CN100445309C - Method for synthesizing chirality function macromolecule polyketone by asymmetric oxonation - Google Patents
Method for synthesizing chirality function macromolecule polyketone by asymmetric oxonation Download PDFInfo
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- CN100445309C CN100445309C CNB2005100483224A CN200510048322A CN100445309C CN 100445309 C CN100445309 C CN 100445309C CN B2005100483224 A CNB2005100483224 A CN B2005100483224A CN 200510048322 A CN200510048322 A CN 200510048322A CN 100445309 C CN100445309 C CN 100445309C
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- polyketone
- diop
- oac
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Abstract
The invention relates to a method of asymmetric carbonylation of chiral functional polymer polyketone. The method employs [(2S, 3S) - DIOP] Pd (OAc) 2 as main catalyst, strong Lewis acid BF3. Et20 as cocatalyst, mixture of ionic liquid and methanol as reaction medium, and the reacting material are propylene and carbon monoxide, the reaction time is 3- 10 hours and condition is 50- 80 Deg. C and 2.0- 6.0 MPa. The produced ployketone is characterizede by larger molecular weight and narrower distribution degree.
Description
Technical field
The present invention relates to a kind of method of asymmetric carbonizing and synthesizing macromolecular polyketone polymer with chirality function.
Background technology
Along with the enhancing of people's environmental consciousness, people more and more pay attention to degradable high polymer material in recent years, and the polyketone that synthesizes by alpha-olefin and carbon monoxide alternating copolymerization is a class novel thermoplastic macromolecular material.Compare with traditional olefin polymer plastics, the polyketone macromolecular material has three big clear superiorities: the raw material of (1) polyketone synthesis is cheap and easy to get.(2) polyketone has photodegradation and biodegradation character, is a kind of green material.(3) further chemically modified of carbonyl in the polyketone is used to develop the functional high molecule material of other types.Shell and Bp company have applied for a large amount of patents with regard to the synthetic and application of polyketone, and with the building-up process industrialization of polyketone macromolecular material, trade(brand)name is respectively Carilon and Ketonex.The polyketone polymer has been processed to fiber, film, and tamanori, resist, wrapping material etc. are applied to automobile, electronics, daily necessities field.The early 1990s in last century, the Pd complex compound catalyst of chiral ligand modification is applied in alpha-olefin and the asymmetric alternating copolymerization repercussion study of carbon monoxide.Product chirality polyketone is except that the general characteristic with common polyketone, also can be used as the piezoelectricity of excellent performance, thermoelectric and ferroelectric material is applied in the optoelectronic equipment, is expected at the chromatogram chiral stationary phase that splits enantiomer, and aspects such as chirality function mould material also have new application prospect.
In the fundamental research field of chirality polyketone, Drent, Sen, Nozaki and Consiglio etc. have carried out independently research.The effective catalyst system of its use is [L
2PdX
2]
N+, L
2Represent the bidentate carbon phosphine part of chelating; Weak coordination of X representative or non-coordination anion part, or neutral ligand.In order to obtain high catalytic activity, generally need to add a large amount of oxygenants, the consumption of common oxygenant is that tens times of metal catalysts precursors arrive hundred times.Having adopted the exhausted mixed solvent has: THF/MeOH, NO
2Me/MeOH,
tBuOH/MeOH/Toluene, CH
2CI
2/ MeOH.Wherein, Sen use (2S, 3S)-DIOP is at organic system NO
2Carried out the asymmetric alternating copolymerization of propylene and carbon monoxide among the Me/MeOH, but the chirality polyketone molecular weight that generates is less relatively, dispersity is also very wide, and this processed and applied to the chirality polyketone is disadvantageous.
Ionic liquid has been widely used in transition metal-catalyzed alkylation, and hydrogenation is in the organic reactions such as hydroformylation; Polymkeric substance synthetic aspect, people have realized acrylic ester polymerization in ionic liquid, and the polymerization of alkene.Recently, Haracre and Shaughbessy have reported the vinylbenzene of use achirality catalyst in ionic liquid and the alternating copolymerization of carbon monoxide respectively, obtained having the polyketone of isostructure, product polyketone has than molecular weight high in the organic system and productive rate.
Summary of the invention:
The method that the purpose of this invention is to provide a kind of asymmetric carbonizing and synthesizing macromolecular polyketone polymer with chirality function.
A kind of method of asymmetric carbonyl process synthesizing chirality function macromolecule polyketone, it is characterized in that this method adopt [(2S, S3)-DIOP] Pd (OAc)
2Be Primary Catalysts, strong Lewis acid (lewis' acid) BF
3Et
2O is as promotor, and reaction medium is the mixture that ionic liquid and methyl alcohol are formed, and ionic liquid is selected from [BMIM] PF
6, [HMIM] PF
6, [OMIM] PF
6, [BMIM] BF
6Or [HPy] PF
6, reactant is propylene and CO (carbon monoxide converter) gas, and at 50 ℃~80 ℃, the CO pressure of 2.0~6.0MPa reacted 3-10 hour down, and asymmetric carbonylation generates chirality function macromolecule polyketone.
The present invention [(2S, 3S)-DIOP] Pd (OAc)
2With BF
3Et
2The mol ratio of O is 1: 2~4.
The volume ratio of ionic liquid of the present invention and methyl alcohol is 10-20: 1.
The promotor that the present invention selects for use is strong Lewis acid BF
3Et
2O, wherein BF
3The quality percentage composition is 46.5%.
[(2S, 3S)-DIOP] Pd (OAc)
2With the propylene mol ratio be 1: 10000-20000.
[(2S, 3S)-DIOP] Pd (OAc)
2With ion liquid mol ratio be 1: 300-500.
The following expression of chiral ligand DIOP of the present invention:
The present invention has following advantage:
1, uses a small amount of strong Lewis acid BF
3Et
2O replaces normally used a large amount of oxygenant.
2, in ion liquid system, the production efficiency of polyreaction improves.
3, in ion liquid system, the molecular weight of polymkeric substance increases, and dispersity narrows down.
4, product polyketone has degree of regioregularity and medium tacticity preferably.
Every operation of the present invention all is to carry out under the anhydrous and oxygen-free condition.Catalyzer and ionic liquid are added in the stainless steel autoclave, after the propylene displacement, under freezing conditions charge into propylene, charging into the pressure of required carbon monoxide, be heated to temperature of reaction and kept 3-10 hour, the unreacted gas of cooling back emptying, and add cold methyl alcohol and carry out sedimentation, grayish solid obtained after the filtration.
The chiral ligand that the present invention uses is a commercialization reagent; Ionic liquid has had very sophisticated synthetic method. and the alternating copolymerization of propylene and carbon monoxide can well carry out in these ionic liquid the insides, and its aftertreatment is also very simple.With respect to organic system, the polyketone that generates in above-mentioned ionic liquid the inside not only molecular weight increases, and dispersity also narrows down, and has medium tacticity.
Embodiment
In the laboratory [(2S, 3S)-DIOP] Pd (OAc)
2Be to prepare like this: with Pd (OAc)
2Join in the ionic liquid with the mixture of chiral ligand DIOP, under agitation add methylene dichloride and methyl alcohol and the BF of a little
3Et
2O, mixture stirs, and drains methylene dichloride and methyl alcohol then, adds 1CH
3OH changes it in reactor over to, replaces with propylene, under cooling, charge into the pressure of propylene and required carbon monoxide then, 50~80 ℃ of down reactions, be cooled to room temperature after, the unreacted gas of emptying, add the cold methanol sedimentation, filtration obtains grayish solid, with its filtration, and with methanol wash several times, heat drying on vacuum line is weighed then.
Embodiment 1
With Pd (OAc)
2(10.3mg, 0.046mmol), (23.0mg, mixture 0.046mmol) join [BMIM] PF of 4ml to DIOP
6In, add CH
2Cl
225ml and CH
3The BF of OH25ml and 2 moles
3Et
2O solution at room temperature stirred one hour, drained CH
2Cl
2And CH
3OH, the methyl alcohol of adding 0.4ml changes it in reactor over to then, with the propylene displacement, charges into the propylene of 35g and the pressure of 4MPa carbon monoxide under cooling, is warming up to 50 ℃, reacts 5 hours.After being cooled to room temperature, the unreacted gas of emptying carries out sedimentation with cold methyl alcohol, filter to obtain grayish solid and to use methanol wash, at the vacuum line heat drying, weigh 2.1g, number-average molecular weight Mn:7.6 * 10
3, dispersity: 1.7,, molecular rotation [Ф]
D 20(c, 5mg/mL, CH
2Cl
2) :+0.84 °.
Embodiment 2
With Pd (OAc)
2(10.3mg, 0.046mmol), (23.0mg, mixture 0.046mmol) join [HMIM] PF of 4ml to DIOP
6In, add CH
2Cl
225ml and CH
3The BF of OH25ml and 2 moles
3Et
2O solution at room temperature stirred one hour, drained CH
2Cl
2And CH
3OH, the methyl alcohol of adding 0.4ml changes it in reactor over to then, with propylene displacement three times, charges into the propylene of 35g and the carbon monoxide of required 4MPa under cooling, is warming up to 50 ℃, reacts the record pressure drop 5 hours.After being cooled to room temperature, the unreacted gas of emptying carries out sedimentation with refrigerated methyl alcohol, filter to obtain grayish solid and several times with methanol wash, at the vacuum line heat drying, weigh 1.2g, number-average molecular weight Mn:8.6 * 10
3, dispersity: 1.7, molecular rotation [Ф]
D 20(c, 5mg/mL, CH
2Cl
2) :+0.62 °.
Embodiment 3
With Pd (OAc)
2(10.3mg, 0.046mmol), (23.0mg, mixture 0.046mmol) join [OIM] PF of 4ml to DIOP
6In, add CH
2Cl
225ml and CH
3The BF of OH25ml and 2 moles
3Et
2O solution at room temperature stirred one hour, drained CH
2Cl
2And CH
3OH, the methyl alcohol of adding 0.4ml changes it in reactor over to then, with the propylene displacement, charges into the propylene of 35g and the carbon monoxide of 4MPa under cooling, is warming up to 50 ℃, reacts the record pressure drop 5 hours.After being cooled to room temperature, the unreacted gas of emptying carries out sedimentation with refrigerated methyl alcohol, filter to obtain grayish solid and several times with methanol wash, at the vacuum line heat drying, weigh 0.42g, number-average molecular weight Mn:9.1 * 10
3, dispersity: 1.6, molecular rotation [Ф]
D 20(c, 5mg/mL, CH
2Cl
2) :+1.00 °.
Embodiment 4
With Pd (OAc)
2(10.3mg, 0.046mmol), (23.0mg, mixture 0.046mmol) join [HM] BF of 4ml to DIOP
4In, add CH
2Cl
225ml and CH
3The BF of OH25ml and 2 moles
3Et
2O solution at room temperature stirred one hour, drained CH
2Cl
2And CH
3OH, the methyl alcohol of adding 0.4ml changes it in reactor over to then, with the propylene displacement, charges into the propylene of 35g and the carbon monoxide of 4MPa under cooling, is warming up to 50 ℃, reacts the record pressure drop 5 hours.After being cooled to room temperature, the unreacted gas of emptying carries out sedimentation with refrigerated methyl alcohol, filter to obtain grayish solid and to use methanol wash, at the vacuum line heat drying, weigh 1.16g, number-average molecular weight Mn:4.5 * 10
3, dispersity: 1.4, molecular rotation [Ф]
D 20(c, 5mg/mL, CH
2Cl
2) :+2.39 °.
Embodiment 5
With Pd (OAc)
2(10.3mg, 0.046mmol), (23.0mg, mixture 0.046mmol) join [BPy] PF of 4ml to DIOP
6In, add CH
2Cl
225ml and CH
3The BF of OH25ml and 2 moles
3Et
2O solution at room temperature stirred one hour, drained CH
2Cl
2And CH
3OH, the methyl alcohol of adding 0.4ml changes it in reactor over to then, with the propylene displacement, charges into propylene and the 4MPa carbon monoxide of 35g under cooling, is warming up to 50 ℃, reacts the record pressure drop 5 hours.After being cooled to room temperature, the unreacted gas of emptying carries out sedimentation with refrigerated methyl alcohol, filter to obtain grayish solid and several times with methanol wash, at the vacuum line heat drying, weigh 0.25g, number-average molecular weight Mn:2.8 * 10
4, molecular rotation [Ф]
D 20(c, 5mg/mL, CH
2Cl
2): 4.2 °.
Claims (6)
1, a kind of method of asymmetric carbonyl process synthesizing chirality function macromolecule polyketone, it is characterized in that this method adopt [(2S, 3S)-DIOP] Pd (OAc)
2Be Primary Catalysts, strong lewis' acid BF
3Et
2O is as promotor, and reaction medium is the mixture that ionic liquid and methyl alcohol are formed, and ionic liquid is selected from [BMIM] PF
6, [HMIM] PF
6, [OMIM] PF
6, [BMIM] BF
6Or [HPy] PF
6, reactant is propylene and CO (carbon monoxide converter) gas, and at 50 ℃~80 ℃, the CO pressure of 2.0~6.0MPa reacted 3-10 hour down, and asymmetric carbonylation generates chirality function macromolecule polyketone; Wherein (2S, 3S)-the DIOP structural table is shown:
2, the method for claim 1, it is characterized in that [(2S, 3S)-DIOP] Pd (OAc)
2With BF
3Et
2The mol ratio of O is 1: 2~4.
3, the method for claim 1, the volume ratio that it is characterized in that ionic liquid and methyl alcohol is 10-20: 1.
4, the method for claim 1 is characterized in that promotor is strong lewis' acid BF
3Et
2O, wherein BF
3The quality percentage composition is 46.5%.
5, the method for claim 1, it is characterized in that [(2S, 3S)-DIOP] Pd (OAc)
2With the propylene mol ratio be 1: 10000-20000.
6, the method for claim 1, it is characterized in that [(2S, 3S)-DIOP] Pd (OAc)
2With ion liquid mol ratio be 1: 300-500.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1055370A (en) * | 1990-04-06 | 1991-10-16 | 国际壳牌研究有限公司 | The preparation method of polyketane polymers |
CN1118602A (en) * | 1993-03-01 | 1996-03-13 | 阿克佐诺贝尔公司 | Polyketone polymer, polyketone products, and a preparative process |
WO1999018143A2 (en) * | 1997-10-06 | 1999-04-15 | Shell Internationale Research Maatschappij B.V. | Polyketone solutions |
CN1477139A (en) * | 2003-07-11 | 2004-02-25 | 天津大学 | Methd for preparing polyketone by means of carbon oxide and olepine copolymerization |
-
2005
- 2005-12-28 CN CNB2005100483224A patent/CN100445309C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1055370A (en) * | 1990-04-06 | 1991-10-16 | 国际壳牌研究有限公司 | The preparation method of polyketane polymers |
CN1118602A (en) * | 1993-03-01 | 1996-03-13 | 阿克佐诺贝尔公司 | Polyketone polymer, polyketone products, and a preparative process |
WO1999018143A2 (en) * | 1997-10-06 | 1999-04-15 | Shell Internationale Research Maatschappij B.V. | Polyketone solutions |
CN1477139A (en) * | 2003-07-11 | 2004-02-25 | 天津大学 | Methd for preparing polyketone by means of carbon oxide and olepine copolymerization |
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