CN102850391B - The method of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and ethylene polymerization - Google Patents

The method of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and ethylene polymerization Download PDF

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CN102850391B
CN102850391B CN201110186156.XA CN201110186156A CN102850391B CN 102850391 B CN102850391 B CN 102850391B CN 201110186156 A CN201110186156 A CN 201110186156A CN 102850391 B CN102850391 B CN 102850391B
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title complex
microwave exposure
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CN102850391A (en
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华炜
孙文华
赵丽梅
刘淇
邴涓林
黄伟
张文娟
陈青葵
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China Petroleum and Chemical Corp
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Abstract

The invention discloses a kind of poplar aldehyde pyridine imine titanous chloride title complex and its preparation method and application, it is characterized in that, described title complex has the structure shown in formula (I), wherein R 1-R 8respective is independently hydrogen, the alkyl of substituted or unsubstituted C1-C8 or halogen.The invention also discloses a kind of method of ethylene polymerization and ethene polymers obtained by this method, under the method is included in the existence of organic solvent, promotor and Primary Catalysts and under olefin polymerization conditions, make olefinic polymerization, described alkene is the mixture of ethene or the alpha-olefin containing ethene and C4-C10; It is characterized in that, described Primary Catalysts is above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex.

Description

The method of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and ethylene polymerization
Technical field
The present invention relates to a kind of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and use the method for ethylene polymerization of above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex.
Background technology
Polyvinyl resin (PE) is the maximum synthetic resins of current production rate, and its low price, better performances, occupies very important status in plastics industry.Catalyzer is the important factor affecting molecular weight of polyethylene and molecular weight distribution etc., develops and has low cost, high reactivity and the good catalyzer of products therefrom performance is one of emphasis direction of polyolefin industry circle development.
At present, industrialized polyethylene catalysts has Ziegler-Natta type catalyzer [DEPat889229 (1953); ITPat545332 (1956); ITPat536899 (1955); Chem.Rev., 2000,100,1169], Phillips type catalyzer [Belg.Pat.530617 (1995); Chem.Rev.1996,96,3327] and metallocene catalyst [W.Kaminsky, MetalorganicCatalystsforSynthesisandPolymerization, Berlin:Springer, 1999].Metallocene catalysis system active centre is considered to the metal cationic complex [CpMR of 14 electronic structures +] (R is alkyl), the Lewis of the metal center structure of sterie configuration on catalytic activity and polymerisate that be acid and surrounding cyclopentadienyl ligand has direct impact.But metallocene catalyst just can demonstrate high reactivity under not only needing a large amount of MAO to exist, and its structural modification difficulty, less stable, limit the practical application of metallocene catalyst to a certain extent.
In recent years, IVB race metal complex catalysts has become the focus of olefin polymerization catalysis research.Such catalyst system is homogeneous catalysis system, is furnished with suitable part simultaneously, and metal complex catalysts can embody the catalytic activity higher than traditional catalyst; In addition, this kind of catalyzer also has the advantage by regulating the structure of part to control catalytic activity and polymer performance.This type of representative catalyzer comprises: the IVB race metal complex catalysts containing β-diamines, di-phenols composition catalyst, FI catalyzer, PI catalyzer and the IVB race metallic mono-cyclopentadinyl composition catalyst containing a non-bridging assistant ligand.Wherein, FI catalyzer and PI catalyzer are the double salicylaldehyde imines or pyrrole imine early transition metal title complex that the nineties, Fujita reported, concrete structure is as shown below.These early transition metal title complexs with greater activity catalysis in olefine polymerization, and by changing reaction conditions or selecting different promotors, can realize the control to polymericular weight.In addition, living polymerization [Chem.Lett., 1999,1065 of alkene can also be realized under some specific conditions; Organometallics, 2001,20,4793; Angew.Chem.Int.Ed., 2000,39,3626; J.Am.Chem.Soc., 2004,126,12023; J.Organomet.Chem., 2005,690,4382.].
FI catalyzer and PI catalyzer can realize higher ethylene polymerization activity, but owing to being subject to the protection of patent, these catalyzer cannot be widely used in the development of China's polyolefine industry.But FI catalyzer and PI catalyzer have caused the upsurge of transition metal compound catalizer research.Research shows, based on most catalyzer of FI catalyst model transformation, such as, has the catalyzer of structure shown in formula 1 and formula 2, presents trend [J.Mol.Catal.A2006,258,275-283 that catalytic reaction activity reduces; J.Am.Chem.Soc.2001,123,6847-6856].Two acyl kitimine titanium complexes (structure as shown in Equation 3) of the exploitation such as Li Yuesheng have good initiating activity (to reach as high as 10 to ethene under the effect of MMAO 5gmol -1(Ti) h -1).The titanium catalyst (structure is such as formula 4 and 5 Suo Shi) with the tridentate ligand of wall effect of the exploitation such as Tang Yong, when X is the S atomic time, can with higher active catalytic ethylene homo and ethene-1-hervene copolymer.
In the past in the several years, also investigated this titanium class composition catalyst several below.
3-chloro-2-imido grpup indoles titanium complex (structure is as shown in Equation 6) can prepare the polyethylene with ultra-high molecular weight under suitable condition, and better heat stability.Particular embodiment at high temperature has high initiating activity and active centre can continue the long period, insertion rate high [J.Polym.Sci.A:Polym.Chem.2007,45, the 3415-3430 of monomer in the copolymerization of ethene and norbornylene; Chinese Patent Application No. 200610165443.1].
6-benzoglyoxaline-pyridine-2-benzoic acid amides-cyclopentadienyl complex compound (structure as shown in Equation 7) under suitable condition can catalyzed ethylene polymerization preferably.Wherein, the compound of aryl substituted amide part can reach 10 to ethylene polymerization activity 7gmol -1(Ti) h -1. [J.Polym.Sci.A:Polym.Chem.2008,46,3396-3410; Chinese Patent Application No. 200810106245.7].
3-chloro-2-imido grpup indoles Binary catalysts (structure as shown in Equation 8) can reach 7.68 × 10 to ethylene polymerization activity under proper condition 6mol -1(Ti) h -1, catalyzed ethylene/1-hervene copolymer activity can reach 6.56 × 10 6gmol -1(Ti) h -1, molecular weight can reach 1245Kg/Mol, and co-monomer content is 0.5-5.0mol% [J.Polym.Sci.A:Polym.Chem.2009,47,357-372; Chinese Patent Application No. 200810119678.6].
In addition, 2-benzoglyoxaline-quinoline-8-N-benzoic amide Binary catalysts (structure as shown in Equation 9) to the polymerization activity of ethene up to 10 7gmol -1(Ti) h -1, and molecular weight, up to 1,480,000, also has good prospects for commercial application [J.Polym.Sci.A:Polym.Chem.2009,47,3154-3169 under suitable conditions; Chinese Patent Application No. 200910079168.5].
Cyclopentadiene-N-(2-toluquinoline) titanium benzoic amide coordination compound (structure as shown in Equation 10) can reach 2.17 × 10 to the polymerization activity of ethene under suitable conditions 6mol -1(Ti) h -1, molecular weight is up to 43.7 ten thousand; The Copolymerization activity of catalyzed ethylene and 1-hexene can reach 2380kgmol -1(Ti) h -1, molecular weight can reach 213kgmol -1, there is good prospects for commercial application [Organometallics2010,29,2459-2464].
In addition, also have one to be (E)-2-(1-(aromatic imine) propyl group)-oxine titanous chloride title complex, under proper condition 1150kgmol is reached to the polymerization activity of ethene -1(Ti) h -1, the Copolymerization activity of catalyzed ethylene and 1-hexene can reach 1560kgmol -1(Ti) h -1, the Copolymerization activity of catalyzed ethylene and 1-octene can reach 576kgmol -1(Ti) h -1, there is certain prospects for commercial application [J.Polym.Sci.PartA:Polym.Chem.2011,49,1887-1894; Chinese Patent Application No. 201110037477.3].
In the research of these catalyzer, can how obtain and be easy to prepare and the olefin polymerization catalyst with more high reaction activity has become the core content of research, be also advance industrialized key as early as possible.
Summary of the invention
In order to improve the activity of olefinic polyreaction further, the object of this invention is to provide a kind of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and utilize the method for the complex-catalyzed ethylene polymerization of this salicylic aldehyde pyridine imine titanous chloride, use salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention can obtain higher olefin polymerizating activity.
The invention provides a kind of salicylic aldehyde pyridine imine titanous chloride title complex, wherein, described title complex has the structure shown in formula (I);
Wherein, R 1-R 8respective is independently hydrogen, the alkyl of substituted or unsubstituted C1-C8 or halogen; Preferably, R 1-R 4respective is independently hydrogen, the alkyl of C1-C4, the haloalkyl of C1-C4 or halogen, R 5-R 8respective is independently the alkyl of hydrogen or C1-C4; More preferably, R 1-R 5and R 7respective is independently hydrogen, methyl, halogenated methyl or halogen, R 6and R 8for the alkyl of C4.
Present invention also offers a kind of preparation method of salicylic aldehyde pyridine imine titanous chloride title complex, the method comprises the following steps:
(1) under aldimine condensation reaction conditions, the 2-amido pyridine type compound of structure shown in the salicylic aldehyde of structure formula (II) Suo Shi and formula (III) is carried out the first contact reacts, obtains the pyridine imine compound shown in formula (IV);
Wherein, R 1-R 8respective is independently hydrogen, substituted or unsubstituted alkyl or halogen; Preferably, R 1-R 4respective is independently hydrogen, the alkyl of C1-C4, the haloalkyl of C1-C4 or halogen, R 5-R 8respective is independently the alkyl of hydrogen or C1-C8;
(2) under protection of inert gas, the drying solution of the pyridine imine compound shown in formula (IV) and metal hydride are carried out the second contact reacts at the temperature of-25 DEG C to 25 DEG C, obtains suspension liquid;
(3) at the temperature of-78 DEG C to 25 DEG C, above-mentioned suspension liquid and TiCl is made 4(THF) 2under complex reaction condition, the 3rd contact reacts is carried out after mixing.
Present invention also offers the application of above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex in ethylene polymerization.
In addition, present invention also offers a kind of method of ethylene polymerization, under the method is included in the existence of organic solvent, promotor and Primary Catalysts and under olefin polymerization conditions, make olefinic polymerization, described alkene is the mixture of ethene or the alpha-olefin containing ethene and C4-C10; It is characterized in that, described Primary Catalysts is above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex.
Salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention has higher catalytic reaction activity, can the copolymerization of the homopolymerization of catalyzed ethylene or the alpha-olefin of ethene and C4-C10 well.Under the synergy of promotor, such catalyzer can with the active catalytic vinyl polymerization higher compared with prior art catalyzer, and catalyzed ethylene homopolymerization activity can reach 531kgmol -1(Ti) h -1, the molecular weight of polymkeric substance can reach 119kgmol -1; The Copolymerization activity of catalyzed ethylene and 1-hexene can reach 287kgmol -1(Ti) h -1, the molecular weight of polymkeric substance can reach 225kgmol -1, catalyzed ethylene and 1-octene copolymer activity can reach 721kgmol -1(Ti) h -1, the molecular weight of polymkeric substance can reach 247kgmol -1.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure of the Primary Catalysts C2 that the embodiment of the present invention obtains;
Fig. 2 is the crystalline structure figure of the Primary Catalysts C4 that the embodiment of the present invention obtains.
Embodiment
Below will be described in detail to the specific embodiment of the present invention.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention has the structure shown in formula (I):
Wherein, R 1-R 8respective is independently hydrogen, the alkyl of substituted or unsubstituted C1-C8 or halogen; Preferably, R 1-R 4respective is independently hydrogen, the alkyl of C1-C4, the haloalkyl of C1-C4 or halogen, R 5-R 8respective is independently the alkyl of hydrogen or C1-C4; More preferably, R 1-R 5and R 7respective is independently hydrogen, methyl, halogenated methyl or halogen, R 6and R 8for the alkyl of C4.The alkyl of described substituted or unsubstituted C1-C8 can be such as the substituted radical after the one or more hydrogen atoms in methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and above-mentioned group are replaced by halogen, nitro, amido.Described halogenated methyl is preferably fluoromethyl, more preferably trifluoromethyl, and described halogen is preferably fluorine, chlorine or bromine.
The present inventor finds under study for action, by specific R 1-R 8coordinate the salicylic aldehyde pyridine imine titanous chloride title complex formed can obtain fabulous catalytic effect as during catalyzer, therefore, preferably,
R 1-R 5and R 7for hydrogen; R 6and R 8for the tertiary butyl; Or
R 1, R 3, R 4, R 5and R 7for hydrogen; R 2for methyl; R 6and R 8for the tertiary butyl; Or
R 1, R 2, R 4, R 5and R 7for hydrogen; R 3for methyl; R 6and R 8for the tertiary butyl; Or
R 2, R 4, R 5and R 7for hydrogen; R 1and R 3for methyl; R 6and R 8for the tertiary butyl; Or
R 1, R 3, R 5and R 7for hydrogen; R 2for trifluoromethyl; R 4for chlorine; R 6and R 8for the tertiary butyl.。
The preparation method of salicylic aldehyde pyridine imine titanous chloride title complex provided by the present invention comprises the following steps:
(1) under aldimine condensation reaction conditions, the 2-amido pyridine type compound of structure shown in the salicylic aldehyde of structure formula (II) Suo Shi and formula (III) is carried out the first contact reacts, obtains the pyridine imine compound shown in formula (IV);
Wherein, R 1-R 8definition identical with above-mentioned formula (I).
(2) under protection of inert gas, the drying solution of the pyridine imine compound shown in formula (IV) and metal hydride are carried out the second contact reacts at the temperature of-25 DEG C to 25 DEG C, obtains suspension liquid;
(3) at the temperature of-78 DEG C to 25 DEG C, above-mentioned suspension liquid and TiCl is made 4(THF) 2under complex reaction condition, the 3rd contact reacts is carried out after mixing.
The add-on of the present invention to salicylic aldehyde described in step (1) and described 2-pyridine amine is not particularly limited, and under preferable case, the mol ratio of described salicylic aldehyde and described 2-pyridine amine can be 1: 1-1.2, and more preferably 1: 1-1.1.
According to the present invention, in step (1), aldimine condensation reaction is one reaction well known in the art, therefore described first catalytic condition can be the reaction conditions of this area routine, but in order to improve the yield of speed of reaction and product, it is 300MHz-300GHz that the condition that described first contact reacts preferably carries out described aldimine condensation reaction under microwave irradiation comprises micro-wave frequency, is preferably 300-1200MHz; The salicylic aldehyde of structure shown in formula (II) relative to 1 mole, the power of microwave exposure is 50-800W, is preferably 100-300W.The prolongation in reaction times is conducive to the raising of the transformation efficiency of reactant or the yield of reaction product, but the reaction times long increase rate to the transformation efficiency of reactant or the yield of reactant is also not obvious, therefore, generally, reaction times can be 0.1-20 minute, is preferably 2-16 minute.
Carry out more smoothly to make the reaction of step (1), under preferable case, the mode of described microwave exposure comprises first carries out the first microwave exposure, the second microwave exposure is carried out after being cooled to 10-35 DEG C, micro-wave frequency of described first microwave exposure is 300MHz-300GHz, is preferably 300-1200MHz; The salicylic aldehyde of structure shown in formula (II) relative to 1 mole, the power of microwave exposure is 50-800W, is preferably 100-300W; Microwave irradiation time is 0.1-10 minute, is preferably 0.5-8 minute; Micro-wave frequency of described second microwave exposure is 300MHz-300GHz, is preferably 300-1200MHz; The salicylic aldehyde of structure shown in formula (II) relative to 1 mole, the power of microwave exposure is 50-800W, is preferably 100-300W; Microwave irradiation time is 0.1-10 minute, is preferably 0.5-8 minute.
According to the present invention, step (1) can be carried out in the presence of solvent, also can not carry out in the presence of solvent, and in order to regulate speed of reaction, under preferable case, in step (1), described first contact reacts is carried out in the presence of an organic.Organic solvent described herein, mainly as reaction medium, can be the organic solvent of various routine known in those skilled in the art.Under preferable case, described organic solvent be selected from toluene, acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and trichloromethane one or more, more preferably toluene.The consumption of described organic solvent can be 0.5-5 times of weight of the salicylic aldehyde of structure shown in formula (II).
According to the present invention, in step (1), in order to obtain pure product, method provided by the invention can also comprise carries out purifying to the crude product of gained.The method of described purifying can adopt and well known to a person skilled in the art various purification process, under preferable case, the crude product that the present invention can be obtained carries out recrystallization, the method of described recrystallization and condition can adopt the method for well known to a person skilled in the art and condition, such as, recrystallization solvent used can one or more for being selected from ethanol, acetone, hexane, are preferably ethanol.
According to the present invention, in step (2), the product of described step (1) gained and the mol ratio of described metal hydride can change in very wide scope, under preferable case, the product of described step (1) gained and the mol ratio of described metal hydride are 1: 1-1.2, more preferably 1: 1-1.1.Described metal hydride can be various metal hydride, is preferably selected from one or more in potassium hydride KH and sodium hydride.
According to the present invention, solvent in the drying solution of the pyridine imine compound shown in formula (IV) described in step (2) can be the organic solvent of various routine known in those skilled in the art, can be such as one or more in toluene, ethyl acetate, benzene, tetrahydrofuran (THF), dimethylbenzene, methylene dichloride and trichloromethane, more preferably toluene.
Second catalytic condition of the present invention can be the reaction conditions of this area routine, and under preferable case, it is 5 DEG C to 20 DEG C that described second catalytic condition comprises temperature of reaction, and the reaction times is preferably 2-6 hour.
In step (3), under preferable case, the reaction product of described step (2) gained and the pyridine imine compound shown in formula (IV) and TiCl 4(THF) 2mol ratio be 1: 1-1.2, more preferably 1: 1-1.1.When step (1) and step (2) are fully carried out and step (1) and step (2) products therefrom all react for next step, also can feeding intake according to the determining step that feeds intake (2) in step (1) and step (3).
Described 3rd catalytic condition comprises temperature of reaction and is preferably-70 DEG C to 20 DEG C, is more preferably-65 DEG C to 10 DEG C; Reaction times is preferably 4-24 hour, more preferably 8-14 hour.
Present invention also offers according to the application of above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex in ethylene polymerization.
In addition, present invention also offers a kind of method of ethylene polymerization, under the method is included in the existence of organic solvent, promotor and Primary Catalysts and under olefin polymerization conditions, make olefinic polymerization, described alkene is the mixture of ethene or the alpha-olefin containing ethene and C4-C10; It is characterized in that, described Primary Catalysts is salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention.
The consumption of the present invention to described catalyzer is not particularly limited, but consider from combined factors such as the molecular weight of the polymkeric substance of polymerization rate, generation and production costs, under preferable case, the mol ratio of described catalyzer and described alkene is 0.01-0.1: 100, more preferably 0.05-0.8: 100.
According to the present invention, the condition of described polyreaction can be the condition of the polyreaction of this area routine, but in order to overcome oxygen inhibition, under preferable case, described polyreaction is carried out in an inert atmosphere, described inert atmosphere refer to not with reactant and any one gas of product generation chemical reaction or the mixture of gas, as one or more in nitrogen, helium and periodic table of elements zero group gas.The condition of described polyreaction comprises temperature of reaction, reaction pressure and reaction times, and such as, described temperature of reaction can be 0-150 DEG C, is preferably 20-100 DEG C; Reaction pressure can be 0.1-10MPa, is preferably 0.1-3MPa; Reaction times can be 15-60 minute, is preferably 15-30 minute.
The kind of the present invention to described promotor is not particularly limited, as long as can improve the activity of described catalyzer, polymerization rate is increased.In the preferred case, described promotor is selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls and haloalkyl aluminium.Described aikyiaiurnirsoxan beta is selected from methylaluminoxane (MAO), modified methylaluminoxane (MMAO) as one or more in part tertiary butyl modification MAO, ethylaluminoxane and isobutyl aluminium alkoxide, and above-mentioned aikyiaiurnirsoxan beta all can obtain from commercial channels.Above-mentioned aikyiaiurnirsoxan beta produces by the hydrolytic action of various conventional trialkyl aluminium compound, such as, MMAO by trimethyl aluminium and compared with higher trialkylaluminum as the hydrolytic action of triisobutyl aluminium produces.Described aluminum alkyls be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and tri-n-octylaluminium one or more.Described haloalkyl aluminium can be selected from chlorination aluminum alkyls, bromination aluminum alkyls and iodate aluminum alkyls one or more; Wherein, described chlorination aluminum alkyls can be selected from again one or more in diethylaluminum chloride, sesquialter ethylmercury chloride aluminium and ethylaluminium dichloride.
According to the present invention, the mol ratio of the metal titanium in the metallic aluminium in described promotor and described catalyzer can change within a large range, and under preferable case, described mol ratio is 500-10000: 1, and further preferably 3500-8000: 1.
Under preferable case, be the ethylene copolymer of 0.5-5 % by mole to obtain alpha-olefin structural unit content (also claiming " the insertion rate of alpha-olefin "), the described mol ratio containing the mixture of the alpha-olefin of ethene and C4-C10 is 1: 0.001-0.1.The ethylene copolymer physical performance of alpha-olefin structural unit content in above-mentioned scope is excellent especially.
According to the present invention, described alpha-olefin can be the alkene of 4-10 for carbonatoms, is preferably selected from least one in 1-hexene, 1-octene and butylene.
According to the present invention, the described organic solvent for ethylene polymerization can be the organic solvent of this area routine, is preferably selected from one or more in toluene, methylene dichloride and hexane, more preferably toluene.
Catalyzer synthesis of the present invention is simple, and may be used for synthetic molecular weight linear polyolefin controlled in a big way.
To be described in further detail the present invention by embodiment below.
Reagent used in embodiment and comparative example is commercially available chemically pure reagent.
In embodiment and comparative example, polyolefinic weight-average molecular weight and molecular weight distribution are all obtained by gel permeation chromatography; The insertion rate of alpha-olefin, by the pyrocarbon spectrogram of polymkeric substance, is carried out anomalous integral analysis ownership to peak and is calculated, specifically can refer to document [quantitative 13cNMRanalysisofsequencedistributionsinpoly (ethylene-co-1-hexene, Anal.Chem.2004,76,5734-5747].
Embodiment 1-5 is for illustration of the preparation of salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention
Embodiment 1
1) by 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde mixes with 0.94g (10mmol) PA, be placed in the microwave oven that frequency is 800MHz, under middle high fire (power of microwave exposure is 200W), heating is taken out after 1 minute and is cooled to room temperature, again in the lower heating of middle high fire 1 minute, obtain reddish black liquid.With ethyl alcohol recrystallization, obtain 2.52g orange crystals 3,5-di-tert-butyl salicylaldehyde 2-pyridine imine, productive rate 81.2%.
With IR, 1hNMR, 13cNMR, the product structure of ultimate analysis to gained characterize, and result is as follows:
IR(KBr，cm -1)：3000(O-H)(w)，2960(s)，2906(m)，2867(m)，1610(CH＝N)(m)，1579(s)，1461(s)，1432(s)，1360(m)，1198(m)，1169(s)，881(m)，791(m)，769(m)，736(m).
1HNMR：(CDCl 3，400MHz，ppm)：δ13.90(s，1H，OH)，9.47(s，1H，CH＝N)，8，50(d，1H，J＝3.60Hz，Py-H)，7.76(t，1H，J＝7.56Hz，Py-H)，7.49(s，1H，Ar-H)，7.35(d，1H，J＝6.24Hz，Py-H)，7.26(s，1H，Ar-H)，7.19(t，1H，J＝5.68Hz，Py-H)，1.50(s，9H，t-Bu-H)，1.34(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ165.8，159.2，157.9，149.0，140.8，138.5，137.0，128.9，128.2，122.3，120.4，118.2，35.2，34.3，31.5，29.5.
Ultimate analysis: C 20h 26n 2o theoretical value (%): C, 77.38; H, 8.44; N, 9.02; Experimental value (%): C, 77.26; H, 8.50; N, 9.09.
From the above results, gained compound is compound shown in formula (IV).
2) at 20 DEG C, drip in the KH of 1mmol by the toluene solution 100mL of 3,5-di-tert-butyl salicylaldehyde 2-pyridine imine (0.324g, 1mmol), stirring reaction 12 hours, obtains yellow suspension.
3) at-78 DEG C, in above-mentioned suspension liquid, the TiCl of yellow powder is added 4(THF) 2(0.334g, 1mmol), allows system slowly rise to room temperature, continues stirring 24 hours.Through silica gel chromatography column purification, (eluent is volume ratio ethyl acetate/petroleum ether=1 to the product generated: 10) obtain 0.25g3 after drying, 5-di-tert-butyl salicylaldehyde-2-pyridine imine-titanous chloride title complex, be designated as Primary Catalysts C1, productive rate is 49%.
The structure confirmation data of this title complex is as follows:
1HNMR(CDCl 3，400MHz)：8.96(s，1H，CH＝N)，8.93(s，1H，Py-H)，8.12(s，1H，Py-H)，7.85(s，1H，Py-H)，7.69(d，1H，J＝7.8Hz，Py-H)，7.53(s，1H，Ar-H)，7.24(s，1H，Ar-H)，1.58(s，9H，t-Bu-H)，1.37(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ162.2，157.8，154.9，147.9，146，7，141.8，134.5，130.4，127.2，124.5，111.8，35.9，31.3，30.1，29.8.
Ultimate analysis: C 20h 25cl 3n 2oTi theoretical value (%): C, 51.81; H, 5.43; N, 6.04; Experimental value (%): C, 51.87; H, 5.41; N, 6.09.
From above can result this complex structure known correct, be title complex formula (I) Suo Shi.
Embodiment 2
1) by 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde mixes with 1.08g (10mmol) 2-amino-5-picoline, be placed in the microwave oven that frequency is 800MHz, take out after 2 minutes in the lower heating of middle high fire and be cooled to room temperature, again in the lower heating of middle high fire 2 minutes, obtain reddish black liquid.With ethyl alcohol recrystallization, obtain 2.36g orange crystals 3,5-di-tert-butyl salicylaldehyde-2-pyridine-5-methylene imine, productive rate 73.8%.
With IR, 1hNMR, 13cNMR, the product structure of ultimate analysis to gained characterize, and result is as follows:
IR(KBr，cm -1)：2997(w)，2958(s)，2906(m)，2868(m)，1612(CH＝N)(m)，1570(s)，1462(s)，1386(m)，1358(m)，1251(m)，1169(s)，1022(m)，881(m)，828(m)，769(w)，680(w).
1HNMR：(CDCl 3，400MHz，ppm)：δ13.93(s，1H，OH)，9.42(s，1H，CH＝N)，8.31(s，1H，Py-H)，7.56(d，1H，J＝7.88Hz，Py-H)，7.46(s，1H，Ar-H)，7.34(s，1H，Ar-H)，7.23(d，2H，J＝8.64Hz，Py-H)，2.37(s，3H，CH 3)，1.48(s，9H，t-Bu-H)，1.32(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ164.8，159.1，155.7，149.2，140.7，139.0，136.9，132.0，128.6，128.0，119.8，118.3，35.2，34.2，31.5，29.5，18.1.
Ultimate analysis: C 21h 28n 2o theoretical value (%): C, 77.74; H, 8.70; N, 8.63; Experimental value (%): C, 77.87; H, 8.64; N, 8.54.
From the above results, gained compound is compound shown in formula (IV).
2) at-10 DEG C, by 3, the toluene solution 100mL of 5-di-tert-butyl salicylaldehyde-2-pyridine-5-methylene imine (0.338g, 1mmol) drips in the KH of 1mmol, and stirring reaction 6 hours, obtains yellow suspension.
3) at-50 DEG C, in above-mentioned suspension liquid, the TiCl of yellow powder is added 4(THF) 2(0.334g, 1mmol), allows system slowly rise to room temperature, continues stirring 12 hours.Through silica gel chromatography column purification, (eluent is volume ratio ethyl acetate/petroleum ether=1 to the product generated: 10) obtain 0.46g3 after purifying drying, 5-di-tert-butyl salicylaldehyde-2-pyridine-5-methylene imine-titanous chloride title complex, be designated as Primary Catalysts C2, productive rate is 52.3%.
The structure confirmation data of this title complex is as follows:
1HNMR：(CDCl 3，400MHz，ppm)：δ8.85(s，1H，CH＝N)，8.81(s，1H，Py-H)，7.93(d，1H，J＝6.42，Py-H)，7.82(s，1H，Ar-H)，7.54(d，1H，J＝7.31Hz，Py-H)，7.18(s，1H，Ar-H)，2.54(s，3H，CH 3)，1.58(s，9H，t-Bu-H)，1.37(s，9H，t-Bu-H). 13CNMR：(CDCl 3，100MHz，ppm)：δ145.3，145.2，143.8，141.5，137.8，132.6，132.2，129.6，122.8，122.1，114.1，111.1，31.9，31.3，29.6，22.8，14.2.
Ultimate analysis: C 21h 27cl 3n 2oTi theoretical value (%): C, 52.80; H, 5.70; N, 5.86; Experimental value (%): C, 52.84; H, 5.75; N, 5.80.
From above can result this complex structure known correct, be title complex formula (I) Suo Shi.The crystalline structure of this title complex adopts monocrystalline X-light ray diffraction, as shown in Figure 1.As shown in Figure 1, this title complex is N^N^O tri-tooth title complex, and metallic perimeter is made up of a part and three chlorine atoms.
Embodiment 3
1) by 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde mixes with 1.08g (10mmol) 4-methyl-2-amino pyridine, be placed in the microwave oven that frequency is 800MHz, take out after 2 minutes in the lower heating of middle high fire and be cooled to room temperature, again in the lower heating of middle high fire 8 minutes, obtain reddish black liquid.With ethyl alcohol recrystallization, obtain 2.39g yellow solid 3,5-di-tert-butyl salicylaldehyde-2-pyridine-4-methylene imine, productive rate 74.5%.
With IR, 1hNMR, 13cNMR, the product structure of ultimate analysis to gained characterize, and result is as follows:
IR(KBr，cm -1)：3049(w)，2960(s)，2908(m)，2868(m)，1607(CH＝N)(s)，1584(s)，1549(s)，1456(s)，1362(m)，1251(m)，1206(m)，1157(m)，1028(w)，947(w)，886(w)，716(w).
1HNMR：(CDCl 3，400MHz，ppm)：δ13.95(s，1H，OH)，9.44(s，1H，CH＝N)，8.35(d，1H，J＝4.48Hz，Py-H)，7.47(t，1H，Py-H)，7.34(s，1H，Ar-H)，7.17(s，1H，Ar-H)，7.01(d，1H，J＝4.73Hz，Py-H)，2.39(s，3H，CH 3)，1.48(s，9H，t-Bu-H)，1.32(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ165.6，159.3，157.9，149.9，148.7，140.7，137.0，128.8，128.1，123.4，121.1，118.3，35.2，34.3，31.5，29.5，21.1.
Ultimate analysis: C 21h 28n 2o theoretical value (%): C, 77.74; H, 8.70; N, 8.63; Experimental value (%): C, 77.62; H, 8.76; N, 8.60.
From the above results, gained compound is compound shown in formula (IV).
2) at-10 DEG C, by 3, the tetrahydrofuran solution 100mL of 5-di-tert-butyl salicylaldehyde-2-pyridine-4-methylene imine (0.338g, 1mmol) is directly added drop-wise in the KH of 1mmol, and stirring reaction 4 hours, obtains yellow suspension.
3) at 0 DEG C, in above-mentioned suspension liquid, the TiCl of yellow powder is added 4. (THF) 2(0.334g, 1mmol), allows system slowly rise to room temperature, continues stirring 8 hours.Through silica gel chromatography column purification, (eluent is volume ratio ethyl acetate/petroleum ether=1 to the product generated: 10) obtain 0.78g3 after purifying drying, 5-di-tert-butyl salicylaldehyde-2-pyridine-4-methylene imine-titanous chloride title complex, be designated as Primary Catalysts C3, productive rate is 86.5%.
The structure confirmation data of this title complex is as follows:
1HNMR：(CDCl 3，400MHz，ppm)：δ8.86(s，1H，CH＝N)，8.81(d，1H，J＝5.08Hz，Py-H)，7.85(s，1H，Py-H)，7.52(s，1H，Ar-H)，7.47(s，1H，Ar-H)，7.38(d，1H，J＝5.02Hz，Py-H)，2.51(s，3H，CH 3)，1.58(s，9H，t-Bu-H)，1.37(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ162.8，158.6，157.7，154.4，154.2，147.8，145.9，137.9，134.4，126.9，112.0，100.1，35.9，31.3，30.1，22.3，14.2.
Ultimate analysis: C 21h 27cl 3n 2oTi theoretical value (%): C, 52.80; H, 5.70; N, 5.86. experimental value (%): C, 52.82; H, 5.75; N, 5.82.
From above can result this complex structure known correct, be title complex formula (I) Suo Shi.
Embodiment 4
1) by 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde and 1.22g (10mmol) 4,6-dimethyl-PA mixes, be placed in the microwave oven that frequency is 800MHz, take out after 2 minutes in the lower heating of middle high fire and be cooled to room temperature, again in the lower heating of middle high fire 4 minutes, obtain reddish black liquid, use ethyl alcohol recrystallization.Obtain 2.04g yellow solid 3,5-di-tert-butyl salicylaldehyde-2-pyridine-4,6-dimethylimino, productive rate is 59.2%.
With IR, 1hNMR, 13cNMR, the product structure of ultimate analysis to gained characterize, and result is as follows:
IR(KBr，cm -1)：3005(w)，2960(s)，2869(m)，1609(CH＝N)(s)，1589(s)，1549(s)，1456(s)，1362(m)，1251(m)，1207(m)，1174(m)，1153(m)，1028(w)，985(w)，716(w).
1HNMR：(CDCl 3，400MHz，ppm)：δ14.07(s，1H，OH)，9.42(s，1H，CH＝N)，7.45(s，1H，Py-H)，7.34(s，1H，Py-H)，6.96(s，1H，Ar-H)，6.89(s，1H，Ar-H)，2.53(s，3H，CH 3)，2.34(s，3H，CH 3)，1.47(s，9H，t-Bu-H)，1.33(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ165.2，159.3，157.7，157.3，149.7，140.5，136.9，128.5，128.0，122.9，118.3，118.0，35.2，34.3，31.6，29.5，24.3，20.9.
Ultimate analysis: C 22h 30n 2o theoretical value (%): C, 78.06; H, 8.93; N, 8.28; Experimental value (%): C, 78.11; H, 8.99; N, 8.20.
From the above results, gained compound is compound shown in formula (IV).
2) at 0 DEG C, drip in the KH of 1mmol by the dichloromethane solution 100mL of 3,5-di-tert-butyl salicylaldehyde-2-pyridine-4,6-dimethylimino (0.338g, 1mmol), stirring reaction 2 hours, obtains yellow suspension.
3) at-10 DEG C, in above-mentioned suspension liquid, the TiCl of yellow powder is added 4. (THF) 2(0.334g, 1mmol), allows system slowly rise to room temperature, continues stirring 6 hours.Through silica gel chromatography column purification, (eluent is volume ratio ethyl acetate/petroleum ether=1 to the product generated: 10) obtain 0.84g3 after purifying drying, 5-di-tert-butyl salicylaldehyde-2-pyridine-4,6-dimethylimino-titanous chloride title complex, is designated as Primary Catalysts C4, and productive rate is 82.2%.
The structure confirmation data of this title complex is as follows:
1HNMR(CDCl 3，400MHz，ppm)：δ8.82(s，1H，CH＝N)，7.82(s，1H，Py-H)，7.50(s，1H，Py-H)，7.24(s，1H，Ar-H)，7.17(s，1H，Py-H)，2.99(s，3H，CH 3)，2.55(s，3H，CH 3)，1.59(s，9H，t-Bu)，1.37(s，9H，t-Bu).
13CNMR：(CDCl 3，100MHz，ppm)：δ161.9，157.2，156.2，154.4，154.3，147.7，134.0，130.0，127.1，125.4，109.1，35.9，34.9，31.3，30.0，22.7，22.0.
Ultimate analysis: C 22h 29cl 3n 2oTi theoretical value (%): C, 53.74; H, 5.94; N, 5.70; Experimental value (%): C, 53.71; H, 5.97; N, 5.73.
From above can result this complex structure known correct, be title complex formula (I) Suo Shi.The crystalline structure of this title complex as shown in Figure 2, as seen from the figure, this crystalline structure and title complex C2 very similar, be also the title complex of N^N^O tridentate ligand.Metal center and part define octahedral chelate structure.
Embodiment 5
1) by 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde mixes with 1.98g (10mmol) 3-chlorine 5-trifluoromethyl PA, be placed in the microwave oven that frequency is 800MHz, take out after 0.5 minute in the lower heating of middle high fire and be cooled to room temperature, again in the lower heating of middle high fire 0.5 minute, obtain reddish black liquid.With ethyl alcohol recrystallization, obtain 1.07g yellow solid 3,5-di-tert-butyl salicylaldehyde-3-chlorine 5-trifluoromethyl PA imines, productive rate is 30.3%.
With IR, 1hNMR, 13cNMR, the product structure of ultimate analysis to gained characterize, and result is as follows:
IR(KBr，cm -1)：3001(w)，2961(s)，2916(m)，2363(s)，2343(m)，1625(CH＝N)(m)，1564(s)，1455(s)，1319(s)，1275(m)，1253(m)，1163(s)，1122(s)，1089(m)，978(w)，738(w).
1HNMR：(CDCl 3，400MHz，ppm)：δ13.68(s，1H，OH)，9.51(s，1H，CH＝N)，8.64(s，1H，Py-H)，8.05(s，1H，Py-H)，7.57(s，1H，Ar-H)，7.37(s，1H，Ar-H)，1.50(s，9H，t-Bu-H)，1.34(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ168.5，160.3，157.2，143.9，141.3，137.7，135.9，130.8，128.7，127.4，125.7，124.3，118.1，35.3，34.3，31.5，29.5.
Ultimate analysis: C 21h 24clF 3n 2o theoretical value (%): C, 61.09; H, 5.86; N, 6.78; Experimental value (%): C, 61.15; H, 5.89; N, 6.73.
From the above results, gained compound is compound shown in formula (IV).
2) at-10 DEG C, by 3, the toluene solution 100mL of 5-di-tert-butyl salicylaldehyde-3-chlorine 5-trifluoromethyl PA imines (0.377g, 1mmol) drips in the KH of 1mmol, and stirring reaction 4 hours, obtains yellow suspension.
3) at 25 DEG C, in above-mentioned suspension liquid, the TiCl of yellow powder is added 4. (THF) 2(0.334g, 1mmol), allows system slowly rise to room temperature, continues stirring 4 hours.Through silica gel chromatography column purification, (eluent is volume ratio ethyl acetate/petroleum ether=1 to the product generated: 10) obtain 0.47g3 after purifying drying, 5-di-tert-butyl salicylaldehyde-3-chloro-5-trifluoromethyl PA imines-titanous chloride title complex, be designated as Primary Catalysts C5, productive rate is 52.9%.
The structure confirmation data of this title complex is as follows:
1HNMR：(CDCl 3，400MHz，ppm)：δ9.74(s，1H，CH＝N)，9.18(s，1H，Py-H)，8.31(s，1H，Py-H)，7.93(s，1H，Ar-H)，7.58(s，1H，Ar-H)，1.58(s，9H，t-Bu-H)，1.39(s，9H，t-Bu-H).
13CNMR：(CDCl 3，100MHz，ppm)：δ162.4，160.5，155.8，154.8，148.5，142.2，140.4，136.4，132.1，127.8，127.3，127.0，123.7，35.8，34.9，31.1，29.9.
Ultimate analysis: C 21h 23cl 4f 3n 2oTi theoretical value (%): C, 44.56; H, 4.10; N, 4.95; Experimental value (%): C, 44.59; H, 4.13; N, 4.98.
From above can result this complex structure known correct, be title complex formula (I) Suo Shi.
Comparative example 1
This comparative example is for illustration of the preparation of reference title complex.
According to document [G.Paolucci, A.Zanella, L.Sperni, V.Bertolasi, M.Mazzeoc, C.Pellecchia.Tridentate [N, N, O] Schiff-basegroup4metalcomplexes:Synthesis, structuralcharacterizationandreactivityinolefinpolymeriz ation [J] .2006,258:275-283] disclosed in method prepare the title complex C of structure as shown in formula V 20h 19cl 3n 2oTi, is designated as Primary Catalysts DC1.
Embodiment 6-32 is for illustration of the method for ethylene polymerization provided by the invention.
Embodiment 6
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 90mL is joined in the stainless steel autoclave of 250mL; when control temperature is 20 DEG C; pressure is 2MPa; then in system, add the toluene solution that 10.3mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C4; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Comparative example 2
Under nitrogen protection, the toluene of 90mL is joined in the stainless steel autoclave of 250mL, when control temperature is 20 DEG C; pressure is 1MPa; then in system, add the toluene solution of 10mL containing 5 μm of ol Primary Catalysts C4, start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 0.01mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain settled solution, do not have polymkeric substance to generate.
Embodiment 7
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 76.3mL is joined in the stainless steel autoclave of 250mL; when control temperature is 40 DEG C; pressure is 1MPa; then in system, add the toluene solution that 13.7mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C4; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 20 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 8
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 80 DEG C; pressure is 0.1MPa; then in system, add the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C4; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 9
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 69.5mL is joined in the stainless steel autoclave of 250mL; when control temperature is 20 DEG C; pressure is 1MPa; then in system, add the toluene solution that 20.5mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring to start, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 10
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 66.1mL is joined in the stainless steel autoclave of 250mL; when control temperature is 20 DEG C; pressure is 1MPa; then in system, add the toluene solution that 23.9mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 20 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 11
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 62.6mL is joined in the stainless steel autoclave of 250mL; when control temperature is 20 DEG C; pressure is 0.5MPa; then in system, add the toluene solution that 27.4mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 12
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 20 DEG C; pressure is 0.1MPa; then in system, add the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.The polymerization activity of resulting polymers, weight-average molecular weight, molecular weight distribution is as shown in table 1.
Embodiment 13
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 40 DEG C; pressure is 1MPa; then in system, add the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring to start, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 14
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 50 DEG C; pressure is 2MPa; then in system, add MAO toluene solution that 17.1mL concentration is 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 15
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 70 DEG C; pressure is 3MPa; then in system, add the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring to start, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 16
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 80 DEG C; pressure is 1MPa; then in system, add the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C3; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 30 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Comparative example 3
Polyolefine is prepared according to the method for embodiment 16, unlike, the Primary Catalysts C3 title complex DC1 that comparative example 1 is obtained replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 17
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 16, unlike, Primary Catalysts C3 Primary Catalysts C2 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 18
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 16, unlike, Primary Catalysts C3 Primary Catalysts C1 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 19
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 16, unlike, Primary Catalysts C3 Primary Catalysts C4 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 20
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 16, unlike, Primary Catalysts C3 Primary Catalysts C5 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 21
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.3mL is joined in the stainless steel autoclave of 250mL; when control temperature is 50 DEG C; pressure is 1MPa; then in system, the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L is added; 1.2mL concentration be the 1-hexene of 0.1mol/L and 10ml containing the toluene solution of 5 μm of ol Primary Catalysts C5, start mechanical stirring and start, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Comparative example 4
Under nitrogen protection; the toluene of 72.3mL is joined in the stainless steel autoclave of 250mL; when control temperature is 50 DEG C; pressure is 1MPa; then in system, add 1-hexene that 1.2mL concentration is 0.1mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C5; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain settled solution, do not have polymkeric substance to generate.
Embodiment 22
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 69.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 20 DEG C; pressure is 1MPa; then in system, the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L is added; 3.6mL concentration be the 1-hexene of 0.3mol/L and 10mL containing the toluene solution of 5 μm of ol Primary Catalysts C5, start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 23
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 61.5mL is joined in the stainless steel autoclave of 250mL; when control temperature is 80 DEG C; pressure is 0.1MPa; then in system, the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L is added; 12mL concentration be the 1-hexene of 1.0mol/L and 10mL containing the toluene solution of 5 μm of ol Primary Catalysts C5, start mechanical stirring and start, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 24
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 72.9mL is joined in the stainless steel autoclave of 250mL; when control temperature is 50 DEG C; pressure is 1MPa; then in system, the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L is added; 3.6mL concentration be the 1-hexene of 0.3mol/L and 10mL containing the toluene solution of 5 μm of ol Primary Catalysts C1, start mechanical stirring, keep 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Comparative example 5
Polyolefine is prepared according to the method for embodiment 24, unlike, the title complex DC1 of Primary Catalysts C1 obtained by comparative example 1 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Embodiment 25
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 24, unlike, Primary Catalysts C1 Primary Catalysts C2 replaces, and obtains polyolefine.The polymerization activity of resulting polymers, weight-average molecular weight, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 26
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 24, unlike, Primary Catalysts C1 Primary Catalysts C3 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 27
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 24, unlike, Primary Catalysts C1 Primary Catalysts C4 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 28
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Under nitrogen protection; the toluene of 69.7mL is joined in the stainless steel autoclave of 250mL; when control temperature is 50 DEG C; pressure is 1MPa; then in system, the toluene solution that 17.1mL concentration is the MAO of 1.46mol/L is added; 4.8mL concentration be the 1-octene of 0.3mol/L and 10mL containing the toluene solution of 5 μm of ol Primary Catalysts C1, start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain polymkeric substance precipitation, respectively wash 3 times with second alcohol and water, vacuum drying, to constant weight, weighs.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Comparative example 6
Under nitrogen protection; the toluene of 69.7mL is joined in the stainless steel autoclave of 250mL; when control temperature is 50 DEG C; pressure is 1MPa; then in system, add 1-octene that 4.8mL concentration is 0.3mol/L and the 10mL toluene solution containing 5 μm of ol Primary Catalysts C1; start mechanical stirring, keep rotating speed to be 500 revs/min.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction starts, stirring reaction 15 minutes.With the ethanolic soln neutralization reaction liquid of 5 % by weight hcl acidifyings, obtain settled solution, do not have polymkeric substance to generate.
Comparative example 7
Polyolefine is prepared according to the method for embodiment 28, unlike, the title complex of Primary Catalysts C1 obtained by comparative example 1 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 29
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 28, unlike, Primary Catalysts C1 Primary Catalysts C2 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 30
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 28, unlike, Primary Catalysts C1 Primary Catalysts C3 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 31
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 28, unlike, Primary Catalysts C1 Primary Catalysts C4 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Embodiment 32
The present embodiment is for illustration of the method for ethylene polymerization of the present invention.
Polyolefine is prepared according to the method for embodiment 28, unlike, Primary Catalysts C1 Primary Catalysts C5 replaces, and obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution, the insertion rate of alpha-olefin is as shown in table 1.
Table 1
Note: in upper table, "---" represents that non-polymer generation maybe cannot survey this index.
As seen from Table 1, the salicylic aldehyde pyridine imine titanous chloride title complex prepared by the present invention has higher catalytic activity, can reach 721kgmol -1(Ti) h -1.By the contrast of embodiment 16 with comparative example 3, the contrast of embodiment 21 and comparative example 4, the contrast of embodiment 24 and comparative example 5, and embodiment 28 can be found out with the contrast of comparative example 7, catalyzer of the present invention is adopted to have higher initiating activity, can the homopolymerization of catalyzed ethylene or the copolymerization of ethene and alpha-olefin mixture well.

Claims (8)

1. a preparation method for salicylic aldehyde pyridine imine titanous chloride title complex, the method comprises the following steps:
(1) under aldimine condensation reaction conditions, the 2-amido pyridine type compound of structure shown in the salicylic aldehyde of structure shown in formula II and formula III is carried out the first contact reacts, obtains the pyridine imine compound shown in formula IV; Described first contact reacts is carried out under microwave exposure, and the mode of described microwave exposure comprises first carries out the first microwave exposure, carries out the second microwave exposure after being cooled to 10-35 DEG C; Micro-wave frequency of described first microwave exposure is 300MHz-300GHz, and the power of microwave exposure is 100-300W, and microwave irradiation time is 0.1-10 minute; Micro-wave frequency of described second microwave exposure is 300MHz-300GHz, and the power of microwave exposure is 100-300W, and microwave irradiation time is 0.1-10 minute;
Wherein, R 1-R 8respective is independently hydrogen, substituted or unsubstituted alkyl or halogen;
(2) under protection of inert gas, the drying solution of the pyridine imine compound shown in formula IV and metal hydride are carried out the second contact reacts at the temperature of 5-20 DEG C, obtains suspension liquid;
(3) at the temperature of-78 DEG C to 25 DEG C, above-mentioned suspension liquid and TiCl is made 4(THF) 2under complex reaction condition, the 3rd contact reacts is carried out after mixing.
2. preparation method according to claim 1, wherein, R 1-R 4respective is independently hydrogen, the alkyl of C1-C4, the haloalkyl of C1-C4 or halogen, R 5-R 8respective is independently the alkyl of hydrogen or C1-C8.
3. preparation method according to claim 1, wherein, in step (1), micro-wave frequency of described first microwave exposure is 300-1200MHz, and the power of microwave exposure is 100-300W, and microwave irradiation time is 0.5-8 minute; Micro-wave frequency of described second microwave exposure is 300-1200MHz, and the power of microwave exposure is 100-300W, and microwave irradiation time is 0.5-8 minute.
4., according to the preparation method in claim 1-3 described in any one, wherein, in step (1), the mol ratio of described salicylic aldehyde and described 2-pyridine amine is 1:1-1.2.
5. preparation method according to claim 1, wherein, in step (2), the mol ratio of the pyridine imine compound shown in formula IV and metal hydride is 1:1-1.2, and the second catalytic time was 2-12 hour.
6. preparation method according to claim 1 or 5, wherein, in step (2), described metal hydride is potassium hydride KH and/or sodium hydride, and the product of described step (1) gained and the mol ratio of described metal hydride are 1:1-1.2.
7. preparation method according to claim 1, wherein, in step (3), described 3rd catalytic temperature is-70 DEG C to 20 DEG C, and the time is 4-24 hour.
8. the preparation method according to claim 1 or 7, wherein, in step (3), the pyridine imine compound shown in described formula IV and TiCl 4(THF) 2mol ratio be 1:1-1.2.
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