CN1353122A - Process for preparing high-activity polyisobutylene - Google Patents
Process for preparing high-activity polyisobutylene Download PDFInfo
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- CN1353122A CN1353122A CN 00130281 CN00130281A CN1353122A CN 1353122 A CN1353122 A CN 1353122A CN 00130281 CN00130281 CN 00130281 CN 00130281 A CN00130281 A CN 00130281A CN 1353122 A CN1353122 A CN 1353122A
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- ether
- boron trifluoride
- activity polyisobutylene
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Abstract
A process for preparing polyisobutylene having high reaction activity features that in the existance of complexing catalyst composed of BF3, ether or alcohol and a third ingredient solvent, the isobutylene or the raw C4 material containing polyisobutylene takes part in polymerization reaction at -30-30 deg.C. The rsultant polyisobutylene has 500-10000 of number average molecular weight, 80% or more of transform rate, and more than 70% of content of alpha-olefin. Its advantages include high selectivity and transform rate, and regulatable molecular weight.
Description
The present invention relates in utilizing iso-butylene or containing carbon four raw materials of iso-butylene, preparation number-average molecular weight 500-10000, whole terminal double bond are greater than 70% lower molecular weight, the method for high-activity polyisobutene under liquid phase state and boron trifluoride catalyst system.
The cationoid polymerisation technology of utilizing lewis acid catalyst to carry out iso-butylene or containing carbon four raw materials of iso-butylene is well-known.Known termination step in above-mentioned polymerization process can cause " terminal " two keys, this pair key can be given polymkeric substance with very high reactive behavior, so that carry out next step functionalization, carry out addition reaction to form corresponding derivatives of poly (iso) butene as epoxidation reaction or with maleic anhydride.If but that the termination step of this process is controlled is bad, two keys both can have highly active terminal location (vinylidene), again can be at the low interior location of reactive behavior, and these position of double bond (wherein R is an alkyl) as follows:
CH
2=C (CH
3) the whole terminal double bond of R (1,1-two replaces)
(CH
3)
2=CHR internal double bonds (three replace)
(CH
3)
2C=C (CH
3) R internal double bonds (four replace)
According to the above, the emphasis of this area is the activity that catalyzer that research can the polymerization iso-butylene improves polyisobutene, and many patents all are being devoted to the work of this respect.As US5,068, point out in 490, utilize boron trifluoride and tertbutyl ether, match as methyl tertiary butyl ether, preparation in advance or in reactor on the spot preparation form complex compound catalyst, under-100 ℃～50 ℃ conditions, through 10 minutes to 3 hours, the raw material that can make iso-butylene or contain iso-butylene generated vinylidene and concentration at the polyisobutene more than 70%.In this patent, lay special stress on, because the complex compound that forms at high temperature might decompose, the temperature of this catalyst system can not surpass 0 ℃, optimum temps is at-60 ℃～-30 ℃.
US4,849, point out also in 572 that the boron trifluoride catalyst that utilizes one or more alcohol or ether to cooperate can cause iso-butylene or contain the raw material of iso-butylene, polymerization under-100 ℃～30 ℃ conditions, in this technology, what advocate is in polymerization process, and catalyzer and polymerization temperature all are lower than-30 ℃ for preferred, and polymerization stops needing be lower than to carry out rapidly under-35 ℃ of conditions, also can obtain vinylidene concentration greater than 60%, isobutene conversion greater than 80% polyisobutene.
Prepare in advance in the catalyzer process above-mentioned, the catalyzer synthesis temperature is generally less than-10 ℃, and particularly the catalyzer after the complexing need be kept at the polymerization that just can help causing the iso-butylene raw material below-10 ℃.This can be because the preservation problem of catalyzer be brought a lot of inconvenience in industrial production, and needing on the one hand increases auxiliary cooling equipment in addition, and also needs to carry out at low temperatures in stopping step, could keep bigger vinylidene content.If deal with improperly, make the high reactivity product that obtains be isomerizated into the lower polyisobutene of reactive behavior easily.
The purpose of this invention is to provide a kind of catalyzer that can at room temperature preserve, thereby the polymerization of iso-butylene can be carried out at normal temperatures, and do not preserve at low temperatures, produce, and output end group olefin(e) centent is greater than 70%, isobutene conversion is greater than 80%.
The invention provides a kind of can be in the boron trifluoride System Catalyst of room temperature preservation, and utilize this catalyzer to cause iso-butylene or contain carbon four hydro carbons of iso-butylene, synthetic have a method of high-activity polyisobutylene.
BF
3The preparation of complex solution.
Pressure is being arranged or do not having under the pressure, BF
3Be passed in the mixing solutions of ether or alcohol and the 3rd component composition, be made into complex solution.The complexing temperature can be from-30 ℃～20 ℃.Ether that is made in advance or alcoholic solution concentration is at 0.05M～14M, preferred 3M～10M.BF
3With ethereal solution complexing gradually, until BF
3Reach 0.5: 1 with the ratio of complexing agent～1.1: 1.This catalyzer storage temperature is-20 ℃～30 ℃, preferred 0 ℃～20 ℃.1～10 day catalyzer shelf time, preferably 1～5 day.Utilize this catalyzer can carry out iso-butylene or contain the polymerization of carbon four hydro carbons of iso-butylene, obtain polyisobutene.Its vinylidene content can reach more than 70%.
Can prepare BF in advance
3The complexing agent of complex compound can be ethers and alcohols, preferred ethers, the ethers that most preferably contains a tertiary carbon atom, as methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, propyl group tertbutyl ether, butyl tertbutyl ether, sec.-propyl are chatted butyl ether or the acid of the sec-butyl tertiary butyl etc.Can be used as the component of dissolving complexing agent is C
5～C
20Alkane, preferred C
5～C
12Alkane is as Skellysolve A, iso-pentane, normal heptane, octane-iso; Can also be halogenated alkane, as methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane etc.
At BF
3The complex compound that forms with ether or alcoholic solution exists down, iso-butylene or contain carbon four hydro carbons of iso-butylene can be in traditional reactor, as tank reactor, tubular reactor carry out intermittently, semicontinuous or successive polymerization process.Reaction heat is removed by refrigerating unit.
Polymerization reaction time can be from 1 minute to several hrs, preferably from 5～50 minutes.
Speed of reaction is relevant with the amount of the catalyzer of use, mainly refers to the ratio of the iso-butylene in catalyzer and the raw material, and the amount of the catalyzer of introducing is 0.05～1% of an iso-butylene weight.
Polymerization temperature is regulated according to the desired molecule amount, and generally at-30 ℃～30 ℃, molecular weight product can be 500～10000.Party pressure generally carries out under barometric point, and in polymerization process, because reactive system self may make reaction process produce certain pressure, but this pressure is usually to not influence of reaction process.
Form under certain situation at raw material, polymerization is preferably carried out under the condition that waits heat, and its isobutylene monomer concentration of stable raw material need be greater than 10%, can be from the raw material of catalytic pyrolysis, also can be from the divinyl raffinate, preferred isobutylene concentration is greater than 30%, most preferably pure isobutene polymerisation.
After reaching polymerization time, stop with terminator.Termination reaction can be carried out at polymerization discharge port place.Need not cooling apparatus.Terminator is the medium that can make catalyst deactivation, thereby polymerization is stopped.For reaching the operable material of this purpose water is arranged, alcohol, the liquid solution of amine or metal is as hydroxy solution of basic metal and alkaline-earth metal or the like.
After termination finishes, need wash several times to remove remaining catalyzer, generally wash with water or alcohol is washed thick polymers.After washing finishes, distill by normal pressure and pressure reducing mode, to remove unreacted iso-butylene, solvent, oligopolymer etc.
The present invention can prepare the end group olefin(e) centent more than 70%, in addition at the polyisobutene more than 80%, the selectivity height, the transformation efficiency height, molecular weight ranges is adjustable.The catalyzer raw material is easy to get, and synthesis technique is reasonable, and reaction conditions is easy to control, realizes industrial production easily.
Embodiment:
The molecular weight of the polyisobutene of the polymerization gained among the embodiment is measured by V.P.O (vapour pressure osmometry).
Vinylidene concentration be by
13The C nmr determination.
Example 1: the methyl tertiary butyl ether (MTBE) of the 24ml that in the container of a 150ml, packs into and 20ml normal hexane, under-5 ℃, be pre-mixed, the speed with 20ml/min feeds BF in container then
3Gas 4000ml carries out complexing, constantly complex solution is stirred fast in this process, uses N simultaneously continuously
2Protection, gaseous line are passed in 10% the NaOH solution to absorb acid constituents.BF
3After adding end, continue inwardly to feed N
2Purge, to guarantee to remove remaining free BF
3The catalyzer of this preparation is placed on preservation under the room temperature state, uses after 2 days.
The divinyl raffinate can be used as polymer raw, and certain isobutylene concentration is 37%.With the raw material molecular sieve drying, the water-content that makes raw material is less than 50ppm.This raw material is joined in traditional tank reactor that has heat exchanger, be cooled to-10 ℃, then to wherein dripping the BF of preparation in advance
3Complex catalyst, general one ton of raw material adds 10 liters catalyzer.Retention time was controlled at 15～20 minutes.
After reaction was finished, the NaOH solution with 10% stopped in the polymerization outlet, makes catalyst deactivation, and added alkali lye destruction remainder catalyst in addition, formed thick polymers.Thick polymers water is cleaned so that remove remainder catalyst phase and unnecessary base resistates.At last, thick polymers is distilled to remove oligopolymer and solvent etc.The product isobutene conversion that obtains like this is 89%, and molecular weight is 1219, and alhpa olefin content is 80%.
Example 2: use the catalyzer identical with embodiment 1, the solvent that only is to use is a trichloromethane, and the catalyzer that obtains was room temperature preservation 2 days, carried out the polymerization of diene raffinate, the product isobutene conversion that obtains is 92%, and molecular weight is 1100, and alhpa olefin content is 89%.
Example 3: using the catalyzer identical with embodiment 2, is catalyzer room temperature preservation 5 days, carries out the polymerization of divinyl raffinate, and the product isobutene conversion that obtains is 90%, and molecular weight is 1208, and alhpa olefin content is 83%.
Example 4: use catalyzer and the polymerizing condition identical with embodiment 1, be the polymeric raw material be catalytic pyrolysis carbon four, the product isobutene conversion that obtains is 90%, molecular weight is 898, alhpa olefin content is 79%.
Example 5: using the catalyzer identical with embodiment 1, is catalyzer room temperature preservation 10 days, has carried out the polymerization of diene raffinate, and the product isobutene conversion that obtains is 80%, and molecular weight is 1160, and alhpa olefin content is 72%.
Comparative example (not being) according to the present invention:
Use Primary Catalysts and the promotor identical, just do not add solvent with embodiment 1.This catalyzer after room temperature preservation 1 is big, has been carried out the polymerization of divinyl raffinate.The conversion rate of products that obtains is 30%, and molecular weight 1800, alhpa olefin content are 44%, and catalyzer has begun variable color, retrogradation.Comparing result sees Table 1.
Table 1 polyisobutene synthesizes example table
| Example | Ic=content % in the raw material | Catalyst system | Storage temperature ℃ | The shelf time sky | Ic=transformation efficiency % | ??Mn | Alhpa olefin content % |
| ????1 | ????37.6 | BF 3-ether-C 6H 14 | ??≥15 | ????2 | ????89 | ??1219 | ????80 |
| ????2 | ????37.6 | BF 3-ether-CHCl 3 | ??≥15 | ????2 | ????92 | ??1110 | ????89 |
| ????3 | ????37.6 | BF 3-ether-CHCl 3 | ??≥15 | ????5 | ????90 | ??1208 | ????83 |
| ????4 | ????16.7 | BF 3-ether-C 6H 14 | ??≥15 | ????2 | ????90 | ??898 | ????79 |
| ????5 | ????37.6 | BF 3-ether-C 6H 14 | ??≥15 | ????10 | ????80 | ??1160 | ????72 |
| Comparative example | ????37.6 | BF 3-ether | ??≥15 | ????1 | ????30 | ??1800 | ????44 |
Claims (10)
1, a kind of preparation method of high-activity polyisobutylene, utilization contains carbon four raw materials of polyisobutene, in the presence of the boron trifluoride System Catalyst, carry out polymerization and prepare high-activity polyisobutylene, it is characterized in that: carbon four raw materials that contain polyisobutene contain iso-butylene greater than 10%, and butadiene content is less than 1500ppm; Polyreaction in the presence of the complex catalyst of boron trifluoride and ether or alcohol and the 3rd component solvent composition, polymerization temperature-30 ℃～30 ℃, polymerization pressure is normal pressure or low pressure, the number-average molecular weight of the polyisobutene of polymerization gained is 500～10000, isobutene conversion reaches more than 80%, and the alhpa olefin content of the polyisobutene product that obtains is more than 70%.
2, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: carbon four raw materials can come autocatalysis or thermo-cracking, also can be from divinyl raffinate or pure iso-butylene.
3, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: the boron trifluoride complex catalyst is selected from alcohol or straight chain, side chain or cyclic ether for one or more.
4, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 3, it is characterized in that: boron trifluoride complex catalyst alcohol is primary alconol or secondary alcohol.
5, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 3, it is characterized in that: the complexing ether of boron trifluoride complex catalyst is alkyl-tert-butyl ether, particularly methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, propyl group tertbutyl ether, butyl tertbutyl ether, sec.-propyl tertbutyl ether or sec-butyl tertbutyl ether.
6, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: the 3rd component solvent of boron trifluoride complex catalyst is to be C with the solvent that dissolves complexing agent in advance
5～C
12Alkane and halogenated alkane, particularly Skellysolve A, iso-pentane, normal heptane, octane-iso, methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane.
7, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: the storage temperature of boron trifluoride complex catalyst is-20 ℃～30 ℃.
8, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: the shelf time of boron trifluoride complex catalyst is 1～20 day.
9, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: the time of polyreaction is 10～50 minutes.
10, according to the preparation method of a kind of high-activity polyisobutylene described in the claim 1, it is characterized in that: use alkali, alcohol, amine to make terminator and come termination reaction.
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|---|---|---|---|
| CNB001302817A CN1189488C (en) | 2000-11-03 | 2000-11-03 | Process for preparing high-activity polyisobutylene |
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|---|---|---|---|
| CNB001302817A CN1189488C (en) | 2000-11-03 | 2000-11-03 | Process for preparing high-activity polyisobutylene |
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| CN1353122A true CN1353122A (en) | 2002-06-12 |
| CN1189488C CN1189488C (en) | 2005-02-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921352A (en) * | 2010-09-28 | 2010-12-22 | 潍坊滨海石油化工有限公司 | Method for producing low-molecular-weight high-activity polyisobutene |
| US7943750B2 (en) | 2007-06-18 | 2011-05-17 | Laboratoire Medidom S.A. | Process for obtaining pure monosialoganglioside GM1 for medical use |
| CN102603950A (en) * | 2012-03-07 | 2012-07-25 | 山东鸿瑞石油化工有限公司 | Preparation method of polyisobutene with low molecular weight and high activity |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054332B (en) * | 2006-04-14 | 2011-05-25 | 中国石油抚顺石油化工公司 | Method of synthesizing poly alpha-olefin oil |
-
2000
- 2000-11-03 CN CNB001302817A patent/CN1189488C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7943750B2 (en) | 2007-06-18 | 2011-05-17 | Laboratoire Medidom S.A. | Process for obtaining pure monosialoganglioside GM1 for medical use |
| US9498490B2 (en) | 2007-06-18 | 2016-11-22 | Laboratoire Medidom Sa | Method for treatment of disease with pure porcine monosialoganglioside GM1 |
| CN101921352A (en) * | 2010-09-28 | 2010-12-22 | 潍坊滨海石油化工有限公司 | Method for producing low-molecular-weight high-activity polyisobutene |
| CN101921352B (en) * | 2010-09-28 | 2011-10-26 | 潍坊滨海石油化工有限公司 | Method for producing low-molecular-weight high-activity polyisobutene |
| CN102603950A (en) * | 2012-03-07 | 2012-07-25 | 山东鸿瑞石油化工有限公司 | Preparation method of polyisobutene with low molecular weight and high activity |
| CN102603950B (en) * | 2012-03-07 | 2013-11-06 | 山东鸿瑞石油化工有限公司 | Preparation method of polyisobutene with low molecular weight and high activity |
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|---|---|
| CN1189488C (en) | 2005-02-16 |
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