CN107663251A - 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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- CN107663251A CN107663251A CN201610608180.0A CN201610608180A CN107663251A CN 107663251 A CN107663251 A CN 107663251A CN 201610608180 A CN201610608180 A CN 201610608180A CN 107663251 A CN107663251 A CN 107663251A
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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, the carbon monoxide-olefin polymeric, to be included：Major catalyst, co-catalyst and chain-transferring agent；The major catalyst chemical constitution is as follows：Wherein, X is halogen；R1‑R10It is identical or different, it is each independently selected from least one of hydrogen, saturation or undersaturated alkyl, oxyl and 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.The method of 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-alkene
A kind of technical deficiencies such as hydrocarbon molecule amount is higher, there is provided catalyst group that long-chain alpha-olefin chain polymerization can be catalyzed under higher temperature
Compound and its method for catalysis long-chain alpha-olefin polymerization；The carbon monoxide-olefin polymeric be catalyzed alpha-olefin chain transfer polymerization when, have compared with
High catalytic activity and good 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 it is special
Sign is that the carbon monoxide-olefin polymeric 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, X is halogen；R1-R10It is identical or different, it is each independently selected from hydrogen, saturation or undersaturated alkyl, hydrocarbon oxygen
At least one of base and 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 unsaturated alkyl, C1-C10Alkoxy and at least one of halogen；Further preferably selected from hydrogen, C1-C6's
Saturation or unsaturated alkyl, C1-C6Alkoxy and at least one of halogen.It is further preferred that R1-R10It is each independent
Ground in hydrogen, methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and bromine extremely
Few one kind.
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 compound 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 phenyl boron, more preferably three pentafluorophenyl group boron；The borate is N, N- bis-
Methyl 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：
For the present invention when carrying out the reaction of alpha-olefin chain transfer polymerization, the carbon monoxide-olefin polymeric still keeps higher at 100 DEG C
Catalytic activity；The molecular weight of resulting polymers can be controlled by the selection of chain-transferring agent and addition so that point of products obtained therefrom
Son amount reduces, 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 body
The catalytic reaction of polymerization, 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 11.3mg (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 4.07g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 407kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=30.27 ten thousand, molecular weight distribution
Mw/Mn=2.04.
Comparative example 1：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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 4.86g
Color solid-like and the polymer for carrying certain elasticity.The weight average molecular weight that polymer is measured during reaction end is Mw=45.27 ten thousand,
Molecular weight distribution mw/mn=2.11.
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 11.3mg (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=18.68 ten thousand, molecular weight distribution
Mw/Mn=1.92.
Embodiment 3
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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 3.41g with certain elasticity.The catalytic efficiency of catalyst system and catalyzing is
341kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=12.16 ten thousand, molecular weight distribution mw/mn=
2.02。
Embodiment 4
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (10 μm of ol) complex
2,15ml 1- decene, 0.8ml MAOs (MAO) (1.53mol/l toluene solution), 0.5ml 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 1.12g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 112kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=8.62 ten thousand, molecular weight distribution
Mw/Mn=2.27.
Embodiment 5：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.9mg (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 3.82g white solids and with the polymer of certain elasticity.Catalyst system and catalyzing is urged
Change efficiency is 382kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end are Mw=24.17 ten thousand, molecular weight distribution
Mw/Mn=1.98.
Embodiment 6：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 10.7mg (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
3.22g polymer.The catalytic efficiency of catalyst system and catalyzing is 322kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=4.04 ten thousand, molecular weight distribution mw/mn=2.07.
Embodiment 7：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 10.7mg (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
1.97g polymer.The catalytic efficiency of catalyst system and catalyzing is 197kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=2.04 ten thousand, molecular weight distribution mw/mn=1.88.
Embodiment 8：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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
Sample is put into vacuum drying chamber to dry 24 hours, obtains 4.65g white solids and with the polymer of certain elasticity.Catalysis
The catalytic efficiency of system is 465kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=27.27 ten thousand, point
Son amount distribution Mw/Mn=2.10.
Embodiment 9：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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
Sample is put into vacuum drying chamber to dry 24 hours, obtains polymer of the 3.34g with certain elasticity.The catalysis effect of catalyst system and catalyzing
Rate is 334kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=15.33 ten thousand, molecular weight distribution Mw/
Mn=1.86.
Embodiment 10：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (10 μm of ol) complex
2,15ml 1-tetradecylenes, 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
Sample is put into vacuum drying chamber to dry 24 hours, obtains 4.16g white solids and with the polymer of certain elasticity.Catalysis
The catalytic efficiency of system is 416kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=24.17 ten thousand, point
Son amount distribution Mw/Mn=2.04.
Embodiment 11：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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
Sample is put into vacuum drying chamber to dry 24 hours, obtains 2.87g white solids and with the polymer of certain elasticity.Catalysis
The catalytic efficiency of system is 287kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=14.16 ten thousand, point
Son amount distribution Mw/Mn=1.91.
Embodiment 12：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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
Sample is put into vacuum drying chamber to dry 24 hours, obtains 3.83g white solids and with the polymer of certain elasticity.Catalysis
The catalytic efficiency of system is 383kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=24.67 ten thousand, point
Son amount distribution Mw/Mn=2.12.
Embodiment 13：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 11.3mg (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
Sample is put into vacuum drying chamber to dry 24 hours, obtains polymer of the 2.02g with certain elasticity.The catalysis effect of catalyst system and catalyzing
Rate is 202kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=16.21 ten thousand, molecular weight distribution Mw/
Mn=1.94.
Embodiment 14：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 12.3mg (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
2.31g polymer.The catalytic efficiency of catalyst system and catalyzing is 231kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=3.42 ten thousand, molecular weight distribution mw/mn=2.07.
Embodiment 15：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 12.3mg (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
1.42g polymer.The catalytic efficiency of catalyst system and catalyzing is 142kg mol-1Ni, the weight average molecular weight of polymer is measured during reaction end
For Mw=1.47 ten thousand, molecular weight distribution mw/mn=1.82.
Embodiment 16：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 10.4mg (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
Sample is put into vacuum drying chamber to dry 24 hours, obtains 5.27g white solids and with the polymer of certain elasticity.Catalysis
The catalytic efficiency of system is 527kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=34.82 ten thousand, point
Son amount distribution Mw/Mn=2.08.
Embodiment 17：
100ml three mouthfuls of reaction bulbs are vacuumized, with nitrogen displacement three times, sequentially add 10.4mg (10 μm of ol) complex
13,15ml 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-alcohol dilute solution terminating reaction, resulting polymers are dissolved with tetrahydrofuran, methanol extraction, so repeatedly for three times, finally
Sample is put into vacuum drying chamber to dry 24 hours, obtains 3.84g white solids and with the polymer of certain elasticity.Catalysis
The catalytic efficiency of system is 384kg mol-1Ni, the weight average molecular weight that polymer is measured during reaction end is Mw=14.72 ten thousand, point
Son amount distribution Mw/Mn=1.98.
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, X is halogen；R1-R10It is identical or different, be each independently selected from hydrogen, saturation or undersaturated alkyl, oxyl and
At least one of 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 unsaturated alkyl, C1-C10Alkoxy and at least one of halogen；It is preferred that
Selected from hydrogen, C1-C6Saturation or unsaturated alkyl, C1-C6Alkoxy 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 compound, 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 phenyl boron, preferably three pentafluorophenyl group boron；It is described
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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| CN105646756A (en) * | 2014-11-14 | 2016-06-08 | 中国科学院上海有机化学研究所 | Applications of diamine nickel catalysts in preparation of functionalized polyolefin oil |
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