CN107663254A - A kind of method of carbon monoxide-olefin polymeric and its catalysis long-chain alpha-olefin polymerization for long-chain alpha-olefin polymerization - Google Patents
A kind of method of carbon monoxide-olefin polymeric and its catalysis long-chain alpha-olefin polymerization for long-chain alpha-olefin polymerization Download PDFInfo
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- CN107663254A CN107663254A CN201610608194.2A CN201610608194A CN107663254A CN 107663254 A CN107663254 A CN 107663254A CN 201610608194 A CN201610608194 A CN 201610608194A CN 107663254 A CN107663254 A CN 107663254A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention, which provides a kind of carbon monoxide-olefin polymeric for long-chain alpha-olefin polymerization and its method for being catalyzed long-chain alpha-olefin polymerization, carbon monoxide-olefin polymeric, to be included：Major catalyst, co-catalyst and chain-transferring agent；The major catalyst is chemical constitution complex as follows：Wherein, R1‑R10It is identical or different, it is each independently selected from hydrogen, saturation or undersaturated alkyl, oxyl or halogen；X is selected from halogen；Co-catalyst is selected from least one of alkylaluminoxane, aryl boron and borate；Chain-transferring agent is selected from trialkylaluminium and/or dialkyl group zinc.The method of carbon monoxide-olefin polymeric catalysis long-chain alpha-olefin polymerization includes：In the presence of an inert gas, long-chain alhpa olefin, major catalyst, co-catalyst and chain-transferring agent contact is made to carry out polymerisation.When the carbon monoxide-olefin polymeric is catalyzed alhpa olefin chain transfer polymerization, there is higher catalytic activity and good heat endurance, the polyalphaolefin controllable for synthetic molecular weight.
Description
Technical field
The present invention relates to the catalyst technical field for olefinic polymerization, is used for long-chain alpha-alkene more particularly, to one kind
The carbon monoxide-olefin polymeric of hydrocarbon chain transfer polymerization and its method for catalysis long-chain alpha-olefin polymerization.
Background technology
Poly alpha olefine synthetic oil (PAO) is to be produced by alpha-olefin under catalyst action by oligomerisation reaction and hydrogenation saturation
The very high oil product of purity.Compared with mineral oil, PAO has high viscosity index, low pour point, high-flash and high temperature performance excellent
The features such as different, still it can not be substituted in many oil products.Prepare significant problem in alpha olefine synthetic oil be explore control poly- α-
Alkene viscosity index (VI), that is, the method for controlling poly alpha olefin molecular weight and its distribution.
Single active center's polyolefin catalyst can control the microstructure of synthesized molecular polyolefin well, particularly
The living polymerization of olefin hydrocarbon molecules can be realized in some conditions, and in the living polymerization of polyolefin, each catalyst can only
The reaction of propagation for being polymerize a polymer chain, so as to accurately control the chemical constitution of molecular polyolefin, molecular weight
And molecular weight distribution.In order to significantly reduce the consumption of the transition metal of price costly in catalytic component, make each catalysis
Agent molecule can synthesize multiple molecular polyolefins, and researcher have developed the coordination chain transfer polymerization of alkene.The coordination of alkene
Chain transfer polymerization can realize " controllable/activity " propagation process of molecular polyolefin, and can realize to molecular polyolefin structure
Design and regulation and control.The research of recent domestic is found, by chain-transferring agent (CSA) (generally alkyl metal cpd, such as alkane
Base aluminium, zinc alkyl etc.) it is used for single site catalysts catalyzed ethylene polymerization, it can show the advantages of many.
Patent document CN103288985A provides a kind of alpha-diimine nickel metal complex (chemical constitution such as formula (II) institute
Show) it is used to be catalyzed ethene, propylene, C6-C18Alpha-olefin homopolymerization or copolymerization, but resulting polymers molecular weight compared with
Height, about 200000~400000, influence its extensive use in PAO.
The content of the invention
The purpose of the present invention is bad for existing alpha-diimine nickel-metal catalyst heat endurance, is catalyzed long-chain alpha-olefin
A kind of technical deficiencies such as molecular weight is higher, there is provided carbon monoxide-olefin polymeric and its catalysis long-chain for long-chain alpha-olefin polymerization
The method of alpha-olefine polymerizing, make the carbon monoxide-olefin polymeric that there is high catalytic activity and good when being catalyzed alpha-olefin chain transfer polymerization
Heat endurance, the poly alpha olefin controllable for synthetic molecular weight.
To achieve these goals, the present invention provides a kind of carbon monoxide-olefin polymeric for long-chain alpha-olefin polymerization, and this is urged
Agent composition includes following component：
Major catalyst, co-catalyst and chain-transferring agent,
The major catalyst is complex of the chemical constitution as shown in formula (I)：
Wherein, R1-R10It is identical or different, it is each independently selected from hydrogen, saturation or undersaturated alkyl, oxyl and halogen
At least one of；X is selected from halogen；
The co-catalyst is selected from least one of alkylaluminoxane, aryl boron and borate；
The chain-transferring agent is selected from trialkylaluminium and/or dialkyl group zinc.
In the present invention, the alkyl includes but is not limited to alkyl, alkenyl, alkynyl, aryl, preferably alkyl or alkenyl.
According to carbon monoxide-olefin polymeric provided by the invention, it is preferable that in formula (I), R1-R10It is each independently selected from hydrogen, C1-
C10Saturation or undersaturated alkyl, C1-C10Alkoxy and at least one of halogen；It is preferably selected from hydrogen, C1-C6Saturation
Or unsaturated alkyl, C1-C6Alkoxy and at least one of halogen, be more preferably selected from hydrogen, C1-C5Saturation or unsaturation
Alkyl, C1-C5Alkoxy and at least one of halogen.It is further preferred that R1-R10It is each independently selected from hydrogen, first
At least one of base, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and bromine.
According to a kind of preferred embodiment of the present invention, the R1-R6It is each independently selected from hydrogen, C1-C5Saturation or insatiable hunger
With alkyl, C1-C5Alkoxy and at least one of halogen；The R7-R10It is hydrogen.It is further preferred that the R1-R6
It is each independently selected from methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and bromine
At least one；The R7-R10It is hydrogen.
According to carbon monoxide-olefin polymeric provided by the invention, it is preferable that the complex in following complex at least
One kind, wherein, R7-R10It is hydrogen：
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Complex 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br；
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Complex 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Complex 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Complex 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Complex 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Complex 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Complex 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Complex 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Complex 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Complex 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Complex 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；
Complex 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl.
According to carbon monoxide-olefin polymeric provided by the invention, it is preferable that the alkylaluminoxane is MAO and/or changed
Property MAO.
The aryl boron is substituted or unsubstituted phenyl boron, more preferably three pentafluorophenyl group boron.
The borate is N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate.
According to carbon monoxide-olefin polymeric provided by the invention, it is preferable that the chain-transferring agent is selected from trimethyl aluminium, triethyl group
At least one in aluminium, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, zinc methide and diethyl zinc
Kind.
According to carbon monoxide-olefin polymeric provided by the invention, it is preferable that in the co-catalyst in aluminium and the major catalyst
The mol ratio of nickel is (10-10000):1；Or the mol ratio of boron and nickel in the major catalyst is (1- in the co-catalyst
500):1。
According to carbon monoxide-olefin polymeric provided by the invention, it is preferable that in the chain-transferring agent in aluminium and the major catalyst
The mol ratio of nickel is (1-1000):1, more preferably (5-500):1；Or zinc and the major catalyst in the chain-transferring agent
The mol ratio of middle nickel is (1-1000):1, more preferably (3-500):1.
The present invention also provides a kind of method of carbon monoxide-olefin polymeric catalysis long-chain alpha-olefin polymerization, and this method includes：Lazy
Property gas in the presence of, make long-chain alpha-olefin, major catalyst, co-catalyst and chain-transferring agent contact carry out polymerisation.
According to method provided by the invention, it is preferable that the temperature of the polymerisation is -78 DEG C~200 DEG C, be preferably -
20 DEG C~150 DEG C, more preferably 30~120 DEG C.
The long-chain alpha-olefin refers to the aliphatic end alkene that carbon number is more than or equal to 5, and method of the invention is particularly suitable
In C6-C18Alpha-olefin.
According to method provided by the invention, it is preferable that the dosage of major catalyst is in the long-chain alpha-olefin polymerization
0.0001-10mmol/L；More preferably 0.001-1mmol/L.
Compared with prior art, the present invention has the advantages that：
When carrying out the reaction of alpha-olefin chain transfer polymerization, the carbon monoxide-olefin polymeric remains to keep higher the present invention at 100 DEG C
Catalytic activity, and the molecular weight that the selection of chain-transferring agent and addition control resulting polymers can be passed through so that products obtained therefrom
Molecular weight reduce, so as to improve the quality of poly alpha olefin product；More important point is that the carbon monoxide-olefin polymeric is used to carry out
The catalytic reaction of polymerisation in bulk, this will have very important significance for poly alpha olefin industrialized production.
Embodiment
The preferred embodiment of the present invention will be more fully described by embodiment below, however, it is to be appreciated that can be with
Various forms realizes the present invention without should be limited by embodiments set forth herein.
Embodiment 1
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 0.5ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, are finally put sample
Enter vacuum drying chamber to dry 24 hours, obtain 3.87g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 387kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=30.42 ten thousand, molecular weight distribution
Mw/Mn=2.07.
Comparative example 1：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), polymerisation 2 is small at 100 DEG C
When after stop, reaction system is in black and with toughness.With hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers tetrahydrochysene
Furans dissolves, methanol extraction, so repeatedly for three times, sample finally is put into vacuum drying chamber and dried 24 hours, it is white to obtain 4.28g
Color solid-like and the polymer for carrying certain elasticity.The weight average molecular weight that polymer is measured during reaction end is Mw=44.74 ten thousand,
Molecular weight distribution mw/mn=2.33.
Comparative example 2：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, 7.2mg (10 μm of ol) contrasts is sequentially added and matches somebody with somebody
Compound 1 (shown in structure such as formula (II)), 15ml 1- decene, (1.53mol/l toluene is molten for 0.8ml MAOs (MAO)
Liquid), polymerisation stops after 2 hours at 90 DEG C, and reaction system is in black and with toughness.It is whole with hydrochloric acid-alcohol dilute solution
Only react, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, sample finally are put into vacuum drying
Case is dried 24 hours, obtains 0.52g white solids and with the polymer of certain elasticity.The catalytic efficiency of catalyst system and catalyzing is
52kg mol-1Ni。
Comparative example 3：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, 7.2mg (10 μm of ol) contrasts is sequentially added and matches somebody with somebody
Compound 1 (shown in structure such as formula (II)), 15ml 1- decene, (1.53mol/l toluene is molten for 0.8ml MAOs (MAO)
Liquid), 0.5ml diethyl zincs (1.0mol/l toluene solution), polymerisation stops after 2 hours at 90 DEG C, and reaction system is in
Black and with toughness.With hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, such as
Sample is finally put into vacuum drying chamber and dried 24 hours, obtained 0.38g white solids and carry certain bullet by this repeatedly for three times
The polymer of property.The catalytic efficiency of catalyst system and catalyzing is 38kg mol-1Ni。
Embodiment 2
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, are finally put sample
Enter vacuum drying chamber to dry 24 hours, obtain 4.04g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 404kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=16.14 ten thousand, molecular weight distribution
Mw/Mn=1.87.
Embodiment 3
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, are finally put sample
Enter vacuum drying chamber to dry 24 hours, obtain polymer of the 2.12g with certain elasticity.The catalytic efficiency of catalyst system and catalyzing is
212kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=10.24 ten thousand, molecular weight distribution mw/mn=
2.06。
Embodiment 4
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml trimethyl aluminiums (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, are finally put sample
Enter vacuum drying chamber to dry 24 hours, obtain 1.10g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 110kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=4.01 ten thousand, molecular weight distribution
Mw/Mn=2.32.
Embodiment 5：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 14.0mg (10 μm of ol) complex
3,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, are finally put sample
Enter vacuum drying chamber to dry 24 hours, obtain 4.42g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 442kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=23.14 ten thousand, molecular weight distribution
Mw/Mn=1.92.
Embodiment 6：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 12.9mg (10 μm of ol) complex
1,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are washed with acetone, and sample finally is put into vacuum drying chamber dries 24 hours, obtains
2.34g polymer.The catalytic efficiency of catalyst system and catalyzing is 234kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=1.22 ten thousand, molecular weight distribution mw/mn=2.02.
Embodiment 7：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 12.9mg (10 μm of ol) complex
1,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are washed with acetone, and sample finally is put into vacuum drying chamber dries 24 hours, obtains
0.97g polymer.The catalytic efficiency of catalyst system and catalyzing is 97kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=0.94 ten thousand, molecular weight distribution mw/mn=1.92.
Embodiment 8：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- laurylenes, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains 4.18g white solids and with the polymer of certain elasticity.Catalytic body
The catalytic efficiency of system is 418kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=20.21 ten thousand, molecule
Amount distribution Mw/Mn=2.01.
Embodiment 9：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- laurylenes, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains polymer of the 3.12g with certain elasticity.The catalytic efficiency of catalyst system and catalyzing
For 312kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=13.27 ten thousand, molecular weight distribution mw/mn
=1.95.
Embodiment 10：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml1- tetradecenes, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains 4.92g white solids and with the polymer of certain elasticity.Catalytic body
The catalytic efficiency of system is 492kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=25.21 ten thousand, molecule
Amount distribution Mw/Mn=2.02.
Embodiment 11：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1-tetradecylenes, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains 3.14g white solids and with the polymer of certain elasticity.Catalytic body
The catalytic efficiency of system is 314kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=11.26 ten thousand, molecule
Amount distribution Mw/Mn=1.97.
Embodiment 12：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- hexadecylenes, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains 3.27g white solids and with the polymer of certain elasticity.Catalytic body
The catalytic efficiency of system is 327kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=23.61 ten thousand, molecule
Amount distribution Mw/Mn=2.12.
Embodiment 13：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 13.4mg (10 μm of ol) complex
2,15ml 1- hexadecylenes, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains polymer of the 2.31g with certain elasticity.The catalytic efficiency of catalyst system and catalyzing
For 231kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=14.21 ten thousand, molecular weight distribution mw/mn
=1.84.
Embodiment 14：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 14.4mg (10 μm of ol) complex
5,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are washed with acetone, and sample finally is put into vacuum drying chamber dries 24 hours, obtains
1.68g polymer.The catalytic efficiency of catalyst system and catalyzing is 168kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=1.37 ten thousand, molecular weight distribution mw/mn=2.02.
Embodiment 15：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 14.4mg (10 μm of ol) complex
5,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs (1.0mol/
L toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With hydrochloric acid-second
Alcohol weak solution terminating reaction, resulting polymers are washed with acetone, and sample finally is put into vacuum drying chamber dries 24 hours, obtains
0.94g polymer.The catalytic efficiency of catalyst system and catalyzing is 94kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=0.71 ten thousand, molecular weight distribution mw/mn=1.92.
Embodiment 16：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 12.6mg (10 μm of ol) complex
13,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 1.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains 4.88g white solids and with the polymer of certain elasticity.Catalytic body
The catalytic efficiency of system is 488kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=28.31 ten thousand, molecule
Amount distribution Mw/Mn=2.01.
Embodiment 17：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 12.6mg (10 μm of ol) complex
13,15ml1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 2.0ml diethyl zincs
(1.0mol/l toluene solution), polymerisation stops after 2 hours at 100 DEG C, and reaction system is in black and with toughness.With
Hydrochloric acid-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally will
Sample is put into vacuum drying chamber and dried 24 hours, obtains 2.27g white solids and with the polymer of certain elasticity.Catalytic body
The catalytic efficiency of system is 227kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=12.21 ten thousand, molecule
Amount distribution Mw/Mn=1.88.
Embodiment 1~4 introduces the molecular weight progress to polymer that chain-transferring agent can be by a relatively large margin compared with comparative example 1
Regulation and control；Compared with comparative example 2, comparative example 3, using metal complex of the invention as major catalyst in use, gathering in high temperature
Polymerization activity is much higher under the conditions of conjunction, and nickel metal complex of the invention has preferable heat endurance.
It is described above various embodiments of the present invention, described above is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
1. a kind of carbon monoxide-olefin polymeric for long-chain alpha-olefin polymerization, it is characterised in that the carbon monoxide-olefin polymeric includes as follows
Component：
Major catalyst, co-catalyst and chain-transferring agent；
The major catalyst is complex of the chemical constitution as shown in formula (I)：
Wherein, R1-R10It is identical or different, it is each independently selected from hydrogen, saturation or undersaturated alkyl, oxyl and halogen
It is at least one；X is selected from halogen；
The co-catalyst is selected from least one of alkylaluminoxane, aryl boron and borate；
The chain-transferring agent is selected from trialkylaluminium and/or dialkyl group zinc.
2. the carbon monoxide-olefin polymeric according to claim 1 for long-chain alpha-olefin polymerization, wherein, in formula (I), R1-R10
It is each independently selected from hydrogen, C1-C10Saturation or undersaturated alkyl, C1-C10Alkoxy and at least one of halogen；It is excellent
Choosing is selected from hydrogen, C1-C6Saturation or unsaturated alkyl, C1-C6Alkoxy and at least one of halogen, be more preferably selected from hydrogen,
C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxy and at least one of halogen.
3. the carbon monoxide-olefin polymeric according to claim 2 for long-chain alpha-olefin polymerization, wherein, in formula (I), R1-R10
Be each independently selected from hydrogen, methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and
At least one of bromine.
4. the carbon monoxide-olefin polymeric according to claim 1 for long-chain alpha-olefin polymerization, wherein, the complex is selected from
At least one of following complex, wherein, R7-R10It is hydrogen：
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Complex 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br；
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Complex 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Complex 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Complex 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Complex 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Complex 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Complex 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Complex 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Complex 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Complex 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Complex 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；
Complex 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl.
5. the carbon monoxide-olefin polymeric according to claim 1 for long-chain alpha-olefin polymerization, wherein, the alkylaluminoxane
For MAO and/or modified methylaluminoxane；The aryl boron is substituted or unsubstituted phenyl boron, preferably 35
Fluorophenyl boron；The borate is N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate.
6. the carbon monoxide-olefin polymeric according to claim 1 for long-chain alpha-olefin polymerization, wherein, the chain-transferring agent choosing
From trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, zinc methide and two
At least one of zinc ethyl.
7. the carbon monoxide-olefin polymeric according to claim 1 for long-chain alpha-olefin polymerization, wherein, in the co-catalyst
The mol ratio of aluminium and nickel in the major catalyst is (10-10000):1；Or in the co-catalyst in boron and the major catalyst
The mol ratio of nickel is (1-500):1.
8. the carbon monoxide-olefin polymeric according to claim 1 for long-chain alpha-olefin polymerization, wherein, in the chain-transferring agent
The mol ratio of aluminium and nickel in the major catalyst is (1-1000):1；Or zinc and nickel in the major catalyst in the chain-transferring agent
Mol ratio be (1-1000):1.
9. the method for the carbon monoxide-olefin polymeric catalysis long-chain alpha-olefin polymerization any one of claim 1-8, its feature exist
In this method includes：In the presence of an inert gas, make long-chain alpha-olefin, major catalyst, co-catalyst and chain-transferring agent contact into
Row polymerisation；The temperature of the polymerisation is preferably -78 DEG C~200 DEG C；More preferably -20 DEG C~150 DEG C.
10. according to the method for claim 9, wherein, the dosage of the major catalyst is 0.0001-10mmol/L；It is preferred that
For 0.001-1mmol/L.
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| EP1169361B1 (en) * | 1999-03-18 | 2008-09-03 | Ineos Europe Limited | Pyridine-imine polymerisation catalyst |
| CN105294778A (en) * | 2015-10-14 | 2016-02-03 | 中山大学 | Nickel base complex, and preparation method and application thereof |
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| EP1169361B1 (en) * | 1999-03-18 | 2008-09-03 | Ineos Europe Limited | Pyridine-imine polymerisation catalyst |
| CN105294778A (en) * | 2015-10-14 | 2016-02-03 | 中山大学 | Nickel base complex, and preparation method and application thereof |
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