CN107118288A - A kind of supported late transition metal catalyst and preparation method thereof - Google Patents
A kind of supported late transition metal catalyst and preparation method thereof Download PDFInfo
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- CN107118288A CN107118288A CN201710377767.XA CN201710377767A CN107118288A CN 107118288 A CN107118288 A CN 107118288A CN 201710377767 A CN201710377767 A CN 201710377767A CN 107118288 A CN107118288 A CN 107118288A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/7003—Bidentate ligand
- C08F4/7004—Neutral ligand
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F212/08—Styrene
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Abstract
The invention provides a kind of supported late transition metal catalyst and preparation method thereof, the supported late transition metal catalyst includes late transition metal α diimine complex and carboxylic polystyrene carrier, and the late transition metal α diimine complex is acted on the carboxylic polystyrene carrier by chemical bonding.An embodiment of the present invention provides a kind of supported late transition metal catalyst, with the catalyst ethene, higher catalytic activity can be obtained in the case of without using co-catalyst, advantageously reduce production cost, and active component is by being covalently bonded on carrier, difficult for drop-off, heat endurance is good.
Description
Technical field
The present invention relates to late transition metal catalyst, be specially it is a kind of can be used for preparing highly -branched polyethylene, and with compared with
The supported late transition metal catalyst of high catalytic activity.
Background technology
Late transition metal catalyst is the metal complexes centered on group VIII metal element, is had to olefinic polymerization
There is very high catalytic activity, be the new single active center's homogeneous catalyst of the another class occurred after metallocene catalyst.
Late transition metal catalyst prepares simple, single active center, catalytic activity height, can also be by changing ligand structure
Polyolefin structure is adjusted, it is easy to obtain the high polymer of narrow molecular weight distribution, structure-controllable, the degree of branching.Although rear mistake
Crossing metallic catalyst has the advantages that uniqueness, but there are still heat endurance is poor, co-catalyst consumption is high, living in use
Property center easy in inactivation, the problems such as disperse uneven in heterogeneous system (slurry polymerization and gas-phase polymerization), the load of catalyst
Change is to solve one of important channel of these problems.
The carrier of late transition metal catalyst can be SiO2、Al2O3、MgCl2, the inorganic material such as molecular sieve or
The organic materials such as cyclodextrin, polystyrene, polysiloxanes, can also be the compound of several different carriers.Mode of loading can be with
It is physical absorption, can also be loaded to catalyst on carrier by the bonding action of functional group, physical absorption operation letter
Single, active force is weak, and catalyst is easy to come off from carrier in catalyzed polymerization process；The latter be then catalyst by covalent bond with
Carrier is connected, and this mode of loading bond strength is big, can be prevented effectively from coming off for catalyst, be current late transition metal catalyst
The study hotspot of load technology.
The content of the invention
A primary object of the present invention is to provide a kind of supported late transition metal catalyst, including late transition metal
Alpha-diimine complex and carboxylic polystyrene carrier, the late transition metal alpha-diimine complex pass through chemical bonding
Act on the carboxylic polystyrene carrier, the structure of the late transition metal alpha-diimine complex is：
Wherein, M is VIII race's late transition metal atom；X is bromine or chlorine；
R1、R2It is respectively selected from hydrogen atom, C1~C10Alkyl, substituted or unsubstituted aryl, or R1、R2With it is adjacent
Carbon atom constitutes acenaphthenyl or phenanthryl together；
R3、R4、R5、R6It is respectively selected from hydrogen atom, C1~C10Alkyl or containing heteroatomic alkyl, C3~C10Cycloalkyl
Or containing heteroatomic cycloalkyl or substituted or unsubstituted aryl；
R7、R8It is respectively selected from hydrogen atom, C1~C5Alkyl, C3~C5Cycloalkyl, or C1~C5Hydroxyl alkane
Base, C3~C5Hydroxyl cycloalkyl, and R7And R8In at least contain oh group.
According to an embodiment of the present invention, the structure of the late transition metal alpha-diimine complex is：
According to an embodiment of the present invention, the quality of late transition metal exists in the late transition metal alpha-diimine complex
Mass content in the loaded late transition metal catalyst is 0.1~1.0%.
According to an embodiment of the present invention, the carboxylic polystyrene is particle diameter between 0.1~100 μm of microballoon.
According to an embodiment of the present invention, the carboxylic polystyrene is made by polymerized monomer copolymerization, and the polymerization is single
Body includes styrene, divinylbenzene and the vinyl monomer containing carboxyl.
According to an embodiment of the present invention, the styrene of the polymerized monomer including 70.0~90.0wt%, 5.0~
15.0wt% divinylbenzene and the 5.0~20.0wt% vinyl monomer containing carboxyl, involved weight percent
Content is on the basis of the gross weight of the polymerized monomer.
According to an embodiment of the present invention, the styrene of the polymerized monomer including 75.0~85.0wt%, 5.0~
10.0wt% divinylbenzene and the 7.0~15.0wt% vinyl monomer containing carboxyl.
According to an embodiment of the present invention, the vinyl monomer containing carboxyl is selected from acrylic acid, methacrylic acid, fourth
One or more in olefin(e) acid, methylene-succinic acid, maleic acid.
Invention further provides a kind of above-mentioned supported late transition metal method for preparing catalyst, including will be described after
Transition metal alpha-diimine complex and carboxylic polystyrene react at 0~50 DEG C, and transition gold after the support type is made
Metal catalyst.
An embodiment of the present invention provides a kind of supported late transition metal catalyst, with the catalyst ethene,
Higher catalytic activity can be obtained in the case of without using co-catalyst, and active component is difficult to come off from carrier, heat is steady
It is qualitative good.
Embodiment
Embodying the exemplary embodiments of inventive features and advantage will describe in detail in the following description.It should be understood that this hair
Bright to have various changes in different embodiments, it is neither departed from the scope of the present invention, and description therein is at this
Purposes of discussion is treated as in matter, and is not used to the limitation present invention.
An embodiment of the present invention provides a kind of supported late transition metal catalyst, including late transition metal α-two Asias
Amine complex and carboxylic polystyrene carrier, late transition metal alpha-diimine complex act on carboxyl by chemical bonding
Change polystyrene, the structure of late transition metal alpha-diimine complex is：
Wherein, M is VIII race's late transition metal atom, such as nickel or palladium；X is bromine or chlorine.
R1、R2Hydrogen atom, C can be respectively selected from1~C10Alkyl, substituted or unsubstituted aryl (such as C6~C10Virtue
Base), or R1、R2Acenaphthenyl or phenanthryl are constituted together with adjacent carbon atom；For example, R1、R2It can be respectively methyl, ethyl, third
Base, phenyl etc., work as R1、R2When constituting acenaphthenyl together with adjacent carbon atom, the structure of late transition metal alpha-diimine complex
For：
R3、R4、R5、R6Hydrogen atom, C can be respectively selected from1~C10Alkyl or containing heteroatomic alkyl, C3~C10Cycloalkanes
Base or containing heteroatomic cycloalkyl or substituted or unsubstituted aryl (such as C6~C10Aryl)；For example, R3、R4、R5、R6
Can be respectively methyl, ethyl, propyl group, cyclopenta, cyclohexyl, phenyl, methoxyl group, chloromethyl (- CH2Cl) etc..
R7、R8Hydrogen atom, C can be respectively selected from1~C5Alkyl, C3~C5Cycloalkyl, C1~C5Hydroxyl alkyl,
C3~C5Hydroxyl cycloalkyl, and R7And R8In at least contain oh group.Such as R7、R8Can be respectively methyl, second
Base, propyl group, methylol, ethoxy etc..
In an embodiment of the present invention, active component late transition metal alpha-diimine complex is bonded by hydroxy chemical
In on carboxylic polystyrene carrier so that the bond strength of active component alpha-diimine complex and carrier is big, can be effective
Active component in polymerization process is avoided to be come off from carrier.
The supported late transition metal catalyst of an embodiment of the present invention, late transition metal alpha-diimine complex passes through
Hydroxy chemical is bonded on carboxylic polystyrene carrier.With the polymerization of the catalyst ethene, carrier surface carboxylic group
Acidity can with activated catalyst formation catalytic active species, greater catalytic can be obtained in the case of without using co-catalyst
Activity, advantageously reduces production cost, and active component is by being covalently bonded on carrier, is difficult in course of reaction from carrier
On come off, heat endurance is good.
In an embodiment of the present invention, the mass content of late transition metal such as nickel or palladium in loaded catalyst is
0.1~1.0%, such as can be 0.2%, 0.4%, 0.6%, 0.8%.
In an embodiment of the present invention, carboxylic polystyrene refers to wrap carboxylic polystyrene, and it can be by polymerizeing
Monomer copolymerization is made, and polymerized monomer may include styrene, divinylbenzene, vinyl monomer containing carboxyl etc..
The present invention is not limited the specific method for preparing carboxylic polystyrene, and for example carboxylic polystyrene can pass through
The methods such as emulsion polymerization, dispersin polymerization, suspension polymerisation are made, wherein being made preferably by the method for dispersin polymerization.
The present invention is not limited the microstructure of the carboxylic polystyrene as carrier, can be made by dispersin polymerization
Carboxylic polystyrene with micro-sphere structure, the average grain diameter of microballoon is preferably 0.1~100 μm.
In an embodiment of the present invention, the styrene of polymerized monomer including 70.0~90.0wt%, 5.0%~
15.0wt% divinylbenzene, the 5.0%~20.0wt% vinyl monomer containing carboxyl, involved weight percent contains
Amount is on the basis of the gross weight of the polymerized monomer.
In another embodiment of the invention, the styrene of polymerized monomer including 75.0~85.0wt%, 5.0%~
10.0wt% divinylbenzene, the 7.0%~15.0wt% vinyl monomer containing carboxyl.
In the polymerized monomer of an embodiment of the present invention, the content of styrene is 75.0~85.0wt%, divinylbenzene
Content is 5.0%~10.0wt%, and carboxyl comonomer content is 7.0%~15.0wt%.
In an embodiment of the present invention, the vinyl monomer containing carboxyl can be acrylic acid, methacrylic acid, butylene
Acid, methylene-succinic acid, maleic acid etc..
In an embodiment of the present invention, active component alpha-diimine complex is bonded with carrier carboxylic polystyrene
Method can be：Carboxylic polystyrene and late transition metal alpha-diimine complex are fitted into two mouthfuls of glass reaction bottles, plus
Enter DMF and NaHCO3, 0~50 DEG C of reaction temperature, stirring reaction 1~10 hour, filtering, washing, dry, mistake after obtained support type
Cross metallic catalyst.
In an embodiment of the present invention, ethene can be carried out by methods such as polymerisation in solution, gas-phase polymerization, slurry polymerizations
Polymerization, to prepare highly -branched polyethylene.For example, the process that solution polymerization process prepares highly -branched polyethylene is：It is anti-using n-hexane
Solvent is answered, the late transition metal alpha-diimine complex loaded using carboxylic polystyrene is anti-at 0~120 DEG C as catalyst
Polymerase 10 .1~12 hour under temperature, 0.1~10MPa reaction pressure are answered, highly -branched polyethylene is made.
Preferably, polymerisation in solution prepare highly -branched polyethylene reaction pressure be 0.5~5MPa, reaction temperature be 20~
100 DEG C, polymerization time is 0.2~4 hour.
Using supported late transition metal catalyst preparation highly -branched polyethylene of the present invention, without using co-catalyst
In the case of can obtain higher catalytic activity, the reaction time is short, and production cost is low；Late transition metal catalyst and carrier carboxyl
Acted on and connected by chemical bonding between change polystyrene, bond strength is big, can be prevented effectively from activated centre in polymerization process
Come off from carrier, catalyst heat endurance is good.
Below, the supported late transition metal catalyst of an embodiment of the present invention is done further in conjunction with specific embodiments
Explanation.Wherein, the part of catalyst passes through nuclear-magnetism1H NMR、13C NMR and elementary analysis carry out exterior syndrome checking, catalyst α-two
Imine nickel late transition metal complex is by elemental analysis, using late transition metal on carrier after ICP method measure load
Content.The average grain diameter of polystyrene microsphere is tested using ESEM (SEM), method of testing is 50 microballoons of random measurement
Particle diameter simultaneously calculates average value.The molecular weight of highly -branched polyethylene is tested using gel permeation chromatograph (GPC), and calculates polyethylene
Molecular weight distribution；Using1H nuclear magnetic resonances instrument is carried out to highly -branched polyethylene1H NMR are characterized, by calculating chemical shift
Non-aromatics methyl H atom at 0.5~1.05ppm accounts for total non-aromatics H atom number of the chemical shift at 0.5~2.1ppm
The ratio of amount, obtains the degree of branching of highly -branched polyethylene.
Embodiment 1
The preparation of carboxylic polystyrene
The pre-treatment of reaction monomers：Styrene and divinylbenzene wash away polymerization inhibitor with 10%NaOH solution, then spend
Ion water washing 3 times, anhydrous magnesium sulfate is dried, and is filtered standby；Methacrylic acid removes inhibition using chromatography on neutral alumina post
It is standby after agent.
Dispersion copolymerization method prepares carboxylic polystyrene：In tri- mouthfuls of glass reaction bottles of 250mL, lead to nitrogen displacement three times,
100mL glycol monoethyl ethers and 20mL deionized waters are added into reaction bulb, is added under 200mg polyvinylpyrrolidones, normal temperature
After stirring and dissolving, 12.0g styrene, 1.5g divinylbenzenes and 1.5g methacrylic acids are added into reaction bulb, is stirred
80mg radical initiator azodiisobutyronitriles are added afterwards, 70 DEG C are warming up under constant agitation speed, are reacted 8 hours, are obtained white
Color emulsion.Rotating speed is washed three times for centrifugation, ethanol under the conditions of 1500r/min, the carboxylated polyphenyl for being dried in vacuo powdered
Ethene carrier, uses ESEM to measure average grain diameter for 3.4 μm.
Hydroxyl alpha-diimine nickel L1a preparation
The preparation of ligand L 1：By 3.64g (20.0mmol) acenaphthenes diketone, 6.04g (40.0mmol) 2,6- dimethyl -4- hydroxyl first
The p-methyl benzenesulfonic acid of base aniline and catalytic amount (258mg, 1.5mmol) is added in 100mL toluene solutions, and back flow reaction 5 is small
When.Solvent is removed, silica gel column chromatography is crossed, obtains the part 6.04g shown in following structural formula (1), yield 67.4%.1H NMR
(400MHz,CDCl3,TMS)：δ=8.32-7.79 (6H, m), δ=7.04 (4H, s), δ=4.61 (4H, d), δ=3.65 (2H,
T), δ=2.34 (12H, s).13C NMR(100MHz,CDCl3,TMS)：δ 161.3,148.2,141.8,139.5,131.3,
130.6,129.3,127.5,127.3,126.7,123.8,65.3,18.9.Elementary analysis：C30H28N2O2(448.56) it is theoretical
Value：C 80.33, H 6.29, N 6.25；Experiment value：C 80.19, H 6.35, N 6.27.
Alpha-diimine nickel L1a preparation：Under nitrogen protection, by equimolar (DME) NiBr2Dichloromethane solution is added dropwise
Into the dichloromethane solution of above-mentioned part, it is stirred at room temperature 10 hours, is filtered to remove insoluble matter, drain solvent, gained solid is used
N-hexane is washed three times, is dried in vacuo to obtain orange/yellow solid, as hydroxyl alpha-diimine Raney nickel L1a, and its structure is such as
Shown in lower structural formula (2).Elementary analysis：C30H28Br2N2NiO2(667.06) theoretical value：C 54.02, H 4.23, N 4.20；It is real
Test value：C 54.19, H 4.08, N 4.15.
Support type alpha-diimine Raney nickel L1b preparation
In the 100mL glass reaction bottles equipped with 40mL solvent DMFs, the above-mentioned carboxylic polystyrenes of 10g, 5g are added above-mentioned
Alpha-diimine nickel L1a and 100mg NaHCO3, reaction 10 hours is stirred at room temperature, filtering, solid is washed three times with ethanol, and vacuum is done
It is dry, produce the alpha-diimine Raney nickel L1b of carboxylic polystyrene load.
ICP method determines nickel content in catalyst L1b：0.47wt%.
Embodiment 2
The preparation of carboxylic polystyrene
The pre-treatment of reaction monomers：Styrene and divinylbenzene wash away polymerization inhibitor with 10%NaOH solution, then spend
Ion water washing 3 times, anhydrous magnesium sulfate is dried, and is filtered standby；Methacrylic acid removes inhibition using chromatography on neutral alumina post
It is standby after agent.
Dispersion copolymerization method prepares carboxylic polystyrene：In tri- mouthfuls of glass reaction bottles of 250mL, lead to nitrogen displacement three times,
120mL glycol monoethyl ethers and 30mL deionized waters are added into reaction bulb, is added under 200mg polyvinylpyrrolidones, normal temperature
After stirring and dissolving, 12.0g styrene, 1.5g divinylbenzenes and 1.5g methacrylic acids are added into reaction bulb, is stirred
80mg radical initiator azodiisobutyronitriles are added afterwards, 70 DEG C are warming up under constant agitation speed, are reacted 8 hours, are obtained white
Color emulsion.Rotating speed is washed three times for centrifugation, ethanol under the conditions of 1000r/min, the carboxylated polyphenyl for being dried in vacuo powdered
Ethene carrier, uses ESEM to measure average grain diameter for 5.1 μm.
Hydroxyl alpha-diimine nickel L2a preparation
The preparation of ligand L 2：By 3.64g (20.0mmol) acenaphthenes diketone, 6.86g (40.0mmol) 2- chloromethyl -4- ethoxys
The p-methyl benzenesulfonic acid of aniline and catalytic amount (258mg, 1.5mmol) is added in 100mL toluene solutions, back flow reaction 5 hours.
Solvent is removed, silica gel column chromatography is crossed, obtains the part 5.82g shown in following structural formula (3), yield 59.6%.1H NMR
(400MHz,CDCl3,TMS)：δ=8.38-7.75 (6H, m), δ=7.43 (2H, s), δ=7.36-7.10 (4H, d), δ=
4.64-4.61 (4H, m), δ=3.67-3.65 (6H, t), δ=2.77 (4H, t).13C NMR(100MHz,CDCl3,TMS)：δ
161.5,149.6,141.7,139.9,131.5,131.3,130.6,129.9,129.5,128.4,127.5,123.6,
122.7,65.0,41.9.Elementary analysis：C30H26Cl2N2O2(517.45) theoretical value：C 69.63, H 5.06, N5.41；Experiment
Value：C 69.50, H 5.28, N 5.39.
Alpha-diimine nickel L2a preparation：Under nitrogen protection, by equimolar (DME) NiBr2Dichloromethane solution is added dropwise
Into the dichloromethane solution of above-mentioned part, it is stirred at room temperature 10 hours, is filtered to remove insoluble matter, drain solvent, gained solid is used
N-hexane is washed three times, is dried in vacuo to obtain orange/yellow solid, as hydroxyl alpha-diimine Raney nickel L2a, and its structure is such as
Shown in lower structural formula (4).Elementary analysis：C30H26Br2Cl2N2NiO2(735.95) theoretical value：C 48.96, H 3.56, N 3.81；
Experiment value：C 47.38, H 3.28, N 3.87.
Support type alpha-diimine Raney nickel L2b preparation
In the 100mL glass reaction bottles equipped with 40mL solvent DMFs, the above-mentioned carboxylic polystyrenes of 10g, 5g are added above-mentioned
Alpha-diimine Raney nickel L2a and 100mg NaHCO3, reaction 10 hours is stirred at room temperature, filtering, solid washes three times with ethanol, very
Sky is dried, and produces the alpha-diimine Raney nickel L2b of carboxylic polystyrene load.
ICP method determines nickel content in catalyst L2b：0.39wt%.
Embodiment 3
The preparation of carboxylic polystyrene
The pre-treatment of reaction monomers：Styrene and divinylbenzene wash away polymerization inhibitor with 10%NaOH solution, then spend
Ion water washing 3 times, anhydrous magnesium sulfate is dried, and is filtered standby；Methacrylic acid removes inhibition using chromatography on neutral alumina post
It is standby after agent.
Dispersion copolymerization method prepares carboxylic polystyrene：In tri- mouthfuls of glass reaction bottles of 250mL, lead to nitrogen displacement three times,
100mL glycol monoethyl ethers and 20mL deionized waters are added into reaction bulb, is added under 200mg polyvinylpyrrolidones, normal temperature
After stirring and dissolving, 12.0g styrene, 1.5g divinylbenzenes and 2.0g methacrylic acids are added into reaction bulb, is stirred
60mg radical initiator azodiisobutyronitriles are added afterwards, 70 DEG C are warming up under constant agitation speed, are reacted 8 hours, are obtained white
Color emulsion.Rotating speed is washed three times for centrifugation, ethanol under the conditions of 1500r/min, the carboxylated polyphenyl for being dried in vacuo powdered
Ethene carrier, uses ESEM to measure average grain diameter for 3.8 μm.
Hydroxyl alpha-diimine nickel L3a preparation
The preparation of ligand L 3：By 1.72g (20.0mmol) 2,3- diacetyl, 6.04g (40.0mmol) 2- ethyl -4- hydroxyl first
The p-methyl benzenesulfonic acid of base aniline and catalytic amount (258mg, 1.5mmol) is added in 100mL toluene solutions, and back flow reaction 5 is small
When.Solvent is removed, silica gel column chromatography is crossed, obtains the part 4.26g shown in following structural formula (5), yield 60.5%.1H NMR
(400MHz,CDCl3,TMS)：δ=7.29 (2H, s), δ=7.18-7.05 (4H, d), δ=4.63 (4H, d), δ=3.66 (2H,
T), δ=2.60 (4H, t), δ=2.07 (6H, t), δ=1.25 (6H, t).13C NMR(100MHz,CDCl3,TMS)：δ168.5,
144.5,139.5,134.0,129.0,125.6,122.4,65.1,23.9,15.3,14.4.Elementary analysis：C22H28N2O2
(352.47) theoretical value：C 74.97, H 8.01, N 7.95；Experiment value：C 75.01, H 8.03, N 7.92.
Alpha-diimine nickel L3a preparation：Under nitrogen protection, by equimolar (DME) NiBr2Dichloromethane solution is added dropwise
Into the dichloromethane solution of above-mentioned part, it is stirred at room temperature 10 hours, is filtered to remove insoluble matter, drain solvent, gained solid is used
N-hexane is washed three times, is dried in vacuo to obtain orange/yellow solid, as hydroxyl alpha-diimine Raney nickel L3a, and its structure is such as
Shown in lower structural formula (6).Elementary analysis：C22H28Br2N2NiO2(570.97) theoretical value：C 46.28, H 4.94, N 4.91；It is real
Test value：C 46.26, H 4.94, N 4.95.
Support type alpha-diimine Raney nickel L3b preparation
In the 100mL glass reaction bottles equipped with 40mL solvent DMFs, the above-mentioned carboxylic polystyrenes of 10g, 5g are added above-mentioned
Alpha-diimine Raney nickel L3a and 100mg NaHCO3, reaction 10 hours is stirred at room temperature, filtering, solid washes three times with ethanol, very
Sky is dried, and produces the alpha-diimine Raney nickel L3b of carboxylic polystyrene load.
ICP method determines nickel content in catalyst L3b：0.44wt%.
Application examples 1
80mL n-hexanes and 40mg are added in glass autoclave linings of the 200mL equipped with polytetrafluoroethylene (PTFE) magnetic stirring bar
The alpha-diimine Raney nickel L1b that carboxylic polystyrene made from embodiment 1 is loaded, with nitrogen displacement autoclave atmosphere three
It is secondary, and a vacuum is taken out, 60 DEG C are heated to, ethene is continuously added into 1MPa pressure, directly will after being stirred 1 hour at 60 DEG C
Ethene atmosphere switches to hydrogen, reacts lower in a hydrogen atmosphere until hydrogenating complete, emptying autoclave to normal pressure, and add a small amount of
Ethanol makes catalyst inactivation.Filtering, removal of solvent under reduced pressure and ethylene low polymer, obtain 7.72g highly -branched polyethylene.According to polymerization
The Production rate catalytic activity of thing is 2.41 × 106G PE/ (mol Ni × h), polymer Mw=5650, molecular weight distribution is
1.4, the degree of branching is 0.36.
Application examples 2
The polymerization of ethene is carried out according to the step identical with application examples 1, difference is that polymerization temperature is set as 40 DEG C, polymerization
Time is set as 0.5 hour, and other conditions are identical.It is 1.68 × 10 according to the Production rate catalytic activity of resulting polymers6g
PE/ (mol Ni × h), polymer Mw=1060, molecular weight distribution is 1.3, and the degree of branching is 0.24.
Application examples 3
The polymerization of ethene is carried out according to the step identical with application examples 1, difference is support type alpha-diimine Raney nickel
L1b consumptions are 60mg, and polymerization pressure is set as 2MPa, and other conditions are identical.It is catalyzed and is lived according to the Production rate of resulting polymers
Property be 4.17 × 106G PE/ (mol Ni × h), polymer Mw=23120, molecular weight distribution is 1.7, and the degree of branching is 0.31.
Application examples 4
The polymerization of ethene is carried out according to the step identical with application examples 1, difference is that using toluene be solvent, polymerization pressure
It is set as 2MPa, polymerization temperature is set as 80 DEG C, and other conditions are identical.It is according to the Production rate catalytic activity of resulting polymers
3.87×106G PE/ (mol Ni × h), polymer Mw=61850, molecular weight distribution is 1.9, and the degree of branching is 0.28.
Application examples 5
The polymerization of ethene is carried out according to the step identical with application examples 1, difference is that catalyst is sub- from support type α-two
Amine Raney nickel L2b, other conditions are identical.It is 2.35 × 10 according to the Production rate catalytic activity of resulting polymers6g PE/
(mol Ni × h), polymer Mw=4860, molecular weight distribution is 1.6, and the degree of branching is 0.32.
Application examples 6
The polymerization of ethene is carried out according to the step identical with application examples 1, difference is that catalyst is sub- from support type α-two
Amine Raney nickel L3b, other conditions are identical.It is 2.17 × 10 according to the Production rate catalytic activity of resulting polymers6g PE/
(mol Ni × h), polymer Mw=6290, molecular weight distribution is 1.9, and the degree of branching is 0.25.
Comparative example 1
The preparation of polystyrene support
By the preparation method of embodiment 1, not carboxylic polyphenyl is prepared using styrene and divinylbenzene as comonomer
Ethene carrier, styrene consumption is 13.5g, and divinylbenzene consumption is 1.5g, and other conditions are identical, obtain powdered polyphenyl
Ethene carrier, uses ESEM to measure average grain diameter for 3.5 μm.
Physisorphtion prepares the alpha-diimine Raney nickel L1c of loaded by polystyrene
In the 100mL glass reaction bottles equipped with 40mL solvent DMFs, the above-mentioned polystyrene supports of 10g, 5g embodiments are added
The 1 alpha-diimine nickel L1a prepared, is heated to 50 DEG C of stirring reactions 12 hours, and filtering, solid is washed three times with ethanol, is dried in vacuo,
Produce the alpha-diimine Raney nickel L1c of loaded by polystyrene.
ICP method determines nickel content：0.26wt%.
The preparation of highly -branched polyethylene
The polymerization of ethene is carried out according to the step identical with application examples 1, the difference is that using the polystyrene of above-mentioned preparation
The alpha-diimine Raney nickel L1c of load, other conditions are identical, and target product is not obtained.
Comparative example 2
The polymerization of ethene is carried out according to the step identical with application examples 1, the difference is that the polyphenyl second prepared using comparative example 1
The alpha-diimine Raney nickel L1c of alkene load, while adding the co-catalyst Et of 1000 molar equivalents2AlCl, other conditions phase
Together.It is 2.15 × 10 according to the Production rate catalytic activity of resulting polymers6G PE/ (mol Ni × h), polymer Mw=4150,
Molecular weight distribution is 2.3, and the degree of branching is 0.27.
Comparative example 3
The polymerization of ethene is carried out according to the step identical with application examples 4, the difference is that the polyphenyl second prepared using comparative example 1
The alpha-diimine Raney nickel L1c of alkene load, while adding the co-catalyst Et of 1000 molar equivalents2AlCl, other conditions phase
Together, micro oil shaped polyethylene product is obtained.It is 7.43 × 10 according to the Production rate catalytic activity of resulting polymers4g PE/(mol
Ni × h), polymer Mw=1180, molecular weight distribution is 2.1, and the degree of branching is 0.16.
Comparative example 4
The polymerization of ethene is carried out according to the step identical with application examples 1, the difference is that the α-two prepared using embodiment 1 is sub-
Amine nickel L1a is as catalyst, and other conditions are identical, and target product is not obtained.
Comparative example 5
The polymerization of ethene is carried out according to the step identical with application examples 1, the difference is that the α-two prepared using embodiment 1 is sub-
Amine nickel L1a is as catalyst, while adding the co-catalyst Et of 1000 molar equivalents2AlCl, other conditions are identical.According to gained
The Production rate catalytic activity of polymer is 2.29 × 106G PE/ (mol Ni × h), polymer Mw=3640, molecular weight distribution
For 2.1, the degree of branching is 0.19.
Comparative example 1 uses the alpha-diimine Raney nickel L1c of loaded by polystyrene, and the catalyst belongs to physical absorption
Co-catalyst is not used in type catalyst, course of reaction, target product is not obtained.Comparative example 2 compares documents 1, uses
Co-catalyst, the catalyst of physical absorption can also come off from carrier during the course of the reaction, but reaction temperature is 60 DEG C, catalysis
Agent is non-deactivated, can normal catalytic vinyl polymerization.Comparative example 3 has equally used co-catalyst, but reaction temperature is 80 DEG C, its physics
Non-refractory after the catalyst of absorption comes off from carrier, partial inactivation causes only to obtain faint product.Application examples 4 of the present invention
Polymerization temperature is 80 DEG C, and catalyst has higher catalytic activity, shows to act on the loaded catalyst obtained by chemical bonding
Difficult for drop-off, catalyst heat endurance is higher.
The late transition metal catalyst that can be seen that carboxylic polystyrene load from above-mentioned application examples and comparative example has
Higher catalytic activity, and be not required to add co-catalyst, substantially reduce production cost.Gained molecular weight of polyethylene narrowly distributing, branch
Change degree is high.Connected between catalyst and carrier by covalent bond, catalyst in the course of the polymerization process can be prevented effectively from and taken off from carrier
Fall, catalyst heat endurance is good.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment described in the invention is not used to limit the scope of the invention merely for exemplary purpose,
Those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus, the invention is not restricted to
Above-mentioned embodiment, and be only defined by the claims.
Claims (9)
1. a kind of supported late transition metal catalyst, including late transition metal alpha-diimine complex and carboxylated polyphenyl second
Alkene carrier, the late transition metal alpha-diimine complex acts on the carboxylic polystyrene carrier by chemical bonding
On, the structure of the late transition metal alpha-diimine complex is：
Wherein, M is VIII race's late transition metal atom；X is bromine or chlorine；
R1、R2It is respectively selected from hydrogen atom, C1~C10Alkyl, substituted or unsubstituted aryl, or R1、R2With adjacent carbon atom
Acenaphthenyl or phenanthryl are constituted together；
R3、R4、R5、R6It is respectively selected from hydrogen atom, C1~C10Alkyl or containing heteroatomic alkyl, C3~C10Cycloalkyl or containing miscellaneous
The cycloalkyl of atom or substituted or unsubstituted aryl；
R7、R8It is respectively selected from hydrogen atom, C1~C5Alkyl, C3~C5Cycloalkyl, or C1~C5Hydroxyl alkyl, C3
~C5Hydroxyl cycloalkyl, and R7And R8In at least contain oh group.
2. catalyst according to claim 1, wherein the structure of the late transition metal alpha-diimine complex is：
3. catalyst according to claim 1, wherein late transition metal in the late transition metal alpha-diimine complex
Mass content of the quality in the supported late transition metal catalyst be 0.1~1.0%.
4. catalyst according to claim 1, wherein the carboxylic polystyrene is particle diameter between 0.1~100 μm
Microballoon.
5. catalyst according to claim 1, wherein the carboxylic polystyrene is made by polymerized monomer copolymerization, it is described
Polymerized monomer includes styrene, divinylbenzene and the vinyl monomer containing carboxyl.
6. catalyst according to claim 5, wherein styrene of the polymerized monomer including 70.0~90.0wt%,
5.0~15.0wt% divinylbenzene and the 5.0~20.0wt% vinyl monomer containing carboxyl, involved weight
Percentage composition is on the basis of the gross weight of the polymerized monomer.
7. catalyst according to claim 5, wherein styrene of the polymerized monomer including 75.0~85.0wt%,
5.0~10.0wt% divinylbenzene and the 7.0~15.0wt% vinyl monomer containing carboxyl.
8. catalyst according to claim 5, wherein the vinyl monomer containing carboxyl is selected from acrylic acid, methyl-prop
One or more in olefin(e) acid, butenoic acid, methylene-succinic acid, maleic acid.
9. a kind of preparation method of the supported late transition metal catalyst described in claim 1 to 8, including by the rear transition
Metal alpha-diimine complex and carboxylic polystyrene react at 0~50 DEG C, and the supported late transition metal is made and urges
Agent.
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