CN110317149A - Big steric hindrance flexibility diimide ligand, the diimine nickel based on it and palladium complex and its catalytic applications - Google Patents
Big steric hindrance flexibility diimide ligand, the diimine nickel based on it and palladium complex and its catalytic applications Download PDFInfo
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- CN110317149A CN110317149A CN201910701033.1A CN201910701033A CN110317149A CN 110317149 A CN110317149 A CN 110317149A CN 201910701033 A CN201910701033 A CN 201910701033A CN 110317149 A CN110317149 A CN 110317149A
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- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
The invention discloses big steric hindrance flexibility diimide ligand, the diimine nickel based on it and palladium complex and its catalytic applications, it is the flexible substituent group by introducing different structure on diimide ligand, obtains the diimine nickel and palladium catalyst of a series of space steric effects.Gained catalyst thermal stability with higher of the invention has very high activity for catalysis in olefine polymerization, and the catalyst can regulate and control the molecular weight and branching density of polyolefin by the length of the chain of change substituent group.
Description
Technical field
The invention belongs to polyolefin preparation technical fields, and in particular to a kind of catalyst of alpha-olefin polymerization.
Background technique
Polyolefine material be in people's production and living and industrial application it is indispensable, be widely used.From its appearance
Since, the exploration to olefin polymerization catalyst is exactly the advanced problems in polymer science field.The quality of polyolefine material,
Performance is closely bound up with catalyst, and the discovery and improvement of new catalyst all play olefinic polymerization industry great each time
Impetus.The successful development for making a general survey of the history of olefinic polymerization industry, technological progress and the discovery of raw catelyst and technology is close
It is related.In olefin polymerization process, catalyst often determines polymerization behavior, particle shape, topological structure and the property of polymer
Energy.The development of olefin polymerization catalysis keeps olefinic polymerization kind more diversified, and performance is more superior, has widened polymer significantly
Practical application area.
Since Brookhart reports alpha-diimine nickel and palladium catalyst for alkene insertion polymerization in nineteen ninety-five for the first time
(J.Am.Chem.Soc., 1995,117,6414.) has carried out a large amount of modifications to alpha-diimine ligand to develop to have and dive
It, can be to the work of catalyst in the N-O- aromatic substituent and ligand backbone that the catalyst of industrial application, especially space are huge
The axial space of property substance plays important protective effect, so that catalyst is able to maintain high activity, high stability, can urge
Change polymerization and obtains heavy polymer.Therefore, it has been reported that many draw about in alpha-diimine ligand in the field
Enter the strategy of the substituent group with rigid space steric hindrance.Substantially, these catalyst not only show good thermal stability and
And the polyolefin with higher molecular weight, adjustable branching density and effectively incorporation polar comonomers can also be generated, but its
The substituent group of rigid space steric hindrance can prevent the insertion of vinyl monomer or dramatically increase the activation energy of vinyl monomer insertion, be unfavorable for
The progress of polymerization.It for the olefinic polymerization of nickel and palladium chtalyst or can be solved using the alpha-diimine ligand with flexible space steric hindrance
The above problem, but have not yet to see related report.
Summary of the invention
Based on the above existing technology problems, the purpose of the present invention is to provide a kind of big steric hindrance flexibility diimines
Ligand, the diimine nickel based on it and palladium complex and its application in catalysis alpha-olefin polymerization, it is to be solved to be
By introducing the flexible substituent group of different structure on alpha-diimine ligand N- aryl moiety, mention it in catalyzed polymerization process
For dynamic steric hindrance, the mode of new modularization and systematization is allowed for finely tune in metal (Ni or Pd) catalytic activity
The space environment of the heart, to obtain the polyolefin that branching density and molecular weight can be regulated and controled by the chain length of substituent group.
To realize goal of the invention, the present invention adopts the following technical scheme:
The present invention discloses big steric hindrance flexibility diimide ligand first, and structural formula is shown in formula I:
Wherein, R is methyl, ethyl or n-propyl.
The synthetic method of big steric hindrance flexibility diimide ligand of the present invention are as follows: under atmosphere of inert gases, by acenaphthenequinone with
After the mixing of 1:2.2~2.5 in molar ratio of the suspension of amine compounds, 6~12h of reaction, gained reaction are stirred at reflux at 90 DEG C
After liquid is cooled to room temperature, sediment is collected by filtration and washs, dry, is i.e. the acquisition big steric hindrance flexibility diimide ligand of target product,
Reaction equation is as follows, and wherein A is the structural formula of acenaphthenequinone, the structural formula that B is amine compounds:
Further, the suspension is the acetonitrile suspension of acenaphthenequinone and the acetic acid suspension of amine compounds.
It is by above-mentioned diimide ligand and nickel compound or palladium compound institute shape the invention also discloses a kind of complex
At diimine nickel complex or diimine palladium complex；
The structural formula such as formula of shown, the described diimine palladium complex of the structural formula of the diimine nickel complex such as formula (II)
(III) shown in:
In formula, R is methyl, ethyl or n-propyl, preferably n-propyl.
It is in atent solvent, by the diimine the present invention further discloses the preparation method of the complex
1:1 is mixed in molar ratio for ligand and nickel compound or palladium compound, reaction 20~for 24 hours is stirred at room temperature, then again after
Reason, i.e. acquisition diimine nickel complex or diimine palladium complex.
Further, the nickel compound is (DME) NiBr2, the palladium compound is (COD) PdMeCl.
Further, the atent solvent is methylene chloride, acetonitrile or acetic acid.
It is for the catalyst as alpha-olefin polymerization, specifically the invention also discloses the application of above-mentioned complex
Including two kinds:
(1) using the diimine nickel complex or diimine palladium complex as the catalyst of alpha-olefine polymerizing, to alkene
Catalytic polymerization is carried out, the high molecular polyolefine of highly -branched is obtained, has a characteristic that the corresponding first of every 1000 methylene
Radix is 70-110, and molecular weight is in 245000-1195000g/mol, and fusing point is at -2~64 DEG C；
(2) using the diimine nickel complex or diimine palladium complex as the catalyst of alpha-olefine polymerizing, to α-alkene
Hydrocarbon and acrylic acid, methyl acrylate carry out catalyzed copolymerization, obtain the high molecular polyolefine copolymer of highly -branched, have as follows
Feature: the corresponding methyl number of every 1000 methylene is 75-95, is inserted into ratio in 0.28-1.21%, molecular weight is in 3600-
71100g/mol。
Preferably, the alpha-olefin is the mixing of one of ethylene, propylene and butylene or arbitrary proportion, most preferably second
Alkene.
Preferably, in above-mentioned polymerization system, there is also cocatalysts: when use diimine nickel complex as urging
When agent, co-catalyst is preferably methylaluminoxane (MAO)；When using diimine palladium complex as catalyst, co-catalysis
Agent is preferably four (3,5- bis- (trifluoromethyl) phenyl) Boratexes (NaBArF).
Preferably, in above-mentioned polymerization reaction, diimine nickel complex reaction temperature is 20~80 DEG C, and diimine palladium is matched
Closing object is 30 DEG C, and alpha-olefin pressure is 1-10 atmospheric pressure, and reaction dissolvent is at least one of methylene chloride, toluene and n-hexane.
The beneficial effects of the present invention are embodied in:
(1) the reason of ligand synthesizes yield with higher, and forefathers synthesize such catalyst ligand low yield is that selection is low
Boiling point methylene chloride as solvent, the present invention using acetonitrile and acetic acid as solvent, R be the yield of methyl be 74%, R is ethyl
The yield that yield is 71%, R is n-propyl is 96%.
(2) present invention gained catalyst thermal stability with higher and there is good catalysis work for olefinic polymerization
Property, it is thermoplastic elastomer (TPE) which, which is catalyzed obtained polyolefin, there is good recoverability.Heat in the system is steady
Determine nickel complex as catalyst agent, can obtain the high molecular polyolefine of highly -branched with catalytic polymerization, and polymeric articles show it is excellent
Good elastic recovery (Strain value is up to 88%), and the degree of branching of polyolefin obtained by catalysis and molecular weight are in temperature
Reveal the variation of rule.In palladium chtalyst alkene (co) polymerization in the system, as flexible substituent group chain length increases, polymer point
Son amount increases, and the trend that polar monomer incorporation and branch chain density reduce is quite obvious.This is provided for manufacture functional macromolecule
A kind of controllable technological means.
Detailed description of the invention
Fig. 1 is the mono-crystalline structures of gained complex Ni1 (a) and Pd1 (b) in the embodiment of the present invention.
Fig. 2 is the nucleus magnetic hydrogen spectrum of the polymer prepared under the conditions of label 1 in the embodiment of the present invention 10.
Fig. 3 is the nucleus magnetic hydrogen spectrum of the polymer prepared under the conditions of label 1 in the embodiment of the present invention 11.
Fig. 4 is the nucleus magnetic hydrogen spectrum of the polymer prepared under the conditions of label 11 in the embodiment of the present invention 11.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
All preparation process of following embodiments are all under dry nitrogen environment using glove box or by standard
What Schlenk technology carried out.
2,6- bis- used in following embodiments (amyl- 3- yl) aniline, (the hept- 4- yl) aniline of 2,6- bis- and (the nonyl- 5- of 2,6- bis-
Base) aniline can be made according to the method for bibliography (Nolan, Chem.Eur.J., 2013,19,17358), or from commercial source
It obtains.
Methylene chloride used in following embodiments, n-hexane and toluene are first dried and have been distilled in a nitrogen environment, with
Remove water removal and oxygen.Remaining reagent used in following embodiments is all obtained from commercial source, not purified direct use.
Deuterated solvents used in following embodiment nuclear magnetic resonance are passing through dry and distillation using preceding.Unless otherwise stated,1H、13C H NMR spectroscopy is recorded at room temperature by 500 spectrometer of Bruker DPX or JNM-ECZ600R spectrometer.
In following embodiments, the polymerization obtained by Ni1~Ni3, Pd1-Pd3 is measured by gel permeation chromatography (GPC)
The molecular weight and molecualr weight distribution of object, and the use of polystyrene is that standard is calibrated.
In following embodiments, polymer is melted to compacting at 150 DEG C, and to obtain test sample, (it is long with 12mm gauge length
Degree, 2mm width and 0.5mm thickness), then at room temperature by Universal Test Machine (UTM2502) with 10mm/
Min carries out stress/strain experiment, and every kind of polymer tests three samples.
In following embodiments, DSC is carried out by the DSC Q2000 of TA Instruments.Sample is quickly heated up to 150
DEG C and keep 5 minutes to remove thermal history, then -50 DEG C are cooled to the rate of 10K/min, finally under nitrogen flowing with identical
Rate be again heated to 150 DEG C (50mL/min).Maximum decalescence point (heat scan) is used as melting temperature (Tm).
Embodiment 1
The present embodiment prepares big steric hindrance flexibility diimide ligand L1, and structure is as follows:
Synthesis process are as follows: in a nitrogen atmosphere, acenaphthenequinone (0.55g, 3mmol, 1.0 equivalent) and 2,6- bis- (amyl- 3- yl) benzene
Amine (1.54g, 6.6mmol, 2.2 equivalent) is suspended in respectively in acetonitrile (40mL) and acetic acid (16mL), is then mixed.By mixture
It is vigorously stirred reaction 12 hours at 90 DEG C, becomes red tan solution.Then, solution is cooled to room temperature, yellow is collected by filtration
Sediment.Solid is washed with acetonitrile, after vacuum drying, L1 obtained is yellow powder, and yield is 74% (1.36g).1H NMR(500MHz,CDCl3) δ 7.84 (d, J=8.2Hz, 2H, Ar-H), 7.32 (t, J=7.7Hz, 2H, Ar-H), 7.19 (m,
6H, Ar-H), 6.68 (d, J=7.1Hz, 2H, Ar-H), 2.62 (m, 4H, CH), 1.66 (m, 4H, CH2),1.57(m,4H,CH2),
1.48(m,4H,CH2),1.40(m,4H,CH2),0.83(s,12H,CH3),0.52(s,12H,CH3).13C NMR(126MHz,
CDCl3) δ 160.52 (C=N), 149.85,140.61,132.80,131.01,129.82,128.77,127.58,124.78,
123.96,123.42,42.61,29.84,27.79,26.29,11.96(CH2CH3) .ESI-MS (m/z): calculate C44H57N2:
613.4522, it is actually measured, 613.4501, [M+H]+.
Embodiment 2
The present embodiment prepares big steric hindrance flexibility diimide ligand L2, and structure is as follows:
Using with the identical method of synthesis L1, difference is: using 2,6- bis- (hept- 4- yl) aniline (1.91g,
6.6mmol, 2.2 equivalents) outside.L2 obtained is yellow powder, and yield is 71% (1.54g).1H NMR(500MHz,CDCl3)δ
7.82 (d, J=8.2Hz, 2H, Ar-H), 7.33-7.29 (m, 2H, Ar-H), 7.19-7.14 (m, 6H, Ar-H), 6.66 (d, J=
7.2Hz, 2H, Ar-H), 2.79-2.73 (m, 4H, CH), 1.54 (ddd, J=16.2,9.3,5.6Hz, 4H, CH2),1.49–
1.38(m,8H,CH2),1.39–1.30(m,4H,CH2),1.30–1.15(m,8H,CH2), 0.91 (tdd, J=13.9,11.2,
6.6Hz,8H,CH2), 0.80 (t, J=7.3Hz, 12H, CH3), 0.34 (t, J=7.3Hz, 12H, CH3).13C NMR(126MHz,
CDCl3) δ 160.51 (C=N), 149.86,140.65,133.41,130.87,129.88,128.58,127.38,124.64,
123.93,123.57,38.98,38.79,37.27,20.66,20.57,14.55,14.00. ESI-MS (m/z): calculating
C52H73N2: 725.5774, it is actually measured, 725.5754, [M+H]+.
Embodiment 3
The present embodiment prepares big steric hindrance flexibility diimide ligand L3, and structure is as follows:
Using with the identical method of synthesis L1, difference is: using 2,6- bis- (nonyl- 5- yl) aniline (2.28g,
6.6mmol, 2.2 equivalents).L3 obtained is yellow powder, and yield is 96.0% (2.41g).1H NMR (500MHz, CDCl3):
δ 7.81 (d, J=8.2Hz, 2H, Ar-H), 7.30 (t, J=7.7Hz, 2H, Ar-H), 7.20-7.14 (m, 6H Ar-H), 6.67
(m,2H,Ar-H),2.76–2.69(m,4H,CH),1.62–1.55(m,4H,CH2),1.44(m,8H,CH2),1.39–1.32(m,
4H,CH2),1.27–1.20(m,8H,CH2),1.18–1.12(m,6H,CH2),0.91–0.71(m,30H,CH2,CH3),0.35
(t, J=6.6Hz, 12H, CH3).13C NMR(126MHz,CDCl3): δ 160.70 (C=N), 150.25,140.96,133.67,
131.20,130.15,128.73,127.64,124.92,124.34,123.78,39.94,36.69,34.92,30.40,
(29.82,23.44,23.00,14.47,13.98.ESI-MS m/z): calculating C60H89N2: 837.7026, it is actually measured,
837.7012,[M+H]+
Embodiment 4
The present embodiment prepares diimine palladium complex Pd1:
Preparation process are as follows: the anhydrous CH of Xiang PeitiL 1 (307mg, 0.50mmol)2Cl2133mg is added in (10mL) solution
(COD)PdMeCl(0.50mmol).After mixture being stirred at room temperature 24 hours, solvent is evaporated under reduced pressure to remove free COD.
Then residue is dissolved in CH2Cl2In (10mL) and it is stirred for 24 hours until most of ligand disappears (TLC monitoring).Decompression
Solvent is evaporated, solid is obtained.With n-hexane (3 × 10mL) washed product and be dried under vacuum, obtain red solid (0.34g,
88.9%).1H NMR(500MHz,CDCl3) δ 8.05 (d, J=8.3Hz, 1H, Ar-H), 8.01 (d, J=8.3Hz, 1H, Ar-
), H 7.48-7.22 (m, 8H, Ar-H), 6.75 (d, J=7.2Hz, 1H, Ar-H), 6.44 (d, J=7.3Hz, 1H, Ar-H),
3.19–3.02(m,2H,CH),3.00–2.91(m,2H,CH),2.18–2.03(m,2H,CH2),2.03–1.88(m,2H,CH2),
1.89–1.80(m,2H,CH2),1.82–1.70(m,2H,CH2), 1.44 (ddt, J=26.7,12.9,6.3Hz, 6H, CH2),
1.28 (d, J=7.2Hz, 2H, CH2), 1.05 (t, J=7.4Hz, 6H, CH3), 0.96 (t, J=7.4Hz, 6H, CH3),0.89
(s,3H,Pd-CH3), 0.50 (dd, J=13.1,7.3Hz, 12H, CH3).13C NMR(126MHz,CDCl3): 172.09 (C=of δ
), N 167.51 (C=N), 144.15,143.84,143.44,137.48,136.47,131.57,131.39,131.14,
128.80,128.70,127.82,127.43,126.96,126.75,126.29,125.83,125.61,125.25,43.08,
42.22,27.83,26.75,26.49,26.25,12.79,12.37,12.19,11.39,4.78(Pd-CH3).MALDI-TOF-
MS (m/z): C is calculated44H56N2Pd:718.35, it is actually measured, 717.37, [M-Me-Cl]+.Anal. C is calculated45H59ClN2Pd:C,
70.21；H,7.73；N,3.64；It is actually measured, C, 70.68；H,7.53；N,3.66.
Embodiment 5
The present embodiment prepares diimine palladium complex Pd2:
Using method identical with synthesis Pd1, difference is to use ligand L 2 instead, has obtained a kind of red powder Pd2
(0.34g, 77.4%).1H NMR(400MHz,CDCl3) δ 8.13 (d, J=8.3Hz, 1H, Ar-H), 8.09 (d, J=8.3Hz,
1H, Ar-H), 7.60-7.27 (m, 8H, Ar-H), 6.74 (d, J=7.2Hz, 1H, Ar-H), 6.48 (d, J=7.3Hz, 1H, Ar-
), H 3.29 (dd, J=20.0,14.2Hz, 2H, CH), 3.18 (dd, J=12.5,6.2Hz, 2H, CH), 2.17-2.00 (m, 2H,
CH2),1.97–1.24(m,24H,CH2),1.20–1.11(m,4H,CH2), 1.06 (t, J=7.2Hz, 6H, CH3),1.00(t,J
=7.3Hz, 6H, CH3),0.97(s,3H,Pd-CH3),0.94–0.79(m,2H,CH2), 0.28 (t, J=7.3Hz, 6H, CH3),
0.20 (t, J=7.3Hz, 6H, CH3).13C NMR(101MHz,CDCl3) δ 171.93 (C=N), 167.57 (C=N),
143.88,143.45,142.98,137.98,136.89,131.20,130.87,130.82,128.32,128.26,127.70,
127.29,126.78,126.54,125.83,125.58,125.34,124.88,39.26,39.00,37.70,37.32,
36.87,36.69,21.12,20.99,20.37,19.76,14.82,14.78,14.10,13.95,4.45(Pd-CH3)
.MALDI-TOF-MS (m/z): calculating C52H72N2Pd:830.47, it is actually measured, 830.44, [M-Me-Cl]+.Anal. it calculates
C53H75ClN2Pd:C,72.17；H,8.57；N,3.18；It is actually measured, 72.11；H,8.53；N,3.13.
Embodiment 6
The present embodiment prepares diimine palladium complex Pd3:
Using method identical with synthesis Pd1, difference is to use ligand L 3 instead, has obtained a kind of red powder Pd3
(0.43g, 87.5%).1H NMR(400MHz,CDCl3) δ 8.03 (d, J=8.2Hz, 1H, Ar-H), 7.99 (d, J=8.2Hz,
1H, Ar-H), 7.61-7.18 (m, 8H, Ar-H), 6.72 (d, J=7.1Hz, 1H, Ar-H), 6.39 (d, J=7.2Hz, 1H, Ar-
H),3.26–3.14(m,2H,CH),3.09–3.01(m,2H,CH),2.15–1.98(m,2H),1.92–1.64(m,6H),
1.53-1.13 (m, 24H), 1.01-0.76 (m, 23H), 0.69 (tt, J=25.1,12.5Hz, 6H), 0.56 (dt, J=20.7,
7.1Hz,2H),0.40–0.18(m,12H,CH3).13C NMR(101MHz,CDCl3) δ 171.78 (C=N), 167.26 (C=
N),143.74,143.53,143.09,138.02,136.97,131.00,130.96,130.60,128.35,128.27,
127.86,127.30,126.89,126.61,125.85,125.82,125.51,124.86,39.93,39.46,35.49,
34.76,34.43,33.92,30.17,29.96,29.93,29.08,23.41,23.29,22.91,22.70,14.37,
14.16,13.69,13.51,4.49(Pd-CH3) .MALDI-TOF-MS (m/z): calculate C60H88N2Pd:942.60, it is practical to survey
, 941.55, [M-Me-Cl]+.Anal. C is calculated61H91ClN2Pd:C,73.69；H,9.23；N,2.82；It is actually measured,
73.88；H,9.20；N,2.87.
Embodiment 7
The present embodiment prepares diimine nickel complex Ni1:
Preparation process are as follows: by ligand L 1 (401mg, 0.65mmol) and (DME) NiBr2(201mg, 0.65mmol) is added to
15mL CH2Cl2In, it is placed in nitrogen atmosphere.Gained mixture is stirred at room temperature 24 hours, then depressurizes lower removing solvent, obtains
It to red solid, is washed, is dried in vacuo with 3 × 10mL n-hexane.The product is separated into red powder, yield 77%
(0.42g).MALDI-TOF-MS (m/z): C is calculated44H56BrN2Ni:749.30, it is actually measured, 749.19, [M-Br]+.Anal.
Calculate C44H56Br2N2Ni:C,63.56；H,6.79；N,3.37；It is actually measured, C, 63.63；H,6.98；N,3.34.
Embodiment 8
The present embodiment prepares diimine nickel complex Ni2:
Using method identical with synthesis Ni1, difference is to use ligand L 2 (338mg, 0.42mmol) instead, has obtained one kind
Red powder Ni2 (0.34g, 86%).MALDI-TOF-MS (m/z): C is calculated52H72BrN2Ni:861.42, it is actually measured,
861.46,[M-Br]+.Anal. C is calculated52H72Br2N2Ni:C,66.19；H,7.69；N,2.97；It is actually measured, C, 66.37；H,
7.96；N,3.01.
Embodiment 9
The present embodiment prepares diimine nickel complex Ni3:
Using method identical with synthesis Ni1, difference is to use ligand L 3 (601mg, 0.57mmol) instead, has obtained one kind
Red powder Ni3 (0.40g, 67%).MALDI-TOF-MS (m/z): C is calculated66H88BrN2Ni:973.55；It is actually measured,
973.58,[M-Br]+.Anal. C is calculated60H88Br2N2Ni:C,68.25；H,8.40；N,2.65；It is actually measured, C, 68.49；H,
8.22；N,2.67.
Embodiment 10
Diimine nickel complex is used to carry out the conventional method of ethylene homo as catalyst: dry first at 90 DEG C of vacuum
The 300mL stainless steel pressure reactor of one connection high-pressure gas pipeline, drying time are at least 1h；Then reactor is adjusted
To required polymerization temperature (the present embodiment set temperature is 20 DEG C, 50 DEG C, 80 DEG C).It is added in a nitrogen atmosphere into reactor
The MAO (additional amount in the present embodiment is 1mmol) of 40mL toluene and requirement, two is sub- needed for then being contained by syringe
The 1mL CH of amine Raney nickel2Cl2It injects in polymerization system (catalyst charge is 2 μm of ol in the present embodiment).Quickly stirring
Under, reactor is pressurizeed and is maintained at 6atm ethylene pressure.After 30min, pressure reactor is vented, polymer is deposited in second
In alcohol, the filtration drying at 50 DEG C, under vacuum condition it is dry at least for 24 hours.
Utilize the catalyzed ethylene polymerization at different temperatures of Ni1, Ni2, Ni3 obtained by above-described embodiment, the property of resulting polymers
It can be as shown in table 1:
In table: Act. is activity, MnFor number-average molecular weight, Mw/MnIt is the degree of branching (every 1000 for molecular weight distribution, brs
The corresponding methyl number of methylene), TmFor fusing point.
As shown in Table 1, as the temperature rises, the high molecular degree of branching of gained is higher and higher, and molecular weight is smaller and smaller.
Embodiment 11
Diimine palladium complex is used to carry out the conventional method of ethylene homo as catalyst: dry first at 90 DEG C of vacuum
The 300mL stainless steel pressure reactor of one connection high-pressure gas pipeline, drying time are at least 1h；Then reactor is adjusted
To required polymerization temperature (the present embodiment set temperature is 30 DEG C).In a nitrogen atmosphere into reactor be added 38mL DCM and
The desired amount of NaBArF (additional amount in the present embodiment is 30 μm of ol), then will contain required diimine palladium chtalyst by syringe
The 2mL CH of agent2Cl2It injects in polymerization system (catalyst charge is 20 μm of ol in the present embodiment).It under fast stirring, will be anti-
It answers device to pressurize and is maintained at 4atm ethylene pressure.After 12h, pressure reactor is vented, polymer is dried under vacuum overnight.
Use diimine palladium complex as catalyst by the conventional method of polar monomer and ethylene copolymer are as follows: first in vacuum
The 300mL stainless steel pressure reactor of dry connection high-pressure gas pipeline, drying time are at least 1h at 90 DEG C；Then will
Reactor is adjusted to required polymerization temperature (the present embodiment set temperature is 30 DEG C).It is added in a nitrogen atmosphere into reactor
38mL DCM and the desired amount of NaBArF (additional amount in the present embodiment is 30 μm of ol), two needed for then being contained by syringe
The 2mL CH of imines palladium catalyst and polar monomer2Cl2Inject polymerization system (in the present embodiment catalyst charge be 20 μm of ol,
The additional amount of polar monomer methyl acrylate MA is 1mol/L) in.Under fast stirring, reactor is pressurizeed and is maintained at 4atm
Ethylene pressure.After 12h, pressure reactor is vented, copolymer is dried under vacuum overnight.
Utilize Pd1, Pd2, Pd3 obtained by above-described embodiment catalyzed ethylene polymerization or catalysis ethylene and third at different temperatures
E pioic acid methyl ester (MA), acrylic acid (AA) copolymerization, the performance of resulting polymers are as shown in table 2:
In table: c is the polar monomer concentration being added, the insertion ratio that Act. is activity, X is polar monomer, MnDivide equally for number
Son amount, Mw/MnIt is the degree of branching (every 1000 methylene corresponding methyl number) for molecular weight distribution, brs
As can be seen from Table 2, flexible chain growth of the diimine palladium catalyst with ligand, high molecular degree of branching drop
It is low.Therefore, as flexible substituent group chain length increases, catalytic activity and polymer molecular weight increase, and polar monomer incorporation and branch
The trend that chain density reduces is quite obvious.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. big steric hindrance flexibility diimide ligand, which is characterized in that the structural formula of the ligand is shown in formula I:
Wherein, R is methyl, ethyl or n-propyl.
2. the synthetic method of big steric hindrance flexibility diimide ligand described in a kind of claim 1, it is characterised in that: by acenaphthenequinone and amination
After the suspension mixing of 1:2.2~2.5 in molar ratio for closing object, 6~12h is stirred to react at 90 DEG C, gained reaction solution is cooled to
After room temperature, sediment is collected by filtration and washs, dry, is i.e. the acquisition big steric hindrance flexibility diimide ligand of target product, reaction equation is such as
Shown in lower, wherein A is the structural formula of acenaphthenequinone, the structural formula that B is amine compounds:
3. synthetic method according to claim 2, it is characterised in that: the suspension is the acetonitrile suspension and amine of acenaphthenequinone
The acetic acid suspension of compound.
4. a kind of complex, it is characterised in that: the complex is by diimide ligand described in claim 1 and nickel compound
Or palladium compound is formed by diimine nickel complex or diimine palladium complex；
The structural formula of the diimine nickel complex is as shown in Formula II, the structural formula of the diimine palladium complex such as formula III institute
Show:
In formula, R is methyl, ethyl or n-propyl.
5. complex according to claim 4, it is characterised in that: the nickel compound is (DME) NiBr2, the palladium chemical combination
Object is (COD) PdMeCl.
6. a kind of preparation method of claim 4 or 5 complex, it is characterised in that: in atent solvent, by claim
1:1 is mixed in molar ratio for diimide ligand described in 1 and nickel compound or palladium compound, and reaction 20~for 24 hours is stirred at room temperature,
Then post-treated again, that is, obtain diimine nickel complex or diimine palladium complex.
7. preparation method according to claim 6, it is characterised in that: the atent solvent is methylene chloride, acetonitrile or second
Acid.
8. a kind of application of claim 4 or 5 complex, it is characterised in that: for urging as alpha-olefin polymerization
Agent.
9. application according to claim 8, which is characterized in that the application includes two kinds:
(1) using the diimine nickel complex or diimine palladium complex as the catalyst of alpha-olefine polymerizing, to alpha-olefin into
Row catalytic polymerization obtains the high molecular polyolefine of highly -branched；
(2) using the diimine nickel complex or diimine palladium complex as the catalyst of alpha-olefine polymerizing, to alpha-olefin with
Acrylic acid, methyl acrylate carry out catalyzed copolymerization, obtain the high molecular polyolefine copolymer of highly -branched.
10. application according to claim 9, it is characterised in that:
(1) high molecular polyolefine of gained highly -branched has a characteristic that the corresponding methyl number of every 1000 methylene is in
70-110, molecular weight is in 245000-1195000g/mol, and fusing point is at -2~64 DEG C；
(2) the high molecular polyolefine copolymer of gained highly -branched has a characteristic that the corresponding first of every 1000 methylene in
Radix is 75-95, is inserted into ratio in 0.28-1.21%, molecular weight is in 3600-71100g/mol.
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