CN102850391A - Salicylaldehyde pyridine imido titanium trichloride complex, its preparation method and application thereof, and polymerization method of ethene - Google Patents
Salicylaldehyde pyridine imido titanium trichloride complex, its preparation method and application thereof, and polymerization method of ethene Download PDFInfo
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Abstract
The invention discloses a salicylaldehyde pyridine imido titanium trichloride complex, its preparation method and an application thereof, and is characterized in that the complex has a structure as shown in the formula (I), wherein R1-R8 each is hydrogen, a substituted or unsubstituted C1-C8 alkyl group or halogen. The invention also discloses a polymerization method of ethene and an ethene polymer prepared by the method. According to the method, alkene undergoes polymerization in the presence of an organic solvent, a cocatalyst and a main catalyst and under the condition of alkene polymerization, wherein the alkene is ethene or a mixture containing ethene and C4-C10 alpha-alkene. The method is characterized in that the main catalyst is the above salicylaldehyde pyridine imido titanium trichloride complex.
Description
Technical field
The method that 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 ethylene polymerization of above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex.
Background technology
Polyvinyl resin (PE) is the synthetic resins of current production rate maximum, its low price, and better performances is occupied very important status in plastics industry.Catalyzer is the important factor that affects molecular weight of polyethylene and molecular weight distribution etc., develop have low cost, high reactivity and the good catalyzer of products therefrom performance are one of emphasis direction of polyolefin industry circle development.
At present, industrialized polyethylene catalysts has Ziegler-Natta type catalyzer [DE Pat 889229 (1953); IT Pat 545332 (1956); IT Pat 536899 (1955); Chem.Rev., 2000,100,1169], Phillips type catalyzer [Belg.Pat.530617 (1995); Chem.Rev.1996,96,3327] and metallocene catalyst [W.Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin:Springer, 1999].The metallocene catalysis system active centre is considered to the metallic cation title complex [CpMR of 14 electronic structures
+] (R is alkyl), the Lewis of metal center sterie configuration acid and cyclopentadienyl ligand on every side has direct impact to the structure of catalytic activity and polymerisate.Yet metallocene catalyst not only needs a large amount of MAO to have the lower high reactivity that just can demonstrate, and its structural modification is difficult, less stable, has limited to a certain extent the practical application of metallocene catalyst.
In recent years, IVB family metal complex catalysts has become the focus of olefin polymerization catalysis research.Such catalyst system is homogeneous catalysis system, is furnished with simultaneously suitable part, and metal complex catalysts can embody the catalytic activity higher than traditional catalyst; In addition, this class catalyzer also has advantages of and can come catalytic activity and polymer performance are controlled by the structure of regulating part.This type of representative catalyzer comprises: contain IVB family metal complex catalysts, di-phenols composition catalyst, FI catalyzer, the PI catalyzer of β-diamines and the IVB family metallic mono-cyclopentadinyl composition catalyst that contains a non-bridging assistant ligand.Wherein, FI catalyzer and PI catalyzer are double salicylaldehyde imines or the pyrrole imine early transition metal title complexs of the Fujita report nineties, and concrete structure is as shown below.These early transition metal title complexs can be with the greater activity catalysis in olefine polymerization, and by changing reaction conditions or selecting different promotors, can realize the control to polymericular weight.In addition, under some specific conditions, can also realize living polymerization [Chem.Lett., 1999,1065 of alkene; 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 be realized higher ethylene polymerization activity, but owing to being subject to the protection of patent, these catalyzer can't be widely used in the development of China's polyolefine industry.Yet FI catalyzer and PI catalyzer have caused the upsurge of transition metal compound catalizer research.Studies show that, based on most catalyzer that FI catalyzer model is transformed, the catalyzer that for example has structure shown in formula 1 and the formula 2, [J.Mol.Catal.A 2006,258,275-283 to have presented the trend 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 exploitations such as Li Yuesheng have preferably to ethene under the effect of MMAO, and initiating activity (reaches as high as 10
5Gmol
-1(Ti) h
-1).The titanium catalyst of the tridentate ligand with wall effect of the exploitations such as Tang Yong (structure is suc as formula shown in 4 and 5), when X is the S atomic time, can be with higher active catalytic ethylene homo and ethene-1-hervene copolymer.
In several years, following several these titanium class composition catalysts have also been worked out in the past.
3-chloro-2-imido grpup indoles titanium complexes (structure 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 the active centre can continue the long period, high [J.Polym.Sci.A:Polym.Chem.2007,45,3415-3430 of the insertion rate of monomer in the copolymerization of ethene and norbornylene; Chinese patent application numbers 200610165443.1].
6-benzoglyoxaline-pyridine-2-benzoic acid amides-cyclopentadienyl complex compound (structure as shown in Equation 7) is catalyzed ethylene polymerization preferably under suitable condition.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 numbers 200810106245.7].
The single cyclopentadiene titanium compounds of 3-chloro-2-imido grpup indoles (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 numbers 200810119678.6].
In addition, 2-benzoglyoxaline-quinoline-8-N-benzoic amide list cyclopentadiene titanium compound (structure as shown in Equation 9) to the polymerization activity of ethene up to 10
7Gmol
-1(Ti) h
-1, and molecular weight also has good prospects for commercial application [J.Polym.Sci.A:Polym.Chem.2009,47,3154-3169 up to 1,480,000 under conditions suitable; Chinese patent application numbers 200910079168.5].
Cyclopentadiene-N-(2-toluquinoline) titanium benzoic amide coordination compound (structure as shown in Equation 10) polymerization activity to ethene under conditions suitable can reach 2.17 * 10
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, have good prospects for commercial application [Organometallics 2010,29,2459-2464].
In addition, also having a kind of is (E)-2-(1-(aromatic imine) propyl group)-oxine titanous chloride title complex, under proper condition the polymerization activity of ethene is reached 1150kgmol
-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, have certain prospects for commercial application [J.Polym.Sci.Part A:Polym.Chem.2011,49,1887-1894; Chinese patent application numbers 201110037477.3].
In the research of these catalyzer, how to obtain to be easy to prepare and have the core content that the olefin polymerization catalyst of high reaction activity has more become research, also be to advance as early as possible industrialized key.
Summary of the invention
In order further to improve the activity of olefinic polyreaction, the method that the purpose 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 complex-catalyzed ethylene polymerization of this salicylic aldehyde pyridine imine titanous chloride uses 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 the formula (I);
Wherein, R
1-R
8Independent separately is alkyl or the halogen of hydrogen, replacement or unsubstituted C1-C8; Preferably, R
1-R
4Independent separately is the alkyl of hydrogen, C1-C4, haloalkyl or the halogen of C1-C4, R
5-R
8Independent separately is the alkyl of hydrogen or C1-C4; More preferably, R
1-R
5And R
7Independent separately is hydrogen, methyl, halogenated methyl or halogen, R
6And R
8Alkyl for C4.
The present invention also provides a kind of preparation method of salicylic aldehyde pyridine imine titanous chloride title complex, and the method may further comprise the steps:
(1) under the aldimine condensation reaction conditions, the 2-amido pyridine type compound of structure shown in the salicylic aldehyde of structure shown in the formula (II) and the formula (III) is carried out the first contact reacts, obtain the pyridine imine compound shown in the formula (IV);
Wherein, R
1-R
8Independent separately is hydrogen, replacement or unsubstituted alkyl or halogen; Preferably, R
1-R
4Independent separately is the alkyl of hydrogen, C1-C4, haloalkyl or the halogen of C1-C4, R
5-R
8Independent separately is the alkyl of hydrogen or C1-C8;
(2) under protection of inert gas, drying solution and the metal hydride of the pyridine imine compound shown in the formula (IV) carried out the second contact reacts under-25 ℃ to 25 ℃ temperature, obtain suspension liquid;
(3) under-78 ℃ to 25 ℃ temperature, make above-mentioned suspension liquid and TiCl
4(THF)
2Under the complex reaction condition, carry out the 3rd contact reacts after mixing.
The present invention also provides the application of above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex in ethylene polymerization.
In addition, the present invention also provides a kind of method of ethylene polymerization, the method is included in organic solvent, promotor and Primary Catalysts and exists under lower and the olefinic polymerization condition, makes olefinic polymerization, and described alkene is ethene or contains ethene and the mixture of the alpha-olefin of 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, the well copolymerization of the alpha-olefin of the homopolymerization of catalyzed ethylene or ethene and C4-C10.Under the synergy of promotor, such catalyzer can be with the active catalytic vinyl polymerization higher than the prior art catalyzer, and catalyzed ethylene homopolymerization activity can reach 531kgmol
-1(Ti) h
-1, the molecular weight of polymkeric substance can reach 119kgmol
-1The 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 will partly be described in detail in embodiment subsequently.
Description of drawings
Fig. 1 is the crystalline structure figure of the Primary Catalysts C2 that makes of the embodiment of the invention;
Fig. 2 is the crystalline structure figure of the Primary Catalysts C4 that makes of the embodiment of the invention.
Embodiment
Below will be elaborated to the specific embodiment of the present invention.Should be understood that, embodiment described herein only is used for description and interpretation 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 the formula (I):
Wherein, R
1-R
8Independent separately is alkyl or the halogen of hydrogen, replacement or unsubstituted C1-C8; Preferably, R
1-R
4Independent separately is the alkyl of hydrogen, C1-C4, haloalkyl or the halogen of C1-C4, R
5-R
8Independent separately is the alkyl of hydrogen or C1-C4; More preferably, R
1-R
5And R
7Independent separately is hydrogen, methyl, halogenated methyl or halogen, R
6And R
8Alkyl for C4.The alkyl of described replacement or unsubstituted C1-C8 for example can be the substituted radical of 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 the above-mentioned group after being replaced by halogen, nitro, amido.Described halogenated methyl is preferably the fluoro methyl, trifluoromethyl more preferably, and described halogen is preferably fluorine, chlorine or bromine.
The present inventor finds under study for action, by specific R
1-R
8Can obtain fabulous catalytic effect when cooperating the salicylic aldehyde pyridine imine titanous chloride title complex form as catalyzer, therefore, preferably,
R
1-R
5And R
7Be hydrogen; R
6And R
8Be the tertiary butyl; Perhaps
R
1, R
3, R
4, R
5And R
7Be hydrogen; R
2Be methyl; R
6And R
8Be the tertiary butyl; Perhaps
R
1, R
2, R
4, R
5And R
7Be hydrogen; R
3Be methyl; R
6And R
8Be the tertiary butyl; Perhaps
R
2, R
4, R
5And R
7Be hydrogen; R
1And R
3Be methyl; R
6And R
8Be the tertiary butyl; Perhaps
R
1, R
3, R
5And R
7Be hydrogen; R
2Be trifluoromethyl; R
4Be chlorine; R
6And R
8Be the tertiary butyl.。
The preparation method of salicylic aldehyde pyridine imine titanous chloride title complex provided by the present invention may further comprise the steps:
(1) under the aldimine condensation reaction conditions, the 2-amido pyridine type compound of structure shown in the salicylic aldehyde of structure shown in the formula (II) and the formula (III) is carried out the first contact reacts, obtain the pyridine imine compound shown in the formula (IV);
Wherein, R
1-R
8Definition identical with above-mentioned formula (I).
(2) under protection of inert gas, drying solution and the metal hydride of the pyridine imine compound shown in the formula (IV) carried out the second contact reacts under-25 ℃ to 25 ℃ temperature, obtain suspension liquid;
(3) under-78 ℃ to 25 ℃ temperature, make above-mentioned suspension liquid and TiCl
4(THF)
2Under the complex reaction condition, carry out the 3rd contact reacts after mixing.
The present invention is not particularly limited the add-on of salicylic aldehyde described in the step (1) and described 2-pyridine amine, and under the preferable case, the mol ratio of described salicylic aldehyde and described 2-pyridine amine can be 1: 1-1.2, more preferably 1: 1-1.1.
According to the present invention, in the step (1), the aldimine condensation reaction is a kind of reaction well known in the art, therefore the 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, described the first contact reacts is preferably carried out described aldimine condensation reaction under microwave irradiation condition comprises that the frequency of microwave is 300MHz-300GHz, is preferably 300-1200MHz; The salicylic aldehyde of structure shown in the formula with respect to 1 mole (II), the power of microwave exposure is 50-800W, is preferably 100-300W.The prolongation in reaction times is conducive to the raising of the yield of the transformation efficiency of reactant or reaction product, but long transformation efficiency or the increase rate of the yield of reactant and not obvious to reactant of reaction times, therefore, generally speaking, reaction times can be 0.1-20 minute, is preferably 2-16 minute.
For the reaction that makes step (1) is carried out more smoothly, under the preferable case, the mode of described microwave exposure comprises carries out first the first microwave exposure, carry out the second microwave exposure after being cooled to 10-35 ℃, the frequency of the microwave of described the first microwave exposure is 300MHz-300GHz, is preferably 300-1200MHz; The salicylic aldehyde of structure shown in the formula with respect to 1 mole (II), 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; The frequency of the microwave of described the second microwave exposure is 300MHz-300GHz, is preferably 300-1200MHz; The salicylic aldehyde of structure shown in the formula with respect to 1 mole (II), 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 for conditioned reaction speed, under the preferable case, in the step (1), described the first contact reacts is carried out in the presence of organic solvent.Organic solvent described herein can be the organic solvent of various routines known in those skilled in the art mainly as reaction medium.Under the preferable case, described organic solvent is selected from one or more in toluene, acetone, ethyl acetate, benzene, dimethylbenzene, methylene dichloride and the trichloromethane, 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 the formula (II).
According to the present invention, in step (1), in order to obtain pure product, method provided by the invention can also comprise that the crude product to gained carries out purifying.The method of described purifying can adopt and well known to a person skilled in the art various purification process, under the 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, for example, the used solvent of recrystallization can for being selected from ethanol, acetone, the hexane one or more, be preferably ethanol.
According to the present invention, in the step (2), the product of described step (1) gained and the mol ratio of described metal hydride can change in very wide scope, under the 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 hydrides, is preferably selected from potassium hydride KH and the sodium hydride one or more.
According to the present invention, solvent described in the step (2) in the drying solution of the pyridine imine compound shown in the formula (IV) can be the organic solvent of various routines known in those skilled in the art, for example can be in toluene, ethyl acetate, benzene, tetrahydrofuran (THF), dimethylbenzene, methylene dichloride and the trichloromethane one or more, more preferably toluene.
The of the present invention second catalytic condition can be the reaction conditions of this area routine, and under the preferable case, the described second catalytic condition comprises that temperature of reaction is 5 ℃ to 20 ℃, and the reaction times is preferably 2-6 hour.
In the step (3), under the preferable case, the reaction product of described step (2) gained is pyridine imine compound and the TiCl shown in the formula (IV)
4(THF)
2Mol ratio be 1: 1-1.2, more preferably 1: 1-1.1.When step (1) with step (2) is fully carried out and step (1) and step (2) products therefrom when all reacting for next step, also can be according to feeding intake feeding intake of determining step (2) and step (3) in the step (1).
The described the 3rd catalytic condition comprises that temperature of reaction is preferably-70 ℃ to 20 ℃, more preferably-65 ℃ to 10 ℃; Reaction times is preferably 4-24 hour, more preferably 8-14 hour.
The present invention also provides according to the application of above-mentioned salicylic aldehyde pyridine imine titanous chloride title complex in ethylene polymerization.
In addition, the present invention also provides a kind of method of ethylene polymerization, the method is included in organic solvent, promotor and Primary Catalysts and exists under lower and the olefinic polymerization condition, makes olefinic polymerization, and described alkene is ethene or contains ethene and the mixture of the alpha-olefin of C4-C10; It is characterized in that, described Primary Catalysts is salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention.
The present invention is not particularly limited the consumption of described catalyzer, but consider from combined factors such as the molecular weight of the polymkeric substance of polymerization rate, generation and production costs, under the preferable case, the mol ratio of described catalyzer and described alkene is 0.01-0.1: 100, and 0.05-0.8 more preferably: 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 the preferable case, described polyreaction is carried out in inert atmosphere, described inert atmosphere refers to not and reactant and any one gas of product generation chemical reaction or the mixture of gas, such as in nitrogen, helium and the periodic table of elements zero group gas one or more.The condition of described polyreaction comprises temperature of reaction, reaction pressure and reaction times, and for example, described temperature of reaction can be 0-150 ℃, is preferably 20-100 ℃; 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 present invention is not particularly limited the kind of described promotor, as long as can improve the activity of described catalyzer, polymerization rate is increased get final product.In the preferred case, described promotor is selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls and the haloalkyl aluminium.Described aikyiaiurnirsoxan beta is selected from methylaluminoxane (MAO), modified methylaluminoxane (MMAO) such as in part tertiary butyl modification MAO, ethylaluminoxane and the isobutyl aluminium alkoxide one or more, and above-mentioned aikyiaiurnirsoxan beta all can obtain from commercial channels.Above-mentioned aikyiaiurnirsoxan beta can produce by the hydrolytic action of various trialkyl aluminium compounds commonly used, and for example, MMAO can produce by the hydrolytic action of trimethyl aluminium and more senior trialkylaluminium such as triisobutyl aluminium.Described aluminum alkyls is selected from one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and the tri-n-octylaluminium.Described haloalkyl aluminium can be selected from one or more in chlorination aluminum alkyls, bromination aluminum alkyls and the iodate aluminum alkyls; Wherein, described chlorination aluminum alkyls can be selected from again one or more in diethylaluminum chloride, sesquialter ethyl aluminum chloride and the ethylaluminium dichloride.
According to the present invention, the mol ratio of the metal titanium in the metallic aluminium in the described promotor and the described catalyzer can change within a large range, and under the preferable case, described mol ratio is 500-10000: 1, and further preferred 3500-8000: 1.
Under the preferable case, be 0.5-5 % by mole ethylene copolymer in order to obtain alpha-olefin structural unit content (also claim " the insertion rate of alpha-olefin "), the mol ratio of the mixture of the described alpha-olefin that contains 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 a in 1-hexene, 1-octene and the butylene.
According to the present invention, described organic solvent for ethylene polymerization can be the organic solvent of this area routine, is preferably selected from toluene, methylene dichloride and the hexane one or more, more preferably toluene.
Catalyzer of the present invention is synthetic simple, and can be for the synthesis of molecular weight controlled linear polyolefin in a big way.
The below will be described in further detail the present invention by embodiment.
Used reagent is commercially available chemically pure reagent in embodiment and the Comparative Examples.
Polyolefinic weight-average molecular weight and molecular weight distribution all obtain by gel permeation chromatography in embodiment and the Comparative Examples; The insertion rate of alpha-olefin carries out integration and analyzes ownership calculating to the peak by the pyrocarbon spectrogram of polymkeric substance, but concrete reference literature [quantitative
13C NMR analysis of sequence distributions in poly (ethylene-co-1-hexene, Anal.Chem.2004,76,5734-5747].
Embodiment 1-5 is used for illustrating the preparation of salicylic aldehyde pyridine imine titanous chloride title complex provided by the invention
Embodiment 1
1) with 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde and 0.94g (10mmol) PA mixes, placing frequency is the microwave oven of 800MHz, after heating 1 minute under the middle high fire (power of microwave exposure is 200W), take out and be cooled to room temperature, in the lower heating of middle high fire 1 minute, get reddish black liquid again.Use ethyl alcohol recrystallization, obtain 2.52g safran crystal 3,5-di-tert-butyl salicylaldehyde 2-pyridine imine, productive rate 81.2%.
With IR,
1H NMR,
13C NMR, ultimate analysis characterize the product structure of gained, and the 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).
1H?NMR：(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).
13C?NMR：(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.
By the above results as can be known, the gained compound is compound shown in the formula (IV).
2) under 20 ℃, the toluene solution 100mL of 3,5-di-tert-butyl salicylaldehyde 2-pyridine imine (0.324g, 1mmol) is dripped in the KH of 1mmol, stirring reaction 12 hours obtains yellow suspension liquid.
3) under-78 ℃, add the TiCl of yellow powder shape in the above-mentioned suspension liquid
4(THF)
2(0.334g, 1mmol) allows system slowly rise to room temperature, continues to stir 24 hours.The product that generates obtains 0.25g 3 after silica gel chromatography column purification (eluent be volume ratio ethyl acetate/petroleum ether=1: 10) drying, 5-di-tert-butyl salicylaldehyde-2-pyridine imine-titanous chloride title complex is designated as Primary Catalysts C1, and productive rate is 49%.
The structural confirmation data of this title complex are as follows:
1H?NMR(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).
13C?NMR：(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.
But this complex structure is correct as can be known by upper result, is title complex shown in the formula (I).
Embodiment 2
1) with 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde and 1.08g (10mmol) 2-amino-5-picoline mixes, placing frequency is the microwave oven of 800MHz, heating is taken out after 2 minutes and is cooled to room temperature under middle high fire, in the lower heating of middle high fire 2 minutes, get reddish black liquid again.Use ethyl alcohol recrystallization, obtain 2.36g safran crystal 3,5-di-tert-butyl salicylaldehyde-2-pyridine-5-methylene imine, productive rate 73.8%.
With IR,
1H NMR,
13C NMR, ultimate analysis characterize the product structure of gained, and the 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).
1H?NMR：(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).
13C?NMR：(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.
By the above results as can be known, the gained compound is compound shown in the formula (IV).
2) under-10 ℃, the toluene solution 100mL of 3,5-di-tert-butyl salicylaldehyde-2-pyridine-5-methylene imine (0.338g, 1mmol) is dripped in the KH of 1mmol, stirring reaction 6 hours obtains yellow suspension liquid.
3) under-50 ℃, add the TiCl of yellow powder shape in the above-mentioned suspension liquid
4(THF)
2(0.334g, 1mmol) allows system slowly rise to room temperature, continues to stir 12 hours.The product that generates obtains 0.46g 3 after silica gel chromatography column purification (eluent be volume ratio ethyl acetate/petroleum ether=1: 10) 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 structural confirmation data of this title complex are as follows:
1H?NMR：(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).
13C?NMR：(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.
But this complex structure is correct as can be known by upper result, is title complex shown in the formula (I).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 three tooth title complexs, is comprised of a part and three chlorine atoms around the metal.
Embodiment 3
1) with 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde and 1.08g (10mmol) 4-methyl-2-amino pyridine mixes, placing frequency is the microwave oven of 800MHz, heating is taken out after 2 minutes and is cooled to room temperature under middle high fire, in the lower heating of middle high fire 8 minutes, get reddish black liquid again.Use 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,
1H NMR,
13C NMR, ultimate analysis characterize the product structure of gained, and the 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).
1H?NMR：(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).
13C?NMR：(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.
By the above results as can be known, the gained compound is compound shown in the formula (IV).
2) under-10 ℃, the tetrahydrofuran solution 100mL of 3,5-di-tert-butyl salicylaldehyde-2-pyridine-4-methylene imine (0.338g, 1mmol) directly is added drop-wise among the KH of 1mmol, stirring reaction 4 hours obtains yellow suspension liquid.
3) under 0 ℃, add the TiCl of yellow powder shape in the above-mentioned suspension liquid
4. (THF)
2(0.334g, 1mmol) allows system slowly rise to room temperature, continues to stir 8 hours.The product that generates obtains 0.78g 3 after silica gel chromatography column purification (eluent be volume ratio ethyl acetate/petroleum ether=1: 10) 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 structural confirmation data of this title complex are as follows:
1H?NMR：(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).
13C?NMR：(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.
But this complex structure is correct as can be known by upper result, is title complex shown in the formula (I).
Embodiment 4
1) with 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde and 1.22g (10mmol) 4,6-dimethyl-PA mixes, placing frequency is the microwave oven of 800MHz, heating is taken out after 2 minutes and is cooled to room temperature under middle high fire, in the lower heating of middle high fire 4 minutes, get reddish black liquid again, use ethyl alcohol recrystallization.Obtain 2.04g yellow solid 3,5-di-tert-butyl salicylaldehyde-2-pyridine-4,6-dimethyl imines, productive rate are 59.2%.
With IR,
1H NMR,
13C NMR, ultimate analysis characterize the product structure of gained, and the 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).
1H?NMR：(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).
13C?NMR：(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.
By the above results as can be known, the gained compound is compound shown in the formula (IV).
2) under 0 ℃, with 3,5-di-tert-butyl salicylaldehyde-2-pyridine-4, the dichloromethane solution 100mL of 6-dimethyl imines (0.338g, 1mmol) drips in the KH of 1mmol, and stirring reaction 2 hours obtains yellow suspension liquid.
3) under-10 ℃, add the TiCl of yellow powder shape in the above-mentioned suspension liquid
4. (THF)
2(0.334g, 1mmol) allows system slowly rise to room temperature, continues to stir 6 hours.The product that generates obtains 0.84g 3 after silica gel chromatography column purification (eluent be volume ratio ethyl acetate/petroleum ether=1: 10) purifying drying, 5-di-tert-butyl salicylaldehyde-2-pyridine-4,6-dimethyl imines-titanous chloride title complex is designated as Primary Catalysts C4, and productive rate is 82.2%.
The structural confirmation data of this title complex are as follows:
1H?NMR(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).
13C?NMR：(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.
But this complex structure is correct as can be known by upper result, is title complex shown in the formula (I).The crystalline structure of this title complex as shown in Figure 2, as seen from the figure, this crystalline structure and title complex C2 are very similar, also are the title complexs of N^N^O tridentate ligand.Metal center and part have formed octahedral chelate structure.
Embodiment 5
1) with 2.34g (10mmol) 3,5-di-tert-butyl salicylaldehyde and 1.98g (10mmol) 3-chlorine 5-trifluoromethyl PA mixes, placing frequency is the microwave oven of 800MHz, heating is taken out after 0.5 minute and is cooled to room temperature under middle high fire, in the lower heating of middle high fire 0.5 minute, get reddish black liquid again.Use 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,
1H NMR,
13C NMR, ultimate analysis characterize the product structure of gained, and the 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).
1H?NMR：(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).
13C?NMR：(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.
By the above results as can be known, the gained compound is compound shown in the formula (IV).
2) under-10 ℃, the toluene solution 100mL of 3,5-di-tert-butyl salicylaldehyde-3-chlorine 5-trifluoromethyl PA imines (0.377g, 1mmol) is dripped in the KH of 1mmol, stirring reaction 4 hours obtains yellow suspension liquid.
3) under 25 ℃, add the TiCl of yellow powder shape in the above-mentioned suspension liquid
4. (THF)
2(0.334g, 1mmol) allows system slowly rise to room temperature, continues to stir 4 hours.The product that generates obtains 0.47g 3 after silica gel chromatography column purification (eluent be volume ratio ethyl acetate/petroleum ether=1: 10) 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 structural confirmation data of this title complex are as follows:
1H?NMR：(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).
13C?NMR：(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.
But this complex structure is correct as can be known by upper result, is title complex shown in the formula (I).
Comparative Examples 1
This Comparative Examples is used for the preparation of explanation reference title complex.
According to document [G.Paolucci, A.Zanella, L.Sperni, V.Bertolasi, M.Mazzeoc, C.Pellecchia.Tridentate[N, N, O] Schiff-base group 4metal complexes:Synthesis, structural characterization and reactivity in olefin polymerization[J] .2006,258:275-283] disclosed method prepares the title complex C of structure shown in formula V
20H
19Cl
3N
2OTi is designated as Primary Catalysts DC1.
Embodiment 6-32 is used for illustrating the method for ethylene polymerization provided by the invention.
Embodiment 6
The present embodiment is used for illustrating 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 the control temperature is 20 ℃; pressure is 2MPa; then add 10.3mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C4; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Comparative Examples 2
Under nitrogen protection, the toluene of 90mL is joined in the stainless steel autoclave of 250mL, when the control temperature is 20 ℃; pressure is 1MPa; then in system, add the toluene solution that 10mL contains 5 μ mol Primary Catalysts C4, the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 0.01mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains settled solution, does not have polymkeric substance to generate.
Embodiment 7
The present embodiment is used for illustrating 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 the control temperature is 40 ℃; pressure is 1MPa; then add 13.7mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C4; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 20 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 80 ℃; pressure is 0.1MPa; then add 17.1mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C4; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 20 ℃; pressure is 1MPa; then add 20.5mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring begins, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 20 ℃; pressure is 1MPa; then add 23.9mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 20 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 20 ℃; pressure is 0.5MPa; then add 27.4mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 20 ℃; pressure is 0.1MPa; then add 17.1mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.The polymerization activity of resulting polymers, weight-average molecular weight, molecular weight distribution is as shown in table 1.
The present embodiment is used for illustrating 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 the control temperature is 40 ℃; pressure is 1MPa; then add 17.1mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring begins, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 50 ℃; pressure is 2MPa; then adding 17.1mL concentration in the system is the MAO toluene solution of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 70 ℃; pressure is 3MPa; then add 17.1mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring begins, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 80 ℃; pressure is 1MPa; then add 17.1mL concentration in the system and be the toluene solution of MAO of 1.46mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C3; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 30 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
Comparative Examples 3
Method according to embodiment 16 prepares polyolefine, and different is that Primary Catalysts C3 replaces with the title complex DC1 that Comparative Examples 1 makes, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 16 prepares polyolefine, and different is that Primary Catalysts C3 replaces with Primary Catalysts C2, obtains polyolefine.Polymerization activity, the weight-average molecular weight of resulting polymers, molecular weight distribution is as shown in table 1.
The present embodiment is used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 16 prepares polyolefine, and different is that Primary Catalysts C3 replaces with Primary Catalysts C1, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 16 prepares polyolefine, and different is that Primary Catalysts C3 replaces with Primary Catalysts C4, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 16 prepares polyolefine, and different is that Primary Catalysts C3 replaces with Primary Catalysts C5, 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 used for illustrating 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 the control temperature is 50 ℃; pressure is 1MPa; then adding 17.1mL concentration in the system is the toluene solution of the MAO of 1.46mol/L; 1.2mL concentration is the 1-hexene of 0.1mol/L and the toluene solution that 10ml contains 5 μ mol Primary Catalysts C5, the beginning mechanical stirring begins, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 Examples 4
Under nitrogen protection; the toluene of 72.3mL is joined in the stainless steel autoclave of 250mL; when the control temperature is 50 ℃; pressure is 1MPa; then adding 1.2mL concentration in the system is the 1-hexene of 0.1mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C5; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains settled solution, does not have polymkeric substance to generate.
Embodiment 22
The present embodiment is used for illustrating 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 the control temperature is 20 ℃; pressure is 1MPa; then adding 17.1mL concentration in the system is the toluene solution of the MAO of 1.46mol/L; 3.6mL concentration is the 1-hexene of 0.3mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C5, the beginning mechanical stirring, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 80 ℃; pressure is 0.1MPa; then adding 17.1mL concentration in the system is the toluene solution of the MAO of 1.46mol/L; 12mL concentration is the 1-hexene of 1.0mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C5, and the beginning mechanical stirring begins, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 used for illustrating 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 the control temperature is 50 ℃; pressure is 1MPa; then adding 17.1mL concentration in the system is the toluene solution of the MAO of 1.46mol/L; 3.6mL concentration is the 1-hexene of 0.3mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C1, the beginning mechanical stirring keeps 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 Examples 5
Method according to embodiment 24 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Comparative Examples 1 prepared title complex DC1, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 24 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C2, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 24 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C3, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 24 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C4, 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 used for illustrating 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 the control temperature is 50 ℃; pressure is 1MPa; then adding 17.1mL concentration in the system is the toluene solution of the MAO of 1.46mol/L; 4.8mL concentration is the 1-octene of 0.3mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C1, the beginning mechanical stirring, and keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains polymer precipitation, respectively washs 3 times with the second alcohol and water, and vacuum drying is to constant weight, weighing.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 Examples 6
Under nitrogen protection; the toluene of 69.7mL is joined in the stainless steel autoclave of 250mL; when the control temperature is 50 ℃; pressure is 1MPa; then adding 4.8mL concentration in the system is the 1-octene of 0.3mol/L and the toluene solution that 10mL contains 5 μ mol Primary Catalysts C1; the beginning mechanical stirring, keeping rotating speed is 500 rev/mins.When polymerization temperature is stablized, in reactor, be filled with 30mol ethene, polyreaction begins, stirring reaction 15 minutes.Ethanolic soln neutralization reaction liquid with 5 % by weight hcl acidifyings obtains settled solution, does not have polymkeric substance to generate.
Comparative Examples 7
Method according to embodiment 28 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Comparative Examples 1 prepared title complex, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 28 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C2, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 28 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C3, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 28 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C4, 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 used for illustrating the method for ethylene polymerization of the present invention.
Method according to embodiment 28 prepares polyolefine, and different is that Primary Catalysts C1 replaces with Primary Catalysts C5, 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
Annotate: "---" expression non-polymer generates and maybe can't survey this index in the upper table.
As seen from Table 1, the salicylic aldehyde pyridine imine titanous chloride title complex that is prepared by the present invention has higher catalytic activity, can reach 721kgmol
-1(Ti) h
-1By the contrast of embodiment 16 with Comparative Examples 3, the contrast of embodiment 21 and Comparative Examples 4, the contrast of embodiment 24 and Comparative Examples 5, and embodiment 28 can find out with the contrast of Comparative Examples 7, adopt catalyzer of the present invention to have higher initiating activity, well the copolymerization of the homopolymerization of catalyzed ethylene or ethene and alpha-olefin mixture.
Claims (12)
1. a salicylic aldehyde pyridine imine titanous chloride title complex is characterized in that, described title complex has the structure shown in the formula (I);
Wherein, R
1-R
8Independent separately is alkyl or the halogen of hydrogen, replacement or unsubstituted C1-C8; Preferably, R
1-R
4Independent separately is the alkyl of hydrogen, C1-C4, haloalkyl or the halogen of C1-C4, R
5-R
8Independent separately is the alkyl of hydrogen or C1-C4; More preferably, R
1-R
5And R
7Independent separately is hydrogen, methyl, halogenated methyl or halogen, R
6And R
8Alkyl for C4.
2. title complex according to claim 1, wherein,
R
1-R
5And R
7Be hydrogen; R
6And R
8Be the tertiary butyl; Perhaps
R
1, R
3, R
4, R
5And R
7Be hydrogen; R
2Be methyl; R
6And R
8Be the tertiary butyl; Perhaps
R
1, R
2, R
4, R
5And R
7Be hydrogen; R
3Be methyl; R
6And R
8Be the tertiary butyl; Perhaps
R
2, R
4, R
5And R
7Be hydrogen; R
1And R
3Be methyl; R
6And R
8Be the tertiary butyl; Perhaps
R
1, R
3, R
5And R
7Be hydrogen; R
2Be trifluoromethyl; R
4Be chlorine; R
6And R
8Be the tertiary butyl.
3. the preparation method of a salicylic aldehyde pyridine imine titanous chloride title complex, the method may further comprise the steps:
(1) under the aldimine condensation reaction conditions, the 2-amido pyridine type compound of structure shown in the salicylic aldehyde of structure shown in the formula (II) and the formula (III) is carried out the first contact reacts, obtain the pyridine imine compound shown in the formula (IV);
Wherein, R
1-R
8Independent separately is hydrogen, replacement or unsubstituted alkyl or halogen; Preferably, R
1-R
4Independent separately is the alkyl of hydrogen, C1-C4, haloalkyl or the halogen of C1-C4, R
5-R
8Independent separately is the alkyl of hydrogen or C1-C8;
(2) under protection of inert gas, drying solution and the metal hydride of the pyridine imine compound shown in the formula (IV) carried out the second contact reacts under-25 ℃ to 25 ℃ temperature, obtain suspension liquid;
(3) under-78 ℃ to 25 ℃ temperature, make above-mentioned suspension liquid and TiCl
4(THF)
2Under the complex reaction condition, carry out the 3rd contact reacts after mixing.
4. preparation method according to claim 3, wherein, in the step (1), described the first contact reacts is carried out under microwave exposure, the mode of described microwave exposure comprises carries out first the first microwave exposure, carry out the second microwave exposure after being cooled to 10-35 ℃, the frequency of the microwave of described the first microwave exposure is 300MHz-300GHz, is preferably 300-1200MHz; 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; The frequency of the microwave of described the second microwave exposure is 300MHz-300GHz, is preferably 300-1200MHz; 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.
5. according to claim 3 or 4 described preparation methods, wherein, in the step (1), the mol ratio of described salicylic aldehyde and described 2-pyridine amine is 1: 1-1.2.
6. preparation method according to claim 3, wherein, in the step (2), the mol ratio of the pyridine imine compound shown in the formula (IV) and metal hydride is 1: 1-1.2, the second catalytic time was 2-12 hour.
7. according to claim 3 or 6 described preparation methods, wherein, in the 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; The second catalytic temperature is-20 ℃ to-80 ℃, and the time is 2-6 hour
8. preparation method according to claim 3, wherein, in the step (3), the described the 3rd catalytic time was 4-24 hour, was preferably 8-14 hour, temperature is-60 ℃ to-85 ℃.
9. according to claim 3 or 8 described preparation methods, wherein, in the step (3), pyridine imine compound and the TiCl shown in the described formula (IV)
4(THF)
2Mol ratio be 1: 1-1.2.
10. the application of the described salicylic aldehyde pyridine imine of any one titanous chloride title complex in ethylene polymerization among the claim 1-2.
Exist under lower and the olefinic polymerization condition 11. the method for an ethylene polymerization, the method are included in organic solvent, promotor and Primary Catalysts, make olefinic polymerization, described alkene is ethene or contains ethene and the mixture of the alpha-olefin of C4-C10; It is characterized in that, described Primary Catalysts is the described salicylic aldehyde pyridine imine of any one among claim 1-2 titanous chloride title complex.
12. method according to claim 11, wherein, described promotor is selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls and the haloalkyl aluminium; The mol ratio of the metal titanium in the metallic aluminium in the described promotor and the described catalyzer is 500-10000: 1, and preferred 3500-8000: 1.
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| CN109517097B (en) * | 2018-11-27 | 2021-07-30 | 山东鲁晶化工科技有限公司 | Polyolefin catalyst, preparation method and application thereof |
| CN112661893A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Main catalyst for copolymerization of ethylene and cycloolefin, and polymerization method and application thereof |
| CN112661893B (en) * | 2019-10-16 | 2023-12-08 | 中国石油化工股份有限公司 | Main catalyst for copolymerization of ethylene and cycloolefin, polymerization method and application thereof |
| CN111205317A (en) * | 2020-02-19 | 2020-05-29 | 山东京博中聚新材料有限公司 | Novel [ ONN ] tridentate fourth subgroup metal complex and preparation method and application thereof |
| CN111205317B (en) * | 2020-02-19 | 2023-02-21 | 山东京博中聚新材料有限公司 | Novel [ ONN ] tridentate fourth subgroup metal complex and preparation method and application thereof |
| CN111747995A (en) * | 2020-07-30 | 2020-10-09 | 上海化工研究院有限公司 | Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof |
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