RU2290995C1 - Method of preparing catalyst for oligomerization of styrene - Google Patents
Method of preparing catalyst for oligomerization of styrene Download PDFInfo
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- RU2290995C1 RU2290995C1 RU2005125353/04A RU2005125353A RU2290995C1 RU 2290995 C1 RU2290995 C1 RU 2290995C1 RU 2005125353/04 A RU2005125353/04 A RU 2005125353/04A RU 2005125353 A RU2005125353 A RU 2005125353A RU 2290995 C1 RU2290995 C1 RU 2290995C1
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- styrene
- palladium
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- oligomerization
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 palladium (II) compound Chemical class 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- 150000003003 phosphines Chemical group 0.000 claims description 4
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- 239000000539 dimer Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 3
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 2
- 239000005061 synthetic rubber Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 abstract 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 7
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GNQWHYWLSGTMSL-OUKQBFOZSA-N [(e)-3-phenylbut-1-enyl]benzene Chemical compound C=1C=CC=CC=1C(C)\C=C\C1=CC=CC=C1 GNQWHYWLSGTMSL-OUKQBFOZSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Предлагаемое изобретение относится к получению катализатора для олигомеризации стирола в димеры, которые используются как сырье в органическом синтезе, в производстве синтетических каучуков, теплоносителей, изоляторного масла, как растворители полистирола.The present invention relates to the preparation of a catalyst for the oligomerization of styrene into dimers, which are used as raw materials in organic synthesis, in the production of synthetic rubbers, coolants, insulating oils, as solvents for polystyrene.
Известен способ получения катализатора для олигомеризации стирола на основе соединений двухвалентного палладия различного состава /Патент GB №1369128, С 07 С 2/04, 02.09.74/, в том числе тетрафторборат ацетилацетонатоциклооктадиен палладия или карбоксилатов палладия, с соединениями трехфтористого бора - веществами, содержащими комплексный анион фтора, например в виде HBF4], которые олигомеризуют стирол в течение 5 ч при 333К под действием каталитической системы Pd(ОСОСН3)2+HBF4+Р(n-Bu)3 при атомарном отношении Pd:B:P=1:2:1 с конверсией стирола в олигомеры, достигающей 1·104 моля стирола на 1 г-ат Pd при содержании димеров 84%.A known method of producing a catalyst for oligomerization of styrene based on compounds of divalent palladium of various compositions / Patent GB No. 1369128, C 07 With 2/04, 09/09/74 /, including tetrafluoroborate acetylacetonatocyclooctadiene palladium or palladium carboxylates, with compounds containing boron trifluoride - substances containing complex fluorine anion, for example, in the form of HBF 4 ], which oligomerize styrene for 5 hours at 333K under the action of the Pd (OCOCH 3 ) 2+ HBF 4+ P (n-Bu) 3 catalyst system with an atomic ratio of Pd: B: P = 1: 2: 1 with the conversion of styrene to oligomers, dos fusing 1 · 10 4 moles of styrene per 1 g-at Pd with a dimer content of 84%.
Известен способ получения катализатора для олигомеризации стирола,G.Myagmarsuren, V.S.Tkach, F.K.Shmidt, M.Mohamad, D.S.Suslov // J.Mol. Cat. A:Chem, 235 (2005), p.154-160, путем взаимодействия бис-ацетилацетоната палладия с эфиратом трехфтористого бора в присутствии соединений трехвалентного фосфора в среде субстрата (стирола) [3]. Для подобных каталитических композиций, например Pd(Acac)2+PPh3+BF3OEt2 при атомарном отношении Pd:P:B=1:2:7 конверсия стирола за 7 ч при 343К достигает 7,5·104 моля стирола на г-ат Pd при содержании димеров 93,0%.A known method of producing a catalyst for oligomerization of styrene, G. Myagmarsuren, VSTkach, FKShmidt, M. Mohamad, DSSuslov // J. Mol. Cat. A: Chem, 235 (2005), p.154-160, by reacting palladium bis-acetylacetonate with boron trifluoride etherate in the presence of trivalent phosphorus compounds in a substrate (styrene) environment [3]. For such catalytic compositions, for example, Pd (Acac) 2+ PPh 3+ BF 3 OEt 2 at an atomic ratio of Pd: P: B = 1: 2: 7, styrene conversion in 7 h at 343K reaches 7.5 · 10 4 moles of styrene per g-at Pd with a dimer content of 93.0%.
Ближайшим аналогом является способ получения катализатора для олигомеризации стирола /Патент РФ №2129043, B 01 J 37/00, B 01 J 31/28, 1999 г./ путем взаимодействия компонентов катализатора - карбоксилата палладия, третичного фосфина и соединения трехфтористого бора в среде стирола, в качестве компонентов катализатора используют карбоксилат палладия общей формулы Pd(OCOR)2, где OCOR - ацетат, бутират, валериат, пальмитат, стеарат, бензоат, третичный фосфин общей формулы PR3, где R - фенил, ортометилфенил, парахлорфенил, ортометоксифенил, параэтоксифенил, эфират трехфтористого бора формулы BF3OEt2, и процесс проводят при температуре 333-363К, при атомарных отношениях Р:Pd=1:3 и В:Pd=5:10.The closest analogue is a method for producing a catalyst for styrene oligomerization / RF Patent No. 2129043, B 01 J 37/00, B 01 J 31/28, 1999 / by reacting the components of the catalyst — palladium carboxylate, tertiary phosphine and boron trifluoride compound in styrene medium , palladium carboxylate of the general formula Pd (OCOR) 2 , where OCOR is acetate, butyrate, valerate, palmitate, stearate, benzoate, tertiary phosphine of the general formula PR 3 , where R is phenyl, orthomethylphenyl, parachlorophenyl, orthomethoxyphenyl, paraethoxyphenyl, are used as catalyst components , ethereal t boron re-fluoride of the formula BF 3 OEt 2 , and the process is carried out at a temperature of 333-363K, with atomic ratios P: Pd = 1: 3 and B: Pd = 5: 10.
Недостатком известных способов является неэффективность способа, так как подобные каталитические композиции характеризуются относительно невысокой конверсией стирола в олигомеры, а также относительно невысокой селективностью по отношению к димерам.A disadvantage of the known methods is the inefficiency of the method, since such catalyst compositions are characterized by a relatively low conversion of styrene to oligomers, as well as a relatively low selectivity with respect to dimers.
Задачей предлагаемого изобретения является создание катализатора повышенной активности для олигомеризации стирола.The objective of the invention is the creation of a catalyst of increased activity for oligomerization of styrene.
Поставленная задача достигается тем, что в способе получения катализатора для олигомеризации стирола путем взаимодействия компонентов катализатора - соединения двухвалентного палладия и соединения трехфтористого бора в среде стирола при температуре 333-353 К, в качестве соединения двухвалентного палладия используют соединение тетрафторборат ацетилацетонатобис(триарилфосфин) палладия общей формулы [(Асас)Pd(PR3)2]BF4, где Асас - ацетилацетонат, PR3 - третичные фосфины, где R - фенил, ортометилфенил, параметилфенил и процесс проводят при атомарном отношении B:Pd=3:10.The problem is achieved in that in the method for producing a catalyst for oligomerization of styrene by the interaction of catalyst components — a compound of divalent palladium and a compound of boron trifluoride in a styrene medium at a temperature of 333-353 K, a tetrafluoroborate acetylacetonatobis (triarylphosphine) palladium compound of the general formula [(Acac) Pd (PR 3 ) 2 ] BF 4 , where Acac is acetylacetonate, PR 3 is tertiary phosphines, where R is phenyl, orthomethylphenyl, parameter phenyl and the process is carried out at the atom in the ratio B: Pd = 3: 10.
Способ осуществляется следующим образом.The method is as follows.
Способ заключается во взаимодействии тетрафторбората ацетилацетонато-бис(триарилфосфин) палладия и эфирата трехфтористого бора в среде стирола при 298К в течение 30 мин. Затем температуру повышают до оптимальной.The method consists in the interaction of tetrafluoroborate acetylacetonato-bis (triarylphosphine) palladium and boron trifluoride etherate in styrene medium at 298K for 30 minutes. Then the temperature is raised to the optimum.
Оптимальные условия процесса: температура 323-363К, предпочтительно 333-353К, атомарное отношение B:Pd=2:20, предпочтительно B:Pd=3:10.Optimum process conditions: temperature 323-363K, preferably 333-353K, atomic ratio B: Pd = 2: 20, preferably B: Pd = 3: 10.
Пример 1.Example 1
В трехгорлую колбу при 298К в атмосфере аргона последовательно вносят 50 мл (0,435 моль) стирола, 0,0142 г (1,74·10-5 моль) тетрафторбората ацетилацетонато-бис(трифенилфосфин) палладия, которые растворяют при перемешивании. Затем микропипеткой приливают 0,011 мл (8,70·10-5 моль) эфирата трехфтористого бора. Перемешивают в течение 30 мин, затем поднимают температуру в колбе до 343 К и проводят олигомеризацию стирола в течение 2 ч.50 ml (0.435 mol) of styrene, 0.0142 g (1.74 · 10 -5 mol) of acetylacetonato-bis (triphenylphosphine) palladium tetrafluoroborate are successively added to a three-necked flask at 298K in an argon atmosphere, which are dissolved with stirring. Then 0.011 ml (8.70 · 10 -5 mol) of boron trifluoride etherate are poured with a micropipette. The mixture is stirred for 30 minutes, then the temperature in the flask is raised to 343 K and styrene is oligomerized for 2 hours.
Полученные олигомеры разделяют перегонкой на вакуумной ректификационной установке. Выделяют 44,6 г димеров стирола (фракция 146-160°С/1 мм рт.ст.) и 0,4 г кубового остатка. В соответствии с данными ИК- и ЯМР Н-спектроскопии и хромато-масс-спектрометрии фракция димеров представлена 1,3-дифенил-1-бутеном. Кубовый остаток состоит в основном из тримеров.The resulting oligomers are separated by distillation in a vacuum distillation unit. 44.6 g of styrene dimers (fraction 146-160 ° C / 1 mm Hg) and 0.4 g of bottoms are isolated. In accordance with the data of IR and NMR H-spectroscopy and chromatography-mass spectrometry, the fraction of dimers is represented by 1,3-diphenyl-1-butene. VAT residue consists mainly of trimers.
Конверсия стирола в олигомеры составляет 25000 моль стирола на 1 г-ат Pd. (~100%)The conversion of styrene to oligomers is 25,000 mol of styrene per 1 g-at Pd. (~ 100%)
Селективность олигомеризации стирола в димеры составляет 91%.The selectivity of styrene oligomerization to dimers is 91%.
Примеры 2-6.Examples 2-6.
Данные примеры иллюстрируют влияние атомарного отношения B:Pd на конверсию стирола в олигомеры. Процедура проведения опытов аналогична примеру 1. Данные представлены в табл.1.These examples illustrate the effect of the atomic ratio B: Pd on the conversion of styrene to oligomers. The experimental procedure is similar to example 1. The data are presented in table.1.
[(Acac)Pd(PPh3)2]BF4+nBF3OEt Т=343К; время опыта - 6 часов; стирол/Pd=120000; n(Pd)=3,7*10-6 мольThe influence of the ratio B / Pd on the conversion of styrene to oligomers in the system
[(Acac) Pd (PPh 3 ) 2 ] BF 4 + nBF 3 OEt T = 343K; experience time - 6 hours; styrene / Pd = 120,000; n (Pd) = 3.7 * 10 -6 mol
Примеры 7-9.Examples 7-9.
Данные примеры иллюстрируют влияние природы третичных фосфинов на конверсию стирола в олигомеры. Олигомеризация стирола в условиях, аналогичных примеру 1. Данные приведены в табл.2.These examples illustrate the effect of the nature of tertiary phosphines on the conversion of styrene to oligomers. Oligomerization of styrene under conditions similar to example 1. The data are shown in table.2.
Примеры 10-15.Examples 10-15.
Данные примеры иллюстрируют влияние температуры процесса на конверсию стирола в олигомеры в присутствии системы [(Acac)Pd(PPh3)2]BF4+5BF3OEt2. Процедура проведения опытов аналогична примеру 1. Данные представлены в табл.3.These examples illustrate the effect of process temperature on the conversion of styrene to oligomers in the presence of the system [(Acac) Pd (PPh 3 ) 2 ] BF 4 + 5BF 3 OEt 2 . The procedure for conducting experiments is similar to example 1. The data are presented in table.3.
Предлагаемый способ позволяет повысить эффективность процесса за счет повышения конверсии стирола в олигомеры по сравнению с известными до 153000 моль стирола / на 1 г-ат Pd и селективность по димерам до 91%.The proposed method allows to increase the efficiency of the process by increasing the conversion of styrene to oligomers in comparison with the known up to 153000 mol of styrene / 1 g-at Pd and selectivity for dimers up to 91%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2487859C1 (en) * | 2012-06-19 | 2013-07-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" | Method of producing 1,3-diphenylbutene-1 |
| RU2737084C1 (en) * | 2020-02-26 | 2020-11-24 | Михаил Эхильевич Шмулевский | Method of producing catalyst for polymerization of styrene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1369128A (en) * | 1972-07-10 | 1974-10-02 | Mitsubishi Chem Ind | Process for producing oligomers from unsaturated monomers |
| EP0531174A2 (en) * | 1991-09-05 | 1993-03-10 | Mitsui Petrochemical Industries, Ltd. | Oligomerization catalyst for alpha-olefins and process for oligomerizing alpha-olefins |
| US5811617A (en) * | 1995-12-13 | 1998-09-22 | Amoco Corporation | Olefin oligomerization process |
| RU2129043C1 (en) * | 1996-07-02 | 1999-04-20 | Иркутский государственный университет | Method of preparing styrene oligomerization catalyst |
| US6734329B1 (en) * | 2000-10-02 | 2004-05-11 | Chevron U.S.A. Inc. | Oligomerization of alpha olefins in the presence of carboxylic acids |
-
2005
- 2005-08-09 RU RU2005125353/04A patent/RU2290995C1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1369128A (en) * | 1972-07-10 | 1974-10-02 | Mitsubishi Chem Ind | Process for producing oligomers from unsaturated monomers |
| EP0531174A2 (en) * | 1991-09-05 | 1993-03-10 | Mitsui Petrochemical Industries, Ltd. | Oligomerization catalyst for alpha-olefins and process for oligomerizing alpha-olefins |
| US5811617A (en) * | 1995-12-13 | 1998-09-22 | Amoco Corporation | Olefin oligomerization process |
| RU2129043C1 (en) * | 1996-07-02 | 1999-04-20 | Иркутский государственный университет | Method of preparing styrene oligomerization catalyst |
| US6734329B1 (en) * | 2000-10-02 | 2004-05-11 | Chevron U.S.A. Inc. | Oligomerization of alpha olefins in the presence of carboxylic acids |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2487859C1 (en) * | 2012-06-19 | 2013-07-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" | Method of producing 1,3-diphenylbutene-1 |
| RU2737084C1 (en) * | 2020-02-26 | 2020-11-24 | Михаил Эхильевич Шмулевский | Method of producing catalyst for polymerization of styrene |
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