CN105732406A - Cycloheptatriene-structure-containing aluminium compound catalysts, synthesis thereof and uses of the catalysts - Google Patents
Cycloheptatriene-structure-containing aluminium compound catalysts, synthesis thereof and uses of the catalysts Download PDFInfo
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- SJLSBMBXHJXCAO-UHFFFAOYSA-M C[Al](C)(N1c(cccc2)c2Sc2ccccc2)[O]=C2C1=CC=CC=C2 Chemical compound C[Al](C)(N1c(cccc2)c2Sc2ccccc2)[O]=C2C1=CC=CC=C2 SJLSBMBXHJXCAO-UHFFFAOYSA-M 0.000 description 1
Abstract
The invention relates to cycloheptatriene-structure-containing aluminium compound catalysts, synthesis thereof and uses of the catalysts, and particularly discloses lactide ring opening polymerization catalyzed by cycloheptatriene-structure-containing aluminium compounds. The catalysts can effectively catalyze lactide ring opening polymerization. High activity of the catalysts may derive from capability of forming smaller chelating rings with aluminum so that ring tension is higher. Activity of the catalysts having sidearm effects is obviously higher than that of the catalysts free of sidearm effects. When a monomer ratio is 100:1 and the temperature is 80 DEG C, the catalysts nearly allow lactide to be completely polymerized. In addition, the sidearm effects influence tacticity of polylactic acid.
Description
Technical field
The present invention relates to the synthesis of the catalyst of aluminum containing cycloheptatriene structure and purposes, under initiator effect, it is possible to catalyzing ring-opening polymerization of lactide efficiently.It is 100:1 in monomer ratio, during temperature 80 DEG C, lactide almost can be made to be polymerized completely.Meanwhile, side arms' effect also have impact on the steric regularity of polylactic acid.
Background technology
Aliphatic polyester such as polylactic acid and polycaprolactone, can be regenerated by biodegradation with it, have received increasing attention in recent years.The more important thing is, we can regulate the physical property of this base polymer in polymerization and the course of processing, so that the field such as its extensive use and biology, medicine, microelectronics.At present, industrial by stannous octoate initiation catalyzing ring-opening polymerization of lactide acquisition polylactic acid.But, there is genotoxic potential and the uncontrollable steric regularity of this system in stannum.The nineties in 20th century, [ChengM, AttygalleAB, LobkovskyEB, the CoatesGW.JAmChemSoc1999 such as Coates；121:11583-4] and [ChisholmMH such as Chisholm, EilertsNW.ChemCommun1996:853-4] synthesized a series of with beta-diimine and three pyrazoles boron be part zinc, magnesium, calcium compounds, efficient obtaining catalyzing ring-opening polymerization of lactide, their research has started the research boom to this field.
Containing Al catalysts because its low toxicity and effective stereoselective receive significant attention.But yet suffer from, containing Al catalysts, the shortcoming that activity is low, thus limiting its application industrially.It is known that the performance of metallic catalyst can pass through steric hindrance and the electronic effect adjustment of part.People have synthesized substantial amounts of containing Al catalysts, [N, O] class such as salicylic alidehyde imine compound (Fig. 1 a, A) [LiuY, DongWS, LiuJYandLiYS.DaltonTrans2014；43:2244-51].[O, N, N, O] class such as schiff bases (Fig. 1 a, B) [OvittTM, the CoatesGW.JAmChemSoc2002 of four teeth；124:1316-26] and salen part [WhitelawEL, LoraineG, MahonMF, JonesMD.DaltonTrans2011；40:11469-73].Existing part is many forms hexa-atomic chelate ring with aluminum, the chelate ring that few employing is less.But, in olefin polymerization, the research of Keim etc. proves, the size reducing chelate ring can be effectively improved SHOP catalyst activity (Fig. 1 b) [KeimW, SchulzRP.JMolCatalA1994 for ethylene oligomerization；92:21-33].So the present invention is by reducing the chelate ring with aluminum of [N, O] class catalyst, improve the catalyst activity to lactide ring-opening polymerisation.
Summary of the invention
It is part that the present invention chooses cycloheptatriene imines ketone, and this part can form five yuan of chelate rings.Brookhart etc. reported nickel compound (Fig. 2, C) [HicksFA, the BrookhartM.Organometallics2001 of a series of base and this part；20:3217-19；HicksFA,JenkinsJC,BrookhartM.Organometallics2003；22:3533-45].It is surprising that although this kind of part does not have a very big steric hindrance, but can the polyethylene of high activity ground catalytic polymerization high molecular.Subsequently, Mazzeo etc. have synthesized this part and titanium (Fig. 2, E) [MinaM, MarinaL, AngelaT, RobertoC, ClaudioP.DaltonTrans2005:3025-31] and aluminum [PappalardoD, MazzeoM, MontefuscoP, TedescoC, PellecchiaC.EurJInorgChem2004；1292-98] compound that formed, and have studied its polymerization activity to ethylene.Although it is reported that, cycloheptatriene imines ketone part in late transition metal can not catalyzed alkene, but never have people its ring-opening polymerisation for lactide.Therefore, the present invention mainly reports the aluminium compound activity for lactide ring-opening polymerisation of such part.
Report display, the structure change that part is small can cause the great variety of transition metal-catalyzed energy.Side arms' effect can regulate and control transition metal-catalyzed energy effectively.Such as, Tang etc. has synthesized a series of negative monovalence part [O, N, X] (X=O, S, Se), its compound for catalysis polymerising ethylene formed with titanium, its activity and molecular weight of product regulate [WangC, MaZ, SunXL such as through hetero atom, GaoY, GuoYH, TangY, ShiLP.Organometallics2006；25:3259-66].Other metal such as chromium, nickel etc. can also be adjusted by similar side arms' effect.But, regulated the ring-opening polymerisation of metal pair lactide by side arms' effect almost without people.
Therefore, the present invention, by regulating the hetero atom substituents of limit arm, regulates the activity of the Al catalysts catalyzed ring opening polymerization rac-lactide that cycloheptatriene imines ketone is part.
The invention provides a kind of by the aluminium compound catalyzing ring-opening polymerization of lactide containing cycloheptatriene structure, under initiator effect, this type of catalyst can catalyzing ring-opening polymerization of lactide efficiently.The high activity of this type of catalyst is likely to come from it and forms less chelate ring with aluminum, has bigger ring strain.The not only Catalysis Rate of the catalyst containing side arms' effect is fast, and can affect the steric regularity of polylactic acid.
Specifically, the first aspect of the invention provides the part containing cycloheptatriene structure of a kind of formula (I),
Wherein
X is nitrogen-containing group, oxy radical, sulfur-containing group, arsenic-containing group or phosphorus-containing groups；
R1、R2、R3、R4、R5、R6、R7、R8、R9It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical or other safing function group, R1、R2、R3、R4、R5、R6、R7、R8、R9Can be the same or different and can cyclization each other；
R10It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical, phenyl, the phenyl of replacement or other safing function group.
In a preferred embodiment, C1-C6Substituted hydrocarbon radical be halohydrocarbyl, it is preferred to-CH2Cl,-CH2CH2Cl。
In a preferred embodiment, described part is 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone, 2-{2-[(2,6-diisopropyl) phenoxy group] anilino-} .alpha.-Tropolone and/or 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone, it is most preferred that for 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone.
The second aspect of the invention provides the aluminum complex containing cycloheptatriene structure of a kind of formula (II), and catalyst can high activity ground catalyzing ring-opening polymerization of lactide:
Wherein
X is nitrogen-containing group, oxy radical, sulfur-containing group, arsenic-containing group or phosphorus-containing groups；
R1、R2、R3、R4、R5、R6、R7、R8、R9It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical or other safing function group, R1、R2、R3、R4、R5、R6、R7、R8、R9Can be the same or different and can cyclization each other；
R10It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical, phenyl, the phenyl of replacement or other safing function group；
Y, Z are selected from aryl, halogen atom, hydrogen atom, C1-C6Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, silicon-containing group, germanic group or containing tin group.
In a preferred embodiment, Y, Z are C1-C6Substituted hydrocarbon radical.
In a preferred embodiment, described aluminum complex is 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone aluminium compound, 2-{2-[(2,6-diisopropyl) phenyl] anilino-} .alpha.-Tropolone aluminium compound and/or 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone aluminium compound, it is preferred to 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone aluminium compound.
The third aspect of the invention provides the method for aluminum complex described in preparation claim 4 or 5, described method includes in organic solvent, at-50-150 DEG C, being reacted 1-50 hour with mol ratio 1:0.1-6 with aluminium compound by the part in any one of claim 1-3, described aluminium compound is AlR12R13R14, wherein R12, R13, R14 are aryl, halogen atom, hydrogen atom, C1-C6Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, silicon-containing group, germanic group or containing tin group, it is preferred to AlMe3。
In a preferred embodiment, described organic solvent is selected from oxolane, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, ether, 2,4-dioxane and 1,2-dichloroethanes.
The fourth aspect of the invention provides a kind of method of catalyzing ring-opening polymerization of lactide, and described method includes being polymerized with the aluminum complex catalysis lactide of second aspect of the present invention.
In a preferred embodiment, described method is when anhydrous and oxygen-free, lactide and initiator are sufficiently mixed, solvent can select oxolane, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, chlorobenzene, ether, 2,4-dioxane or 1,2-dichloroethanes, is subsequently adding the solution (solvent is ibid) of catalyst, reacts at-50-100 DEG C.
The fifth aspect of the invention provide a kind of regulate and control polylactic acid stereoscopic regularity method, described method includes being polymerized with the aluminum complex catalysis lactide of second aspect of the present invention.
Accompanying drawing explanation
Fig. 1. salicylic alidehyde imine class Al catalysts (A), salen class Al catalysts (B)；(b) chelate ring size in SHOP class catalyst on ethylene oligomerization activity impact；
Fig. 2. the metallic compound of cycloheptatriene imines ketone part；
The mono-crystalline structures of Fig. 3 .2-[2-(phenoxy group) anilino-] .alpha.-Tropolone aluminium compound (catalyst 1)；
The mono-crystalline structures of Fig. 4 .2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone aluminium compound (catalyst 3)；
Fig. 5. the molecular weight (■) of the polylactic acid of catalyst 1 catalyzing ring-opening polymerization of lactide and molecular weight distribution (▲) and monomer conversion between relation, polymerizing condition: 50 micro-catalyst that rub, catalyst concn: benzyl alcohol concentration: lactide concentration=1:1:100,7 milliliters of toluene, 80 DEG C.
Detailed description of the invention
Examples described below show the not ipsilateral of the present invention, the data provided include the synthesis of part, the synthesis of metallic compound, lactide ring-opening polymerization method, the wherein synthesis of metallic compound, ring opening polymerisation process is all carry out under anhydrous and oxygen-free, the material of all sensitivities leaves in the glove box refrigerator of-30 DEG C, and all solvents both pass through strict drying and dewater, and lactide adopts dichloromethane and normal hexane recrystallization purifying, being not particularly illustrated, all of raw material directly uses after buying.
The silicagel column silica gel of 200-300 order, nuclear-magnetism Bruker400MHz nuclear-magnetism instrument.Elementary analysis is measured by China Science & Technology University's physics and chemistry center.By GPC mensuration, (case temperature is 45 DEG C to molecular weight and molecualr weight distribution for polystyrene type pillar, HR2 and HR4, uses Water1515 and Water2414 pump.Mobile phase is oxolane, flow velocity be 1.0 milliliters per minute, adopting polydisperse polystyrene is standard).Mass spectrum ThermoLTQOrbitrapXL (ESI+) or P-SIMS-GlyofBrukerDaltonicsInc (EI+) measures.Single crystal X diffraction analysis adopts OxfordDiffractionGeminiSUltraCCD single crystal diffraction instrument, CuK αRoom temperature radiates.Part reference literature synthesis (Fig. 3) [HicksFA, BrookhartM.OrgLett2000 containing cycloheptatriene；2:219-21].
Embodiment 1
The synthesis of 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone
Under a nitrogen atmosphere, with the Schlenk bottle of magneton adds three (two benzal-BASE acetone) two palladiums (0.09 gram, 0.01 mmoles, from An Naiji company buy), 1,1 '-dinaphthalene-2,2 '-bis-diphenyl phosphines (0.012 gram, 2.0 mmoles, from An Naiji company buy), 2-trifluoromethanesulfonic acid base .alpha.-Tropolone (0.53 gram, 2.0 mmoles), 2-phenoxybenzamine (0.44 gram, 2.4 mmoles, buy from An Naiji company) and 4 milliliters of toluene.Mixture stirs 24 hours at 80 DEG C, and room temperature is down in reaction end, filters with the silicagel columns of 10 centimetres, 200 milliliters of dichloromethane rinse.Finally with petroleum ether: ethyl acetate=10:1 leacheate is crossed post and obtained yellow product (0.48 gram, productivity 83%).1HNMR(400MHz,CDCl3): δ=8.75 (s, 1H, NH), 7.52 7.47 (m, 1H, CH), 7.29 (d, J=7.3Hz, 2H, CH), 7.23 (d, J=1.1Hz, 1H, CH), 7.20 7.17 (m, 2H, CH), 7.14 (d, J=4.4Hz, 2H, CH), 7.07 (m, J=9.1,1H, CH), 6.93 (d, J=7.7Hz, 2H, CH), 6.76 (d, J=8.3Hz, 1H, CH).13CNMR(100MHz,CDCl3): δ=177.25 (C=O), 156.55 (C-N), 152.94,150.62,137.37,135.78,131.00,129.87,152.75,126.69,124.88,124.79,124.01,123.73,120.00,118.48,111.04ppm.HRMS (m/z): calculate C19H16NO2: 290.1181, actually measured: 290.1176 [M+H]+。
Embodiment 2
2-{2-[(2,6-diisopropyl) phenoxy group] anilino-} synthesis of .alpha.-Tropolone
Under a nitrogen atmosphere, with the Schlenk bottle of magneton adds three (two benzal-BASE acetone) two palladiums (0.09 gram, 0.01 mmoles), 1,1'-dinaphthalene-2,2'-double; two diphenyl phosphine (0.012 gram, 2.0 mmoles), 2-trifluoromethanesulfonic acid base .alpha.-Tropolone (0.53 gram, 2.0 mmoles), 2-[(2,6-diisopropyl) phenyl] aniline (0.65 gram, 2.4 mmoles) and 4 milliliters of toluene.Mixture stirs 24 hours at 80 DEG C, and room temperature is down in reaction end, filters with the silicagel columns of 10 centimetres, 200 milliliters of dichloromethane rinse.Finally with petroleum ether: ethyl acetate=10:1 leacheate is crossed post and obtained yellow product (0.45 gram, productivity 60%).1HNMR(400MHz,CDCl3): δ=8.99 (s, 1H, NH), 7.53 7.45 (m, 1H, CH), 7.38 7.25 (m, 2H, CH), 7.25 7.14 (m, 5H, CH), 7.08 7.00 (m, 1H, CH), 6.78 (m1H, CH), 6.52 6.44 (m, 1H, CH), 2.94 (m, 2H, CH (CH3)2), 1.10 (dd, J=13.8,6.9Hz, 4H, CH3)ppm.13CNMR(100MHz,CDCl3): δ=177.35 (C=O), 153.71 (C-N), 152.74,148.36,141.64,137.42,135.88,130.82,126.73,126.68,126.20,124.83,124.52,124.49,121.67,114.22,111.00,27.17 [CH (CH3)2],24.42[CH(CH3)2],22.58[CH(CH3)2] ppm.HRMS (m/z): calculate C25H28NO2: 374.2120, actually measured: 374.2115 [M+H]+。
Embodiment 3
The synthesis of 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone
Under a nitrogen atmosphere, with the Schlenk bottle of magneton adds three (two benzal-BASE acetone) two palladiums (0.09 gram, 0.01 mmoles), 1,1'-dinaphthalene-2,2'-double; two diphenyl phosphine (0.012 gram, 2.0 mmoles), 2-trifluoromethanesulfonic acid base .alpha.-Tropolone (0.53 gram, 2.0 mmoles), 2-diaminodiphenyl sulfide (0.44 gram, 2.4 mmoles, buy from An Naiji company) and 4 milliliters of toluene.Mixture stirs 24 hours at 80 DEG C, and room temperature is down in reaction end, filters with the silicagel columns of 10 centimetres, 200 milliliters of dichloromethane rinse.Finally with petroleum ether: ethyl acetate=10:1 leacheate is crossed post and obtained yellow product (0.48 gram, productivity 83%).1HNMR(400MHz,CDCl3): δ=8.86 (s, 1H, NH), 7.42 (s, 2H, CH), 7.46 7.13 (m, 9H, CH), 7.06 (t, J=10.2Hz, 1H, CH), 6.96 (d, J=10.3Hz, 1H, CH), 6.74 (t, J=9.1Hz, 1H, CH) ppm.13CNMR(100MHz,CDCl3): δ=177.23 (C=O), 152.97 (C-N), 138.25,137.37,135.72,134.13,133.52,131.93,131.46 (, 131.17,129.37,128.50,127.58,126.55,124.92,124.84ppm.HRMS (m/z): calculate C19H16NOS:306.0953, actually measured: 306.0941 [M+H]+。
Embodiment 4
The synthesis of 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone aluminium compound (catalyst 1)
In glove box, in the Schlenk bottle of magneton, add 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone (0.50 gram, 1.73 mmoles) and 25 milliliters of toluene.Toluene solution that dropping trimethyl aluminium (is bought from An Naiji company) (1.2 equivalents, 1.3 milliliters, 1.6 moles every liter, 2.07 mmoles).Mixture is stirred at room temperature 24 hours, goes out the washing of product normal hexane, finally obtain the product 0.6 gram (productivity 85%) of yellow after draining.Yield 0.54 gram (productivity 90%).1HNMR(400MHz,CDCl3): δ=7.31 7.13 (m, 8H, CH), 7.10 7.04 (m, 1H, CH), 6.98 (d, J=11.5Hz, 1H, CH), 6.94 (dd, J=7.9,1.7Hz, 1H, CH), 6.92 6.82 (m, 3H, CH),-0.76 (s, 6H, CH3).13CNMR(100MHz,CDCl3): δ=172.98 (C=O), 164.90 (C-N), 155.96,151.27,138.60,138.53,133.57,129.88,127.21,126.53,126.14,124.18,123.99,123.50,121.97,119.54,118.91 ,-9.55 (Al-Me). and elementary analysis: calculate C, 73.03；H,5.84；N, 4.06. survey: C, and 73.33；H,5.73；N, 4.27.EIMS (m/z): calculate C20H17AlNO2: 330.1075, actual measurement: 330.1036 [M-CH3]+。
Embodiment 5
2-{2-[(2,6-diisopropyl) phenyl] anilino-} synthesis of .alpha.-Tropolone aluminium compound (catalyst 2)
Synthesis step ibid, puts into 2-{2-[(2,6-diisopropyl) phenyl] anilino-} .alpha.-Tropolone (0.50 gram, 1.34 mmoles), yield 0.46 gram (productivity 80%).1HNMR(400MHz,CDCl3): δ=7.39 6.83 (m, 11H, CH), 6.46 (dd, J=8.1,1.7Hz, 1H, CH), 2.98 (m, J=6.5Hz, CH (CH3)2), 1.04 (t, J=6.9Hz, 12H, CH (CH3)2),-0.66(s,6H,Al(CH3)2).13CNMR(100MHz,CDCl3): δ=172.97 (C=O), 165.33 (C-N), 152.73,147.81,141.81,138.57,138.49,130.75,127.16,126.43,126.25,124.62,123.39,122.37,122.03,114.53,31.75,26.71,24.67,23.19,22.82,14.29 ,-9.41 (Al-Me). and elementary analysis, calculate: C, 75.50；H,7.51；N, 3.26. survey: C, and 75.23；H,7.21；N, 3.40.EIMS (m/z): calculate C26H29AlNO2: 414.2014, actual measurement: 414.2018 [M-CH3]+。
Embodiment 6
The synthesis (catalyst 3) of 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone aluminium compound
Synthesis step ibid, puts into 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone (0.53 gram, 1.74 mmoles), yield 0.55 gram (productivity 88%).1HNMR(400MHz,CDCl3): δ=7.31 (d, J=7.3Hz, 2CH), 7.21 (dd, J=19.7,6.8Hz, 6H, CH), 7.13 7.04 (m, 3H, CH), 6.96 (d, J=7.8Hz, 1H, CH), 6.80 (t, J=9.5Hz, 1H, CH), 6.53 (d, J=11.4Hz, 1H, CH),-0.74 (d, J=13.8Hz, 6H, CH3).13CNMR(100MHz,CDCl3): δ=172.87 (C=O), 165.54 (C-N), 141.10,139.05,138.78,134.22,133.60,133.49,130.73,129.54,128.26,127.83,127.17,126.53,125.97,123.74,121.22,-9.23 (Al-Me). elementary analysis, calculate: C, 69.78；H,5.58；N, 3.88. survey: C, and 69.53；H,5.52；N, 3.90.EIMS (m/z): calculate C20H17AlNOS:346.0846, actual measurement: 346.0840 [M-CH3]+。
Embodiment 7
Catalyzing ring-opening polymerization of lactide
In glove box, with the Schlenk bottle of magneton adds rac-lactide (0.72 gram, 5 mmoles, buy from lark prestige company), benzylalcohol (50 micro-rub, buy from nine ancient cooking vessel companies) and 6 milliliters of toluene.Put into after 80 DEG C of oil baths are heated 20 minutes, the catalyst (50 micro-rub) of preparation in the embodiment 4-6 being dissolved in advance in 1 milliliter of toluene is squeezed into reaction bulb with syringe needle, after stirring arrival presets the time, take out to drain on a small quantity and record conversion ratio with nucleus magnetic hydrogen spectrum analysis, record molecular weight and molecualr weight distribution (result shows in Table 1) with GPC.Last product goes out with methanol extraction after being down to room temperature.
In table 1 it can be seen that 1,2,3 three kind of catalyst can catalyzing ring-opening polymerization of lactide efficiently, and molecular weight distribution is very narrow.From conversion ratio it can be seen that the catalysis activity of catalyst 1 is the highest, at catalyst: benzylalcohol: lactide=1:1:100, temperature is 80 DEG C is, it is possible to converted 92% in 2 hours.The stereoselective (isotacticity is 0.58) that catalyst 3 has had in room temperature, dichloromethane solution.
Fig. 5 shows the relation between molecular weight and molecualr weight distribution and the monomer conversion of the polylactic acid of catalyst 1 catalyzing ring-opening polymerization of lactide.Along with the increase of monomer conversion, the molecular weight of polylactic acid linearly increases, and molecular weight distribution is almost constant, illustrates that this catalyst lactide ring-opening polymerisation is living polymerization.
Table 1. lactide is under above-mentioned catalyst and AaLower ring-opening polymerisation
aPolymerizing condition, 50 micro-catalyst that rub, 7 milliliters of toluene, 80 DEG C.
bRecord with nucleus magnetic hydrogen spectrum.
cCalculate molecular weight=144.13 × (lactide concentration/benzyl alcohol concentration) × conversion ratio %+108.13.11st row, calculates molecular weight=144.13 × (lactide concentration/catalyst concn) × conversion ratio.
dGPC numerical value is that styrene numerical value in oxolane is multiplied by 0.58.
eSolvent is dichloromethane.
Claims (10)
1. the part containing cycloheptatriene structure of formula (I),
Wherein
X is nitrogen-containing group, oxy radical, sulfur-containing group, arsenic-containing group or phosphorus-containing groups；
R1、R2、R3、R4、R5、R6、R7、R8、R9It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical or other safing function group, R1、R2、R3、R4、R5、R6、R7、R8、R9Can be the same or different and can cyclization each other；
R10It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical, phenyl, the phenyl of replacement or other safing function group.
2. part according to claim 1, wherein C1-C6Substituted hydrocarbon radical be halohydrocarbyl, it is preferred to-CH2Cl,-CH2CH2Cl。
3. part according to claim 1, described part is 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone, 2-{2-[(2,6-diisopropyl) phenoxy group] anilino-} .alpha.-Tropolone and/or 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone.
4. the aluminum complex containing cycloheptatriene structure of a formula (II):
Wherein
X is nitrogen-containing group, oxy radical, sulfur-containing group, arsenic-containing group or phosphorus-containing groups；
R1、R2、R3、R4、R5、R6、R7、R8、R9It is hydrogen, C1The alkyl of-C6, halogen, C1-C6Substituted hydrocarbon radical or other safing function group, R1、R2、R3、R4、R5、R6、R7、R8、R9Can be the same or different and can cyclization each other；
R10It is hydrogen, C1-C6Alkyl, halogen, C1-C6Substituted hydrocarbon radical, phenyl, the phenyl of replacement or other safing function group；
Y, Z are selected from aryl, halogen atom, hydrogen atom, C1-C6Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, silicon-containing group, germanic group or containing tin group, it is preferred to C1-C6Alkyl.
5. aluminum complex according to claim 3, described aluminum complex is 2-[2-(phenoxy group) anilino-] .alpha.-Tropolone aluminium compound, 2-{2-[(2,6-diisopropyl) phenoxy group] anilino-} .alpha.-Tropolone aluminium compound and/or 2-[2-(benzene sulfydryl) anilino-] .alpha.-Tropolone aluminium compound.
6. the method preparing aluminum complex described in claim 4 or 5, described method includes in organic solvent, at-50-150 DEG C, is reacted with aluminium compound by the part in any one of claim 1-3, and described aluminium compound is AlR12R13R14, wherein R12, R13, R14 are aryl, halogen atom, hydrogen atom, C1-C6Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, silicon-containing group, germanic group or containing tin group, it is preferred to trimethyl aluminium.
7. the mol ratio 1:0.1-6 of method according to claim 6, described part and aluminium compound, the time of described reaction is 1-50 hour.
8. method according to claim 6, described organic solvent is selected from oxolane, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, ether, 2,4-dioxane and 1,2-dichloroethanes.
9. a method for catalyzing ring-opening polymerization of lactide, described method includes with the aluminum complex catalysis lactide polymerization described in claim 4 or 5.
10. the method regulating and controlling polylactic acid stereoscopic regularity, described method includes with the aluminum complex catalysis lactide polymerization described in claim 4 or 5.
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| CN107955030A (en) * | 2017-12-12 | 2018-04-24 | 新泰中学 | Chiral aluminum complex containing acetylacetone,2,4-pentanedione derivative and its preparation method and application |
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| CN102822180A (en) * | 2010-02-19 | 2012-12-12 | 陶氏环球技术有限责任公司 | Metal-ligand complexes and catalysts |
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| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955030A (en) * | 2017-12-12 | 2018-04-24 | 新泰中学 | Chiral aluminum complex containing acetylacetone,2,4-pentanedione derivative and its preparation method and application |
| CN107955030B (en) * | 2017-12-12 | 2020-09-08 | 新泰中学 | Chiral aluminum complex containing acetylacetone derivative, and preparation method and application thereof |
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