CN105482000A - Olefin polymerization catalyst as well as preparation method and application method thereof - Google Patents
Olefin polymerization catalyst as well as preparation method and application method thereof Download PDFInfo
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- CN105482000A CN105482000A CN201410479028.8A CN201410479028A CN105482000A CN 105482000 A CN105482000 A CN 105482000A CN 201410479028 A CN201410479028 A CN 201410479028A CN 105482000 A CN105482000 A CN 105482000A
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Abstract
The invention relates to a catalyst for olefin polymerization. The catalyst comprises a complex whose chemical structural formula is shown as Formula (I) as the main catalyst. In the Formula (I), the X stands for halogen; the values of the R1-R8 can be identical or different; the R1-R8 are respectively and independently selected from hydrogen atom, halogen, C1-C20 alkyls, heterocyclic compound group or organic groups containing oxygen atom, nitrogen atom, boron atom, sulfur atom, phosphorus atom, silicon atom, germanium atom or tin atom; and loops are optionally formed by the R1 and the R2 as well as the R5 and the R6 mutually. And the invention also provides an olefin polymerization method, wherein the olefin polymerization method comprises the step of carrying on olefin polymerization reaction under the existence of the olefin polymerization catalyst provided by the invention.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of catalyst for olefines polymerizing and preparation method thereof.More specifically, relate to class alpha-diimine nickel olefine polymerization catalyzer and a technology of preparing thereof, and the application of gained catalyzer in olefinic polymerization.
Background technology
China is that synthetic resins consumes fastest-rising country, also be maximum synthetic resins importer, current polyolefin production proportion nearly 60%, olefin resin has excellent environment compatibility compared with other resin material, in developed country's automobile industry, be used to the material that emphasis is promoted, the world production amount in 2003 just reaches 8,330 ten thousand tons; Wherein polyethylene is with fastest developing speed, that output is maximum, purposes is extremely wide synthetic resins, reaches 5,110 ten thousand tons then.Industrialized polyethylene catalysts has Ziegler-Natta type catalyzer (DEPat889229 (1953); ITPat545332 (1956) and ITPat536899 (1955); Chem.Rev., 2000,100,1169 and this special issue pertinent literature), Phillips type catalyzer (Belg.Pat.530617 (1955); Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, MetalorganicCatalystsforSynthesisandPolymerization, Berlin:Springer,, and the efficient ethylene oligomerization of the rear transition metal metal compounding material type of development in recent years and polymerizing catalyst 1999).Such as nineteen ninety-five, Brookhart etc. report the title complex of a class alpha-diimine Ni (II), can highly active polymerising ethylene (J.Am.Chem.Soc., 1995,117,6414-6415).
Because alpha-diimine nickel catalyzator has high reactivity, and polymericular weight and the degree of branching can in very large range regulate and control and receive much attention.The companies such as DuPont have applied for multiple patent (WO96/23010, WO98/03521, WO98/40374, WO99/05189, WO99/62968, WO00/06620, US6,103,658, US6,660,677).This kind of alpha-diimine nickel catalyzator, can highly active catalyzed ethylene oligomerisation or polymerization under normal temperature or low temperature under methylaluminoxane or aluminum alkyls effect.But when raising temperature of reaction higher than 50 DEG C, this kind of alpha-diimine nickel catalyst activity reduces rapidly, prepared poly molecular weight with polymerisation temperature improves and declines rapidly.Existing ethene gas-phase polymerization processing requirement polymerization temperature is more than 85 DEG C, and vinyl solution polymerization technique requires that polymerization temperature is 150-250 DEG C, and original late transition metal catalyst cannot meet the requirement of existing gas phase, solution method ethylene polymerization plants.Catalyzer prepared by this patent still can keep higher ethylene polymerization activity at relatively high temperatures, and resulting polymers molecular weight is higher, and molecular weight distribution is narrower.
Summary of the invention
One of the object of the invention is the deficiency overcoming prior art existence, a kind of alpha-nickel diimine compound catalyzer with good thermal stability is provided, under methylaluminoxane or aluminum alkyls activation, catalyzed ethylene polymerization under comparatively high temps can be realized, the branched polyethylene of preparation high molecular.
First embodiment of the present invention provides a kind of catalyzer for vinyl polymerization, and described catalyzer comprises the title complex of chemical structural formula as shown in (I) as Primary Catalysts:
In formula (1), X is halogen; R
1-R
8may be the same or different, be selected from hydrogen atom, halogen, C independently of one another
1-C
20alkyl, heterocyclic compound group or containing the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
1and R
2, R
5and R
6optionally be in ring.
In one preferred embodiment, described X is selected from chlorine or bromine.
In one preferred embodiment, described title complex is selected from the title complex of formula II or formula III structure;
Wherein, X is chlorine or bromine; R
3, R
4, R
7-R
11may be the same or different, be selected from hydrogen atom, halogen, C respectively
1-C
20alkyl, heterocyclic compound group.
In further preferred implementation, described title complex is selected from least one in following compound:
1) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=Me, X=Br;
2) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=Me, R
9=H, X=Br;
3) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=iPr, X=Br;
4) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=CHPh
2, X=Br;
5) title complex, wherein R shown in formula (II)
3=R
7=H, R
4=R
8=R
9=CHPh
2, X=Br;
6) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=R
9=CHPh
2, X=Br;
7) title complex, wherein R shown in formula (III)
11=Ph, R
10=H, X=Br;
8) title complex, wherein R shown in formula (III)
11=Ph, R
10=Cl, X=Br;
9) title complex, wherein R shown in formula (III)
11=Ph, R
10=CH
3, X=Br;
10) title complex, wherein R shown in formula (III)
11=Ph, R
10=iPr, X=Br;
11) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=Me, X=Cl;
12) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=Me, R
9=H, X=Cl;
13) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=iPr, X=Cl;
14) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=CHPh
2, X=Cl;
15) title complex, wherein R shown in formula (II)
3=R
7=H, R
4=R
8=R
9=CHPh
2, X=Cl;
16) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=R
9=CHPh
2, X=Cl;
17) title complex, wherein R shown in formula (III)
11=Ph, R
10=H, X=Cl;
18) title complex, wherein R shown in formula (III)
11=Ph, R
10=Cl, X=Cl;
19) title complex, wherein R shown in formula (III)
11=Ph, R
10=CH
3, X=Cl; And
20) title complex, wherein R shown in formula (III)
11=Ph, R
10=iPr, X=Cl.
Wherein Me represents methyl, Ph represents phenyl, iPr represents sec.-propyl.
In a preferred embodiment of the present invention, described catalyzer also comprises promotor, described promotor is selected from least one in alkylaluminoxane, aluminum alkyls and chloralkane, at least one in preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride.
In further preferred embodiment, the mol ratio of the metal in the metallic aluminium in described promotor and described Primary Catalysts is 200-5000.
Second embodiment of the present invention relates to a kind of preparation method of described catalyzer, wherein, and the preparation method of described title complex:
1) in the presence of a catalyst, the aniline of 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone and replacement is refluxed in a solvent, the obtained alpha-diimine part of reaction;
2) under the condition of anhydrous and oxygen-free, by step 1) the described alpha-diimine part that obtains and (DME) NiX
2carry out coordination reaction, obtain chemical structure such as formula the title complex shown in (I).
In a preferred embodiment of the present invention, described step 1) in catalyzer be acetic acid and/or described step 1) in solvent be ethanol.
In a preferred embodiment of the present invention, the temperature of reaction of described reaction is 70-80 DEG C, preferably 78 DEG C, and the time of described backflow is 1-7 days.
In a preferred embodiment of the present invention, the mol ratio of the aniline of described 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone and replacement is 1:1 ~ 1:10, preferred 1:1 ~ 1:3.
The concrete preparation process of title complex of the present invention and catalyzer is as follows:
1, the general method of part synthesis
A) 9,10-dihydro-9,10-ethylene anthracenes-11, the aniline of 12-diketone and replacement is that catalyzer refluxes 1-7 days in etoh solvent with acetic acid, except parlkaline aluminum oxide pillar after desolventizing after filtering, with petrol ether/ethyl acetate (20:1) drip washing, be separated and obtain product;
B) 9,10-dihydro-9,10-ethylene anthracenes-11, the aniline of 12-diketone and replacement is catalyzer backflow 1-7 days with p-methyl benzenesulfonic acid in toluene, parlkaline aluminum oxide pillar after reaction solution evaporate to dryness, with petrol ether/ethyl acetate (20:1) drip washing, is separated and obtains product.
9,10-dihydro-9,10-ethylene anthracene-11,12-diimide ligands of above-mentioned all synthesis all obtain confirmation by nuclear-magnetism, infrared and ultimate analysis.
2, the general method of nickel (II) title complex synthesis
Under protection of inert gas, by (DME) NiCl
2or (DME) NiBr
2dichloromethane solution in molar ratio (1:1 ~ 1:1.2) be added drop-wise to 9,10-dihydro-9,10-ethylene anthracene-11, in the solution of 12-diimide ligand, stirring at room temperature, separates out precipitation, the drying of filtration washed with diethylether final vacuum just obtains 9,10-dihydro-9,10-ethylene anthracene-11,12-diimine nickel complex.
3rd embodiment of the present invention relates to a kind of method of olefinic polymerization, under described method is included in the existence of catalyzer of the present invention, carries out olefinic polyreaction.
In a preferred embodiment of the present invention, the temperature of reaction of described polyreaction is polymerization temperature is-78 DEG C ~ 200 DEG C, is preferably-20 DEG C ~ 150 DEG C; Polymerization pressure is 0.01 ~ 10.0MPa, preferably 0.01 ~ 2.0MPa.
Catalyzer prepared by the present invention may be used for all polymerizations or the copolymerization of alkene, be specially adapted to the copolymerization of ethylene homo conjunction or ethene and other alpha-olefin, wherein alpha-olefin adopts at least one in propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
In preferred implementations more of the present invention, be wherein polymerized the solvent used and be selected from alkane, aromatic hydrocarbon or halohydrocarbon.A kind of in preferred hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, ethylene dichloride or their mixture, most preferably be a kind of in hexane, toluene, heptane or their mixture.
The present invention compared with prior art has the following advantages:
It is obtained that complex ligand of the present invention can adopt the aniline of 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone and replacement with acetic acid to be that catalyzer refluxes in ethanol, and part synthetic method is more simple.
Catalyzer of the present invention, can highly active catalyzed ethylene polymerization under methylaluminoxane or aluminum alkyls effect.(higher than 80 degree) higher polymerization activity can be still kept especially under higher polymerization temperature.(namely diimine nickel catalyzer activity more than 50 degree of previous literature or patent report significantly decays, and molecular weight significantly reduces).
Catalyzer of the present invention has the ability of the copolymerization of good catalyzed ethylene and high alpha-olefin, and Copolymerization activity is high.
Embodiment
Describe the present invention below in conjunction with embodiment, but it is to be appreciated that described embodiment is only for carrying out exemplary description to the present invention, and any restriction can not be formed to protection scope of the present invention.Allly be included in rational conversion in invention teachings of the present invention and combination all falls into protection scope of the present invention.
The analysis and characterization instrument used in the present invention is as follows:
Nuclear magnetic resonance analyser: BrukerDMX300 (300MHz), tetramethylsilane (TMS) is interior mark.
Embodiment 1
The present embodiment title complex as shown in structure formula II, wherein R
4, R
8for methyl, R
3, R
7, R
9for hydrogen, X is Br.
1) preparation of part:
11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-methyl naphthylamines):
9,10-dihydro-9,10-ethylene anthracene-11,12-diketone (1.14g, 4.8mmol) and 2-methyl naphthylamines (1.63g, 10.4mmol), 0.5g tosic acid is catalyzer, 100mL reflux in toluene 1 day, except desolventizing after filtering, residuum methylene dichloride dissolves, parlkaline aluminum oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, is separated and obtains product, except desolventizing obtains yellow solid, productive rate is 46%.
1HNMR(CDCl
3,δ,ppm):2.46(s,6H),4.86(s,2H),7.05-7.36(m,14H)，7.62－7.72(m，6H)。
2) preparation of title complex 1: bromination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-methyl naphthylamines)] closes nickel (II): by 10ml (DME) NiBr
2(277mg, dichloromethane solution 0.9mmol) is added drop-wise to 10ml11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-methyl naphthylamines) part (461mg, 0.9mmol) dichloromethane solution in, stirring at room temperature 6 hours, separate out precipitation, after filtration washed with diethylether, drying obtains dark red powder solid, and productive rate is 90%.Ultimate analysis (C
38h
28br
2n
2ni): C, 62.42; H, 3.86; N, 3.83; Experimental value (%): C, 62.56; H, 4.03; N, 4.16.
3) 10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 7.3mg (10 μm of ol) title complex 1 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 50 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 8.62 × 10
6gmol
-1(Ni) h
-1.
Embodiment 2
10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 6.6mg (10 μm of ol) title complex 1 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 90 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 6.28 × 10
6gmol
-1(Ni) h
-1.
Embodiment 3
The present embodiment title complex as shown in structure formula II, wherein R
3, R
4, R
7, R
8for methyl, R
9for hydrogen, X is Br.
1) preparation of part: 11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,4-dimethyl-naphthylamine): 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone (1.82g, 7.8mmol) He 2,4-dimethyl-naphthylamine (2.98g, 17.4mmol), 0.5g tosic acid is catalyzer, 100mL reflux in toluene 1 day, except desolventizing after filtering, residuum methylene dichloride dissolves, parlkaline aluminum oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, separation obtains product, and except desolventizing obtains yellow solid, productive rate is 42%.
1HNMR(CDCl
3,δ,ppm):2.45(s,6H),2.67(s,6H),4.86(s,2H),7.05-7.34(m,14H)，7.60－7.71(m，4H)。
2) preparation of title complex 2: bromination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,4-dimethyl-naphthylamine)] closes nickel (II): by 10ml (DME) NiBr
2(155mg, dichloromethane solution 0.5mmol) is added drop-wise to 10ml11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,4-dimethyl-naphthylamine) part (270mg, in dichloromethane solution 0.5mmol), stirring at room temperature 6 hours, separates out precipitation, after filtration washed with diethylether, drying obtains dark red powder solid, and productive rate is 87%.Ultimate analysis (C
40h
32br
2n
2ni): C, 63.28; H, 4.25; N, 3.69; Experimental value (%): C, 63.42; H, 4.56; N, 3.92.
3.10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 7.6mg (10 μm of ol) title complex 2 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 90 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 4.72 × 10
6gmol
-1(Ni) h
-1.
Embodiment 4
The present embodiment title complex as shown in structure formula II, wherein R
4, R
8for diphenyl-methyl, R
3, R
7, R
9for hydrogen, X is Br.
1) preparation of part: 11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-diphenyl-methyl naphthylamines): 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone (1.82g, 7.8mmol) with 2-diphenyl-methyl naphthylamines (5.38g, 17.4mmol), 0.5g tosic acid is catalyzer, 100mL reflux in toluene 1 day, except desolventizing after filtering, residuum methylene dichloride dissolves, parlkaline aluminum oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, separation obtains product, and except desolventizing obtains yellow solid, productive rate is 30%.
1HNMR(CDCl
3,δ,ppm):4.88(s,2H),5.32(s，2H)，7.05-7.35(m,34H)，7.60-7.70(m，6H)。
2) preparation of title complex 4: bromination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-diphenyl-methyl naphthylamines)] closes nickel (II): by 10ml (DME) NiBr
2(155mg, dichloromethane solution 0.5mmol) is added drop-wise to 10ml11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-diphenyl-methyl naphthylamines) part (408mg, 0.5mmol) dichloromethane solution in, stirring at room temperature 6 hours, separate out precipitation, after filtration washed with diethylether, drying obtains dark red powder solid, and productive rate is 87%.Ultimate analysis (C
62h
44br
2n
2ni): C, 71.91; H, 4.28; N, 2.71; Experimental value (%): C, 71.46; H, 4.63; N, 2.52.
3) 10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 10.4mg (10 μm of ol) title complex 4 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 90 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 3.27 × 10
6gmol
-1(Ni) h
-1.
Embodiment 5
The present embodiment title complex as shown in structure formula III, wherein R
11for phenyl, R
10for methyl, X is Br.
1) preparation of part: 11, 12-(9, 10-dihydro-9, 10-ethylene anthracene) two (contractings 2, 6-bis-(diphenyl-methyl)-4-monomethylaniline): 9, 10-dihydro-9, 10-ethylene anthracene-11, 12-diketone (2.10g, 9.0mmol) He 2, 6-bis-(diphenyl-methyl)-4-monomethylaniline (8.66g, 19.7mmol), 0.5g tosic acid is catalyzer, 100mL reflux in toluene 1 day, except desolventizing after filtering, residuum methylene dichloride dissolves, parlkaline aluminum oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, separation obtains product, except desolventizing obtains yellow solid, productive rate is 36%.
1HNMR(CDCl
3,δ,ppm):2.15(s,6H),4.95(s,2H),5.34(s，4H),6.70(s,4H),6.97(d,J＝6.9Hz,8H),7.06(d,J＝7.4Hz,8H),7.12-7.35(m,32H)。
2) preparation of title complex 9: bromination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,6-DIPAs)] closes nickel (II): by 10ml (DME) NiBr
2(506mg, dichloromethane solution 1.6mmol) is added drop-wise to 10ml11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,6-bis-(diphenyl-methyl)-4-monomethylaniline) part (1723mg, in dichloromethane solution 1.6mmol), stirring at room temperature 6 hours, separates out precipitation, after filtration washed with diethylether, drying obtains dark red powder solid, and productive rate is 88%.Ultimate analysis (C
82h
64br
2n
2ni): C, 76.00; H, 4.98; N, 2.16; Experimental value (%): C, 76.27; H, 5.24; N, 2.52.
3) 10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 12.96mg (10 μm of ol) title complex 9 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 90 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 5.21 × 10
6gmol
-1(Ni) h
-1.
Embodiment 6
The present embodiment title complex as shown in structure formula II, wherein R
4, R
8for methyl, R
3, R
7, R
9for hydrogen, X is Cl.
1) preparation of title complex 11: nickel (II) is closed in chlorination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-methyl naphthylamines)]: by 10ml (DME) NiCl
2(352mg, dichloromethane solution 1.6mmol) is added drop-wise to 10ml11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2-methyl naphthylamines) part (820mg, 1.6mmol) dichloromethane solution in, stirring at room temperature 6 hours, separate out precipitation, after filtration washed with diethylether, drying obtains orange red powder solid, and productive rate is 87%.Ultimate analysis (C
38h
28cl
2n
2ni): C, 71.06; H, 4.39; N, 4.36; Experimental value (%): C, 71.32; H, 4.88; N, 4.24.
2) 10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 6.4mg (10 μm of ol) title complex 11 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 80 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 5.20 × 10
6gmol
-1(Ni) h
-1.
Embodiment 7
The present embodiment title complex as shown in structural formula (II), wherein R
3, R
4, R
7, R
8for methyl, R
9for hydrogen, X is Cl.
1) preparation of title complex 12: nickel (II) (1) is closed in chlorination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,4-dimethyl-naphthylamine)]: by 10ml (DME) NiCl
2(352mg, dichloromethane solution 1.6mmol) is added drop-wise to 10ml11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,4-dimethyl-naphthylamine) part (864mg, in dichloromethane solution 1.6mmol), stirring at room temperature 6 hours, separates out precipitation, after filtration washed with diethylether, drying obtains orange red powder solid, and productive rate is 90%.Ultimate analysis (C
40h
32cl
2n
2ni): C, 71.67; H, 4.81; N, 4.18; Experimental value (%): C, 71.87; H, 5.02; N, 3.88.
2) 10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 6.7mg (10 μm of ol) title complex 12 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.At 80 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 3.22 × 10
6gmol
-1(Ni) h
-1.
Embodiment 8
10atm vinyl polymerization: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 7.3mg (10 μm of ol) title complex 1 and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000,10ml hexene.At 80 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 5.27 × 10
6gmol
-1(Ni) h
-1.
Comparative example 1
10atm ethene: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 7.2mg (10 μm of ol) comparative catalyst A (its structure is such as formula (IV)) and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000,10ml hexene.At 90 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 0.08 × 10
6gmol
-1(Ni) h
-1.
Comparative example 2
10atm ethene: churned mechanically 1L stainless steel polymeric kettle will be housed at 130 DEG C of successive drying 6hrs, and vacuumize while hot and use N
2gas replaces 3 times.Add 6.2mg (10 μm of ol) comparative catalyst B (its structure is as formula V) and then vacuumize and replace 3 times with ethene.Inject the hexane of 500ml, then add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000,10ml hexene.At 90 DEG C, keep the ethylene pressure of 10atm, vigorous stirring reaction 30min.Neutralize with the ethanolic soln of 5% hcl acidifying, obtain polyethylene, polymerization activity is 0.02 × 10
6gmol
-1(Ni) h
-1.
Table 1
As can be seen from Table 1, relative to the title complex of comparative example 1 and 2, when using metal complexes of the present invention to use as Primary Catalysts, under high temperature polymerization condition, polymerization activity wants high a lot, and the molecular weight of resulting polymers is apparently higher than comparative example resulting polymers.
Claims (10)
1., for a catalyzer for vinyl polymerization, described catalyzer comprises the title complex of chemical structural formula as shown in (I) as Primary Catalysts:
In formula (1), X is halogen; R
1-R
8may be the same or different, be selected from hydrogen atom, halogen, C independently of one another
1-C
20alkyl, heterocyclic compound group or containing the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
1and R
2, R
5and R
6optionally be in ring.
2. catalyzer according to claim 1, is characterized in that, described X is selected from chlorine or bromine; R
1-R
8may be the same or different, be selected from methyl independently of one another, ethyl or sec.-propyl, described R
2and R
5be selected from hydrogen, methyl, vinyl or bromine independently of one another, and R
1and R
2, R
5and R
6optionally be in ring.
3. catalyzer according to claim 1 and 2, is characterized in that, described title complex is selected from the title complex of formula II or formula III structure;
Wherein, X is chlorine or bromine; R
3, R
4, R
7-R
11may be the same or different, be selected from hydrogen atom, halogen, C independently of one another
1-C
20alkyl, heterocyclic compound group.
4. the catalyzer according to any one of claim 1-3, is characterized in that, described title complex is selected from least one in following compound:
1) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=Me, X=Br;
2) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=Me, R
9=H, X=Br;
3) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=iPr, X=Br;
4) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=CHPh
2, X=Br;
5) title complex, wherein R shown in formula (II)
3=R
7=H, R
4=R
8=R
9=CHPh
2, X=Br;
6) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=R
9=CHPh
2, X=Br;
7) title complex, wherein R shown in formula (III)
11=Ph, R
10=H, X=Br;
8) title complex, wherein R shown in formula (III)
11=Ph, R
10=Cl, X=Br;
9) title complex, wherein R shown in formula (III)
11=Ph, R
10=CH
3, X=Br;
10) title complex, wherein R shown in formula (III)
11=Ph, R
10=iPr, X=Br;
11) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=Me, X=Cl;
12) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=Me, R
9=H, X=Cl;
13) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=iPr, X=Cl;
14) title complex, wherein R shown in formula (II)
3=R
7=R
9=H, R
4=R
8=CHPh
2, X=Cl;
15) title complex, wherein R shown in formula (II)
3=R
7=H, R
4=R
8=R
9=CHPh
2, X=Cl;
16) title complex, wherein R shown in formula (II)
3=R
7=R
4=R
8=R
9=CHPh
2, X=Cl;
17) title complex, wherein R shown in formula (III)
11=Ph, R
10=H, X=Cl;
18) title complex, wherein R shown in formula (III)
11=Ph, R
10=Cl, X=Cl;
19) title complex, wherein R shown in formula (III)
11=Ph, R
10=CH
3, X=Cl; And
20) title complex, wherein R shown in formula (III)
11=Ph, R
10=iPr, X=Cl.
5. the catalyzer according to any one of Claims 1 to 4, it is characterized in that, described catalyzer also comprises promotor, described promotor is selected from least one in alkylaluminoxane, aluminum alkyls and chloralkane, at least one in preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride.
6. catalyzer according to claim 5, is characterized in that, the mol ratio of the metal in the metallic aluminium in described promotor and described Primary Catalysts is 200-5000.
7. a preparation method for the catalyzer according to any one of claim 1 ~ 6, is characterized in that, the preparation method of described title complex comprises:
1) in the presence of a catalyst, the aniline of 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone and replacement is refluxed in a solvent, the obtained alpha-diimine part of reaction;
2) under the condition of anhydrous and oxygen-free, by step 1) the described alpha-diimine part that obtains and (DME) NiX
2carry out coordination reaction, obtain the title complex of chemical structural formula as shown in (I).
8. method according to claim 7, is characterized in that, described step 1) in catalyzer be acetic acid and/or described step 1) in solvent be ethanol.
9. the method according to any one of claim 7 or 8, is characterized in that, the mol ratio of the aniline of described 9,10-dihydro-9,10-ethylene anthracene-11,12-diketone and replacement is 1:1 ~ 1:10, preferred 1:1 ~ 1:3.
10. a method for olefinic polymerization, is characterized in that, under described method is included in the existence of the catalyzer according to any one of claim 1 ~ 6, carries out olefinic polyreaction.
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