CN105906747B - A kind of salicylaldiminato titanium complex and its preparation method and application containing terminal double bond - Google Patents
A kind of salicylaldiminato titanium complex and its preparation method and application containing terminal double bond Download PDFInfo
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- CN105906747B CN105906747B CN201610236912.8A CN201610236912A CN105906747B CN 105906747 B CN105906747 B CN 105906747B CN 201610236912 A CN201610236912 A CN 201610236912A CN 105906747 B CN105906747 B CN 105906747B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
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- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
Abstract
The invention discloses a kind of salicylaldiminato titanium complex and its preparation method and application containing terminal double bond.The preparation method of the catalyst is by the ligand containing terminal double bond to pull out hydrogen through n-BuLi, then be coordinated with titanium tetrachloride and slough lithium chloride and react to obtain.And ligand is made with containing fluoroaniline by condensation reaction by the salicylide containing terminal double bond.Since group is introduced in suitable position, such catalyst activity in catalyzed ethylene polymerization is very high, has very strong control force to chain tra nsfer, can prepare ultra-high molecular weight polyethylene.Ethylene homo is catalyzed in the case where methylaluminoxane is as co-catalyst and normal pressure, activity is up to 1.6 × 107gPE·mol‑1Ti·h‑1, prepared molecular weight of polyethylene is 3,000,000 or more, and narrow molecular weight distribution, product property is uniform, can be applied to by gel spinning in high-end field, such as flak jackets and offshore platform hawser.
Description
Technical field
The invention belongs to olefin coordination polymerization field, be related to the Phenoxy-imine ligand containing terminal double bond synthesis and by its with
The preparation method of titanium coordination composition olefin polymerization catalysis and its application in terms of synthesizing super high molecular weight polyethylene.
Background technique
Molecular weight has highly important influence for the performance of polyethylene product, additional as the height in polythene material
It is worth product, ultra-high molecular weight polyethylene shows many attracting advantageous properties, and if density is small (extremely light), brilliant low temperature is anti-
Punching property, high intensity, perfect resist chemical performance, powerful radiation resistance, excellent moisture-proof, wear resistence, compared with
Low dielectric constant and brilliant anti-ballistic performance.Therefore, ultra-high molecular weight polyethylene is widely used in artificial skelecton, artificial limb,
The helmet, flak jackets, the protective armor, fishing line, the various fields such as reinforced door of cockpit on offshore platform hawser and aircraft.
Currently, the catalyst of production super high molecular weight mainly has three classes.The first kind is Z-N catalyst, and the technique for preparing UHMWPE is originated from
The production technology of HDPE, only different on specific process detail, Z-N catalyst is the mainstream catalysis for producing UHMWPE
Agent, most of UHMWPE product all produce (Macromol.Symp., 2008,274,148-153) by it.Second class is metallocene
Catalyst, for producing high-performance UHMWPE (S.T.Wang, M.OH, US0293562A1,2008.).Third class be the new century with
Come the non-metallocene catalyst gradually developed, it can be precisely controlled the micro-structure and accumulation shape of UHMWPE, had potential high
It holds application value (Chem.Rev., 2011,111,2363-2449).However, produced using traditional catalyst
UHMWPE comes with some shortcomings in performance.The UMMWPE molecular weight distribution of Z-N catalyst synthesis is very wide (5~20), chain structure
Inhomogenous and chain entanglement degree is high, be also easy to produce in thermoforming processing melt body defect and crystal boundary (Biomacromolecules,
2005,6,942-947) a large amount of low molecular weight components, are had in gel spinning and are preferentially dissolved in decahydronaphthalene, and then reduce macromolecule
Measure the solubility of component, the final mechanical property for influencing UHMWPE fiber.The UHMWPE of Z-N catalyst preparation as knee joint/
Easily division generation sub-micron grade particle enters human body to hipbone alternative materials in use for some time, causes all kinds of inflammation, this
Class UHMWPE chain structure is inhomogenous and the short disadvantage of service life hinders it in the application of high-end field.Use metallocene catalysis
Agent can obtain that chain structure is more uniform, the relatively narrow UHMWPE of molecular weight distribution, but metallocene catalyst is to polymer molecular weight
Control is not so good as Z-N catalyst, and cost needed for reaching equivalent molecule amount is higher, it is difficult to industrially promote.1998, Mitsui Chemicals
Company develops a series of adjacent fluorine substituted type benzene oxygen imine catalysts, and this kind of catalyst activity is high, can be effective in polymerization process
Inhibit chain tra nsfer, and Z-N catalyst is better than to the control of polymer molecular weight, it can synthetic molecular weight narrow distribution, chain structure
Uniform UHMWPE product.
Since adjacent fluorine-type benzene oxygen imine catalyst is spread with the growth of polymerization time in the course of the polymerization process, ligand structure
The influence of the factors such as stability, " activity " speciality are difficult to protect this for a long time, and synthesized molecular weight of polyethylene distribution is inevitable
Ground broadens, and the growth of molecular weight of polyethylene is also restrained, and then influences its processing performance.Some researchers are using modification catalysis
The mode (J.Polym.Sci.Pol.Chem., 2013,51,1630-1635) of agent component, it is suppressed that molecular weight of polyethylene distribution
Polydispersion trend and chain entanglement behavior, achieve certain effect.
Summary of the invention
The first purpose of this invention is to overcome the defect of existing above-mentioned technology, is provided a kind of for narrow point of synthetic molecular weight
The synthetic method of the salicylaldiminato catalyst of the stable structure of cloth UHMWPE.
A second object of the present invention is to provide the preparation methods of the salicylaldiminato catalyst containing terminal double bond.
Third object of the present invention is to be used for the salicylaldiminato catalyst for containing terminal double bond applied to olefinic polymerization
Prepare UHMWPE.
A kind of salicylaldiminato titanium complex containing terminal double bond, shown in structure such as formula (1):
In formula (1), R1For CH2=CH-A-, A C1~C8Alkyl, R2And R3It is all hydrogen；Alternatively, R1For C1~C4Alkyl, R2
For allyloxy, R3For fluorine.
In the present invention, since group is introduced in suitable position, such catalyst activity in catalyzed ethylene polymerization is very high,
There is very strong control force to chain tra nsfer, ultra-high molecular weight polyethylene can be prepared.In methylaluminoxane as co-catalyst and normal pressure
Lower catalysis ethylene homo, activity is up to 1.6 × 107gPE·mol-1Ti·h-1, prepared molecular weight of polyethylene up to 3,000,
000 or more, narrow molecular weight distribution, product property is uniform, can be applied to by gel spinning technique in high-end field, such as shellproof
Clothing and offshore platform hawser.The feature that the present invention has catalyst synthetic route short, easy to operate, only by introducing terminal double bond
Catalyst performance can be improved, prepare ultra-high molecular weight polyethylene product, and prepared ultra-high molecular weight polyethylene is chaining
Homogeneity on structure is better than traditional Z-N catalyst and metallocene catalyst, even better than the benzene oxygen imines catalysis of traditional structure again
Agent, high added value, differentiated products exploitation on have significant advantage.
Preferably, R1For allyl, 3- alkene butyl, 4- alkene amyl, 5- alkene hexyl, 6- alkene heptyl or 7- alkene octyl, R2For
Hydrogen, R3For hydrogen；
Or R1For methyl, isopropyl or tert-butyl, R2For allyloxy, R3For fluorine.
The present invention provides the preparation methods of the salicylaldiminato titanium complex described in one kind, include the following steps:
(1) group containing terminal double bond is introduced on salicylide ring by directly purchase or nucleophilic substitution；
(2) molar ratio that 1:1~5 are pressed by the salicylide containing terminal double bond and containing fluoroaniline, is to urge with p-methyl benzenesulfonic acid
Agent, reaction obtain the ligand containing terminal double bond；
(3) Phenoxy-imine ligand containing terminal double bond is reacted with ether dissolution with n-BuLi, then with titanium tetrachloride
Reaction obtains the salicylaldiminato titanium complex.
Specific preparation process is as follows:
1) it is directly commercially available the water sample aldehyde that benzene oxygen ortho position is replaced by allyl, substituted type quinhydrones and allylic alkylation halogen are pressed 1:
The molar ratio of 1~1:10, using potassium iodide as catalyst, acetonitrile is solvent, 1-8h is stirred to react at 40-120 DEG C, through extracting
Take, precipitate and chromatogram column technique obtains the phenol of allyloxy substitution, then phenol that allyl is replaced with paraformaldehyde by 1:3~1:15
Molar ratio, using magnesium chloride as catalyst, tetrahydrofuran is solvent, be stirred to react 3-12h at 40-100 DEG C, through extraction and
Column chromatography obtains the salicylide of allyloxy substitution；
2) molar ratio that 1:1~1:5 is pressed by the salicylide containing terminal double bond and containing fluoroaniline, is to urge with p-methyl benzenesulfonic acid
Agent, ethyl alcohol are solvent, are stirred to react 2-10h at 30-90 DEG C, through chromatography post separation, are recrystallized to give containing terminal double bond
Ligand；
3) under the conditions of anhydrous and oxygen-free, by the Phenoxy-imine ligand containing terminal double bond with ether dissolution, with n-BuLi
1:1~1:2 reacts in molar ratio, and then 1:1~1:1.5 reacts in molar ratio with titanium tetrachloride, is filtered, and is concentrated, washing etc.
Step obtains complex.
The present invention also provides a kind of preparation methods of polyethylene, comprising the following steps:
In the presence of the salicylaldiminato titanium complex, polymerization reaction occurs for ethylene, obtains the polyethylene.
Preferably, polymerization reaction carries out in a solvent, solvent for use is in toluene, chlorobenzene, n-hexane or isoparaffin
One or more.
Preferably, polymerization reaction carries out under the conditions of strength mechanical stirring or magnetic agitation, revolving speed is 50~
1000rpm。
Preferably, polymerization reaction also requires that co-catalyst is added, co-catalyst used is aikyiaiurnirsoxan beta, alkyl aluminum or chlorine
Change one or more of alkyl aluminum.
As a further preference, aikyiaiurnirsoxan beta is methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide；Alkyl aluminum is
Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or tri-n-octylaluminium；Chlorination alkyl aluminum is aluminium diethyl monochloride, ethyl aluminum dichloride
Or sesquialter ethylmercury chloride aluminium.
Preferably, the molar ratio Al/Ti of metallic aluminium and catalyst metals center titanium is 100-10000 in co-catalyst,
Polymerization temperature is 0-120 DEG C, polymerization pressure 0.1-10MPa, polymerization time 1min-3h, using toluene or chlorobenzene as solvent,
Using mechanical stirring or magnetic agitation.
Preferably, Al/Ti is 100-3000, polymerization temperature is 10-100 DEG C, polymerization pressure 0.1-2MPa, when polymerization
Between 1min-2h, using toluene or chlorobenzene as solvent, using mechanical stirring.
Specific step is as follows for the preparation method:
1) empty reaction kettle is vacuumized and is heated and drive steam, then passed to nitrogen or argon atmosphere displacement, repeat 2~5
It is secondary, finally make that 100ml toluene is added into reaction kettle, adds methylaluminoxane full of ethylene gas in reaction kettle, it is final to add
Enter the toluene solution of the salicylaldiminato complex A containing 1-5 μm of ol, mole of methylaluminoxane and salicylaldiminato complex A
Than obtaining the toluene solution system of catalyst for 500~5000:1.
2) reaction temperature is set as 0~100 DEG C, and polymerization reaction 1min~5h, then uses hydrochloric acid containing 1vol% under normal pressure
Ethanol solution terminate reaction.
3) material is poured out from reaction kettle, filters, obtains polymer crude product, successively with ethyl alcohol and distillation water washing；So
It dries in 30~100 DEG C of vacuum drying oven to constant weight afterwards, obtains polymeric articles.
4) resulting polymers product is weighed, work of the titanium catalyst of salicylaldiminato containing terminal double bond in vinyl polymerization is calculated
Property；Measure the molecular weight and molecualr weight distribution of polymeric articles, the hot property of test polymer product.
Compared with prior art, the effect the present invention is based on terminal double bond in stable complex structure is prepared for new
Catalyst has the advantage that
1) the salicylaldiminato titanium catalyst containing terminal double bond has very high activity when being catalyzed ethylene homo, and activity can
Up to 1.6 × 107gPE·mol-1Ti·h-1。
2) the salicylaldiminato titanium catalyst containing terminal double bond need not be using the methods of modified MAO, can be directly not severe
Ultra-high molecular weight polyethylene of the synthetic molecular weight 3,000,000 or more under conditions of quarter.
3) the salicylaldiminato titanium catalyst containing terminal double bond is good in polymerization stability, preferably remains single centre
The characteristic of catalyst, synthesized polymer molecular weight narrow distribution preferably overcome general benzene oxygen imine catalyst poly-
The drawbacks of molecular weight distribution affected by various factors broadens during conjunction.
Detailed description of the invention
Fig. 1 is the catalyst nuclear magnetic spectrogram in embodiment 1；
Fig. 2 is the polyethylene melting curve in embodiment 2；
Fig. 3 is the polyethylene GPC curve in embodiment 2；
Fig. 4 is the catalyst nuclear magnetic spectrogram in embodiment 3；
Fig. 5 is the polyethylene melting curve in embodiment 4；
Fig. 6 is the polyethylene GPC curve in embodiment 4.
Specific embodiment
Data given by the specific embodiment of the invention include the preparation and representation of ligand and complex, converging operation,
Polymerizing condition and polymerizate.Ligands and complexes A's1H-NMR characterization is all made of Bruker Avance DMX400 nuclear magnetic resonance spectrometer,
TMS is as internal standard, using CDCl3Make solvent.Elemental analysis carries out on CE EA1112 elemental analyser, is fired using quantitative oxygen
Burning method makees detector with conductance cell.The molecular weight determination of polyethylene uses exclusion chromatography (HT-GPC), with 1 at 150 DEG C,
2,4- trichloro-benzenes show four kinds of inspections such as poor, capillary viscosity instrument, right angle laser light scattering and 7 ° of low-angle light scatterings in carrying for mobile phase
It surveys on the Viscotek 350A chromatograph of device and measures.Melting point polymer and crystallization enthalpy measurement use Perkin-Elmer DSC 7
It is carried out on differential scanning calorimeter, sweep speed is 10 DEG C/min, and scanning range is 40~160 DEG C.
The present invention is illustrated with following specific embodiments, but the scope of the present invention is not limited to following embodiment.
Embodiment 1
The present embodiment titanium catalyst of salicylaldiminato containing terminal double bond is denoted as A1, structural formula are as follows:
Wherein, " --- --- -- " it is coordinate bond.
The titanium catalyst of salicylaldiminato containing terminal double bond A1Preparation method comprise the concrete steps that:
Step 1: ligand L1Preparation
Ligand L1Structural formula are as follows:
Ligand L1Preparation: 30mmol 3- allyl salicylide and 2,3,5,6- tetrafluoroaniline of 30mmol are dissolved in
In 30ml dehydrated alcohol, 60.8mg p-methyl benzenesulfonic acid is added, 6h is then reacted at 80 DEG C, is concentrated, ties again in ethanol
Crystalline substance obtains 7.21g (23.3mmol) ligand L1, molar yield 77.7%.
Ligand L1Related detection and analysis data it is as follows:
Elemental analysis: L1(C16H11F4NO, 309.26g/mol) actual measurement/theoretical value: C be 62.29% (62.14%)；H
For 3.52% (3.59%)；N is 4.52% (4.53%).
1H NMR(400MHz,CDCl3) δ 12.62 (s, 1H, OH), 8.81 (s, 1H, CH=N), 7.33 (d, J=7.4Hz,
1H, Ar-H), 7.27 (dd, J=7.7,1.5Hz, 1H, Ar-H), 6.99-6.86 (m, 2H, Ar-H), 6.04 (ddt, J=16.8,
10.1,6.6Hz,1H,CH2- CH=CH2),5.15–5.06(m,2H,CH2- CH=CH2), 3.47 (d, J=6.6Hz, 2H, CH2-
CH=CH2)。
Step 2: the salicylaldiminato titanium catalyst A containing allyl1Preparation
By the 1mmol ligand L1It is dissolved in the dry ether solvent of 10ml, is slowly added dropwise at -78 DEG C into solution
1mmol n-BuLi/hexane solution is restored to room temperature, stirs 3h.Obtained solution is slowly dropped at -78 DEG C
In 0.5mmol titanium tetrachloride/dichloromethane solution, it is restored to room temperature, stirs 19h.Solvent is drained, 12ml methylene chloride mistake is added
Filter obtains dark red solution, drains, and 1.5ml ether and the washing of 10ml hexane is added, stands, topples over supernatant liquor；30ml is used again
N-hexane washs in three times, drains solvent, obtains 0.302g (0.410mmol) brick-red solid, molar yield 82.1%.
Catalyst A1Related detection and analysis data it is as follows:
Elemental analysis: A1(C32H20O2N2F8TiCl2, 735.29g/mol) actual measurement/theoretical value: C 51.86%
(52.27%)；H is 2.65% (2.74%)；N is 3.75% (3.81%).
1H NMR(400MHz,CDCl3) δ 8.26 (s, 2H, CH=N), 7.44 (d, J=7.2Hz, 2H, Ar-H), 7.31 (d,
J=7.7Hz, 2H, Ar-H), 7.00 (t, J=7.6Hz, 2H, Ar-H), 6.88-6.75 (m, 2H, Ar-H), 5.86 (ddt, J=
16.9,10.0,6.9Hz,2H,CH2- CH=CH2), 5.18 (dd, J=17.0,1.5Hz, 2H, CH2- CH=CH2),5.09(dd,
J=10.0,1.0Hz, 2H, CH2- CH=CH2), 3.17 (ddd, J=138.8,15.6,6.9Hz, 4H, CH2- CH=CH2)。
This step 2 is carried out under conditions of anhydrous and oxygen-free.
Embodiment 2
The present embodiment is for illustrating catalyst A1Purposes.Titanium catalyst A1It is reacted for catalyzed ethylene polymerization, it is specific to walk
Suddenly it is:
Steam is driven Step 1: empty reaction kettle is vacuumized and heated, nitrogen atmosphere displacement is then passed to, is repeated 3 times, most
Make that 100ml toluene is added into reaction kettle, adds methylaluminoxane, ultimately joins containing 2 full of ethylene gas in reaction kettle eventually
The salicylaldiminato complex A of μm ol1Toluene solution, methylaluminoxane and salicylaldiminato complex A1Molar ratio be
2000:1 obtains the toluene solution system of catalyst.
Step 2: set reaction temperature as 10 DEG C, polymerization reaction 30min under normal pressure, then with the hydrochloric acid containing 1vol%
Ethanol solution terminates reaction.
Step 3: pouring out material from reaction kettle, filter, obtain polymer crude product, successively with ethyl alcohol and distillation washing
It washs；Then it dries in 50 DEG C of vacuum drying oven to constant weight, obtains polymeric articles.
Step 4: weighing resulting polymers product is 2.71g, titanium-containing catalyst A is calculated1Activity in vinyl polymerization is
2.71×106gPE·mol-1Ti·h-1；Polymerizate measures its molecular weight and molecualr weight distribution by GPC, as a result are as follows: weight is equal
Molecular weight Mw=2490000, molecular weight distribution Mw/Mn=1.62.DSC tests its hot property, and display PE heat fusion joint is Tm=
134.4℃。
Change polymeric reaction condition (reaction temperature and reaction time), other are shown in Table 1 with embodiment 2, gained polymerization result.
1 catalyst A of table1The result of (2 μm of ol) catalyzed ethylene polymerization reaction
Embodiment 3
The present embodiment titanium catalyst of salicylaldiminato containing terminal double bond is denoted as A2, structural formula are as follows:
Wherein, " --- --- -- " it is coordinate bond.
The titanium catalyst of salicylaldiminato containing terminal double bond A2Preparation method comprise the concrete steps that:
Step 1: fortified phenol O1Preparation
Fortified phenol O1Structural formula be
Fortified phenol O1Preparation: 583.6mmol tert-butyl hydroquinone and 285.96mmol potassium carbonate are added to
In 300ml anhydrous acetonitrile, 2h is stirred., 583.6mmol allyl bromide, bromoallylene and 31.74mmol potassium iodide is then added, is heated to solvent
Reflux, work overtime 4h.Stop heating, be cooled to room temperature, pour the mixture into 30ml deionized water, with 180ml ether point three
Secondary extraction organic layer, then organic phase is washed with 200ml saturated brine, with the dry organic layer of sodium sulphate.Then it is added into solution
200ml petroleum ether (60~90 DEG C) stirs 2h, unreacted tert-butyl hydroquinone is settled out, with column chromatography (200~300
Mesh silica gel, petrol ether/ethyl acetate=20:1) isolated 56.3g (270.2mmol) product, molar yield 46%.
The reaction process carries out in nitrogen atmosphere.
Fortified phenol O1Related detection and analysis data it is as follows:
Elemental analysis: O1(C13H18O2, 206.29g/mol) actual measurement/theoretical value: C be 74.48% (75.69%)；H is
8.75% (8.80%).
1H NMR(400MHz,CDCl3) δ 6.89 (d, J=2.7Hz, 1H, Ar-H), 6.63-6.54 (m, 2H, Ar-H),
6.05 (ddd, J=22.7,10.6,5.4Hz, 1H, CH2CH=CH2), 5.40 (dd, J=17.2,1.6Hz, 1H, CH2CH=
CH2), 5.27 (dd, J=10.5,1.3Hz, 1H, CH2CH=CH2),4.76(s,1H,OH),4.54–4.42(m,2H,CH2CH=
CH2),1.39(s,9H,C(CH3)3).
Step 2: substituted salicylic aldehydes O2Preparation
Substituted salicylic aldehydes O2Structural formula be
Substituted salicylic aldehydes O2Preparation: it is dry to disperse 150ml for 200mmol magnesium chloride and 300mmol paraformaldehyde
In THF, 300mmol triethylamine is added, stirs 10min, 109.8mmol fortified phenol O is then added1, stirred at 70 DEG C
5h.Stop reaction, be cooled to room temperature, be added 200ml hydrochloric acid (1N), 150ml ether is added and extracts organic layer in three times, uses
100ml saturated brine washs organic phase, and it is dry that solid sodium sulfate is added.Concentration, by crude product column chromatography (200~300 mesh
Silica gel, pure petroleum ether) separation, obtain 8.2g (35.0mmol) bronzing liquid, molar yield 31.9%.
Elemental analysis: O2(C14H18O3, 234.30g/mol) actual measurement/theoretical value: C be 71.51% (71.77%)；H is
7.84% (7.74%).
1H NMR(400MHz,CDCl3) δ 11.51 (s, 1H, OH), 9.81 (s, 1H, CH=O), 7.21 (d, J=3.0Hz,
1H, Ar-H), 6.82 (d, J=3.1Hz, 1H, Ar-H), 6.06 (ddd, J=22.6,10.6,5.3Hz, 1H, CH2CH=CH2),
5.43 (dd, J=17.3,1.5Hz, 1H, CH2CH=CH2), 5.31 (dd, J=10.5,1.4Hz, 1H, CH2CH=CH2),4.52
(d, J=5.3Hz, 2H, CH2CH=CH2),1.41(s,9H,C(CH3)3).
Step 3: ligand L2Preparation
Ligand L2Structural formula are as follows:
Ligand L2Preparation: by 33.83mmol substituted tert-butyl salicylide O2And 33.83mmol2,3,4,5,6- phenyl tetrafluorides
Amine is dissolved in 30ml dehydrated alcohol, adds 50.6mg p-methyl benzenesulfonic acid, and 8h is then reacted at 80 DEG C, concentration, in second
8.44g (21.1mmol) ligand L is recrystallized to give in alcohol2, molar yield 62.5%.
Ligand L2Related detection and analysis data it is as follows:
Elemental analysis: L2(C20H18F5NO2, 399.36g/mol) actual measurement/theoretical value: C be 60.46% (60.15%)；H
For 4.49% (4.54%)；N is 3.32% (3.51%).
1H NMR(400MHz,CDCl3) δ 12.57 (s, 1H, OH), 8.77 (s, 1H, CH=N), 7.16 (d, J=3.0Hz,
1H, Ar-H), 6.70 (d, J=3.0Hz, 1H, Ar-H), 6.07 (ddt, J=17.2,10.6,5.3Hz, 1H, CH2CH=CH2),
5.43 (dd, J=17.3,1.5Hz, 1H, CH2CH=CH2), 5.31 (dd, J=10.5,1.4Hz, 1H, CH2CH=CH2),4.52
(dt, J=5.3,1.4Hz, 2H, CH2CH=CH2),1.45(s,9H,C(CH3)3)。
Step 4: the titanium catalyst of salicylaldiminato containing terminal double bond A2Preparation
By the 1mmol ligand L2It is dissolved in the dry ether solvent of 10ml, is slowly added dropwise at -78 DEG C into solution
1mmol n-BuLi/hexane solution is restored to room temperature, stirs 3h.Obtained solution is slowly dropped at -78 DEG C
In 0.5mmol titanium tetrachloride/dichloromethane solution, it is restored to room temperature, stirs 19h.Solvent is drained, 12ml methylene chloride mistake is added
Filter obtains dark red solution, drains, and 1.5ml ether and the washing of 10ml hexane is added, stands, topples over supernatant liquor；30ml is used again
N-hexane washs in three times, drains solvent, obtains 0.206g (0.23mmol) brick-red solid, molar yield 45.1%.
Catalyst A2Related detection and analysis data it is as follows:
Elemental analysis: A2(C40H34O4N2F10TiCl2, 915.47g/mol) actual measurement/theoretical value: C 51.54%
(52.48%)；H is 3.59% (3.74%)；N is 2.89% (3.06%).
1H NMR(400MHz,CDCl3) δ 8.18 (s, 2H, CH=N), 7.26 (s, 2H, Ar-H), 6.71 (s, 2H, Ar-H),
6.05 (ddd, J=15.0,9.6,4.3Hz, 2H, CH2CH=CH2), 5.43 (d, J=17.2Hz, 2H, CH2CH=CH2),5.33
(d, J=10.4Hz, 2H, CH2CH=CH2), 4.52 (d, J=4.2Hz, 4H, CH2CH=CH2),1.31(s,18H,C(CH3)3).
This step 4 is carried out under conditions of anhydrous and oxygen-free.
Embodiment 4
A kind of titanium catalyst of salicylaldiminato containing terminal double bond A2Purposes.The titanium catalyst A2For being catalyzed ethylene
Polymerization reaction comprises the concrete steps that:
Steam is driven Step 1: empty reaction kettle is vacuumized and heated, nitrogen atmosphere displacement is then passed to, is repeated 3 times, most
Make that 100ml toluene is added into reaction kettle, adds methylaluminoxane, ultimately joins containing 2 full of ethylene gas in reaction kettle eventually
The salicylaldiminato complex A of μm ol2Toluene solution, methylaluminoxane and salicylaldiminato complex A2Molar ratio be
2000:1 obtains the toluene solution system of catalyst.
Step 2: set reaction temperature as 10 DEG C, polymerization reaction 1min under normal pressure, then with the second of the hydrochloric acid containing 1vol%
Alcoholic solution terminates reaction.
Step 3: pouring out material from reaction kettle, filter, obtain polymer crude product, successively with ethyl alcohol and distillation washing
It washs；Then it dries in 50 DEG C of vacuum drying oven to constant weight, obtains polymeric articles.
Step 4: weighing resulting polymers product is 0.54g, titanium-containing catalyst A is calculated2Activity in vinyl polymerization is
1.6×107gPE·mol-1Ti·h-1；Polymerizate measures its molecular weight and molecualr weight distribution by GPC, as a result are as follows: divides equally again
Son amount Mw=330000, molecular weight distribution Mw/Mn=1.36.DSC tests its hot property, and display PE heat fusion joint is Tm=137.4
℃。
Change polymeric reaction condition (reaction temperature and reaction time), other are shown in Table 3 with embodiment 2, gained polymerization result.
3 catalyst A of table2The result of (2 μm of ol) catalyzed ethylene polymerization reaction
Claims (8)
1. a kind of salicylaldiminato titanium complex containing terminal double bond, which is characterized in that shown in structure such as formula (1):
In formula (1), R1For C1~C4Alkyl, R2For allyloxy, R3For fluorine.
2. salicylaldiminato titanium complex according to claim 1, which is characterized in that R1For methyl, isopropyl or tertiary fourth
Base, R2For allyloxy, R3For fluorine.
3. a kind of preparation method of polyethylene, which comprises the following steps:
In the presence of salicylaldiminato titanium complex of any of claims 1 or 2 and co-catalyst, it is anti-that polymerization occurs for ethylene
It answers, obtains the polyethylene；
The co-catalyst is one or more of aikyiaiurnirsoxan beta, alkyl aluminum or chlorination alkyl aluminum.
4. the preparation method of polyethylene according to claim 3, which is characterized in that polymerization reaction carries out in a solvent, institute
It is one or more of toluene, chlorobenzene, n-hexane or isoparaffin with solvent.
5. the preparation method of polyethylene according to claim 3, which is characterized in that polymerization reaction in strength mechanical stirring or
It is carried out under the conditions of magnetic agitation, revolving speed is 50~1000rpm.
6. the preparation method of polyethylene according to claim 3, which is characterized in that aikyiaiurnirsoxan beta is methylaluminoxane, ethyl
Aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide；Alkyl aluminum is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or tri-n-octylaluminium；Kelene
Base aluminium is aluminium diethyl monochloride, ethyl aluminum dichloride or sesquialter ethylmercury chloride aluminium.
7. the preparation method of polyethylene according to claim 3, which is characterized in that metallic aluminium and catalyst in co-catalyst
The molar ratio Al/Ti of metal center titanium is 100-10000:1, and polymerization temperature is 0-120 DEG C, polymerization pressure 0.1-10MPa, is gathered
Time 1min-3h is closed, using toluene or chlorobenzene as solvent, using mechanical stirring or magnetic agitation.
8. the preparation method of polyethylene according to claim 7, which is characterized in that Al/Ti 100-3000:1, polymerization temperature
Degree is 10-100 DEG C, polymerization pressure 0.1-2MPa, polymerization time 1min-2h, using toluene or chlorobenzene as solvent, using machine
Tool stirring.
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