CN115888836A - Supported catalyst, application and preparation method of hydrogenated olefin polymer - Google Patents
Supported catalyst, application and preparation method of hydrogenated olefin polymer Download PDFInfo
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- CN115888836A CN115888836A CN202211503981.2A CN202211503981A CN115888836A CN 115888836 A CN115888836 A CN 115888836A CN 202211503981 A CN202211503981 A CN 202211503981A CN 115888836 A CN115888836 A CN 115888836A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 150000001336 alkenes Chemical class 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011986 second-generation catalyst Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 150000004696 coordination complex Chemical class 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000005865 alkene metathesis reaction Methods 0.000 description 5
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 5
- 239000004913 cyclooctene Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011988 third-generation catalyst Substances 0.000 description 3
- -1 aluminum trichloride magnesium dichloride ethanol Chemical compound 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- WNHXJHGRIHUOTG-UHFFFAOYSA-N but-2-enyl acetate Chemical compound CC=CCOC(C)=O WNHXJHGRIHUOTG-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011985 first-generation catalyst Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
The invention provides a supported catalyst, a preparation method and application thereof, and a preparation method of a hydrogenated olefin polymer. The load typeThe catalyst comprises: a first carrier and a metal catalyst supported on the first carrier; wherein the first carrier comprises at least one of: nano silicon dioxide, molecular sieve, mgCl 2 ·AlCl 3 nEtOH or an ionic liquid carrier comprising:
MgCl 2 ·AlCl 3 n in nEtOH is a positive integer between 2 and 6; the metal catalyst comprises at least one of:
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a supported catalyst, a preparation method and application thereof, and a preparation method of a hydrogenated olefin polymer.
Background
Olefin metathesis as one of the effective methods for constructing novel carbon-carbon double bonds, many novel polymer materials and novel techniques have been developed, and for example, ring-opening olefin metathesis polymerization is one of the techniques. Currently, the catalysts used in ring-opening olefin metathesis polymerization reactions and other metathesis reactions in a wide range of applications are catalysts based on molybdenum systems and ruthenium systems.
In order to develop end-capped functional polymers based on ring-opening olefin metathesis polymerization, a variety of catalysts have been developed, including: first, second and third generation catalysts of Grubbs and first and second generation catalysts of Hoveyda-Grubbs. However, these catalysts have the disadvantages of difficult reuse and difficult product separation, and the subsequent catalytic hydrogenation of the catalytic polymer is not achieved.
Disclosure of Invention
In view of the above, the invention provides a supported catalyst, a preparation method and application thereof, and a preparation method of a hydrogenated olefin polymer, so as to solve the technical problems that the existing catalyst is difficult to reuse and separate products, and the subsequent catalytic hydrogen hydrogenation reaction of the polymer is difficult to realize.
In order to achieve the above object, the present invention provides a supported catalyst comprising: a first support and a metal catalyst supported on the first support;
wherein the first carrier comprises at least one of: nano silicon dioxide, molecular sieve, mgCl 2 ·AlCl 3 nEtOH or an ionic liquid carrier comprising:
According to an embodiment of the invention, wherein the second carrier comprises: and (4) nano silicon dioxide.
According to the embodiment of the present invention, wherein the mass ratio of the metal catalyst to the first carrier is 1: (20 to 2000).
The invention also provides a method for preparing the supported catalyst, which comprises the following steps: dissolving a metal catalyst in a first organic solution to obtain a precursor solution;
dispersing the first carrier in a second organic solution to obtain a pretreatment product;
adding the precursor solution into the pretreated product, and stirring and reacting for a preset time to obtain a supported catalyst;
wherein the metal catalyst comprises at least one of:
or->
The first carrier includes at least one of: nano silicon dioxide, molecular sieve, mgCl 2 ·AlCl 3 nEtOH or an ionic liquid carrier comprising:
According to an embodiment of the invention, wherein the second carrier comprises: and (4) nano silicon dioxide.
According to an embodiment of the present invention, wherein the first organic solution and the second organic solution are mutual soluble solutions, the first organic solution and the second organic solution each comprise at least one of: methylene chloride, toluene, tetrahydrofuran, benzene, tetrachloromethane, 1, 4-dioxane, or 1, 2-dichloroethane.
According to the embodiment of the invention, the preset time for stirring is 20-70 minutes; the preset time of the reaction is 10 to 120 minutes.
The invention also provides an application of the supported catalyst in the catalytic hydrogenation reaction of olefin polymers, wherein the supported catalyst is used for catalyzing the hydrogen hydrogenation reaction of the olefin polymers; the supported catalyst is the supported catalyst or is prepared by the preparation method.
The present invention also provides a method for preparing a hydrogenated olefin polymer based on a supported catalyst, comprising:
carrying out catalytic polymerization reaction on olefin and polar monomer by using a supported catalyst to obtain an olefin polymer;
adding the olefin polymer, the supported catalyst and the reaction solution into a high-pressure hydrogen hydrogenation device, and introducing hydrogen to perform catalytic hydrogenation reaction to obtain a hydrogenated olefin polymer;
wherein the pressure of the high-pressure hydrogen is 2 MPa-10 MPa, and the supported catalyst is the supported catalyst or prepared by the preparation method.
According to an embodiment of the present invention, in which olefin and polar monomer are catalytically polymerized by using a supported catalyst to obtain an olefin polymer, the method comprises:
immersing containers containing the supported catalysts, the reaction solution, the polar monomer and the olefin with different capacities into an oil bath with preset temperature for reaction for preset time to obtain a reacted product, wherein the preset temperature is 30-60 ℃, and the preset time in the oil bath is 1-3 hours;
filtering and evaporating a product after reaction to obtain a separated polymer;
the separated polymer is washed and dried to obtain an olefin polymer.
Based on the technical scheme, the invention can at least realize one of the following technical effects:
(1) According to the invention, the ionic liquid is introduced into the second carrier to form the ionic liquid carrier, the supported catalyst is formed based on the ionic liquid carrier and the metal catalyst load, the ionic liquid can change the surface morphological characteristics of the second carrier, and the ionic liquid is loaded on the surface of the second carrier to form a medium for anchoring the metal catalyst, so that the direct interaction between the surface of the second carrier and the homogeneous metal catalyst can be prevented, and the steric hindrance and poisoning effect of the second carrier on the metal center can be reduced.
(2) The supported catalyst provided by the invention changes a homogeneous metal catalyst into a heterogeneous catalyst, so that the supported catalyst can improve the utilization efficiency of the catalyst and ash removal by recovering the catalyst, increase the reuse and product separation of the catalyst, reduce the content of heavy metal and desalt the color of a polymer.
(3) The supported catalyst provided by the invention can provide the application of the catalytic performance of subsequent hydrogen hydrogenation for the unsaturated polymer of the polymerization system.
Drawings
FIG. 1 schematically shows a flow diagram of a method for preparing a supported catalyst according to an embodiment of the invention;
FIG. 2 schematically shows a schematic diagram of a method of preparing a supported catalyst according to an embodiment of the invention;
FIG. 3 schematically shows a flow diagram of a process for producing a hydrogenated olefin polymer based on a supported catalyst according to an embodiment of the present invention;
FIG. 4 schematically shows NMR spectra of an olefin polymer before and after hydrogenation.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
In view of the problems of the prior art that the conventional catalyst is difficult to recycle and separate products in the ring-opening polymerization of olefin metathesis, and to implement the application of the catalyst in the subsequent hydrogen hydrogenation of catalytic polymer, there is a need for a catalyst system to solve at least some of the above technical problems.
Based on this, in one aspect, the present invention provides a supported catalyst comprising: a first carrier and a metal catalyst supported on the first carrier.
According to an embodiment of the invention, the first carrier may comprise at least one of: nano silicon dioxide, molecular sieve, mgCl 2 ·AlCl 3 nEtOH (aluminum trichloride magnesium dichloride ethanol complex) or an ionic liquid carrier.
According to an embodiment of the invention, mgCl 2 ·AlCl 3 N in nEtOH is a positive integer between 2 and 6.
According to embodiments of the present invention, the ionic liquid carrier may be formed by introducing an ionic liquid to the surface of the second carrier and/or within the second carrier.
According to embodiments of the present invention, the ionic liquid carrier may comprise:
According to an embodiment of the present invention, the second support may be nanosilica.
According to the embodiment of the invention, by introducing the ionic liquid into the second carrier, the ionic liquid can change the surface morphological characteristics of the second carrier, and cover the surface of the carrier to form the medium for anchoring the metal catalyst, so that the direct interaction between the surface of the second carrier and the metal catalyst can be prevented, and the steric hindrance and poisoning effect of the second carrier on the metal center can be reduced.
According to an embodiment of the present invention, the metal catalyst has a catalytic activity, which is supported on the surface and/or inside of the first carrier.
According to an embodiment of the present invention, the metal catalyst may include at least one of the following metal complexes: grubbs second generation catalysts
Grubbs third generation catalyst->
Hoveyda-Grubbs second generation catalyst>
Or an ionic liquid substituted Hoveyda-Grubbs second generation catalyst
According to an embodiment of the present invention, the mass ratio of the metal catalyst to the first support may be 1: (20 to 2000), preferably, 1.
According to the embodiment of the present invention, the metal catalyst can be uniformly supported on the first support by the above-mentioned mass ratio of the metal catalyst to the first support, and a high supporting amount can be obtained.
According to the embodiment of the invention, the supported catalyst provided by the invention can change a homogeneous metal catalyst into a heterogeneous catalyst, so that the supported catalyst can improve the utilization efficiency of the catalyst and ash removal by recovering the catalyst, increase the reuse and product separation of the catalyst, reduce the content of heavy metal and fade the color of a polymer.
The following examples illustrate the structure of several supported catalysts according to the invention so that the skilled person can better understand the solution.
Specifically, the supported catalyst having the structure of the present invention may be as the following structural formula (I) 1 )～(I 6 ) The structure of any one of, for example:
it should be noted that the structure of the supported catalyst shown above is merely exemplary, and does not limit the protection scope of the present invention, and in some other embodiments, other different types or forms of supported catalyst structures may be selected according to actual needs, and are not limited herein.
On the other hand, the invention also provides a preparation method based on the supported catalyst.
FIG. 1 schematically shows a flow diagram of a method for preparing a supported catalyst according to an embodiment of the invention; fig. 2 schematically shows a schematic diagram of a method for preparing a supported catalyst according to an embodiment of the present invention.
As shown in fig. 1, the preparation method may include: operations S110 to S130.
In operation S110, a metal catalyst is dissolved in a first organic solution to obtain a precursor solution.
In operation S120, the first carrier is dispersed in the second organic solution to obtain a pretreated product.
In operation S130, the precursor solution is added to the pretreated product, and the supported catalyst is obtained after stirring and reacting for a predetermined time.
According to an embodiment of the present invention, a metal catalyst may be dissolved in a first organic solvent under an inert atmosphere to form a supported catalyst precursor solution.
According to an embodiment of the present invention, the metal catalyst may include at least one of the following metal complexes:
grubbs second generation catalysts
Grubbs third generation catalyst->
Hoveyda-Grubbs second generation catalyst>
Or an ionic liquid-substituted Hoveyda-Grubbs secondary catalyst>
According to an embodiment of the present invention, the pre-treatment product may be a solution in which the first carrier is dispersed.
According to an embodiment of the invention, the first carrier comprises at least one of: nano silicon dioxide, molecular sieve, mgCl 2 ·AlCl 3 nEtOH or ionic liquid vehicle, mgCl 2 ·AlCl 3 N in nEtOH is a positive integer between 2 and 6.
According to embodiments of the present invention, the ionic liquid carrier may comprise:
According to an embodiment of the present invention, the second support may include nano-silica.
According to an embodiment of the present invention, the first organic solvent and the second organic solvent may be mutual soluble solutions, and each of the first organic solution and the second organic solution may include at least one of: methylene chloride, toluene, tetrahydrofuran, benzene, tetrachloromethane, 1, 4-dioxane, or 1, 2-dichloroethane.
According to the embodiment of the invention, the precursor solution is added into the pretreated product, the mixture is stirred for the preset time, and after the reaction is carried out for the preset time in the stirring process, the supported catalyst can be obtained by filtering, leaching and draining the solid.
According to embodiments of the present invention, the pre-trial time for stirring may be 20 to 70 minutes; the preset reaction time may be 10 to 120 minutes.
Referring to fig. 2, according to the embodiment of the present invention, the reaction may be understood as a process in which the metal catalyst in the precursor solution is supported on the first carrier in the pretreated product, and finally, a supported catalyst is formed.
The method for preparing the supported catalyst exemplified by the ionic liquid carrier is described in further detail below with specific examples. It should be noted that, although the following describes the preparation method of the supported catalyst exemplified by the ionic liquid carrier of the present invention, it is understood that this specific example can realize the supported catalyst of the present invention in various forms, and is not intended to limit the present invention.
Examples 1 to 2 exemplify the preparation of an ionic liquid carrier, and examples 3 to 8 exemplify the preparation of a supported catalyst using an ionic liquid carrier as a first carrier.
Example 1
Preparing an ionic liquid carrier I, wherein the ionic liquid carrier I has the structure:
preparing the ionic liquid carrier I may include: 17.47g of 1-methyl-3-butylimidazolium chloride and 26.67g of anhydrous AlCl were added to a round-bottomed flask under an inert gas atmosphere 3 And stirring for at least 24 hours to obtain the ionic liquid. The ionic liquid is added to the calcined silica and stirred again for at least 24 hours,followed by rinsing with hot dichloromethane provided ionic liquid vehicle I.
Example 2
Preparing an ionic liquid carrier II, wherein the structure of the ionic liquid carrier II is as follows:
preparing the ionic liquid carrier II may include: under an inert gas atmosphere, 27.65g of 1-methyl-3- [3- (triethylsiloxy) propyl group]Imidazolium chloride was added to the calcined silica and stirred for at least 24 hours, followed by 2 equivalents (26.67 g) of anhydrous AlCl 3 And stirred overnight, followed by rinsing with hot dichloromethane, to afford ionic liquid carrier II.
Example 3
Preparation of the above Supported catalyst of formula (I) 1 ) The process of (2):
specifically, under the atmosphere of inert gas, grubbs second generation catalyst
10mg of the metal complex are dissolved in methylene chloride and added to the ionic liquid carrier I->
Stirring the dichloromethane solution for 60 minutes, filtering and leaching the solid, and pumping to obtain the supported catalyst (I) 1 )。
Example 4
Preparation of the above Supported catalyst 2 ) The process of (2):
specifically, under the inert gas atmosphere, grubbs third generation catalyst is added
10mg of metal complex are dissolved in dichloromethane and added to 1g of ionic liquid carrier I->
Stirring the dichloromethane solution for 60 minutes, filtering and leaching the solid, and pumping to obtain the supported catalyst (I) 2 )。
Example 5
Preparation of the above Supported catalyst of formula (I) 3 ) The process of (2):
specifically, under the inert gas atmosphere, the ionic liquid substituted Hoveyda-Grubbs second generation catalyst
10mg of the metal complex are dissolved in methylene chloride and added to the ionic liquid carrier I->
Stirring the dichloromethane solution for 60 minutes, filtering and leaching the solid, and pumping to obtain the supported catalyst (I) 3 )。
Example 6
Preparation of the above Supported catalyst of formula (I) 4 ) The process of (2):
specifically, under the atmosphere of inert gas, grubbs second generation catalyst
10mg of the metal complex are dissolved in methylene chloride and added to the ionic liquid carrier II dispersed with 1g>
Stirring the dichloromethane solution for 60 minutes, filtering and leaching the solid, and pumping to obtain the supported catalyst (I) 4 )。
Example 7
Preparation of the above Supported catalyst of formula (I) 5 ) The process of (2):
specifically, under the inert gas atmosphere, grubbs third generation catalyst is added
10mg of the metal complex are dissolved in methylene chloride and added to the ionic liquid carrier II dispersed with 1g>
Stirring the dichloromethane solution for 60 minutes, filtering and leaching the solid, and pumping to obtain the supported catalyst (I) 5 )。
Example 8
Preparation of the above Supported catalyst of formula (I) 6 ) The process of (2):
specifically, under the inert gas atmosphere environment, the ionic liquid substituted Hoveyda-Grubbs second generation catalyst
10mg of the metal complex is dissolved in methylene chloride and added to the solution in which 1 is dispersedg Ionic liquid Carrier II
Stirring the dichloromethane solution for 60 minutes, filtering and leaching the solid, and pumping to obtain the supported catalyst (I) 6 )。
In another aspect, the invention also provides the use of a supported catalyst for catalyzing hydrogenation reactions in olefin polymers. The supported catalyst may be a supported catalyst having any of the above structures, or a supported catalyst prepared by the above preparation method.
According to embodiments of the present invention, the supported catalyst can be used to catalyze hydrogen hydrogenation reactions of olefin polymers.
In another aspect, the present invention also provides a method for preparing a hydrogenated olefin polymer based on the supported catalyst.
FIG. 3 schematically shows a flow chart of a method for producing a hydrogenated olefin polymer based on a supported catalyst according to an embodiment of the present invention.
As shown in fig. 3, the method may include: operation S310 to operation S320.
In operation S310, an olefin and a polar monomer are catalytically polymerized using a supported catalyst to obtain an olefin polymer.
In operation S320, the olefin polymer, the supported catalyst, and the reaction solution are added to a high-pressure hydrogen hydrogenation apparatus, and hydrogen is introduced to perform a catalytic hydrogenation reaction, thereby obtaining a hydrogenated olefin polymer.
According to the embodiment of the present invention, the supported catalyst may be a supported catalyst having any one of the above structures, or may be a supported catalyst prepared by the above preparation method.
According to embodiments of the present invention, the pressure of the high pressure hydrogen may be 2MPa to 10MPa, and the olefin may include one or both of cyclooctene and norbornene; the polar monomer may include at least one of: 1, 4-butenediol, dimethyl maleate, butenediamide, maleic acid, 1, 4-acetoxy-2-butene or 1, 4-dichloro-2-butadiene.
According to an embodiment of the present invention, the polymerization temperature of the polymerization reaction may include 30 to 60 ℃, and preferably, the polymerization temperature may be 30 ℃, 40 ℃, 50 ℃, 60 ℃. The polymerization pressure in the polymerization reaction may be atmospheric polymerization.
According to embodiments of the present invention, the polymerization reaction is generally carried out in an organic solvent, such as an organic solvent of a hydrocarbon, a cyclic hydrocarbon or an aromatic hydrocarbon. To further facilitate reactor operation and polymerization of the product, in some preferred embodiments, the organic solvent may also employ hydrocarbons of less than 12 carbons, including, but not limited to, methylene chloride, tetrahydrofuran, toluene, and mixtures thereof, for example.
The above descriptions of the temperature, pressure, olefin type, organic solvent, polymerization process and the like used in the polymerization process are only exemplary according to the embodiments of the present invention, so that those skilled in the art can understand the scheme of the present invention and do not intend to limit the protection scope of the present invention.
According to the embodiment of the invention, olefin and polar monomer are subjected to catalytic polymerization reaction by using a supported catalyst to obtain an olefin polymer, which comprises the following steps:
and (2) immersing containers containing the supported catalysts, the reaction solution, the polar monomer and the olefin with different capacities into an oil bath with a preset temperature for reaction for a preset time to obtain a product after the reaction, wherein the preset temperature is 30-60 ℃, and the preset time in the oil bath is 1-3 hours. The product after the reaction was filtered and evaporated to give an isolated polymer. The separated polymer is washed and dried to obtain an olefin polymer.
According to an embodiment of the present invention, different volumes of supported catalyst, reaction solution, polar monomer and olefin can be transferred to a flask vessel via syringe and continuously purged with nitrogen.
According to the embodiment of the invention, flask containers containing different volumes of supported catalyst, reaction solution, polar monomer and olefin are placed under vacuum, nitrogen is charged, and the flask containers are immersed in an oil bath at a preset temperature for a preset time to obtain a reacted product.
According to an embodiment of the present invention, the product after the reaction may be filtered and the supported catalyst and the solution may be separated, the solution may be evaporated under vacuum, precipitated into formaldehyde to obtain a separated polymer, and the separated polymer may be washed and vacuum-dried for a predetermined time to obtain a white solid olefin polymer.
The polymerization of an olefin polymer with the supported catalyst described above to give an olefin polymer will be described in further detail with reference to specific examples. It should be noted that, although the process of the present invention based on the supported catalyst is described below as an example, it is understood that the specific example can realize the preparation of the olefin polymer of the present invention in various forms, and is not intended to limit the present invention.
Example 9 illustrates a preparation process for producing an olefin polymer by catalytic polymerization based on a supported catalyst and polymerization results of the olefin polymer; example 10 illustrates a hydrogenated olefin polymer obtained after hydrogen hydrogenation reaction based on the polymer prepared in example 9.
Example 9
In this embodiment, a supported catalyst with one of the above structures is used to perform polymerization of cyclooctene and polar internal olefin monomers, specifically:
the supported catalyst (250 mg), anhydrous dichloromethane (40 mL), 1, polar internal olefin monomer (e.g., 4-acetoxy-2-butene (0.3 mmol)), and cyclooctene (15 mmol) were transferred by syringe to a 100mL flask vessel with a continuous nitrogen purge. The flask and its contents were placed under vacuum and then refilled with nitrogen. Immediately after immersing the flask in an oil bath at 40 ℃ for 2 hours, the supported catalyst and the solution were separated by filtration, and then the solution was evaporated to dryness under vacuum and then precipitated into 200mL of methanol to obtain an isolated polymer. Further washed with methanol (3X 50 mL) and dried in vacuo for 6 hours to give an olefin polymer as a white solid.
Table 1 shows the polymerization results of the olefin polymers prepared.
TABLE 1
In Table 1, a represents polymerization conditions of a polymerization reaction, that is, 15mmol of cyclooctene, 0.3mmol of an internal olefin monomer, 250mg of a supported catalyst (carrier), and 40ml of methylene chloride; b represents the average of the yields of at least two replicates; c represents according to 1 Calculating the percent of reaction of the polar internal olefin monomer in the polymer by the integral ratio of repeating units and internal olefin protons in the H NMR (nuclear magnetic resonance) spectrum; d represents the molecular weight determined by gel chromatography (SEC) with multi-angle light scattering from polystyrene standards.
As can be seen from Table 1, the supported catalyst provided by the invention can catalyze the polymerization reaction of cyclooctene and polar internal olefin monomers under certain conditions to generate olefin polymers, and the value of the number average molecular weight ranges from 20 x 10 3 ～70×10 3 The molecular weight distribution is 1-1.6.
Example 10
The reaction solution and the supported catalyst system (including the polymerized olefin polymer and the supported catalyst) after the reaction without recrystallization treatment in example 9 were transferred to a high-pressure hydrogen hydrogenation apparatus and hydrogen gas was introduced to perform a hydrogen hydrogenation reaction of the polymer, which specifically comprises the following steps:
taking a part of olefin polymer out of the reactor as a sample before hydrogenation for testing, adding the rest reaction liquid into a high-pressure hydrogen hydrogenation device, introducing hydrogen under the hydrogen pressure of 3MPa for reacting for 8 hours, purifying the reaction product, extracting the hydrogenated olefin polymer, and carrying out hydrogenation 1 And H NMR spectrum testing.
It should be noted that, the purification treatment of the reaction product may include: the supported catalyst and the solution were separated by filtration, and then the solution was evaporated to dryness under vacuum, and then precipitated into 200mL of methanol to obtain an isolated polymer. Further washing with methanol (3X 50 mL) was conducted, and vacuum drying was conducted for 6 hours to obtain a hydrogenated olefin polymer as a white solid.
FIG. 4 schematically shows NMR spectra of an olefin polymer before and after hydrogenation.
As shown in fig. 4, it can be seen from fig. 4 that the non-double bond-adjacent methylene peak integrated after hydrogenation of 6.67 was integrated as compared with the non-double bond-adjacent methylene peak integrated before hydrogenation of 4.14 under the criterion that the nuclear magnetic peak integrated intensity of the carbon-carbon double bond was 1, and the non-double bond-adjacent methylene peak integrated after hydrogenation of 6.67 was increased. This is because part of the carbon-carbon double bonds in the molecular chain become saturated carbon-carbon double bonds, resulting in that part of the double bonds and methylene groups adjacent to the double bonds become non-double bond-adjacent methylene groups, and therefore, the peak integral of the non-double bond-adjacent methylene groups of the hydrogenated olefin polymer increases. Therefore, the supported catalyst provided by the invention can catalyze the hydrogen hydrogenation reaction of olefin polymers under certain conditions, and the hydrogenation catalytic efficiency can reach 56.3% through nuclear magnetic integral calculation.
According to the embodiment of the invention, after the olefin polymer is prepared by the supported catalyst with the structure, hydrogen is introduced to continuously catalyze the olefin polymer to obtain the hydrogenated olefin polymer, so that the hydrogenated olefin polymer with higher molecular force and saturation can be obtained in the application of subsequent catalytic hydrogenation reaction of the olefin polymer.
The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above embodiments are only examples of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A supported catalyst comprising: a first support and a metal catalyst supported on the first support;
wherein the first carrier comprises at least one of: nano silicon dioxide, molecular sieve, mgCl 2 ·AlCl 3 nEtOH or an ionic liquid carrier, said ionic liquid carrierThe body includes:
2. the supported catalyst of claim 1, wherein the second support comprises: the nano silicon dioxide.
3. The supported catalyst of claim 1, wherein the mass ratio of the metal catalyst to the first support is 1: (20 to 2000).
4. A process for the preparation of a supported catalyst as claimed in any one of claims 1 to 3, comprising:
dissolving a metal catalyst in a first organic solution to obtain a precursor solution;
dispersing the first carrier in a second organic solution to obtain a pretreated product;
adding the precursor solution into the pretreated product, and stirring and reacting for a preset time to obtain a supported catalyst;
wherein the metal catalyst comprises at least one of:
the first carrier includes at least one of: nano silicon dioxideMolecular sieves, mgCl 2 ·AlCl 3 nEtOH or an ionic liquid carrier comprising:
5. The production method according to claim 4, wherein the second carrier includes: the nano silicon dioxide.
6. The production method according to claim 4, wherein the first organic solution and the second organic solution are mutually soluble solutions, each of the first organic solution and the second organic solution including at least one of: methylene chloride, toluene, tetrahydrofuran, benzene, tetrachloromethane, 1, 4-dioxane, or 1, 2-dichloroethane.
7. The preparation method according to claim 4, wherein the preset time of the stirring is 20 to 70 minutes; the preset time of the reaction is 10 to 120 minutes.
8. Use of a supported catalyst for catalyzing a hydrogenation reaction in an olefin polymer, wherein the supported catalyst is used for catalyzing a hydrogen hydrogenation reaction of the olefin polymer; the supported catalyst is prepared by the supported catalyst according to any one of claims 1 to 3 or the preparation method according to any one of claims 4 to 7.
9. A process for preparing a hydrogenated olefin polymer based on a supported catalyst, comprising:
carrying out catalytic polymerization reaction on olefin and polar monomer by using a supported catalyst to obtain an olefin polymer;
adding the olefin polymer, the supported catalyst and the reaction solution into a high-pressure hydrogen hydrogenation device, and introducing hydrogen to perform catalytic hydrogenation reaction to obtain a hydrogenated olefin polymer;
wherein the pressure of the high-pressure hydrogen is 2MPa to 10MPa, and the supported catalyst is prepared by the supported catalyst according to any one of claims 1 to 3 or the preparation method according to any one of claims 4 to 7.
10. The method of claim 9, wherein the catalytically polymerizing the olefin and the polar monomer with the supported catalyst to obtain the olefin polymer comprises:
immersing containers containing the supported catalyst, the reaction solution, the polar monomer and the olefin with different capacities into an oil bath with a preset temperature for reaction for a preset time to obtain a reacted product, wherein the preset temperature is 30-60 ℃, and the preset time in the oil bath is 1-3 hours;
filtering and evaporating the product after the reaction to obtain a separated polymer;
washing and drying the separated polymer to obtain the olefin polymer.
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