CN102093494B - Metal olefin polymerization catalyst containing 8-hydroxyquinoline imine ligand and preparation method thereof - Google Patents
Metal olefin polymerization catalyst containing 8-hydroxyquinoline imine ligand and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical catalyst, particularly relates to a metal olefin polymerization catalyst containing 8-hydroxyquinoline imine ligand and a preparation method thereof. The expression formula of the catalyst is MLCl3 or CP'MLCl2, wherein L represents tridentate anionic ligand which contains N and O atoms and is capable of coordinating with metals. The catalyst has a peculiar and novel structure and has high catalysis activity on catalytic vinyl polymerization, and is simple to prepare; a component A and a component B methylaluminoxane or modified methylaluminoxane of the catalyst are matched to be used for the catalyticvinyl polymerization reaction so as to prepare high molecular weight polyethylene product.
Description
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to oxine imine ligand metal olefin polymerization catalyst and preparation method thereof.
Technical background
Macromolecular materials industry is one of main mainstay industry of Chinese national economy, of close concern to each other with people's daily life, and polyolefine accounts for 35% of whole macromolecular material.Polyolefine is the mainstay industry of modern Macromolecular materials industry, and olefin polymerization catalysis is the core of polyolefine industry.Because organo-metallic olefin polymerization catalysis not only can efficient catalytic olefinic polymerization under gentle condition, and microtexture that can cutting polymkeric substance, so can design new function polyolefine material and improve the performance that has polymkeric substance on molecular level, therefore the research in this field is one of contemporary chemical forward position and focus always.Since nineteen fifty-three, olefin polymerization catalysis came out, Ziegler-Natta catalyst system, metallocene catalysis system and " after luxuriant " three important milestones of catalytic systems for polymerization of olefins are there are in short 50 years.
In recent years, olefin polymerization catalysis is to be all the focus of research in industry member or in academia.The catalyzer of various structures, comprises that metallocene catalyst and non-metallocene catalyst are in the news successively.File report has been shown in synthesizing of schiff bases oxine imine derivative, have not been reported but be used for catalysis in olefine polymerization with oxine imines as part synthetic compound.The present invention will utilize the olefin polymerization catalysis of the synthetic a series of excellent performances of oxine imine ligand.
Summary of the invention
The object of this invention is to provide two kinds of catalytic activitys high, the simple oxine imine ligand of synthesis technique metal complexes olefin polymerization catalysis and preparation method thereof.
Olefin polymerization catalysis provided by the invention is by 8-hydroxyl quinaldine red, and the aniline of various replacements is starting raw material, makes a series of oxine imine derivative parts through series reaction step
la-Le; The MCl of part and equimolar amount
4(M=Ti, Zr or Hf) or part pull out after H and the CpMCl of equimolar amount with NaH
3(M=Ti or Zr) reaction, after filtration, drain, recrystallization, obtain metal complexes MLCl
3or Cp'MLCl
2(Cp'=cyclopentadienyl or pentamethyl-cyclopentadienyl).This two classes catalyzer is all homogeneous phase single site catalysts, have high catalytic activity, and catalytic life is greater than 2 hours under gentle condition.By changing the substituted radical on part, can regulate the activity of the catalyzed ethylene polymerization of catalyzer, and can obtain the polyethylene of different molecular weight.
Catalyzer expression formula provided by the invention is MCl
4(M=Ti, Zr or Hf) and CpMCl
3(M=Ti or Zr), L represent oxine imine derivative part (be a kind of contain can with the O of metal-complexing, three tooth single anion ligands of N atom), concrete structure formula is:
Reaction process prepared by above-mentioned oxine imines class ligand metal title complex olefin polymerization catalysis is as follows:
concrete steps are as follows:
(1) preparation of 2-aldehyde radical-oxine
Its structural formula is:
In 100 mL tri-neck round-bottomed flasks, add successively 8-hydroxyl quinaldine red (1.973 g, 12.4 mmol), tin anhydride (1.75 g, 15.8mmol), Isosorbide-5-Nitrae-dioxane 70ml and water 0.75 ml, be slowly warming up to 100
oc, after the lower 20h of stirring that refluxes, TLC detection reaction is carried out completely.Thing to be mixed filters after being cooled to room temperature, and selenium powder is washed twice with 5ml methylene dichloride.After concentrated after filtrate merges, column chromatography for separation obtains pure products, productive rate approximately 71%.
replace the preparation of oxine imines class part
Its structural formula is:
Wherein,
la: R=H;
lb: R=Me;
lc: R=Et;
ld: R=
ipr;
le: R=Cl.
-
ldpreparation: in 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30 mL dehydrated alcohols, be heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (3.5 mmol, 10-20 mL ethanol) of various substituted anilines from constant pressure funnel.6 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, the column chromatography for separation purified ligand of purifying to obtain, productive rate 63-78%.
Preparation: in 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30-50 mL dehydrated alcohol, 3 ~ 4,98% formic acid, is heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (3.5 mmol, 10-20 mL ethanol) of 2,6-DCA from constant pressure funnel.10 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, the column chromatography for separation purified ligand of purifying to obtain.Productive rate approximately 25%.
the non-metallocene olefin polymerization catalyst preparation of hydroxyquinoline imines class part and the 4th group 4 transition metal coordination:
Its structural formula is:
Wherein, (1a) M=Ti, R=H; (1b) M=Ti, R=Me; (1c) M=Ti, R=Et; (1d) M=Ti, R=
ipr; (1e) M=Ti, R=Cl; (2a) M=Zr, R=H; (2b) M=Zr, R=Me; (2c) M=Zr, R=Et; (2d) M=Zr, R=
ipr; (2e) M=Zr, R=Cl; (3a) M=Hf, R=H; (3b) M=Hf, R=Me; (3c) M=Hf, R=Et; (3d) M=Hf, R=
ipr; (3e) M=Hf, R=Cl.
Catalyzer
1a-1epreparation, under the protection of and high-purity argon gas anhydrous in anaerobic, carry out.The part that 0.25 mmol is made by step (2) is dissolved in the dry toluene that 20ml processed, and at room temperature stirs 5 min.Under-78 ° of C low temperature, by TiCl
4the toluene solution of (0.25 mmol) is slowly added dropwise in the toluene solution of part, slowly rises to room temperature, continues stirring reaction 6 h, drains, and adds 20-50 mL Skellysolve A, leaves standstill, and filters, then with normal hexane washing 2-3 time, obtain scarlet (
1a-
1c) or brown (
1e) solid, productive rate 70%-93%.
Catalyzer
2a-2e, 3a-3epreparation, under the protection of and high-purity argon gas anhydrous in anaerobic, carry out.The part that 0.25 mmol is made by step (2) is dissolved in the anhydrous THF that 20ml processed, and at room temperature stirs 5 min.0
ounder C, slowly import in the THF suspension liquid of NaH (24mg, 1.0 mmol) with bridge.After returning to room temperature, continue to leave standstill after stirring 2h, filter, remove excessive NaH, filtrate is cooled to-78 ° of C, is added dropwise to ZrCl
4or HfCl(0.25 mmol) THF solution, continue stirring reaction 12 h after slowly rising to room temperature, drain, add 20-50 mL toluene, leave standstill, remove by filter NaCl, filtrate is drained, and methylene dichloride/normal hexane recrystallization obtains scarlet or brown solid, productive rate 70%-93%.
hydroxyquinoline imines class part and Ti, the metallocene calalyst for polymerization of olefine preparation of Zr coordination:
Its structural formula is:
Wherein, (4a) Cp'=Cp, M=Ti, R=H; (4b) Cp'=Cp, M=Ti, R=Me; (4c) Cp'=Cp, M=Ti, R=Et; (4d) Cp'=Cp, M=Ti, R=
ipr; (4e) Cp'=Cp, M=Ti, R=Cl; (5a) Cp'=Cp*, M=Ti, R=H; (5b) Cp'=Cp*, M=Ti, R=Me; (5c) Cp'=Cp*, M=Ti, R=Et; (5d) Cp'=Cp*, M=Ti, R=
ipr; (5e) Cp'=Cp*, M=Ti, R=Cl; (6a) Cp'=Cp, M=Zr, R=H; (6b) Cp'=Cp, M=Zr, R=Me; (6c) Cp'=Cp, M=Zr, R=Et; (6d) Cp'=Cp, M=Zr, R=
ipr; (6e) Cp'=Cp, M=Zr, R=Cl; (7a) Cp'=Cp*, M=Zr, R=H; (7b) Cp'=Cp*, M=Zr, R=Me; (7c) Cp'=Cp*, M=Zr, R=Et; (7d) Cp'=Cp*, M=Zr, R=
ipr; (7e) Cp'=Cp*, M=Zr, R=Cl.
Catalyzer
4a-4e, 5a-5e, 6a-6e, 7a-7epreparation, under the protection of and high-purity argon gas anhydrous in anaerobic, carry out.By the THF solution of part 0
oc is slowly added drop-wise in the THF suspension liquid of NaH, returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc is slowly added drop-wise to Cp'MCl
3in the THF solution of (Cp'=Cp or Cp*, M=Ti or Zr), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains orange or dark red solid with toluene/pentane recrystallization.
(5) above-mentioned catalyzer is for the reaction of normal pressure catalyzed ethylene polymerization, and concrete steps are as follows:
Vinyl polymerization carries out under anhydrous and oxygen-free condition.Catalyzer dissolves with toluene in advance, is made into the solution of 0.0025mol/L.Under ethene atmosphere with syringe to the toluene solution that adds successively 2.5 μ mol catalyst A components in polymerization bottle, under stirring, add 30-40 mL toluene, at 30 ℃, keep 5-10 min, the toluene solution initiated polymerization that adds the methylaluminoxane (MMAO) of a certain amount of catalyst B component methylaluminoxane (MAO) or modification, the mol ratio of A component and B component is 1000:1-4000:1.The cumulative volume of reaction system generally remains on 50 mL(different volumes useable solvents toluene and regulates), after reaction 30 min, mixture is poured into (ethanol/HCl in the ethanolic soln of acidifying
conc=95:5).Fully stir 4-6 hour, by polymer filtration, and with washing with alcohol, vacuum-drying 24 hours under 80 oC.Active amt level is 10
4-10
5g PE/ (molMh), the molecular weight of polyethylene order of magnitude is 10
4-10
5g/mol.
(6) above-mentioned catalyzer is for the reaction of high pressure catalyzed ethylene polymerization, and concrete steps are as follows
The reaction system that first autoclave is treated to anhydrous and oxygen-free, is warming up to temperature of reaction.By substituting gas, make it as ethene atmosphere.Syringe is to the toluene solution that adds successively 2.5 μ mol catalyst A components in polymerization reaction kettle, intense mechanical adds 40 mL toluene under stirring, at 30-100 ℃, keep 5-10 min, add the toluene solution of a certain amount of catalyst B component MAO, initiated polymerization, the mol ratio of A component and B component is 1000:1-4000:1.Be forced into 10atm, reaction 10-60min.Close steel cylinder, venting, making it is a normal atmosphere.With the ethanolic soln (ethanol/HCl of acidifying
conc=95:5) termination polymerization.Mixture is poured into (ethanol/HCl in the ethanolic soln of acidifying
conc=95:5).Fully stir 4-6 hour, by polymer filtration, and by washing with alcohol, vacuum-drying 24 hours at 80 ℃.Active amt level is 10
6-10
7g PE/ (mol Mh), the molecular weight of polyethylene order of magnitude is 10
5g/mol.
Catalyst activity of the present invention is high, and synthesis technique is easy, can obtain High molecular weight polyethylene.Fig. 1 is
1dcrystalline structure, Fig. 2 is
6bcrystalline structure, Fig. 3 is
6dcrystalline structure, Fig. 4 is
7dcrystalline structure.
Accompanying drawing explanation
Fig. 1. catalyzer
1dcrystalline structure.
Fig. 2. catalyzer
6bcrystalline structure.
Fig. 3. catalyzer
6dcrystalline structure.
Fig. 4. catalyzer
7dcrystalline structure.
Embodiment
embodiment provided by the invention is as follows:
embodiment 1:[ONN]
h (
la) preparation:
In 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30mL dehydrated alcohol, be heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (0.38g, 3.5 mmol, 20ml ethanol) of aniline from constant pressure funnel.6 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, column chromatography for separation (V methylene dichloride: V sherwood oil=1:3,1% triethylamine), drains final vacuum and is dried to obtain purified ligand
la, productive rate 63%.
embodiment 2:[ONN]
me (
lb) preparation:
In 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30mL dehydrated alcohol, be heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (0.42g, 3.5 mmol, 20mL ethanol) of 2,6-xylidine from constant pressure funnel.6 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, column chromatography for separation (V methylene dichloride: V sherwood oil=1:3,1% triethylamine), drains final vacuum and is dried to obtain purified ligand
lb, productive rate 78%.
embodiment 3:[ONN]
et (
lc) preparation:
In 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30mL dehydrated alcohol, be heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (0.52g, 3.5 mmol, 20mL ethanol) of 2,6-Diethyl Aniline from constant pressure funnel.6 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, column chromatography for separation (V methylene dichloride: V sherwood oil=1:3,1% triethylamine), drains final vacuum dry, obtains purified ligand
ld,, productive rate 76%.
embodiment 4:[ONN]
iPr (
ld) preparation:
In 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30mL dehydrated alcohol, be heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (0.62g, 3.5 mmol, 20mL ethanol) of 2,6-DIPA from constant pressure funnel.6 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, column chromatography for separation (V methylene dichloride: V sherwood oil=1:3,1% triethylamine), drains final vacuum and is dried to obtain purified ligand
ld, productive rate 72%.
embodiment 5:[ONN]
cl (
le) preparation:
In 100 mL tri-neck round-bottomed flasks, add successively 2-aldehyde radical-oxine (0.6 g, 3.5 mmol), 30mL dehydrated alcohol, 3 ~ 4,98% formic acid, is heated to 80-100 ℃.Slowly drip wherein the ethanolic soln (3.5 mmol, 10-20 mL ethanol) of 2,6-DCA from constant pressure funnel.10 h that reflux, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, column chromatography for separation (V methylene dichloride: V sherwood oil=1:3, the 1% triethylamine) purified ligand of purifying to obtain
le, productive rate approximately 25%.
embodiment 6:titanium complex Ti[ONN]
hcl
3(
1a) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, by part
la(62 mg, 0.25 mmol) be dissolved in the dry toluene that 20ml heavily steamed, at room temperature stir 5 min.Under-78 ° of C low temperature, by TiCl
4the toluene solution of (0.25 mmol) is slowly added dropwise in the toluene solution of part, slowly rises to room temperature, continues stirring reaction 6 h, drains, and adds 20-50 mL Skellysolve A, leaves standstill, and filters, then with normal hexane washing 2-3 time, obtains scarlet powder, productive rate 86%.
embodiment 7:titanium complex Ti[ONN]
mecl
3(
1b) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, by part
lb(70 mg, 0.25 mmol) is dissolved in the dry toluene that 20ml heavily steamed, and at room temperature stirs 5 min.Under-78 ° of C low temperature, by TiCl
4the toluene solution of (0.25 mmol) is slowly added dropwise in the toluene solution of part, slowly rises to room temperature, continues stirring reaction 6 h, drains, and adds 20-50 mL Skellysolve A, leaves standstill, and filters, then with normal hexane washing 2-3 time, obtains scarlet powder, productive rate 86%.
embodiment 8:titanium complex Ti[ONN]
etcl
3(
1c) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, by part
lc(76 mg, 0.25 mmol) is dissolved in the dry toluene that 20ml heavily steamed, and at room temperature stirs 5 min.Under-78 ° of C low temperature, by TiCl
4the toluene solution of (0.25 mmol) is slowly added dropwise in the toluene solution of part, slowly rises to room temperature, continues stirring reaction 6 h, drains, and adds 20-50 mL Skellysolve A, leaves standstill, and filters, then with normal hexane washing 2-3 time, obtains scarlet powder, productive rate 85%.
embodiment 9:titanium complex Ti[ONN]
iPrcl
3(
1c) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, by part
ld(83 mg, 0.25 mmol) is dissolved in the dry toluene that 20ml heavily steamed, and at room temperature stirs 5 min.Under-78 ° of C low temperature, by TiCl
4the toluene solution of (0.25 mmol) is slowly added dropwise in the toluene solution of part, slowly rises to room temperature, continues stirring reaction 6 h, drains, and adds 20-50 mL Skellysolve A, leaves standstill, and filters, then with normal hexane washing 2-3 time, obtains scarlet powder, productive rate 93%.
embodiment 10:titanium complex Ti[ONN]
clcl
3(
1c) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, by part
le(79 mg, 0.25 mmol) is dissolved in the dry toluene that 20ml heavily steamed, and at room temperature stirs 5 min.Under-78 ° of C low temperature, by TiCl
4the toluene solution of (0.25 mmol) is slowly added dropwise in the toluene solution of part, slowly rises to room temperature, continues stirring reaction 6 h, drains, and adds 20-50 mL Skellysolve A, leaves standstill, and filters, then with normal hexane washing 2-3 time, obtains scarlet powder, productive rate 70%.
embodiment 11:half-sandwich zirconium complex CpZr[ONN]
hcl
2(
6a) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lathe THF solution of (62 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to CpZrCl with bridge
3in the THF solution of (66mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains scarlet powder, productive rate 73% with toluene/normal hexane recrystallization.
embodiment 12:half-sandwich zirconium complex CpZr[ONN]
mecl
2(
6b) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lbthe THF solution of (70 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to CpZrCl with bridge
3in the THF solution of (66mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains scarlet powder, productive rate 78% with toluene/normal hexane recrystallization.
embodiment 13:half-sandwich zirconium complex CpZr[ONN]
etcl
2(
6c) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lcthe THF solution of (76 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to CpZrCl with bridge
3in the THF solution of (66mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains red powder, productive rate 75% with toluene/normal hexane recrystallization.
embodiment 14:half-sandwich zirconium complex CpZr[ONN]
iPrcl
2(
6d) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
ldthe THF solution of (83 mg, 0.25mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to CpZrCl with bridge
3in the THF solution of (66mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains red crystals, productive rate 81% with toluene/pentane recrystallization.
embodiment 15:half-sandwich zirconium complex CpZr[ONN]
clcl
2(
6e) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
ldthe THF solution of (79 mg, 0.25mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to CpZrCl with bridge
3in the THF solution of (66mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains brown ceramic powder, productive rate 61% with toluene/normal hexane recrystallization.
embodiment 16:half-sandwich zirconium complex Cp*Zr[ONN]
hcl
2(
7a) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lathe THF solution of (62 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to Cp*ZrCl with bridge
3in the THF solution of (82.6 mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains orange powder, productive rate 73% with toluene/normal hexane recrystallization.
embodiment 17:half-sandwich zirconium complex Cp*Zr[ONN]
mecl
2(
7b) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lbthe THF solution of (70 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to Cp*ZrCl with bridge
3in the THF solution of (82.6 mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains orange powder, productive rate 70% with toluene/normal hexane recrystallization.
embodiment 18:half-sandwich zirconium complex Cp*Zr[ONN]
etcl
2(
7c) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lcthe THF solution of (76 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to Cp*ZrCl with bridge
3in the THF solution of (82.6 mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains orange powder, productive rate 69% with toluene/normal hexane recrystallization.
embodiment 19:half-sandwich zirconium complex Cp*Zr[ONN]
iPrcl
2(
7d) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
ldthe THF solution of (83 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to Cp*ZrCl with bridge
3in the THF solution of (82.6 mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains orange powder, productive rate 68% with toluene/normal hexane recrystallization.
embodiment 20:half-sandwich zirconium complex Cp*Zr[ONN]
clcl
2(
7e) preparation:
Under the protection of and high-purity argon gas anhydrous in anaerobic, part
lethe THF solution of (79 mg, 0.25 mmol) is 0
oc is slowly added drop-wise in the THF suspension liquid of NaH (48 mg, 2.0 mmol), returns to after room temperature is reacted 2h again and leaves standstill, and filters.Filtrate is cooled to-78
oc slowly imports to Cp*ZrCl with bridge
3in the THF solution of (82.6 mg, 0.25 mmol), slowly return to after room temperature and continue to stir after 12h, drain, molten with toluene, remove by filter insoluble NaCl, filtrate is drained, and obtains orange powder, productive rate 55% with toluene/normal hexane recrystallization.
embodiment 21:the reaction of normal pressure catalyzed ethylene polymerization:
Vinyl polymerization carries out under anhydrous and oxygen-free condition.Catalyzer dissolves with toluene in advance, is made into the solution of 0.0025mol/L.Under ethene atmosphere with syringe to the toluene solution that adds successively 2.5 μ mol catalyst A components in polymerization bottle, under violent stirring, add 40 mL toluene, under certain temperature, keep 5-10 min, add the toluene solution of a certain amount of (1000-4000:1 Al/Ti) catalyst B component MAO, initiated polymerization, the cumulative volume of reaction system generally remains on 50 mL(different volumes useable solvents toluene and regulates), react after 30 min-120min, mixture is poured into (ethanol/HCl in the ethanolic soln of acidifying
conc=95:5).Fully stir 4 hours, by polymer filtration, and with washing with alcohol 3 times, vacuum-drying 24 hours under 80 oC.Active amt level is 10
4-10
5g PE/ (molMh), the molecular weight of polyethylene order of magnitude is 10
4-10
5g/mol.
embodiment 22:the reaction of high pressure catalyzed ethylene polymerization:
The reaction system that first autoclave is treated to anhydrous and oxygen-free, is warming up to temperature of reaction.By substituting gas, making in still is ethene atmosphere.Syringe is to the toluene solution that adds successively 10 μ mol catalyst A components in polymerization reaction kettle, intense mechanical adds 40 mL toluene under stirring, at 30-100 ℃, keep 5-10 min, add the toluene solution of a certain amount of catalyst B component MAO, initiated polymerization, the mol ratio of A component and B component is 1000:1-4000:1.Be forced into 10atm, reaction 30-120 min.Close steel cylinder, venting, making it is a normal atmosphere.With the ethanolic soln (ethanol/HCl of acidifying
conc=95:5) termination polymerization.Mixture is poured into (ethanol/HCl in the ethanolic soln of acidifying
conc=95:5).Fully stir 4-6 hour, by polymer filtration, and by washing with alcohol, vacuum-drying 24 hours at 80 ℃.Active amt level is 10
6-10
7g PE/ (mol Mh), the molecular weight of polyethylene order of magnitude is 10
5g/mol.
Claims (5)
1. an oxine imine ligand metal olefin polymerization catalyst, is characterized in that, expression formula is MLCl
3, M=Ti, Zr or Hf, L represent a kind of contain can with the O of metal-complexing, three tooth single anion ligands of N atom, its structure is shown below:
；
Its concrete preparation process is as follows:
By 8-hydroxyl quinaldine red, the aniline of various replacements is starting raw material, makes a series of oxine imine derivative parts through series reaction step; The MCl of part and equimolar amount
4reaction, M=Ti, Zr or Hf, after filtration, drain, recrystallization, obtain metal complexes MLCl
3,productive rate: 70%-93%, whole reaction process is as follows:
2. an oxine imine ligand metal olefin polymerization catalyst, is characterized in that, expression formula is CpMLCl
2, M=Ti or Zr, L represent a kind of contain can with the O of metal-complexing, three tooth single anion ligands of N atom, its structure is shown below:
Its concrete preparation process is as follows:
By 8-hydroxyl quinaldine red, the aniline of various replacements is starting raw material, makes a series of oxine imine derivative parts through series reaction step; Part pulls out CpMCl after H with NaH
3reaction, after filtration, drain, recrystallization, obtain metal complexes Cp'MLCl
2,cp' is cyclopentadienyl or pentamethyl-cyclopentadienyl; M=Ti, or Zr; Productive rate: 55%-81%; Whole reaction process is as follows:
3. a preparation method for olefin polymerization catalysis as claimed in claim 1, is characterized in that concrete steps are as follows:
By 8-hydroxyl quinaldine red, the aniline of various replacements is starting raw material, makes a series of oxine imine derivative parts through series reaction step; The MCl of part and equimolar amount
4reaction, M=Ti, Zr or Hf, after filtration, drain, recrystallization, obtain metal complexes MLCl
3,productive rate: 70%-93%, whole reaction process is as follows:
4. a preparation method for olefin polymerization catalysis as claimed in claim 2, is characterized in that concrete steps are as follows:
By 8-hydroxyl quinaldine red, the aniline of various replacements is starting raw material, makes a series of oxine imine derivative parts through series reaction step; Part pulls out CpMCl after H with NaH
3reaction, after filtration, drain, recrystallization, obtain metal complexes Cp'MLCl
2,cp' is cyclopentadienyl or pentamethyl-cyclopentadienyl; M=Ti, or Zr; Productive rate: 55%-81%; Whole reaction process is as follows:
5. olefin polymerization catalysis as claimed in claim 1 or 2, in the application of preparing in polyethylene, is characterized in that concrete steps are as follows:
Vinyl polymerization carries out under anhydrous and oxygen-free condition; Described olefin polymerization catalysis dissolves with toluene in advance, is made into the solution of 0.0025mol/L; Under ethene atmosphere with syringe to the toluene solution that adds successively the olefin polymerization catalysis described in 2.5 μ mol in polymerization bottle, under stirring, add 30-40 mL toluene, at 30-100 ℃, keep 5-10 min; Then add the toluene solution initiated polymerization of the methylaluminoxane of a certain amount of catalyzer methylaluminoxane or modification, the mol ratio of the methylaluminoxane of olefin polymerization catalysis and methylaluminoxane or modification is 1000:1-4000:1; The cumulative volume of reaction system remains on 50 mL, after reaction 5 min-60min, mixture is poured in the ethanolic soln of acidifying, fully stirs 4-6 hour, by polymer filtration, and by washing with alcohol, vacuum-drying 24 hours under 80 oC, active amt level is 10
4-10
5g PE/ (mol Mh), the molecular weight of polyethylene order of magnitude is 10
4-10
5g/mol.
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| CN102311462A (en) * | 2011-04-01 | 2012-01-11 | 中国科学院化学研究所 | Chinoline imine IVB-group monocyclopentadienyl complex and preparation method and application thereof |
| CN103772439B (en) * | 2012-10-26 | 2016-07-13 | 中国石油化工股份有限公司 | A kind of quinoline benzimidazole Group IVB list half metallocene and its preparation method and application and the method for olefinic polyreaction |
| CN113583060B (en) * | 2020-04-30 | 2023-10-13 | 中国石油化工股份有限公司 | Iron complex and preparation method thereof, iron catalyst and application thereof, and polybutadiene and preparation method thereof |
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| US6020493A (en) * | 1999-05-06 | 2000-02-01 | Equistar Chemicals, Lp | Single-site catalyst preparation |
| CN101258174A (en) * | 2005-09-07 | 2008-09-03 | 伊奎斯塔化学有限公司 | Olefin polymerization catalyst system |
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| US6020493A (en) * | 1999-05-06 | 2000-02-01 | Equistar Chemicals, Lp | Single-site catalyst preparation |
| CN101258174A (en) * | 2005-09-07 | 2008-09-03 | 伊奎斯塔化学有限公司 | Olefin polymerization catalyst system |
Non-Patent Citations (2)
| Title |
|---|
| "half-sandwich group 4 salicyloxazoline catalysts";Stuart R. Coles, et al;《organometallics》;20061116(第25期);第6019-6029页 * |
| Stuart R. Coles, et al."half-sandwich group 4 salicyloxazoline catalysts".《organometallics》.2006,(第25期),第6019-6029页. |
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