-phenyl-1-(cyclohexyl methyl) base ethane isomer of heat conduction fluid and synthesis method of isomer |
| CN106349000B (en) * | 2015-07-17 | 2018-10-26 | 江苏中能化学科技股份有限公司 | Heat-conducting fluid 1- phenyl -1- (cyclohexyl toluene) base ethane isomers and its synthetic method |
| CN106673936A (en) * | 2016-12-14 | 2017-05-17 | 郑文亚 | Preparation method of bibenzyl |
| CN107266292A (en) * | 2017-07-24 | 2017-10-20 | 湖北阿泰克生物科技股份有限公司 | A kind of method for synthesizing Symwhite-337 |
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