CN104788489A - SiO2-supported alpha-diimine compound and application of metal complex of SiO2-supported alpha-diimine compound - Google Patents

SiO2-supported alpha-diimine compound and application of metal complex of SiO2-supported alpha-diimine compound Download PDF

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CN104788489A
CN104788489A CN201510216647.2A CN201510216647A CN104788489A CN 104788489 A CN104788489 A CN 104788489A CN 201510216647 A CN201510216647 A CN 201510216647A CN 104788489 A CN104788489 A CN 104788489A
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alpha
diimine
load
compound
sio
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CN104788489B (en
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杨敏
胡博文
李琴
侯彦辉
韩伟伟
翟飞帆
刘宾元
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Hebei University of Technology
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Abstract

The invention relates to a SiO2-supported alpha-diimine compound and application of a metal complex of the SiO2-supported alpha-diimine compound. The structural formula of the compound is as shown in the specification, wherein R1 and R2 are same or different C6-C60 aromatic hydrocarbon, R3 is H or C1-C20 hydrocarbon, R4 is C1-C20 hydrocarbon, R5 is C1-C20 hydrocarbon, and n=1, 2, 3, 4, 5, 6 or 7. The compound is supported on a SiO2 carrier in a covalent bonding way, the metal complex is used as a main catalyst for being applied in olefin polymerization, and during olefin polymerization, the supported metal complex has good thermal stability when being used as the catalyst, can be applicable to high reaction temperature above 80 DEG C and can still keep relatively high activity. The formula is as described in the specification.

Description

A kind of SiO 2the alpha-diimine compound of load and the application of metal complexes thereof
Technical field
The present invention relates to olefin catalytic polymerization field, be specially a kind of SiO 2the alpha-diimine compound of load and the application of metal complexes thereof.
Background technology
Coordination polymerization process synthesis polyolefine material because of its various aspects of performance excellent and cheap, be widely used in produce, life numerous areas.The core of polyolefine technology of preparing is catalyst system, and the continuous research of catalyst system, exploitation have promoted the development of High performance polyolefin technology of preparing.On the basis of traditional Z iegler-Natta catalyzer, people develop metallocene catalyst and non-metallocene catalyst in succession.Non-metallocene catalyst is divided into again front transition non-metallocene catalyst and rear transition non-metallocene catalyst.Nineteen ninety-five Brookhart etc. reports the late transition metal catalyst (J Am ChemSoc, 1995,117:6414) of a kind of alpha-diimine nickel, palladium, afterwards concern (the WO96/23010 of this class catalyzer extremely investigator; US6103658; Macromolecules, 2000,33:2320; J Am Chem Soc, 2003,125:3068; Angew Chem Int Ed, 2004,43:1821; J Am Chem Soc, 2013,135:16316; Catalysis journal, 2011,32 (3): 490; Macromoleculares, 2009,42:7789; CN201010177711.8; CN201210051457.6; CN201210276331.9; CN201010572741.9; Macromol Chem Phys, 2011,212:367).Alpha-diimine late transition metal catalyst, as other late transition metal catalyst, has a lot of excellent features: to air and moisture not too responsive; Synthesize easy, good stability; Oxytropism is relatively weak, catalysis polar monomer and olefin-copolymerization can prepare functional polyolefin; Catalytic activity is high; Ligand structure variable range is large, regulates and controls by changing the physical properties etc. of ligand structure to the chain structure of polymkeric substance, molecular weight and distribution and polymkeric substance.
Although the alpha-diimine late transition metal catalyst of homogeneous phase has plurality of advantages, in practical application in industry, still there is a lot of problem, as the sticky still phenomenon produced in catalysis in olefine polymerization process, and reaction heat is difficult to withdraw from; The form of polymkeric substance is difficult to control; The consumption of promotor methylaluminoxane is more, and cost is high; Poor heat stability, is not suitable with current industrial conventional poly-unit.The important channel addressed these problems is exactly by supported for alpha-diimine late transition metal catalyst.
Usually, the supported method of alkene catalyst is mainly divided three classes: (1) by physical adsorption directly by catalyst cupport on carrier magnesium chloride or silica gel, although this method is easy, but the reactive force of catalyzer and carrier is more weak, and in catalyzed polymerization process, catalyst active center easily comes off.(2) promotor or other compound-modified modified carrier supported catalyst is adopted.Such as patent CN200810025909.7 adopts the polynite/magnesium chloride of triethyl aluminum modification as the carrier of alpha-diimine nickel catalyzator; Promotor methylaluminoxane and diimine nickel catalyzer load on silica gel to use by patent CN201210051947.6 respectively; Soares etc. (Polymer, 2010,51:2271) have employed different aluminum alkyls process magnesium chloride, then by alpha-diimine nickel catalyst cupport.(3) functional group that catalyzer contains and carrier are carried out chemical reaction, by the covalent linkage that formed between the two by catalyst cupport on carrier, this mode of loading can make catalyzer be combined with carrier very securely, avoid catalyzer from coming off carrier, reduce the impact of functional group on catalyst activity of carrier surface, and catalytic activity does not reduce, even also increase.Such as patent CN201110189126.4 reports the load of alpha-diimine palladium catalyst on the magnesium chloride support of acryloyl rate modification; Document (Macromolecules, 2002,35:6074; Macromolecules, 2006,39:6341; J Mol Catal A:Chem, 2008,287:57; Appl Catal A:Gen, 2004,262:13; Polymer, 2010,51:2271) reacted by the aniline in alpha-diimine ligand structure and active group, active group again with silicon-dioxide or magnesium chloride, utilize the mode of covalent bond by catalyst cupport at carrier surface.Compared with other carrying method, there is more advantage by the method for covalent supporting, but existing document after just being reacted by the aniline in alpha-diimine ligand structure and active group again with silicon-dioxide or magnesium chloride load, this method limits substituent change on aniline, thus reduces the Modulatory character of catalyst structure to polymer architecture.
Summary of the invention
The present invention seeks to be difficult to control for the sticky still existed in homogeneous phase alpha-diimine late transition metal catalyst practical application in current techniques, polymer morphology, the deficiency such as promotor consumption is many, poor heat stability, a kind of alpha-diimine compound and SiO thereof are provided 2the alpha-diimine metal complexes of load.Alpha-diimine on the naphthalene nucleus of acenaphthenequinone by active group and SiO 2carrier carries out chemical reaction, utilizes the mode of covalent bond by catalyst cupport at SiO 2on carrier.Specifically by with the alpha-diimine compound of alkoxyl silicone and SiO 2carrier react, thus in the mode of covalent bond by its load at SiO 2on carrier, obtain SiO 2the alpha-diimine compound of load, this SiO 2the alpha-diimine compound of load coordinates with the metallic compound of nickel (II), palladium (II) and obtains SiO 2the metal complexes of load alpha-diimine, and it can be used as Primary Catalysts to apply in olefin polymerization.
The technical solution adopted in the present invention is:
A kind of alpha-diimine compound, the structural formula of this compound is such as formula 1,2 or 3:
Wherein, R 1, R 2identical or different C 6-C 60aromatic hydrocarbyl, R 3h or C 1-C 20alkyl, R 4c 1-C 20alkyl,
R 5c 1-C 20alkyl, n=1,2,3,4,5,6 or 7;
Ar is the one with following building stone:
Wherein, R ' is C 1-C 20alkyl, n '=1,2,3,4,5,6 or 7.
A kind of SiO 2the alpha-diimine compound of load is by described alpha-diimine compound and carrier S iO 2be obtained by reacting, comprise the following steps: under mechanical stirring, in the reaction flask being added with toluene, add alpha-diimine compound, after it dissolves completely, add carrier S iO 2, its proportioning is: every 50mL toluene adds the alpha-diimine compound of 0.2-20mmol, and the alpha-diimine compound of every 0.2-20mmol adds 1 gram of SiO 2, reflux 10-72 hour, reaction obtains SiO after terminating rear filtration, tetrahydrofuran (THF) washing, vacuum-drying 2the alpha-diimine compound of load.
A kind of SiO 2the alpha-diimine metal complexes of load is SiO 2the alpha-diimine nickel (II) of load or palladium (II) title complex, obtained by following methods, comprises the steps:, through vacuumizing, in the reactor of nitrogen replacement, to add anhydrous methylene chloride, SiO 2the metallic compound of the alpha-diimine compound of load, nickel (II) or palladium (II), wherein SiO 2alpha-diimine compound metallizing thing mol ratio contained in load alpha-diimine compound is 1:1, the metal compound concentrations of nickel or palladium is 0.01-1mmol/mL, mechanic whirl-nett reaction 16-24 hour under room temperature, vacuum filtration, solid with methylene chloride washing, filtration, obtain SiO after vacuum-drying 2the alpha-diimine nickel (II) of load or palladium (II) title complex;
Described nickel or the metallic compound of palladium preferably (DME) NiBr 2, (DME) NiCl 2, Ni (CH 3cOO) 2, (COD) PdCl 2, (COD) PdClCH 3or (COD) PdMe (NCMe).
A kind of SiO 2the application of the alpha-diimine metal complexes of load, is characterized by described SiO 2the alpha-diimine metal complexes of load is applied to the vapour phase polymerization of ethene or propylene as Primary Catalysts, or in the liquid-phase bulk polymerization of olefinic monomer or slurry polymerization, slurry polymerization evaluation experimental comprises the steps: through vacuumizing, in the reactor of nitrogen replacement, add the anhydrous solvent that volume is reaction vessel 15 ~ 25%, the olefinic monomer added respectively again, Primary Catalysts and promotor, temperature of reaction is-20-120 DEG C, polymerization time is 0.5-4 hour, then the concentration expressed in percentage by volume adding solvent volume 10-20% is the concentrated hydrochloric acid acidic ethanol of 10%, make reaction terminating, with water, washing with alcohol, filtered polymeric, vacuum-drying obtains product,
Described anhydrous solvent is toluene or normal hexane; When described olefinic monomer is gas, olefin gas pressure is 0.1-10MPa; When olefinic monomer is liquid, in often liter of solvent, olefinic monomer add-on is 0.1-10mol; Primary Catalysts add-on is Primary Catalysts 1 × 10 -5-1 × 10 -3mol/L solvent, the molar basis of the metal that the mole number of Primary Catalysts contains with it; The mol ratio of promotor and Primary Catalysts is 20-2000:1;
Described olefinic monomer be specially in ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornylene, vinyl norbornene, ethylidene norbornene, Dicyclopentadiene (DCPD), Isosorbide-5-Nitrae-divinyl, vinylbenzene, alpha-methyl styrene and Vinylstyrene one or more;
Described promotor is aluminum alkyls, alkylaluminoxane or boride, preferred AlEt 2cl, AlEtCl 2, Al 2et 3cl 3, Al 2me 2cl 4, AlEt 3, Al (i-Bu) 3, methylaluminoxane (MAO), ethylaluminoxane (EAO), modified methylaluminoxane (MMAO), B (C 6f 5) 4or B (C 6h 3(CF 3) 2) 4.
Beneficial effect of the present invention: alpha-diimine compound is passed through chemical reaction load at SiO by the present invention 2on carrier, the SiO of synthesis 2load alpha-diimine compound coordinates with the compound of nickel (II), palladium (II) again, obtains SiO 2the metal complexes of load alpha-diimine, and as Primary Catalysts and promotor with the use of being applied in being polymerized of alkene.This carrying method is that alpha-diimine compound is linked at SiO by the effect of covalent bonding 2carrier, such carrying method accurately can control the charge capacity of catalyzer on carrier, and covalent linkage reactive force between catalyzer and carrier is strong, and catalyzer in polymerization process can be avoided to come off from carrier.Due to alpha-diimine on the naphthalene nucleus of acenaphthenequinone by active group and SiO 2load is carried out in carrier reaction, so with aniline in alpha-diimine structure in the past by active group and SiO 2reaction load Method compare, this method can not affect substituent change on aniline, and the Modulatory character of catalyst structure to polymer architecture is large; And carrier is away from catalyst metal active centre, decreases SiO 2the functional group of carrier surface is on the impact of metal active centres.Compared with the alpha-diimine catalyzer poor heat stability (just losing catalytic activity at 60 DEG C) of classical Brookhart, this type of supported catalyst Heat stability is good when olefinic polymerization, be applicable to the temperature of reaction of more than 80 DEG C high, and still keep greater activity.This type of supported catalyst structure variable range is large, by changing SiO 2substituting group on the alpha-diimine compound structure of load, can regulate and control the molecular chain structure of polymerization activity, polymkeric substance, molecular weight and distribution thereof.This type of SiO 2load alpha-diimine granules of catalyst form is good, glues the situation of still when obviously can improve the polymerization of non-supported catalyst.In addition, required promotor and Primary Catalysts compare just can demonstrate higher activity 100 time, and the promotor consumption of more non-load reduces several times.The present invention is applicable to gas phase polymerization apparatus or the slurry polymerization device of existing heterogeneous catalyst catalyzed alkene.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of pure carrier silicas;
Fig. 2 is the SiO in embodiment 23 2the scanning electron microscope (SEM) photograph of load alpha-diimine nickel (II) title complex e1Ni.
Embodiment
Below in conjunction with embodiment, the present invention is described further.It should be noted that, following embodiment can not as limiting the scope of the invention, and any improvement made on basis of the present invention is all without prejudice to spirit of the present invention.
The present invention relates to alpha-diimine compound and SiO thereof 2the preparation method of load alpha-diimine metal complexes is as follows:
(1) 5-bromo acenaphthenequinone and the compound with A structure are obtained by reacting the compound of structure as shown in B;
(2) compd B prepared by step (1) be obtained by reacting structure compound as shown at c with substituent amine;
(3) Compound C prepared by step (2) in the system through vacuumizing, after nitrogen replacement respectively with an alkoxyl group dialkyl group silicon, dialkoxy one alkyl silicon, tri-alkoxy pasc reaction, catalyzer is Platinum (0)-1,3-divinyl-1,1,3, the xylene solution (Pt ~ 2%) of 3-tetramethyldisiloxane, obtains the compound of structure as shown in D, F, H respectively;
(4) Compound D prepared by step (3), F, H respectively with SiO 2carrier is obtained by reacting corresponding SiO 2load alpha-diimine compd E, G, I;
(5) SiO prepared by step (4) 2alpha-diimine compd E, G, I of load are obtained by reacting SiO with the compound of nickel (II), palladium (II) respectively under anhydrous and oxygen-free condition 2the alpha-diimine nickel (II) of load or palladium (II) title complex.
One, SiO 2the synthesis of the alpha-diimine compound of load
Embodiment 1
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e1 of acenaphthenequinone
Its syntheti c route is as follows:
Concrete operation step is as follows:
The synthesized reference document [J Am Chem Soc, 2013,135 (46): 17469] of 5-bromo acenaphthenequinone, the synthesized reference document [J Med Chem, 2011,54 (13): 4659] of 4-allyloxy phenol a1
The synthesis of 5-(4-allyloxy phenoxy group) acenaphthenequinone b1:
The 5-bromo acenaphthenequinone of 12.7g (48.6mmol) is added, 13.8g (100mmol) K in the reaction flask of 100ml 2cO 3, the DMF of 33ml drying, starts to stir.In whipping process, add 15g (100mmol) a1,60 DEG C of reactions, thin layer chromatography following response thing reacts completely, stopped reaction.The dark brown solution of reaction is poured in saturated NaCl solution and becomes brown suspension, with dichloromethane extraction 2-3 time, the anhydrous MgSO of organic phase 4drying, reduction vaporization falls solvent and obtains dark-brown oil, drains cooling and obtains compound b1 (namely as the structure of B compound, wherein R 3=H, n=1, Ar=C 6h 4o) brown crystal 15g, productive rate is 93.7%. 1H NMR(400MHz,CDCl 3):δ8.60(d,J＝8.4Hz,1H),δ8.11(d,J＝6.9Hz,1H),δ8.00(d,J＝8.0Hz,1H),δ7.84(t,J＝7.7Hz,1H),δ7.15(d,J＝9.0Hz,2H),δ7.03(d,J＝9.0Hz,2H),δ6.93(d,J＝8.0Hz,1H),δ6.16-6.02(m,1H),δ5.46(d,J＝17.3Hz,1H),δ5.34(d,J＝10.5Hz,1H),δ4.59(d,J＝5.1Hz,2H).MS(ESI)m/z 331(M+H +)。
The synthesis of two (2,6-di-isopropyl) the benzene imines c1 of 5-(4-allyloxy phenoxy group) acenaphthenequinone:
Add the compound b1 of 2.54g (7.7mmol) in the reaction flask of 250ml, the 2,6-DIPA of 3.36g (19mmol) and the anhydrous methanol of 150ml, and instill 10 anhydrous formic acids, this mixture back flow reaction 48 hours.Thin layer chromatography following response, complete to raw material reaction, obtain clarification burgundy solution, purify through silica gel column chromatography after solution is concentrated, obtain compound c1 (namely as the structure of C compound, wherein R 1=R 2=2,6-DIPA base) yellow solid 1.45g, productive rate is 35%. 1H NMR(400MHz,CDCl 3):δ8.23(d,J＝8.4Hz,1H),δ7.37(t,J＝7.8Hz,1H),δ7.26-7.13(m,6H),δ7.02(d,J＝9.0Hz,2H),δ6.93(d,J＝9.0Hz,2H),δ6.64(d,J＝7.2Hz,1H),δ6.48-6.41(m,2H),δ6.12-5.99(m,1H),δ5.43(d,J＝17.2Hz,1H),δ5.31(d,J＝10.5Hz,1H),δ4.53(d,J＝5.2Hz,2H),δ3.03-2.99(m,4H),δ1.25-1.21(m,12H),δ0.99-0.95(m,12H).MS(ESI)m/z 649(M+H +)。
5-{4-[3-(oxyethyl group dimethyl-silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines d1 of acenaphthenequinone:
The compound c1 of 1.45g (2.24mmol) is added in 100ml reaction flask under nitrogen atmosphere, 2.29g (22mmol) dimethylethoxysilane, 0.5mL Platinum (0)-1,3-divinyl-1,1, the xylene solution (Pt ~ 2%) of 3,3-tetramethyldisiloxane and 60mL dry toluene.Reflux is after 12 hours, and reaction mixture, through being separated by post layer chromatography, obtains 1.14g solid product d1 (namely as the structure of D compound, wherein R 1=R 2=2,6-DIPA base, R 3=H, n=1, Ar=C 6h 4o, R 4=methyl, R 5=ethyl), productive rate is 56%. 1H NMR(400MHz,CDCl 3):δ8.26(d,J＝8.3Hz,1H),δ7.39(t,J＝7.5Hz,1H),δ7.32-7.15(m,6H),δ7.03(d,J＝6.9Hz,2H),δ6.92(d,J＝6.9Hz,2H),δ6.67(d,J＝7.2Hz,1H),δ6.49-6.43(m,2H),δ3.94(t,J＝6.7Hz,2H),δ3.74-3.68(m,2H),δ3.09-3.02(m,4H),δ1.91-1.83(m,2H),δ1.27-1.21(m,15H),δ1.02-0.98(m,12H),δ0.74(t,J＝8.4Hz,2H),δ0.17(s,6H).MS(ESI)m/z 753(M+H +)。
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } preparation of two (2,6-di-isopropyl) the benzene imines loaded article e1 of acenaphthenequinone:
Be equipped with in the reaction flask of the dry toluene of 50mL and add 2mmol compound d1, after it dissolves completely, add 1g SiO 2(calcined 4 hours through 200 DEG C).Reflux is after 72 hours, and suction filtration reaction mixture, gained solid product e1 with after anhydrous tetrahydro furan washing, obtains product after vacuum-drying again.Ultimate analysis: C, 15.39%; N, 0.74%.Loaded article e1 after anhydrous tetrahydro furan washing still can be measured to C, N element in compound d1, and in loaded article e1, C, N element ratio, close to C, N element ratio in d1, illustrate that compound d1 load is on carrier.
Embodiment 2
5-{4-[3-(silicon-dioxide methylenedioxymethamphetamine silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article g1 of acenaphthenequinone
Its syntheti c route is as follows:
5-{4-[3-(diethoxymethyl silicon) propoxy-] phenoxy group } two (2,6-di-isopropyl) the benzene imines f1 of acenaphthenequinone is (namely as the structure of F compound, wherein R 1=R 2=2,6-DIPA base, R 3=H, n=1, Ar=C 6h 4o, R 4=methyl, R 5=ethyl) identical with compound d1 preparation process in embodiment 1, wherein adopt 2.95g (22mmol) diethoxymethylsilane to replace dimethylethoxysilane; The concrete synthesis step of loaded article g1 is identical with the synthesis step of loaded article e1 in embodiment 1.The ultimate analysis of loaded article g1: C, 22.12%; N, 1.10%.
Embodiment 3
5-{4-[3-(silicon-dioxide three oxygen base silicon) propoxy-] phenoxy group } its syntheti c route of synthesis of two (2,6-di-isopropyl) the benzene imines loaded article i1 of acenaphthenequinone is as follows:
5-{4-[3-(triethoxysilicane) propoxy-] phenoxy group } two (2,6-di-isopropyl) the benzene imines h1 of acenaphthenequinone is (namely as the structure of H compound, wherein R 1=R 2=2,6-DIPA base, R 3=H, n=1, Ar=C 6h 4o, R 5=ethyl) identical with compound d1 preparation process in embodiment 1, wherein adopt 3.61g (22mmol) triethoxyl silane to replace dimethylethoxysilane; The concrete synthesis step of loaded article i1 is identical with the synthesis step of loaded article e1 in embodiment 1.The ultimate analysis of loaded article i1: C, 33.66%; N, 1.67%.
Embodiment 4
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } synthesis of two [2,6-bis-(diphenyl-methyl)-4-methyl] the benzene imines loaded article e2 of acenaphthenequinone
Its syntheti c route is as follows:
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-methyl] the benzene imines c2 of 5-(4-allyloxy phenylol) acenaphthenequinone:
Be equipped with in the reaction flask of the toluene solution of 2,6-bis-(diphenyl-methyl)-4-monomethylaniline (0.805g, 1.8mmol), slowly drip the toluene solution (0.9mL, 2.0M) of trimethyl aluminium.Then be heated to 100 DEG C of reactions 2 hours, after being cooled to room temperature, the toluene solution of 5-(4-allyloxy phenylol) acenaphthenequinone b1 (0.297g, 0.9mmol) slowly instilled wherein, and be heated to 100 DEG C of reactions 20 hours.Then the 10mL NaOH aqueous solution is added.This mixed solution through extraction into ethyl acetate, organic phase MgSO 4drying, after solution is concentrated, be separated through post layer chromatography, obtain 0.116g solid product c2, productive rate is 11%. 1HNMR(400MHz,CDCl 3):δ7.78(d,J＝8.5Hz,1H),δ7.16-7.09(m,20H),δ6.99-6.78(m,17H),δ6.78-6.63(m,12H),δ6.18(d,J＝7.5Hz,1H),δ6.14-6.04(m,2H),δ5.94(d,J＝8.0Hz,1H),δ5.72(d,J＝5.8Hz,4H),δ5.47(d,J＝17.2Hz,1H),δ5.34(d,J＝9.6Hz,1H),δ4.58(d,J＝5.4Hz,2H),δ2.26(d,6H).MS(MALDI-TOF):m/z 1173(M +).
5-{4-[3-(oxyethyl group dimethyl-silicon) propoxy-] phenoxy group } two [2,6-bis-(diphenyl-methyl)-4-methyl] the benzene imines d2 of acenaphthenequinone is (namely as the structure of D compound, wherein R 1=R 2=[2,6-bis-(diphenyl-methyl)-4-methyl] phenyl, R 3=H, n=1, Ar=C 6h 4o, R 4=methyl, R 5=ethyl) identical with compound d1 preparation process in embodiment 1, the preparation process of loaded article e2 is identical with the preparation process of loaded article e1 in embodiment 1.The ultimate analysis of loaded article e2: C, 26.28%; N, 0.69%.
Embodiment 5
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } acenaphthenequinone two (its syntheti c route of synthesis of 8-p-methylphenyl naphthalene imines loaded article e3 is as follows:
The concrete synthesis step of loaded article e3 is identical with the synthesis step of loaded article e2 in embodiment 4, wherein adopts (0.420g, 1.8mmol) 8-p-methylphenyl naphthylamines to replace 2,6-bis-(diphenyl-methyl)-4-monomethylaniline.The ultimate analysis of loaded article e3: C, 17.29%; N, 0.71%.
Embodiment 6
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group with asymmetric hexichol replaces } acenaphthenequinone (2,6-di-isopropyl) synthesis of benzene imines [2,6-bis-(diphenyl-methyl)-4-methyl] benzene imines loaded article e4
Its syntheti c route is as follows:
The preparation process of loaded article e4 is identical with the preparation process of loaded article e2 in embodiment 4, with 2 of 8mmol, the 2,6-DIPA of 6-bis-(diphenyl-methyl)-4-monomethylaniline and 8mmol replaces 2,6-bis-(diphenyl-methyl)-4-monomethylaniline.The ultimate analysis of loaded article e4: C, 19.07%; N, 0.65%.
Embodiment 7
5-{4-[4-(titanium dioxide siloxy dimethyl-silicon) butoxy] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e5 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e5 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 16.2g (100mmol) a2 to replace a1.The ultimate analysis of loaded article e5: C, 15.78%; N, 0.77%.
Embodiment 8
5-{3-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e6 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e6 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 15g (100mmol) a3 to replace a1.The ultimate analysis of loaded article e6: C, 13.28%; N, 0.66%.
Embodiment 9
5-{2-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e7 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e7 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 15g (100mmol) a4 to replace a1.The ultimate analysis of loaded article e7: C, 10.79%; N, 0.54%.
Embodiment 10
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] naphthyloxy } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e8 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e8 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 20.0g (100mmol) a5 to replace a1.The ultimate analysis of loaded article e8: C, 18.46%; N, 0.84%.
Embodiment 11
5-{5-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] naphthyloxy } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e9 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e9 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 20.0g (100mmol) a6 to replace a1.The ultimate analysis of loaded article e9: C, 19.29%; N, 0.88%.
Embodiment 12
5-{2-[6-(titanium dioxide siloxy dimethyl-silicon) propoxy-] naphthyloxy } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e10 of acenaphthenequinone
The concrete synthesis step of loaded article e10 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 20.0g (100mmol) a7 to replace a1.The ultimate analysis of loaded article e10: C, 19.81%; N, 0.91%.
Embodiment 13
5-{4-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e11 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e11 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 24.2g (100mmol) a8 to replace a1.The ultimate analysis of loaded article e11: C, 22.01%; N, 0.95%.
Embodiment 14
5-{4-{2-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenyl } propyl group-2-} phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e12 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e12 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 26.2g (100mmol) a9 to replace a1.The ultimate analysis of loaded article e12: C, 19.38%; N, 0.81%.
Embodiment 15
5-{4-[3-(titanium dioxide siloxy dimethyl-silicon) the third sulfydryl] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e13 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e13 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 16.6g (100mmol) a10 to replace a1.The ultimate analysis of loaded article e13: C, 16.31%; N, 0.81%.
Embodiment 16
5-{4-{ [3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] methyl } phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e14 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e14 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 16.4g (100mmol) a11 to replace a1.The ultimate analysis of loaded article e14: C, 17.44%; N, 0.85%.
Embodiment 17
5-{4-{2-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] ethyl } phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e15 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e15 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 16.4g (100mmol) a12 to replace a1.The ultimate analysis of loaded article e15: C, 18.29%; N, 0.87%.
Embodiment 18
5-{4-{ [3-(titanium dioxide siloxy dimethyl-silicon) the third sulfydryl] methyl } phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e16 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e16 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 19.0g (100mmol) a13 to replace a1.The ultimate analysis of loaded article e16: C, 14.86%; N, 0.72%.
Embodiment 19
5-{4-{2-[3-(titanium dioxide siloxy dimethyl-silicon) the third sulfydryl] ethyl } phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e17 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e17 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 19.4g (100mmol) a14 to replace a1.The ultimate analysis of loaded article e17: C, 17.88%; N, 0.85%.
Embodiment 20
5-{4-[2-methyl-3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e18 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e18 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 16.4g (100mmol) a15 to replace a1.The ultimate analysis of loaded article e18: C, 14.95%; N, 0.73%.
Embodiment 21
5-{4-[2-ethyl-3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenoxy group } synthesis of two (2,6-di-isopropyl) the benzene imines loaded article e19 of acenaphthenequinone
Its syntheti c route is as follows:
The concrete synthesis step of loaded article e19 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 17.8g (100mmol) a16 to replace a1.The ultimate analysis of loaded article e19: C, 14.96%; N, 0.71%.
Embodiment 22
5-{4-{4-[3-(titanium dioxide siloxy dimethyl-silicon) propoxy-] phenyl } phenoxy group } preparation of two (2,6-di-isopropyl) the benzene imines loaded article e20 of acenaphthenequinone
Its syntheti c route is as follows,
The concrete synthesis step of loaded article e20 is identical with the synthesis step of loaded article e1 in embodiment 1, wherein adopts 22.6g (100mmol) a17 to replace a1.The ultimate analysis of loaded article e20: C, 21.05%; N, 0.93%.
Two, SiO 2the synthesis of the alpha-diimine metal complexes of load
Embodiment 23
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e1Ni:
Through vacuumizing, in the reactor of nitrogen replacement, in reaction flask, adding the alpha-diimine loaded article e1 containing 1mmol alpha-diimine compound obtained in anhydrous methylene chloride 30mL, embodiment 1, then add (DME) NiBr 21mmol, mechanical stirring 24 hours under room temperature.Vacuum filtration, solid with methylene chloride washs three filtrations, obtains load alpha-nickel diimine compound e1Ni after vacuum-drying.ICP measures, and in alpha-diimine nickel (II) the title complex e1Ni of load, nickel content is 1.4% (Wt).The pure carrier S iO of comparison diagram 1 2stereoscan photograph, the SiO that the present invention obtains 2the granular size of load alpha-diimine nickel (II) title complex e1Ni (scanning electron microscope (SEM) photograph is shown in Fig. 2) and form and SiO 2carrier almost consistent, and spherical in shape or class is spherical, SiO is described 2the particle form of load alpha-diimine nickel (II) title complex is good.
Embodiment 24
SiO 2the synthesis of load alpha-diimine nickel (II) title complex g1Ni:
The loaded article g1 prepared by embodiment 2 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex g1Ni.It is 1.8% (Wt) that ICP measures nickel content in alpha-diimine nickel (II) title complex of load.
Embodiment 25
SiO 2the synthesis of load alpha-diimine nickel (II) title complex i1Ni:
The loaded article i1 prepared by embodiment 3 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex i1Ni.It is 2.6% (Wt) that ICP measures nickel content.
Embodiment 26
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e2Ni:
The loaded article e2 prepared by embodiment 4 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e2Ni.It is 2.39% (Wt) that ICP measures nickel content.
Embodiment 27
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e3Ni:
The loaded article e3 prepared by embodiment 5 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e3Ni.It is 1.48% (Wt) that ICP measures nickel content.
Embodiment 28
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e4Ni:
The loaded article e4 prepared by embodiment 6 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e4Ni.It is 2.36% (Wt) that ICP measures nickel content.
Embodiment 29
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e5Ni:
The loaded article e5 prepared by embodiment 7 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e5Ni.It is 1.62% (Wt) that ICP measures nickel content.
Embodiment 30
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e6Ni:
The loaded article e6 prepared by embodiment 8 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e6Ni.It is 2.3% (Wt) that ICP measures nickel content.
Embodiment 31
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e7Ni:
The loaded article e7 prepared by embodiment 9 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e7Ni.It is 2.14% (Wt) that ICP measures nickel content.
Embodiment 32
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e8Ni:
The loaded article e8 prepared by embodiment 10 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e8Ni.It is 1.76% (Wt) that ICP measures nickel content.
Embodiment 33
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e9Ni:
The loaded article e9 prepared by embodiment 11 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e9Ni.It is 1.85% (Wt) that ICP measures nickel content.
Embodiment 34
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e10Ni:
The loaded article e10 prepared by embodiment 12 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e10Ni.It is 1.92% (Wt) that ICP measures nickel content.
Embodiment 35
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e11Ni:
The loaded article e11 prepared by embodiment 13 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e11Ni.It is 1.98% (Wt) that ICP measures nickel content.
Embodiment 36
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e12Ni:
The loaded article e12 prepared by embodiment 14 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e12Ni.It is 1.71% (Wt) that ICP measures nickel content.
Embodiment 37
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e13Ni:
The loaded article e13 prepared by embodiment 15 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e13Ni.It is 1.69% (Wt) that ICP measures nickel content.
Embodiment 38
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e14Ni:
The loaded article e14 prepared by embodiment 16 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e14Ni.It is 1.78% (Wt) that ICP measures nickel content.
Embodiment 39
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e15Ni:
The loaded article e15 prepared by embodiment 17 replaces the loaded article e1 in embodiment 23, operates same embodiment 23, obtains load alpha-diimine nickel (II) title complex e15Ni.It is 1.83% (Wt) that ICP measures nickel content.
Embodiment 40
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e16Ni:
The loaded article e16 prepared by embodiment 18 replaces the loaded article e1 in embodiment 23, (DME) NiCl 2replace (DME) NiBr 2, operate same embodiment 23, obtain load alpha-diimine nickel (II) title complex e16Ni.It is 1.51% (Wt) that ICP measures nickel content.
Embodiment 41
SiO 2the synthesis of load alpha-diimine nickel (II) title complex e17Ni:
The loaded article e17 prepared by embodiment 19 replaces the loaded article e1 in embodiment 23, Ni (CH 3cOO) 2replace (DME) NiBr 2, operate same embodiment 23, obtain load alpha-diimine nickel (II) title complex e17Ni.It is 1.78% (Wt) that ICP measures nickel content.
Embodiment 42
SiO 2the synthesis of load alpha-diimine palladium (II) title complex e1Pd:
Through vacuumizing, in the reactor of nitrogen replacement, the loaded article e1 obtained in the embodiment 1 of 1.5g (containing 0.42mmol alpha-diimine) is joined in 20mL anhydrous methylene chloride and stirs, then add 0.109g (0.41mmol) (COD) PdClCH 310mL anhydrous methylene chloride, stirred at ambient temperature reacts 20 hours, vacuum filtration, and solid with methylene chloride washs three filtrations, obtains alpha-diimine palladium (II) the title complex e1Pd 1.55g of load after vacuum-drying.It is 2.7% (Wt) that ICP measures palladium content.
Embodiment 43
SiO 2the synthesis of load alpha-diimine palladium (II) title complex g1Pd:
The loaded article g1 prepared by embodiment 2 replaces the loaded article e1 in embodiment 42, (COD) PdCl 2replace (COD) PdClCH 3, operate same embodiment 42, obtain load alpha-diimine palladium (II) title complex g1Pd.It is 2.13% (Wt) that ICP measures palladium content.
Embodiment 44
SiO 2the synthesis of load alpha-diimine palladium (II) title complex i1Pd:
The loaded article i1 prepared by embodiment 3 replaces the loaded article e1 in embodiment 42, operates same embodiment 42, obtains load alpha-diimine palladium (II) title complex i1Pd.It is 3.27% (Wt) that ICP measures palladium content.
Embodiment 45
SiO 2the synthesis of load alpha-diimine palladium (II) title complex e2Pd:
The loaded article e2 prepared by embodiment 4 replaces the loaded article e1 in embodiment 42, operates same embodiment 42, obtains load alpha-diimine palladium (II) title complex e2Pd.It is 3.07% (Wt) that ICP measures palladium content.
Embodiment 46
SiO 2the synthesis of load alpha-diimine palladium (II) title complex e18Pd:
The loaded article e18 prepared by embodiment 20 replaces the loaded article e1 in embodiment 42, operates same embodiment 42, obtains load alpha-diimine palladium (II) title complex e18Pd.It is 2.48% (Wt) that ICP measures palladium content.
Embodiment 47
SiO 2the synthesis of load alpha-diimine palladium (II) title complex e19Pd:
The loaded article e19 prepared by embodiment 21 replaces the loaded article e1 in embodiment 42, operates same embodiment 42, obtains load alpha-diimine palladium (II) title complex e19Pd.It is 2.10% (Wt) that ICP measures palladium content.
Embodiment 48
SiO 2the synthesis of load alpha-diimine palladium (II) title complex e20Pd:
The loaded article e20 prepared by embodiment 22 replaces the loaded article e1 in embodiment 42, operates same embodiment 42, obtains load alpha-diimine palladium (II) title complex e20Pd.It is 2.0% (Wt) that ICP measures palladium content.
Olefinic polyreaction
Embodiment 49
Load alpha-nickel diimine compound e1Ni is as Primary Catalysts catalyzed ethylene polymerization
50ml dry toluene is added in the 250ml reactor being filled with ethene through nitrogen replacement for three times again, stirring is warmed up to 30 DEG C, pass into ethene to make to keep pressure 0.1MPa in reactor, (0.021g, in suspension, contained Ni content is 5 × 10 to add the load alpha-nickel diimine compound e1Ni of embodiment 23 gained respectively -6mol), the promotor MAO (3.5mL of 1.4mol/L, promotor and Primary Catalysts mol ratio are 1000:1), polymerization time is 1 hour, then adding 10ml concentration expressed in percentage by volume is that the acidic ethanol (namely volume ratio is 37% concentrated hydrochloric acid: dehydrated alcohol=1:9) of 1% is to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polyethylene 3.15g.Its activity is 6.3 × 10 5g/molh (active calculated by the polymerisate quality/amount × per hour of metallics (in the catalyzer)), polymkeric substance Mw (weight-average molecular weight) is 4.3 × 10 5g/mol, MWD (molecular weight distribution) are 4.3 (GPC records). 13it is 35/1000 carbon atom that C NMR measures polymer branching degree.
Embodiment 50
Load alpha-nickel diimine compound g1Ni is as Primary Catalysts catalyzed ethylene polymerization
The load alpha-nickel diimine compound g1Ni prepared by embodiment 24 replaces the load alpha-nickel diimine compound e1Ni in embodiment 49, operates same embodiment 49.Its activity is 5.9 × 10 5g/molh, polymkeric substance Mw are 4.0 × 10 5g/mol, MWD are 4.1, and polymer branching degree is 40/1000 carbon atom.
Embodiment 51
Load alpha-nickel diimine compound i1Ni is as Primary Catalysts catalyzed ethylene polymerization
50ml anhydrous n-hexane is added in the 250ml reactor being filled with ethene through nitrogen replacement for three times again, stirring is warmed up to 80 DEG C, pass into ethene to make to keep pressure 5.0MPa in reactor, (in solvent, contained Ni content is 8 × 10 to add the load alpha-nickel diimine compound i1Ni of embodiment 25 gained respectively -6mol), promotor AlEt 2cl (mol ratio of promotor and Primary Catalysts is 500:1), polymerization time is 2 hours, the acidic ethanol then adding 10ml 10% to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polyethylene.Its activity is 5.3 × 10 6g/molh, polymkeric substance Mw are 2.7 × 10 5g/mol, MWD are 3.6.Polymer branching degree is 115/1000 carbon atom.
Embodiment 52
Load alpha-nickel diimine compound e2Ni is as Primary Catalysts catalyzed ethylene polymerization
The load alpha-nickel diimine compound e2Ni prepared by embodiment 26 replaces the load alpha-nickel diimine compound i1Ni in embodiment 51, and pass into ethene and make to keep pressure 2.0MPa in reactor, temperature of reaction is 80 DEG C, operates same embodiment 51.Its activity is 3.9 × 10 6g/molh, polymkeric substance Mw are 4.8 × 10 5g/mol, MWD are 2.4.Polymer branching degree is 85/1000 carbon atom.
Embodiment 53
Load alpha-nickel diimine compound e3Ni is as Primary Catalysts catalyzed ethylene polymerization
The load alpha-nickel diimine compound e3Ni prepared by embodiment 27 replaces the load alpha-nickel diimine compound i1Ni in embodiment 51, passes into ethene and makes to keep pressure 1.0MPa in reactor, operate same embodiment 51.Its activity is 2.0 × 10 6g/molh, polymkeric substance Mw are 6.5 × 10 5g/mol, MWD are 3.2.Polymer branching degree is 76/1000 carbon atom.
Embodiment 54
Load alpha-nickel diimine compound e4Ni is as Primary Catalysts catalysis 1-butylene and ethylene copolymer
The load alpha-nickel diimine compound e4Ni prepared by embodiment 28 replaces the load alpha-nickel diimine compound i1Ni in embodiment 51, pass into ethene, 1-butylene, 1-butylene and ethylene molar ratio are 0.5, make to keep pressure 2.0MPa in reactor, temperature of reaction is 100 DEG C, operates same embodiment 51.Its activity is 8.2 × 10 5g/molh, polymkeric substance Mw are 4.1 × 10 5g/mol, MWD are 2.3.Polymer branching degree is 93/1000 carbon atom.
Embodiment 55
Load alpha-nickel diimine compound e5Ni is polymerized as Primary Catalysts catalyzing propone
50ml anhydrous n-hexane is added in the 250ml reactor being filled with propylene through nitrogen replacement for three times again, stirring is warmed up to 40 DEG C, pass into propylene to make to keep pressure 2.0MPa in reactor, (in solvent, contained Ni content is 1 × 10 to add the load alpha-nickel diimine compound e5Ni of embodiment 29 gained respectively -5mol), promotor AlEtCl 2(mol ratio of promotor and Primary Catalysts is 100:1), polymerization time is 1 hour, the acidic ethanol then adding 10ml 10% to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polypropylene.Its activity is 5.4 × 10 5g/molh, polymkeric substance Mw are 2.9 × 10 5g/mol, MWD are 3.1.
Embodiment 56
Load alpha-nickel diimine compound e6Ni is as Primary Catalysts catalyzed ethylene and copolymerization of propylene
The load alpha-nickel diimine compound e6Ni prepared by embodiment 30 replaces the load alpha-nickel diimine compound e5Ni in embodiment 55, temperature of reaction 60 DEG C, pass into ethene, propylene (pressure ratio 1:1), in reactor, total pressure keeps 2.0MPa, operates same embodiment 55.Its activity is 2.4 × 10 6g/molh, polymkeric substance Mw are 5.8 × 10 5g/mol, MWD are 3.0.Polymer branching degree is 77/1000 carbon atom.
Embodiment 57
Load alpha-nickel diimine compound e7Ni is as Primary Catalysts catalysis 1-hexene and ethylene copolymer
50mL dry toluene is added in the 250ml reactor being filled with ethene through nitrogen replacement for three times again, add the 1-hexene of 2mL respectively, stirring is warmed up to 80 DEG C, pass into ethene to make to keep pressure 1.0MPa in reactor, (in solvent, contained Ni content is 5 × 10 to the load alpha-nickel diimine compound e7Ni of embodiment 31 gained -6mol), promotor Al 2et 3cl 3(mol ratio of promotor and Primary Catalysts is 300:1), polymerization time is 1 hour, the acidic ethanol then adding 10ml 10% to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polyethylene.Its activity is 7.1 × 10 5g/molh, polymkeric substance Mw are 4.7 × 10 5g/mol, MWD are 2.9.Polymer branching degree is 105/1000 carbon atom.
Embodiment 58
Load alpha-nickel diimine compound e8Ni is polymerized as Primary Catalysts catalysis 1-butylene
In the 250ml reactor through nitrogen replacement three times, add the 1-butylene of 50ml anhydrous n-hexane, 2.8g, stir and cool to-20 DEG C, (in solvent, contained Ni content is 5 × 10 to add the load alpha-nickel diimine compound e8Ni of embodiment 32 gained respectively -5mol), promotor MAO (mol ratio of promotor and Primary Catalysts is 20:1), polymerization time is 4 hours, then the acidic ethanol of 10ml 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product poly 1-butene.Its activity is 3.2 × 10 5g/molh, polymkeric substance Mw are 5.4 × 10 5g/mol, MWD are 3.5.
Embodiment 59
Load alpha-nickel diimine compound e9Ni is polymerized as Primary Catalysts catalysis 1-butylene
The load alpha-nickel diimine compound e9Ni prepared by embodiment 33 replaces the load alpha-nickel diimine compound e8Ni in embodiment 58, temperature of reaction 40 DEG C, promotor AlEt 2cl (mol ratio of promotor and Primary Catalysts is 500:1), operates same embodiment 58.Its activity is 3.4 × 10 5g/molh, polymkeric substance Mw are 5.6 × 10 5g/mol, MWD are 3.3.
Embodiment 60
Load alpha-nickel diimine compound e10Ni is polymerized as Primary Catalysts catalysis 1-amylene
In the 250ml reactor through nitrogen replacement three times, add 50ml dry toluene, 5mL 1-amylene, stir and be warmed up to 60 DEG C, (in solvent, contained Ni content is 3 × 10 to add the load alpha-nickel diimine compound e10Ni of embodiment 34 gained respectively -5mol), promotor MAO (mol ratio of promotor and Primary Catalysts is 2000:1), polymerization time is 2 hours, then the acidic ethanol of 10ml 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product and gather 1-amylene.Its activity is 1.8 × 10 5g/molh, polymkeric substance Mw are 3.9 × 10 5g/mol, MWD are 3.1.
Embodiment 61
Load alpha-nickel diimine compound e12Ni is as Primary Catalysts catalysis 1-hexene oligomerization
The load alpha-nickel diimine compound e12Ni prepared by embodiment 36 replaces the load alpha-nickel diimine compound e10Ni in embodiment 60, the 1-hexene of 4.2g, temperature of reaction 40 DEG C, promotor AlEt 2cl (mol ratio of promotor and Primary Catalysts is 800:1), operates same embodiment 60.Its activity is 8.9 × 10 4g/molh, polymkeric substance Mw are 3.6 × 10 5g/mol, MWD are 2.9.
Embodiment 62
Load alpha-nickel diimine compound e13Ni is polymerized as Primary Catalysts catalysis 1-heptene
The load alpha-nickel diimine compound e13Ni prepared by embodiment 37 replaces the load alpha-nickel diimine compound e10Ni in embodiment 60, the 1-heptene of 4.9g, temperature of reaction 40 DEG C, promotor MAO (mol ratio of promotor and Primary Catalysts is 1500:1), operates same embodiment 60.Its activity is 9.0 × 10 4g/molh, polymkeric substance Mw are 3.5 × 10 5g/mol, MWD are 3.3.
Embodiment 63
Load alpha-nickel diimine compound e14Ni is polymerized as Primary Catalysts catalysis 1-decene
The load alpha-nickel diimine compound e14Ni prepared by embodiment 38 replaces the load alpha-nickel diimine compound e10Ni in embodiment 60, the 1-decene of 2.8g, temperature of reaction 40 DEG C, promotor MAO (mol ratio of promotor and Primary Catalysts is 1200:1), operates same embodiment 60.Its activity is 8.5 × 10 4g/molh, polymkeric substance Mw are 3.6 × 10 5g/mol, MWD are 3.2.
Embodiment 64
Load alpha-nickel diimine compound e15Ni is polymerized as Primary Catalysts catalysis Dicyclopentadiene (DCPD)
In the 250ml reactor through nitrogen replacement three times, add 50ml dry toluene, 3g Dicyclopentadiene (DCPD), stir and be warmed up to 60 DEG C, (in solvent, contained Ni content is 5 × 10 to add the load alpha-nickel diimine compound e15Ni of embodiment 39 gained respectively -6mol), promotor Al 2me 2cl 4(mol ratio of promotor and Primary Catalysts is 100:1), polymerization time is 2 hours, the acidic ethanol then adding 10ml 10% to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product and gather Dicyclopentadiene (DCPD).Its activity is 5.6 × 10 5g/molh, polymkeric substance Mw are 4.2 × 10 5g/mol, MWD are 3.0.
Embodiment 65
Load alpha-nickel diimine compound e16Ni is polymerized as Primary Catalysts catalysis Dicyclopentadiene (DCPD)
The load alpha-nickel diimine compound e16Ni prepared by embodiment 40 replaces the load alpha-nickel diimine compound e15Ni in embodiment 64, temperature of reaction 40 DEG C, promotor MAO (mol ratio of promotor and Primary Catalysts is 800:1), operates same embodiment 64.Its activity is 6.0 × 10 5g/molh, polymkeric substance Mw are 5.1 × 10 5g/mol, MWD are 3.0.
Embodiment 66
Load alpha-nickel diimine compound e17Ni is as Primary Catalysts catalysis norbornene polymerization
In the 250ml reactor through nitrogen replacement three times, add 50ml dry toluene, 2.3g norbornylene, stir and be warmed up to 40 DEG C, (in solvent, contained Ni content is 1 × 10 to add the load alpha-nickel diimine compound e17Ni of embodiment 41 gained respectively -5mol), promotor MAO (mol ratio of promotor and Primary Catalysts is 600:1), polymerization time is 1 hour, then the acidic ethanol of 10ml 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polynorbornene.Its activity is 9.0 × 10 5g/molh, polymkeric substance Mw are 6.3 × 10 5g/mol, MWD are 3.8.
Embodiment 67
Load alpha-diimine palladium complex e1Pd is as Primary Catalysts catalysis norbornylene and Dicyclopentadiene (DCPD) copolymerization
The load alpha-diimine palladium complex e1Pd prepared by embodiment 42 replaces the load alpha-nickel diimine compound e17Ni in embodiment 66, add 2g norbornylene and 0.3g Dicyclopentadiene (DCPD), temperature of reaction 50 DEG C, promotor MAO (mol ratio of promotor and Primary Catalysts is 1000:1), operates same embodiment 66.Its activity is 6.3 × 10 5g/molh, polymkeric substance Mw are 5.2 × 10 5g/mol, MWD are 3.6.
Embodiment 68
Load alpha-diimine palladium complex g1Pd is as Primary Catalysts catalyzed ethylene base norbornene polymerization
In the 250ml reactor through nitrogen replacement three times, add 50ml dry toluene, 3g vinyl norbornene, stir and be warmed up to 30 DEG C, (in solvent, contained Pd content is 5 × 10 to add the load alpha-diimine palladium complex g1Pd of embodiment 43 gained respectively -6mol), promotor MMAO (mol ratio of promotor and Primary Catalysts is 1500:1), polymerization time is 0.5 hour, then the acidic ethanol of 10ml 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polyvinyl norbornylene.Its activity is 1.9 × 10 5g/molh, polymkeric substance Mw are 3.9 × 10 5g/mol, MWD are 4.3.
Embodiment 69
Load alpha-diimine palladium complex i1Pd is as Primary Catalysts catalysis norbornylene and vinyl norbornene copolymerization
The load alpha-diimine palladium complex i1Pd prepared by embodiment 44 replaces the load alpha-diimine palladium complex g1Pd in embodiment 68, add 2g norbornylene and 0.3g vinyl norbornene, temperature of reaction 50 DEG C, promotor MAO (mol ratio of promotor and Primary Catalysts is 1000:1), operates same embodiment 68.Its activity is 4.9 × 10 5g/molh, polymkeric substance Mw are 4.8 × 10 5g/mol, MWD are 3.5.
Embodiment 70
E2Pd is polymerizing styrene catalyzed as Primary Catalysts for load alpha-diimine palladium complex
In the 250ml reactor through nitrogen replacement three times, add 50ml dry toluene, 2g vinylbenzene, stir and be warmed up to 40 DEG C, (in solvent, contained Pd content is 5 × 10 to add the load alpha-diimine palladium complex e2Pd of embodiment 45 gained respectively -6mol), promotor MMAO (mol ratio of promotor and Primary Catalysts is 800:1), polymerization time is 1.5 hours, then the acidic ethanol of 10ml 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polystyrene.Its activity is 1.3 × 10 6g/molh, polymkeric substance Mw are 4.6 × 10 5g/mol, MWD are 3.6.
Embodiment 71
Load alpha-diimine palladium complex e18Pd is as Primary Catalysts catalysis norbornylene and styrene copolymerized
The load alpha-diimine palladium complex e18Pd prepared by embodiment 46 replaces the load alpha-diimine palladium complex e2Pd in embodiment 70, and add 2g norbornylene and 0.4g vinylbenzene, promotor is B (C 6h 3(CF 3) 2) 4, operate same embodiment 70.Its activity is 5.0 × 10 5g/molh, polymkeric substance Mw are 4.5 × 10 5g/mol, MWD are 3.4.
Embodiment 72
Load alpha-diimine palladium complex e19Pd is polymerized as Primary Catalysts catalysis 1,3-butadiene
In the 250ml reactor through nitrogen replacement three times, add the 1,3-butadiene of 50ml dry toluene, 2.7g, stir and be warmed up to 70 DEG C, (in solvent, contained Pd content is 1 × 10 to add the load alpha-diimine palladium complex e19Pd of embodiment 47 gained respectively -5mol), promotor Al (i-Bu) 3(mol ratio of promotor and Primary Catalysts is 300:1), polymerization time is 3 hours, then adds 10ml acidic ethanol to reaction terminating, with water, washing with alcohol, filtered polymeric, then in 60 DEG C of vacuum drying ovens dry 8 hours, obtain product.Its activity is 4.5 × 10 4g/molh, polymkeric substance Mw are 2.0 × 10 5g/mol, MWD are 3.1.
Embodiment 73
Load alpha-diimine palladium complex e20Pd is as Primary Catalysts catalysis Vinylstyrene and styrene copolymerized
50ml dry toluene, 5g Vinylstyrene, 2g vinylbenzene is added in the 250ml reactor through nitrogen replacement three times, stirring is warmed up to 110 DEG C, and (in solvent, contained Pd content is 2 × 10 to add the load alpha-diimine palladium complex e20Pd of embodiment 48 gained respectively -5mol), promotor AlEt 3(mol ratio of promotor and Primary Catalysts is 2000:1), polymerization time is 2 hours, then adds 10ml acidic ethanol to reaction terminating, with water, washing with alcohol, filtered polymeric, then in 60 DEG C of vacuum drying ovens dry 8 hours, obtain product.Its activity is 2.1 × 10 5g/molh, polymkeric substance Mw are 2.3 × 10 5g/mol, MWD are 3.1.
Embodiment 74
Load alpha-diimine palladium complex e2Pd is as Primary Catalysts catalyzed ethylene polymerization
The load alpha-diimine palladium complex e2Pd prepared by embodiment 45 replaces the load alpha-nickel diimine compound i1Ni in embodiment 51, and (in solvent, contained Pd content is 8 × 10 -6mol), pass into ethene and make to keep pressure 2.0MPa in reactor, promotor is B (C 6f 5) 4, operate same embodiment 51.Its activity is 3.9 × 10 6g/molh, polymkeric substance Mw are 4.1 × 10 5g/mol, MWD are 2.4.Polymer branching degree is 102/1000 carbon atom.
Unaccomplished matter of the present invention is known technology.

Claims (6)

1. an alpha-diimine compound, the structural formula that it is characterized by this compound is as follows:
Wherein, R 1, R 2identical or different C 6-C 60aromatic hydrocarbyl, R 3h or C 1-C 20alkyl, R 4c 1-C 20alkyl, R 5c 1-C 20alkyl, n=1,2,3,4,5,6 or 7;
Ar is the one with following building stone:
Wherein, R ' is C 1-C 20alkyl, n '=1,2,3,4,5,6 or 7.
2. a SiO 2the alpha-diimine compound of load, it is characterized by is by described alpha-diimine compound and carrier S iO 2be obtained by reacting, comprise the following steps: under mechanical stirring, in the reaction flask being added with toluene, add alpha-diimine compound, after it dissolves completely, add carrier S iO 2, its proportioning is: every 50mL toluene adds the alpha-diimine compound of 0.2-20mmol, and the alpha-diimine compound of every 0.2-20mmol adds 1 gram of SiO 2, reflux 10-72 hour, reaction obtains SiO after terminating rear filtration, tetrahydrofuran (THF) washing, vacuum-drying 2the alpha-diimine compound of load.
3. a SiO 2the alpha-diimine metal complexes of load, is characterized by SiO 2the alpha-diimine nickel (II) of load or palladium (II) title complex, obtained by following methods, comprises the steps:, through vacuumizing, in the reactor of nitrogen replacement, to add anhydrous methylene chloride, SiO 2the metallic compound of the alpha-diimine compound of load, nickel (II) or palladium (II), wherein SiO 2alpha-diimine compound metallizing thing mol ratio contained in load alpha-diimine compound is 1:1, the metal compound concentrations of nickel or palladium is 0.01-1mmol/mL, mechanic whirl-nett reaction 16-24 hour under room temperature, vacuum filtration, solid with methylene chloride washing, filtration, obtain SiO after vacuum-drying 2the alpha-diimine nickel (II) of load or palladium (II) title complex.
4. SiO as claimed in claim 3 2the alpha-diimine metal complexes of load, is characterized by metallic compound preferably (DME) NiBr of described nickel or palladium 2, (DME) NiCl 2, Ni (CH 3cOO) 2, (COD) PdCl 2, (COD) PdClCH 3or (COD) PdMe (NCMe).
5. a SiO as claimed in claim 3 2the application of the alpha-diimine metal complexes of load, is characterized by this title complex and is applied in the vapour phase polymerization of ethene or propylene or the liquid-phase bulk polymerization of olefinic monomer or slurry polymerization as Primary Catalysts.
6. a SiO as claimed in claim 3 2the application of the alpha-diimine metal complexes of load, is characterized by this title complex preferably as Primary Catalysts application in olefin polymerization, comprises following reaction conditions: polymeric reaction temperature is-20-120 DEG C; When olefinic monomer is gas, pressure is 0.1-10MPa; Olefinic monomer be specially in ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornylene, vinyl norbornene, ethylidene norbornene, Dicyclopentadiene (DCPD), Isosorbide-5-Nitrae-divinyl, vinylbenzene, alpha-methyl styrene and Vinylstyrene one or more.
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CN108530562A (en) * 2017-03-03 2018-09-14 天津工业大学 The application of a kind of alpha-diimine compound and its load type gold metal complex with bis-alkoxy silicon in olefin polymerization
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