CN102558246B - Bimetal benzyloxy compound and preparation method and application thereof - Google Patents
Bimetal benzyloxy compound and preparation method and application thereof Download PDFInfo
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Abstract
The embodiment of the invention discloses a bimetal benzyloxy compound and a preparation method and an application thereof. The bimetal benzyloxy compound is prepared by taking o-diaminobenzene, 2,4-di-tert-butyl-6-chloromethyl phenol, triethylamine, tricyclic pentadiene-based rare-earth tetrahydrofuran coordination complex, an ethyl benzyloxy zinc compound and a dibenzyloxyl zinc tetrahydrofuran coordination complex. The bimetal benzyloxy compound prepared with the method can be used for effectively catalyzing copolymerization of epoxy cyclohexane and CO2. The invention further provides an application of the bimetal benzyloxy compound with a structure shown as a formula I to catalysis of the copolymerization of epoxy cyclohexane and CO2. As proved by an experimental result, the bimetal benzyloxy compound prepared with the method can be taken as a single-component catalyst for catalyzing copolymerization of epoxy cyclohexane and CO2, and has high catalytic activity; a prepared copolymer has high molecular weight; and more than 104g of copolymer can be prepared with every mole of bimetal benzyloxy compound, and Mn is more than 104.
Description
Technical field
The present invention relates to bimetal compound technical, more particularly, relate to a kind of bimetal benzyloxy compound and preparation method thereof and application.
Background technology
Along with expanding economy, carbonic acid gas be fixed on the utilization of resources and there is important meaning protection of the environment aspect, therefore obtained research widely.The aliphatic polycarbonate (APC) of being prepared by carbonic acid gas and epoxy compounds copolymerization not only has photodegradation and biological degradability, also has the performance of good blocking oxygen and water simultaneously.In aliphatic polycarbonate, the poly-tetrahydrobenzene carbonic ether (PCHC) of preparing due to carbonic acid gas and epoxy cyclohexane (CHO) copolymerization has higher glass transition temperature and thermal degradation, be subject to people's attention gradually, the catalyzer of exploitation catalysis carbonic acid gas and epoxy cyclohexane copolymerization has become the focus of Recent study.
Compare with monometallic title complex, bimetal complexes has unique catalytic perfomance, and catalytic reaction activity is higher, and therefore, the copolymerization synthetic and catalysis carbonic acid gas and epoxy cyclohexane of bimetal complexes has caused people's interest widely gradually.2005, the people such as Lee synthesized a series of energy highly active catalytic epoxy cyclohexanes and CO
2the bimetal complexes of the benzene bridging imido grpup zinc of copolymerization, its catalytic activity is obviously than catalytic activity high (Lee, the B.Y. of beta-diimine base zinc monometallic title complex; Kwon, H.Y.; Lee, S.Y.J.Am.Chem.Soc.2005,127,3031).2007, the people such as Limberg reported the bimetal alkyl of beta-diimine base zinc of chromene bridging and the synthetic method of sulfonyl compound, find that it can catalysis epoxy cyclohexane and CO
2copolymerization (Pilz, M.F.; Limberg, C.Organometallics 2007,26, and 3668).2008, the people such as Harder utilized the beta-diimine part of bridging to synthesize monometallic and the bimetal complexes of a series of calcium and zinc, find that this bimetal complexes has higher catalytic activity (Piesik, D.F.-J. than monometallic title complex; Range, S.; Harder, S.Organometallics 2008,27, and 6178).The people such as Williams have reported can high reactivity ground catalysis epoxy cyclohexane and CO by the stable many metal acetates Zn complex of macrocyclic structure and many metal acetates cobalt complex
2copolymerization (Kember, M.R.; Knight, P.D.; Reung, P.T.R.; Williams, C.K.Angew.Chem.Int.Ed.2009,48,931.; Kember, M.R.; White, A.J.P.; Williams, C.K.Inorg.Chem.2009,48,9535.; Kember, M.R.; White, A.J.P.; Williams, C.K.Macromolecules 2010,43, and 2291).
But, up to now, can catalysis epoxy cyclohexane and CO
2the clear and definite assorted bimetal benzyloxy compound of rare earth-zinc of structure of copolymerization have not been reported.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of bimetal benzyloxy compound and preparation method thereof and application, and this bimetal benzyloxy compound can catalysis epoxy cyclohexane and CO
2copolymerization.
The invention provides a kind of bimetal benzyloxy compound, have suc as formula the structure shown in I,
Formula I,
Wherein, Ln is thulium.
Preferably, described Ln is neodymium, ytterbium or yttrium.
The present invention also provides a kind of preparation method of bimetal benzyloxy compound, comprising:
Step is a) by O-Phenylene Diamine, and 2,4-di-t-butyl-6-chloro-methyl phenol and triethylamine mix, and back flow reaction, obtains anilino bridging four phenol;
Step b) described anilino bridging four phenol are reacted in ether solvent with three cyclopentadienyl base rare earth tetrahydrofuran (THF) title complexs;
Step c) by step b) product that obtains reacts in ether solvent with ethyl benzyloxy zn cpds, then adds benzyloxy zinc tetrahydrofuran (THF) title complex, and reaction, obtains bimetal benzyloxy compound.
Preferably, described O-Phenylene Diamine, the mol ratio of 2,4-di-t-butyl-6-chloro-methyl phenol and triethylamine is 0.8～1.2: 3～5: 3～5.
Preferably, described step b), the mol ratio of anilino bridging four phenol and described three cyclopentadienyl base rare earth tetrahydrofuran (THF) title complexs is 0.8～1.2: 0.8～1.2.
Preferably, temperature of reaction described step b) is 20～50 ℃.
The mol ratio of the product preferably, described step b) obtaining and ethyl benzyloxy zn cpds is 0.8～1.2: 0.8～1.2.
Preferably, described by step b) product that the obtains temperature of reaction of reacting in ether solvent with ethyl benzyloxy zn cpds is 0～20 ℃;
The described temperature of reaction that adds benzyloxy zinc tetrahydrofuran (THF) title complex to react is 20～50 ℃.
Preferably, described step a) in back flow reaction be specially:
Take methylene dichloride as solvent back flow reaction 60～90 hours in the oil bath of 50～70 ℃.
The present invention also provides a kind of bimetal benzyloxy compound with formula I structure at catalysis epoxy cyclohexane and CO
2the application of copolymerization aspect,
Formula I,
Wherein, Ln is thulium.
From above-mentioned technical scheme, can find out, the invention provides a kind of bimetal benzyloxy compound and preparation method thereof, the present invention is with O-Phenylene Diamine, 2,4-di-t-butyl-6-chloro-methyl phenol, triethylamine, three cyclopentadienyl base rare earth tetrahydrofuran (THF) title complexs, ethyl benzyloxy zn cpds and benzyloxy zinc tetrahydrofuran (THF) title complex are raw material, prepare bimetal benzyloxy compound.The bimetal benzyloxy compound that the present invention prepares is catalysis epoxy cyclohexane and CO effectively
2copolymerization.
The present invention also provides a kind of bimetal benzyloxy compound with formula I structure at catalysis epoxy cyclohexane and CO
2the application of copolymerization aspect, experimental result shows, bimetal benzyloxy compound prepared by the present invention can be used as the copolymerization of single component catalyst catalysis carbonic acid gas and epoxy cyclohexane, catalytic activity is high, the molecular weight of copolymer of preparation is high, wherein, every mole of bimetal benzyloxy compound can prepare and be greater than 10
4the multipolymer of g, M
n> 10
4.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The invention discloses a kind of bimetal benzyloxy compound, have suc as formula the structure shown in I,
Formula I,
Wherein, Ln is thulium, is preferably neodymium, ytterbium or yttrium.
Bimetal benzyloxy compound provided by the invention comprises two rare earth, three zinc atoms and two anilino bridging four aryloxy ligands, and its general formula is (Zn-L-Ln-OCH
2ph)
2zn (OCH
2ph)
2.Described L is anilino bridging aryloxy ligands, described L=N, and N, N ', N '-tetra-(3,5-di-tert-butyl-2-hydroxybenzyl)-benzene-1,2-diamine.The chemical name of L is N, N, and N ', N '-tetra--(3,5-di-t-butyl-2-hydroxybenzyl)-1,2-phenylenediamine, the chemical formula of L is (C
66h
92n
2o
4)
4-, structural formula is suc as formula shown in II:
Formula II.
The present invention also provides a kind of preparation method of bimetal benzyloxy compound, comprising:
Step is a) by O-Phenylene Diamine, and 2,4-di-t-butyl-6-chloro-methyl phenol and triethylamine mix, and back flow reaction, obtains anilino bridging four phenol;
Step b) described anilino bridging four phenol are reacted in ether solvent with three cyclopentadienyl base rare earth tetrahydrofuran (THF) title complexs;
Step c) by step b) product that obtains reacts in ether solvent with ethyl benzyloxy zn cpds, then adds benzyloxy zinc tetrahydrofuran (THF) title complex, and reaction, obtains bimetal benzyloxy compound, and reaction process is as follows:
According to the present invention, described step a) in O-Phenylene Diamine, the mol ratio of 2,4-di-t-butyl-6-chloro-methyl phenol and triethylamine is preferably 0.8～1.2: 3～5: 3～5, more preferably 0.9～1.1: 3～4: 3～4, most preferably be 1: 4: 4.Described back flow reaction is specially: take methylene dichloride as solvent back flow reaction 60～90 hours in the oil bath of 50～70 ℃, be preferably and take methylene dichloride as solvent back flow reaction 72 hours in the oil bath of 60 ℃.The chemical structural formula of anilino bridging four phenol that step a) obtains is as shown in formula III:
Formula III.
Described step a) in 2,4-di-t-butyl-6-chloro-methyl phenol is preferably according to document Casiraghi, G.; Casnati, G.Synthesis.1980, the method providing in 2,124 preparation, preparation process is as follows:
Described 2, the preparation method of 4-di-t-butyl-6-chloro-methyl phenol is specially:
To reaction flask, adding mol ratio is 2,4-DTBP and the formaldehyde of 1: 1, and adds appropriate sodium hydrate solid and methyl alcohol, react after 24 hours, and with hydrochloric acid acidizing reaction liquid, to PH, be 2～3, solution layering, uses CH
2cl
2extraction lower floor organic phase is filtered to obtain glassy yellow clear liquid by described organic phase after anhydrous sodium sulfate drying, is spin-dried for, and obtains yellow thick solid, uses hexane recrystallization, obtains 2,4-di-t-butyl-6-methylolphenol;
By described 2,4-di-t-butyl-6-methylolphenol is dissolved in sherwood oil, under 60 ℃ of oil baths, pass into dry hydrogen chloride gas, react after 4 hours, to above-mentioned reaction solution, add appropriate anhydrous sodium sulphate to be dried, then continue reaction 4 hours, filter to obtain colorless clear liquid, after concentrated, put into refrigerator cold-storage, obtain 2,4-di-t-butyl-6-chloro-methyl phenol crystal.
According to the present invention, described step b) in, three cyclopentadienyl base rare earth tetrahydrofuran (THF) coordination chemistry formulas are LnCp
3(THF), described ethyl benzyloxy zn cpds chemical formula is EtZn (OCH
2ph), described benzyloxy zinc tetrahydrofuran (THF) coordination chemistry formula is [Zn (OCH
2ph)
2]
2(THF).Described step b) anilino bridging four phenol and described LnCp in
3(THF) mol ratio is preferably 0.8～1.2: 0.8～1.2, more preferably 0.9～1.1: 0.9～1.1, most preferably be 1: 1.Described step b) in, temperature of reaction is preferably 20～50 ℃, more preferably 20～40 ℃, most preferably is 30～40 ℃.Described step b) in, the reaction times is preferably 10～48 hours, more preferably 20～48 hours, most preferably is 25～40 hours.Described step b) four phenol of anilino bridging described in and LnCp
3(THF) in ether solvent, after reaction, also preferably include: remove ether solvent, extraction residuum, the centrifugal precipitation of removing, concentrates clear liquid, obtains the crystal of (THF) LnL-H.Described ether solvent is preferably tetrahydrofuran (THF), ether or glycol dimethyl ether.Described step b) reaction process is as follows:
Described step b) LnCp in
3(THF) preferably according to document Wilkinson, G; Brmingham, J.M.J.Am.Chem.Soc.1954.76, the method preparation that 6210-6211 provides, is specially:
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add appropriate LnCl
3and THF, stir 3 hours, with syringe, inject and LnCl
3the mol ratio NaCp that is 3: 1, under room temperature, stir, obtain reaction solution;
Described reaction solution is transferred to centrifugal bottle, and the centrifugal NaCl generating except dereaction, obtains clear liquid, and described clear liquid is transferred to crystallization bottle, puts into refrigerator cold-storage, i.e. crystallize out LnCp
3(THF).
Described step c) product and the EtZn (OCH that in, described step b) obtain
2ph) mol ratio is preferably 0.8～1.2: 0.8～1.2, more preferably 0.9～1.1: 0.9～1.1, most preferably be 1: 1.Described by step b) product and the EtZn (OCH that obtain
2the temperature of reaction of Ph) reacting in ether solvent is preferably 0～20 ℃, more preferably 5～20 ℃, most preferably is 8～15 ℃.Step c) described in, add [Zn (OCH
2ph)
2]
2(THF) temperature of reaction of reaction is preferably 20～50 ℃, and more preferably 25～45 ℃, 30～40 ℃.Described step c) in, ether solvent is preferably tetrahydrofuran (THF), ether or glycol dimethyl ether.
According to the present invention, add [Zn (OCH
2ph)
2]
2(THF),, after reaction, also comprise:
Remove ether solvent, obtain residuum, with varsol, residuum is extracted, centrifugal, get the upper strata stillness of night, concentrated, obtain (ZnL-Ln-OCH
2ph)
2zn (OCH
2ph)
2crystal.Described varsol is preferably toluene or normal hexane.
Described step c) reaction process is as follows:
Described step c) EtZn (OCH in
2ph) preparation method is preferably:
By 3.00mmol ZnEt
2(2.0mL) toluene solution joins in 20mL tetrahydrofuran (THF), under the condition of the ice-salt baths of-15 ℃, the toluene solution that adds 3.00mmol phenylcarbinol by the mol ratio of 1: 1, return to room temperature, stirring at room, uses 20mL n-hexane extraction, obtain clear liquid, in described clear liquid, add 1mL tetrahydrofuran (THF) tube sealing, refrigeration, obtains EtZn (OCH
2ph).
Described [Zn (OCH
2ph)
2]
2(THF) preparation method is preferably:
By 3.00mmol ZnEt
2(2.0mL) toluene solution joins in 20mL tetrahydrofuran (THF), under ice-salt bath condition of-15 ℃, the toluene solution that adds 6.00mmol phenylcarbinol by the mol ratio of 1: 2, returns to room temperature, reacts 10 minutes, obtain white precipitate, stir, obtain white powder, use tetrahydrofuran (THF) washed twice, drain, obtain Zn (OCH
2ph)
2]
2(THF).
The present invention also provides a kind of bimetal benzyloxy compound with formula I structure at catalysis epoxy cyclohexane and CO
2the application of copolymerization aspect,
Formula I,
Wherein, Ln is thulium, is preferably neodymium, ytterbium or yttrium.
The bimetal benzyloxy compound of described formula I structure can be used as single component catalyst when the copolymerization of catalysis carbonic acid gas and epoxy cyclohexane, specifically comprises the following steps:
Under the solvent-free inert atmosphere of anhydrous and oxygen-free, the bimetal benzyloxy compound of formula I structure is dissolved in epoxy cyclohexane, under agitation condition, evenly pass into an atmospheric carbon dioxide, carry out copolyreaction anyway under the condition of 40～90 ℃, the reaction times is 20～30 hours;
With the methyl alcohol containing volume fraction 5% hydrochloric acid, stop described copolyreaction, add methyl alcohol, obtain copolymerization product, dry, obtain poly-tetrahydrobenzene carbonic ether.
The mol ratio of described epoxy cyclohexane and catalyzer is preferably 1000～6000: 1, more preferably 2000～5000: 1.
To the molecular weight determination of poly-tetrahydrobenzene carbonic ether, there is no particular restriction in the present invention, includes but not limited to following methods:
To gather tetrahydrobenzene carbonic ether and be made into tetrahydrofuran solution, determining molecular weight and molecular weight distribution on the PL-50 type gel permeation chromatograph that PL company produces.Concrete test condition is: 40 ℃ of temperature, and tetrahydrofuran (THF) is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards to proofread and correct molecular weight.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
The preparation of 2,4-di-t-butyl-6-chloro-methyl phenol
To reaction flask, adding mol ratio is 2,4-DTBP and the formaldehyde of 1: 1, and adds appropriate sodium hydrate solid and methyl alcohol, react after 24 hours, and with hydrochloric acid acidizing reaction liquid, to PH, be 3, solution layering, uses CH
2cl
2extraction lower floor organic phase is filtered to obtain glassy yellow clear liquid by described organic phase after anhydrous sodium sulfate drying, is spin-dried for, and obtains yellow thick solid, uses hexane recrystallization, obtains 2,4-di-t-butyl-6-methylolphenol;
By described 2,4-di-t-butyl-6-methylolphenol is dissolved in sherwood oil, then under 60 ℃ of oil baths, pass into dry hydrogen chloride gas, react after 4 hours, in above-mentioned reaction solution, add appropriate anhydrous sodium sulphate to be dried, then continue reaction 4 hours, filter to obtain colorless clear liquid, after concentrated, refrigeration is 10 hours, obtains 2,4-di-t-butyl-6-chloro-methyl phenol.
Embodiment 2
Anilino bridging four phenol LH
4preparation
In round-bottomed flask, by the feed ratio of 1: 4: 4, add 2 of O-Phenylene Diamine, embodiment 1 preparation, 4-di-t-butyl-6-chloro-methyl phenol and triethylamine, mix, take methylene dichloride as solvent back flow reaction 72 hours in the oil bath of 60 ℃, by resultant of reaction recrystallization in acetonitrile and methylene dichloride, obtain anilino bridging four phenol.
Embodiment 3
NdCp
3(THF) preparation
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add LnCl
3and THF, stir 3 hours, with syringe, inject and NdCl
3mol ratio is the NaCp of 3: 1, under room temperature, stirs, and obtains reaction solution;
Described reaction solution is transferred to centrifugal bottle, and the centrifugal NaCl generating except dereaction, is transferred to crystallization bottle by clear liquid, puts into refrigerator cold-storage, i.e. crystallize out NdCp
3(THF).
Embodiment 4～5
Respectively with YbCl
3and YCl
3for raw material, adopt the preparation method identical with embodiment 3, preparation YbCp
3and YCp (THF)
3(THF).
Embodiment 6
(THF) LNd-H's is synthetic
Under room temperature, the tetrahydrofuran solution of anilino bridging four phenol of 3.00 mmoles (2.94 grams) embodiment, 2 preparations is added to 3.00 mmoles (1.23 grams) NdCp
3(THF), in tetrahydrofuran solution, stirring at room is reacted 20 hours at 30 ℃, pumps tetrahydrofuran solvent;
With 20 ml n-hexane extraction residuums, the centrifugal precipitation of removing, shifts the clear liquid obtaining, concentrated, then in clear liquid, adds 1 milliliter of tetrahydrofuran (THF), refrigerates 5 days, separates out blue colored crystal, and (THF) LNd-H, is 2.80 grams, and productive rate is 78%.
(THF) infrared spectra of LNd-H (KBr, cm
-1): 3572 (s), 3447 (s), 2966 (w), 2904 (s), 2866 (s), 1604 (s), 1477 (s), 1442 (s), 1411 (s), 1361 (s), 1303 (s), 1276 (s), 1238 (s), 1203 (s), 1165 (s), 1134 (s), 1111 (s), 1022 (s), 910 (s), 875 (s), 833 (s), 806 (s), 759 (s), 740 (s), 682 (s), 524 (s), 435 (s); Ultimate analysis: Nd:11.81%, C:70.64%, H:8.83%, N:2.03%.
Embodiment 7
(THF) LYb-H's is synthetic
Under room temperature, the tetrahydrofuran solution of anilino bridging four phenol of 3.00 mmoles (2.94 grams) embodiment, 2 preparations is added to 3.00 mmole YbCp
3(THF), in the tetrahydrofuran solution of (1.32 grams), stirring at room is reacted 20 hours at 30 ℃, pumps tetrahydrofuran solvent;
With 20 ml n-hexane extraction residuums, the centrifugal precipitation of removing, shifts the clear liquid obtaining, concentrated, then in clear liquid, adds 1 milliliter of tetrahydrofuran (THF), refrigerates 6 days, separates out yellow crystals, and (THF) LYb-H, is 2.97 grams, and productive rate is 81%.(THF) infrared spectra of LYb-H (KBr, cm
-1): 3568 (s), 3441 (s), 2958 (w), 2900 (s), 2866 (s), 1604 (s), 1477 (s), 1442 (s), 1415 (s), 1361 (s), 1303 (s), 1273 (s), 1238 (s), 1203 (s), 1165 (s), 1134 (s), 1107 (s), 1022 (s), 910 (s), 875 (s), 837 (s), 806 (s), 759 (s), 744 (s), 682 (s), 528 (s), 439 (s); Ultimate analysis: Yb:13.88%, C:67.99%, H:8.28%, N:2.25%.
Embodiment 8
(THF) LY-H's is synthetic
Under room temperature, the tetrahydrofuran solution of anilino bridging four phenol of 3.00 mmoles (2.94 grams) embodiment, 2 preparations is added to 3.00 mmole YCp
3(THF), in the tetrahydrofuran solution of (1.07 grams), stirring at room is reacted 20 hours at 30 ℃, pumps tetrahydrofuran solvent;
With 20 ml n-hexane extraction residuums, the centrifugal precipitation of removing, shifts the clear liquid obtaining, concentrated, then in clear liquid, adds 1 milliliter of tetrahydrofuran (THF), refrigerates 5 days, separates out light yellow crystal, and (THF) LY-H, is 2.56 grams, and productive rate is 75%.(THF) infrared spectra of LY-H (KBr, cm
-1): 3564 (s), 3445 (s), 2964 (w), 2904 (s), 2859 (s), 1605 (s), 1477 (s), 1442 (s), 1426 (s), 1362 (s), 1310 (s), 1278 (s), 1243 (s), 1211 (s), 1166 (s), 1134 (s), 1107 (s), 1022 (s), 910 (s), 875 (s), 837 (s), 806 (s), 759 (s), 744 (s), 682 (s), 528 (s), 447 (s); Ultimate analysis: Y:7.98%, C:72.99%, H:8.89%, N:2.45%; Nucleus magnetic resonance (400MHz, C
6d
6): 7.60～6.41 (m, 12H, ArH), 4.42 (d, 2H, ArCH
2n), 4.04 (d, 2H, ArCH
2n), 3.76 (br, s, 4H, α-CH
2tHF), 3.42 (m, 4H, ArCH
2n), 1.98 (br, s, 4H, β-CH
2tHF), 1.85～1.05 (m, 72H, C (CH
3)
3).
Embodiment 9
EtZn (OCH
2synthesizing Ph)
By 3.00mmol ZnEt
2(2.0mL) toluene solution joins in 20mL tetrahydrofuran (THF), under ice-salt bath condition of-15 ℃, adds the toluene solution of 3.00mmol phenylcarbinol by the mol ratio of 1: 1, returns to room temperature, and stirred overnight at room temperature, uses 20mL n-hexane extraction, obtains clear liquid;
In described clear liquid, add 1mL tetrahydrofuran (THF) tube sealing, refrigerate 5 days, separate out clear crystal EtZn (OCH
2ph) 0.46g, productive rate is 73%.
Embodiment 10
[Zn (OCH
2ph)
2]
2(THF) synthesize
By 3.00mmol ZnEt
2(2.0mL) toluene solution joins in 20mL tetrahydrofuran (THF), under ice-salt bath condition of-15 ℃, the toluene solution that adds 6.00mmol phenylcarbinol by the mol ratio of 1: 2, returns to room temperature, reacts 10 minutes, obtain white precipitate, stir, obtain white powder, use tetrahydrofuran (THF) washed twice, drain, obtain Zn (OCH
2ph)
2]
2(THF) 0.77g, productive rate is 81%.
Embodiment 11
(ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2synthetic
Under the condition of ice-salt bath, the tetrahydrofuran solution of 3.00 mmole title complex (THF) LNd-H is joined to 3.00 mmole title complex EtZn (OCH by the mol ratio of 1: 1
2ph) in tetrahydrofuran solution, return to room temperature, at 15 ℃, react 20 hours, then at room temperature by the mol ratio of 2: 1, add 1.50 mmoles [Zn (OCH
2ph)
2]
2(THF) tetrahydrofuran solution reacts 20 hours at 25 ℃, removes tetrahydrofuran (THF), with 20 milliliters of toluene and n-hexane extraction, obtains clear liquid;
In described clear liquid, add 1 milliliter of glycol dimethyl ether, be placed in room temperature, after 5 days, separate out blue colored crystal, i.e. (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
22.15 grams, productive rate is 50%.(ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2infrared spectra (KBr, cm
-1): 3062 (s), 3032 (s), 2956 (s), 2866 (s), 1602 (s), 1469 (s), 1450 (s), 1415 (s), 1384 (s), 1357 (s), 1301 (s), 1240 (s), 1199 (s), 1170 (s), 1124 (s), 1016 (s), 966 (s), 918 (s), 881 (s), 833 (s), 740 (s), 698 (s), 524 (s), 435 (s); Ultimate analysis: Nd:16.48%, C:67.40%, H:7.64%, N:1.68%.
Embodiment 12
(ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2synthetic
Under the condition of ice-salt bath, the tetrahydrofuran solution of 3.00 mmole title complex (THF) LYb-H is slowly added to 3.00 mmole title complex EtZn (OCH by the mol ratio of 1: 1
2ph) in tetrahydrofuran solution, return to room temperature, at 12 ℃, react 25 hours, then at room temperature by the mol ratio of 2: 1, add 1.50 mmoles [Zn (OCH
2ph)
2]
2(THF) tetrahydrofuran solution reacts 25 hours at 30 ℃, with 20 milliliters of toluene and n-hexane extraction, obtains clear liquid;
In described clear liquid, add 1 milliliter of tetrahydrofuran (THF), be placed in room temperature, within 7 days, separate out 2.41 grams of yellow crystals, i.e. (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2, productive rate is 55%.(ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2infrared spectra (KBr, cm
-1): 3062 (s), 3030 (s), 2956 (s), 2866 (s), 1604 (s), 1475 (s), 1448 (s), 1413 (s), 1388 (s), 1361 (s), 1309 (s), 1240 (s), 1197 (s), 1166 (s), 1047 (s), 1022 (s), 913 (s), 877 (s), 837 (s), 734 (s), 696 (s), 611 (s), 526 (s), 441 (s) 1384 (s); Ultimate analysis: Yb:18.03%, C:66.47%, H:7.63%, N:1.98%.
Embodiment 13
(ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.0876 gram of (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2(0.0305 mmole), passes into an atmospheric carbon dioxide equably, and in the oil bath of 70 ℃, constant temperature, after 3 minutes, adds and (ZnL-Nd-OCH with syringe
2ph)
2zn (OCH
2ph)
2mol ratio 6.2 milliliters of (61 mmole) the epoxy cyclohexane monomers that are 2000: 1, polyreaction 22 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add methyl alcohol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 2.69 grams of poly-tetrahydrobenzene carbonic ethers, productive rate 46%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 4.36 ten thousand, molecular weight distribution (M
w/ M
n) be 2.74.The results show, (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 8.82 * 10
4gram multipolymer/mole.
Embodiment 14
(ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.0759 gram of (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2(0.0264 mmole), passes into an atmospheric carbon dioxide equably, at 70 ℃ of oil bath constant temperature, after 3 minutes, with syringe, adds and (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2mol ratio 10.7 milliliters of (105.6 mmole) the epoxy cyclohexane monomers that are 4000: 1, polyreaction 22 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add ethanol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 3.64 grams of poly-tetrahydrobenzene carbonic ethers, productive rate 34%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 6.01 ten thousand, molecular weight distribution (M
w/ M
n) be 3.04.The results show, (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 13.78 * 10
4gram multipolymer/mole.
Embodiment 15
ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.0363 gram of ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2(0.0127 mmole), passes into an atmospheric carbon dioxide equably, at 70 ℃ of oil bath constant temperature, after 3 minutes, with syringe, adds and ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2mol ratio 7.72 milliliters of (71.1 mmole) the epoxy cyclohexane monomers that are 6000: 1, polyreaction 23 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add methyl alcohol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 0.76 gram of poly-tetrahydrobenzene carbonic ether, productive rate 17.4%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 3.43 ten thousand, molecular weight distribution (M
w/ M
n) be 2.55.The results show, ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 10.30 * 10
4gram multipolymer/mole.
Embodiment 16
(ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.1236 gram of (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2(0.0430 mmole), passes into an atmospheric carbon dioxide equably, at 80 ℃ of oil bath constant temperature, after 3 minutes, with syringe, adds and (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2mol ratio 8.8 milliliters of (86.6 mmole) the epoxy cyclohexane monomers that are 2000: 1, polyreaction 23 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add methyl alcohol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 3.23 grams of poly-tetrahydrobenzene carbonic ethers, productive rate 37.9%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 2.02 ten thousand, molecular weight distribution (M
w/ M
n) be 3.03.The results show, (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 7.48 * 10
4gram multipolymer/mole.
Embodiment 17
(ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.1197 gram of (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph) 2 (0.0417 mmoles), pass into an atmospheric carbon dioxide equably, at 60 ℃ of oil bath constant temperature, after 3 minutes, with syringe, add and (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2mol ratio 8.5 milliliters of (83.63 mmole) the epoxy cyclohexane monomers that are 2000: 1, polyreaction 23 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add methyl alcohol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 3.50 grams of poly-tetrahydrobenzene carbonic ethers, productive rate 42.7%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 3.56 ten thousand, molecular weight distribution (M
w/ M
n) be 3.12.The results show, (ZnL-Nd-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 8.39 * 10
4gram multipolymer/mole.
Example 18
(ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.0947 gram of (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2(0.0323 mmole), passes into an atmospheric carbon dioxide equably, at 70 ℃ of oil bath constant temperature, after 3 minutes, with syringe, adds and (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2mol ratio 6.56 milliliters of (64.6 mmole) the epoxy cyclohexane monomers that are 2000: 1, polyreaction 22 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add methyl alcohol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 3.34 grams of poly-tetrahydrobenzene carbonic ethers, productive rate 51%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 5.74 ten thousand, molecular weight distribution (M
w/ M
n) be 2.85.The results show, (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 10.36 * 10
4gram multipolymer/mole.
Example 19
(ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2catalysis CO
2copolymerization with epoxy cyclohexane
Under argon shield, in the reaction flask of processing through dehydration and deoxidation, add 0.1481 gram of (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2(0.0505 mmole), passes into an atmospheric carbon dioxide equably, at 70 ℃ of oil bath constant temperature, after 3 minutes, with syringe, adds and (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2mol ratio 10.30 milliliters of (101.43 mmole) the epoxy cyclohexane monomers that are 2000: 1, polyreaction 10 hours, by the methyl alcohol termination reaction containing 5% hydrochloric acid, add methyl alcohol, obtain multipolymer, by after described multipolymer vacuum-drying to constant weight, obtain 7.41 grams of poly-tetrahydrobenzene carbonic ethers, productive rate 74.6%.
GPC surveys the number-average molecular weight (M of multipolymer
n) be 1.96 ten thousand, molecular weight distribution (M
w/ M
n) be 2.72.The results show, (ZnL-Yb-OCH
2ph)
2zn (OCH
2ph)
2catalytic activity be 14.60 * 10
4gram multipolymer/mole.
Experimental result shows, bimetal benzyloxy compound prepared by the present invention can be used as the copolymerization of single component catalyst catalysis carbonic acid gas and epoxy cyclohexane, and catalytic activity is high, and the molecular weight of copolymer of preparation is high, wherein, every mole of bimetal benzyloxy compound can prepare and be greater than 10
4the multipolymer of g, M
n> 10
4.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a bimetal benzyloxy compound, has suc as formula the structure shown in I,
Wherein, Ln is neodymium or ytterbium.
2. a preparation method for the bimetal benzyloxy compound of the structure shown in formula I, is characterized in that, comprising:
Step is a) by O-Phenylene Diamine, and 2,4-di-t-butyl-6-chloro-methyl phenol and triethylamine mix, and back flow reaction obtains anilino bridging four phenol of the structure shown in formula III;
Step b) described anilino bridging four phenol are reacted in ether solvent with three cyclopentadienyl rare earth tetrahydrofuran (THF) title complexs;
Described step b) in, three cyclopentadienyl rare earth tetrahydrofuran (THF) coordination chemistry formulas are LnCp
3(THF);
Step c) by step b) product that obtains reacts in ether solvent with ethyl benzyloxy zn cpds, then adds benzyloxy zinc tetrahydrofuran (THF) title complex, and reaction, obtains bimetal benzyloxy compound; Described benzyloxy zinc tetrahydrofuran (THF) coordination chemistry formula is [Zn (OCH
2ph)
2]
2(THF);
Wherein, Ln is neodymium or ytterbium.
3. preparation method according to claim 2, is characterized in that, described O-Phenylene Diamine, and the mol ratio of 2,4-di-t-butyl-6-chloro-methyl phenol and triethylamine is 0.8～1.2:3～5:3～5.
4. preparation method according to claim 2, is characterized in that, described step b) in the mol ratio of anilino bridging four phenol and described three cyclopentadienyl rare earth tetrahydrofuran (THF) title complexs be 0.8～1.2:0.8～1.2.
5. preparation method according to claim 2, is characterized in that, described step b) temperature of reaction be 20～50 ℃.
6. preparation method according to claim 2, is characterized in that, described step b) product obtaining and the mol ratio of ethyl benzyloxy zn cpds be 0.8～1.2:0.8～1.2.
7. preparation method according to claim 2, is characterized in that,
Described by step b) product that the obtains temperature of reaction of reacting in ether solvent with ethyl benzyloxy zn cpds is 0～20 ℃;
The described benzyloxy zinc tetrahydrofuran (THF) title complex that adds, reaction, temperature of reaction is 20～50 ℃.
8. preparation method according to claim 2, is characterized in that, described step a) middle back flow reaction is specially:
Take methylene dichloride as solvent back flow reaction 60～90 hours in the oil bath of 50～70 ℃.
9. a bimetal benzyloxy compound with formula I structure is at catalysis epoxy cyclohexane and CO
2the application of copolymerization aspect,
Wherein, Ln is neodymium or ytterbium.
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| CN101693754A (en) * | 2009-10-12 | 2010-04-14 | 中国科学院长春应用化学研究所 | Application of rare-earth complexes chelated by tridentate carbazolyl in conjugated diene and polar monomer copolymerization catalyst system |
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| CN101693754A (en) * | 2009-10-12 | 2010-04-14 | 中国科学院长春应用化学研究所 | Application of rare-earth complexes chelated by tridentate carbazolyl in conjugated diene and polar monomer copolymerization catalyst system |
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