Process for preparing conjugated diene (co)polymers in the presence of a catalytic system comprising a pyridyl iron (III) complex
10793653 · 2020-10-06
Assignee
Inventors
- Giovanni Ricci (Parma, IT)
- Guido Pampaloni (Pontedera, IT)
- Anna Sommazzi (Novara, IT)
- Massimo Guelfi (Pietrasanta, IT)
- Francesco Masi (Sant′ Angelo Lodigiano, IT)
Cpc classification
C08L9/00
CHEMISTRY; METALLURGY
International classification
C08L9/00
CHEMISTRY; METALLURGY
C08F4/70
CHEMISTRY; METALLURGY
Abstract
A process for preparing conjugated diene (co)polymers comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): wherein: R.sub.1, R.sub.2, R.sub.3 and R.sub.4, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R.sub.5 represents a hydrogen atom, or is selected from linear or branched, optionally halogenated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, OCOR.sub.6 groups or OR.sub.6 groups wherein R.sub.6 is selected from linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups. n is 3; (b) at least one co-catalyst selected from organo-aluminum derivatives, preferably from: (b.sub.1) aluminum compounds having general formula (III): Al(R.sub.7)(R.sub.8)(R.sub.9) (IIl) wherein R.sub.7 represents a hydrogen atom, or is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R.sub.8 and R.sub.9, identical or different, are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; (b.sub.2) aluminoxanes having general formula (IV): (R.sub.10).sub.2AlO[-AI(R.sub.11)O-].sub.m-AI-(R.sub.12).sub.2 (IV), wherein R.sub.10, R.sub.11 and R.sub.12, identical or different, represent a hydrogen atom, or a halogen atom such as chlorine, bromine, iodine, fluorine; or are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b.sub.3) partially hydrolyzed organo-aluminum derivatives; (b.sub.4) haloaluminum alkyls having general formula (V) or (VI): AI(R.sub.13).sub.p(X).sub.3-p (V) AI.sub.2(R.sub.13).sub.q(X).sub.3-q (VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R.sub.13, identical or different, are selected from linear or branched C.sub.1-C.sub.20 alkyl groups; X represents a chlorine or bromine atom, preferably chlorine; provided that said co-catalyst (b) is not selected from organo-boron derivatives. ##STR00001##
Claims
1. Process for preparing conjugated diene (co)polymers comprising polybutadiene comprising (co)polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): ##STR00030## wherein: R.sub.1, R.sub.2, R.sub.3 and R.sub.4, identical or different, represent a hydrogen atom; or are selected from a linear or branched, optionally halogenated C.sub.1-C.sub.20 alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group; R.sub.5 represents a hydrogen atom, or is selected from a linear or branched, optionally halogenated C.sub.1-C.sub.20 alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group; X, identical or different, represent a halogen atom; or are selected from a linear or branched C.sub.1-C.sub.20 alkyl group, an OCOR.sub.6 group or an OR.sub.6 group wherein R.sub.6 is selected from a linear or branched C.sub.1-C.sub.20 alkyl group; n is 3; (b) at least one co-catalyst selected from the following organo-aluminum derivatives: (b.sub.1) aluminum compounds having general formula (III):
Al(R.sub.7)(R.sub.8)(R.sub.9) (III) wherein R.sub.7 represents a hydrogen atom, or is selected from a linear or branched C.sub.1-C.sub.20 alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxy group; Rs and R9, identical or different, are selected from a linear or branched C.sub.1-C.sub.20 alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group; (b.sub.2) aluminoxanes having general formula (IV):
(R.sub.10).sub.2AlO[Al(R.sub.11)O-].sub.m-Al(R.sub.12).sub.2(IV) wherein R.sub.10, R.sub.11 and R.sub.12, identical or different, represent a hydrogen atom, or a halogen atom, or are selected from a linear or branched C.sub.1-C.sub.20 alkyl group, a cycloalkyl group or an aryl group, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b.sub.3) partially hydrolyzed organo-aluminum derivatives; (b.sub.4) haloaluminum alkyls having general formula (V) or (VI):
Al(R.sub.13).sub.p(X).sub.3-p(V)
Al.sub.2(R.sub.13).sub.q(X).sub.3-q(VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R.sub.13, identical or different, are selected from a linear or branched C.sub.1-C.sub.20 alkyl group; X represents a chlorine or bromine atom; wherein polybutadiene obtained has a higher content of 1,2 unit than 1,4 cis unit.
2. Process for preparing conjugated diene (co)polymers including polybutadiene according to claim 1, wherein in said pyridyl iron (III) complex having general formula (I) or (II): R.sub.1, R.sub.2, R.sub.3 and R.sub.4, identical or different, represent a hydrogen atom; or are selected from a linear or branched C.sub.1-C.sub.20 alkyl group; R.sub.5 is selected from an aryl group optionally substituted with one or more of a methyl, ethyl, Cert-butyl or iso-propyl group; is selected from a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a 2-tert-butylphenyl group, a 2-iso-propylphenyl group, a 2,6-diethylphenyl group, a 2,6-di-iso-propylphenyl group, or a 2,4,6-trimethylphenyl group; or is an optionally substituted cyclohexyl group; X, mutually identical, represent a halogen atom; n is 3.
3. Process for preparing conjugated diene (co)polymers comprising polybutadiene according to claim 1, wherein said aluminum compounds having general formula (III) (b.sub.1) are selected from: diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, di-iso-butyl-aluminum hydride (DIBAH), diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenyl-n-propylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolyl-iso-propylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzyl-iso-propylaluminum hydride, diethylaluminum ethoxide, di-iso-butylaluminum ethoxide, dipropylaluminum ethoxide, trimethylaluminum, triethylaluminum (TEA), tri-n-propylaluminum, tri-iso-butylaluminum (TIBA), tri-n-butylaluminum, tripentylaluminum, trihexylaluminum, triciclohexylaluminum, trioctylalurninurn, trip henylaluminum, tri-p-tolylaluminum, tribenzylalurninurn, ethyldiphenylaluminum, ethyl-di-p- tolylaluminum, ethyldibenzylaluminum, diethylphenylaluminum, diethyl-p-tolylaluminum or diethylbenzylaluminum, or mixtures thereof.
4. Process for preparing conjugated diene (co)polymers comprising polybutadiene according to claim 1, wherein said aluminoxanes having general formula (IV), (b.sub.2) are selected from: methylaluminoxane (MAO), ethylaluminoxane, n-butylaluminoxane , tetra-iso-butylaluminoxane (TTMPAO), Cert-butylaluminoxane, tetra-(2,4,4-trimethylpentyl)aluminooxane (TIOAO), tetra-(2,3-dimethylbutyl)aluminoxane (TDMBAO) or tetra-(2,3,3-trimethylbutyl)aluminoxane (TTMBAO), or mixtures thereof.
5. Process for preparing conjugated diene (co)polymers comprising polybutadiene according to claim 1, wherein said partially hydrolyzed organo-aluminum-derivatives (b.sub.3) are selected from aluminum compounds having general formula (III) added with at least one protonating compound, the aluminum compound having general formula (III) and the protonating compound being used in a molar ratio ranging from 0.001:1 to 0.2:1; said protonating compound is selected from: water; alcohols; alcohols with higher molecular weight; carboxylic acids; or mixtures thereof.
6. Process for preparing conjugated diene (co)polymers comprising polybutadiene according to claim 1, wherein said haloaluminum alkyls having general formula (V) or (VI) are selected from: diethylchloroaluminum (AlEt.sub.2Cl), dimethylaluminumchloride (AlMe.sub.2Cl), ethylaluminumdichloride (AlEtCl.sub.2), di-iso-butylaluminumchloride [Al(i-Bu).sub.2Cl), ethylaluminumsesquichloride (Al.sub.2Et.sub.3Cl.sub.3) or methylaluminumsesquichloride (Al.sub.2Me.sub.3Cl.sub.3).
7. Process for preparing conjugated diene (co)polymers comprising polybutadiene according to claim 1 wherein said conjugated diener are selected from at least one of: 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), or 2,3-dimethyl-1,3-butadiene.
8. Process for preparing conjugated diene (co)polymers including polybutadiene according to claim 1 wherein: said (co)polymerization is carried out in the presence of at least one inert organic solvent selected from: saturated aliphatic hydrocarbons selected from butane, pentane, hexane or heptane, or mixtures thereof; saturated cycloaliphatic hydrocarbons selected from cyclopentane or cyclohexane, or mixtures thereof; mono-olefins selected from 1-butene or 2-butene, or mixtures thereof; aromatic hydrocarbons selected from benzene, toluene or xylene, or mixtures thereof; halogenated hydrocarbons selected from methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene or chlorotoluene, or mixtures thereof; or selected from said at least one conjugated diene to be (co)polymerized; and/or the concentration of said at least one conjugated diene to be (co)polymerized in said at least one inert organic solvent ranges from 5% by weight to 50% by weight with respect to the total weight of the mixture of said at least one conjugated diene to be (co)polymerized and said at least one inert organic solvent; and / or said process is carried out at a temperature ranging from 70 C. to +100 C.
9. The process for preparing conjugated diene (co)polymers comprising polybutadiene of claim 1 wherein R.sub.5 is substituted with at least one linear or branched C.sub.2-C.sub.12 alkyl group or linear or branched C.sub.2-C.sub.12 alkoxyl group at one or both of the 2 and 6 positions.
10. The process for preparing conjugated diene (co)polymers comprising polybutadiene of claim 9 wherein R.sub.5 is substituted with said alkyl group which is one or more of an ethyl, Cert-butyl or iso-propyl group.
11. The process for preparing conjugated diene (co)polymers comprising polybutadiene of claim 1 wherein R.sub.4 is selected from a linear or branched, optionally halogenated C.sub.1-C.sub.20 alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.
12. The process for preparing conjugated diene (co)polymers comprising polybutadiene of claim 9 wherein R.sub.4 is selected from a linear or branched, optionally halogenated C.sub.1-C.sub.20 alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.
Description
EXAMPLES
(1) Reagents and Materials
(2) The list below shows the reagents and materials used in the following examples of the invention, any pre-treatments thereof and their manufacturer: iron (III) chloride (FeCl.sub.3) (Aldrich): purity 99.9%, used as such; methylaluminoxane (MAO) (toluene solution 10% by weight) (Crompton): used as such; aniline (Aldrich): distilled at reduced pressure and stored in an inert atmosphere; hydrochloric acid in 37% aqueous solution (Aldrich): used as such; o-toluidine (Aldrich): distilled at reduced pressure and stored in an inert atmosphere; 2-iso-propylaniline (Aldrich): distilled at reduced pressure and stored in an inert atmosphere; 2-tert-butylaniline (Aldrich): distilled at reduced pressure and stored in an inert atmosphere; 2,6-di-iso-propylaniline (Aldrich): distilled at reduced pressure and stored in an inert atmosphere; ethyl ether (Aldrich): pure, 99%, distilled over sodium (Na) in an inert atmosphere; 2,4,6-tri-methylaniline (Aldrich): distilled at reduced pressure and stored in an inert atmosphere; 2-pyridinecarboxaldehyde (Aldrich): used as such; 2-acetylpyridine (Aldrich): used as such; cyclohexylamine (Aldrich): used as such; ethyl acetate (Aldrich): used as such; hexane (Aldrich): pure, 99%, distilled over sodium (Na) in an inert atmosphere; heptane (Aldrich): pure, 99%, distilled over sodium (Na) in an inert atmosphere; methanol (Carlo Erba, RPE): used as such; anhydrous methanol (Aldrich): purity 99.8%, used as such; ethanol (Carlo Erba, RPE): used as such; anhydrous ethanol (Aldrich): purity 99.8%, used as such; pentane (Aldrich): purity 99.8%, used as such; chloroform (Aldrich): pure, 99.9%, used as such; sodium borohydride (Aldrich): purity 99%, used as such; anhydrous sodium sulfate (Na.sub.2SO.sub.4) (Aldrich): pure, 99%, used as such; magnesium sulfate (MgSO4) (Aldrich): pure, 99%, used as such; toluene (Aldrich): pure, 99.5%, distilled over sodium (Na) in an inert atmosphere; 1,3-butadiene (Air Liquide): pure, 99.5%, evaporated from the container before each production, dried by passing it through a molecular sieve packed column and condensed inside the reactor that was pre-cooled to 20 C.; isoprene (Aldrich): pure, 99%, refluxed over calcium hydride for 2 hours, then distilled trap-to-trap and stored in a nitrogen atmosphere at 4 C.; formic acid (HCOOH) (Aldrich): purity 95%, used as such; p-toluenesulfonic acid monohydrate (CH.sub.3C.sub.6H.sub.4SO.sub.3H.H.sub.2O) (Aldrich): purity 98%, used as such; hydrofluoric acid (HF) (40% aqueous solution) (Aldrich): used as such; sulfuric acid (H.sub.2SO.sub.4) (96% aqueous solution) (Aldrich): used as such, or diluted with distilled water (1/5); nitric acid (HNO.sub.3) (70% aqueous solution) (Aldrich): used as such; sodium carbonate (Na.sub.2CO.sub.3) (Aldrich): used as such; silver nitrate (AgNO.sub.3) (Aldrich): used as such; deuterated tetrachloroethylene (C.sub.2D.sub.2Cl.sub.4) (Acros): used as such; hexamethyldisiloxane (HMDSO) (Acros): used as such; deuterated chloroform (CDCl.sub.3) (Acros): used as such; deuterated dichloromethane (CD.sub.2Cl.sub.2) (Acros): used as such; tetramethylsilane (TMS) (Acros): used as such.
(3) The analysis and characterization methodologies reported below were used.
(4) Elementary Analysis
(5) a) Determination of Fe
(6) For the determination of the quantity by weight of iron (Fe) in the pyridyl iron complexes used for the purpose of the present invention, an exactly weighed aliquot, operating in dry-box under nitrogen flow, of about 30 mg-50 mg of sample, was placed in a 30 ml platinum crucible, together with a mixture of 1 ml of 40% hydrofluoric acid (HF), 0.25 ml of 96% sulfuric acid (H.sub.2SO.sub.4) and 1 ml of 70% nitric acid (HNO.sub.3). The crucible was then heated on a hot plate increasing the temperature until white sulfur fumes appeared (about 200 C.). The mixture thus obtained was cooled to room temperature and 1 ml of 70% nitric acid (HNO.sub.3) was added, then it was left again until fumes appeared. After repeating the sequence another two times, a clear, almost colorless, solution was obtained. 1 ml of nitric acid (HNO.sub.3) and about 15 ml of water were then added cold, then heated to 80 C. for about 30 minutes. The sample thus prepared was diluted with MilliQ pure water until it weighed about 50 g, precisely weighed, to obtain a solution on which the instrumental analytical determination was carried out using a Thermo Optek IRIS Advantage Duo ICP-OES (plasma optical emission) spectrometer, for comparison with solutions of known concentration. For this purpose, for every analyte, a calibration curve was prepared in the range 0 ppm-10 ppm, measuring calibration solutions by dilution by weight of certified solutions.
(7) The solution of sample prepared as above was then diluted again by weight in order to obtain concentrations close to the reference ones, before carrying out spectrophotometric measurement. All the samples were prepared in double quantities. The results were considered acceptable if the individual repeated test data did not have a relative deviation of more than 2% with respect to their mean value.
(8) b) Determination of Chlorine
(9) For said purpose, samples of the pyridyl iron complexes used for the purpose of the present invention, about 30 mg-50 mg, were precisely weighed in 100 ml glass beakers in dry-box under nitrogen flow. 2 g of sodium carbonate (Na.sub.2CO.sub.3) were added and, outside the dry-box, 50 ml of MilliQ water. It was brought to the boil on the hot plate, under magnetic stirring, for about 30 minutes. It was left to cool, then 1/5 diluted sulfuric acid (H.sub.2SO.sub.4) was added, until acid reaction and was then titrated with 0.1 N silver nitrate (AgNO.sub.3) with a potentiometric titrator.
(10) c) Determination of Carbon, Hydrogen and Nitrogen
(11) The determination of carbon, hydrogen and nitrogen, in the pyridyl iron complexes used for the purpose of the present invention, as well as in the ligands used for the purpose of the present invention, was carried out through a Carlo Erba automatic analyzer Mod. 1106.
(12) .sup.13C-HMR and .sup.1H-HMR Spectra
(13) The .sup.13C-HMR and .sup.1H-HMR spectra were recorded using a nuclear magnetic resonance spectrometer mod. Bruker Avance 400, using deuterated tetrachloroethylene (C.sub.2D.sub.2Cl.sub.4) at 103 C., and hexamethyldisiloxane (HDMSO) as internal standard, or using deuterated chloroform (CDCl.sub.3), at 25 C., and tetramethylsilane (TMS) as internal standard. For this purpose, polymeric solutions were used with concentrations equal to 10% by weight with respect to the total weight of the polymeric solution.
(14) The microstructure of the polymers [i.e. 1,4-cis (%) 1,4-trans (%) and 1.2(%) unit content for polybutadiene and 1,4-cis (%), 1,4-trans (%) and 3.4(%) unit content for polyisoprene] was determined through the analysis of the aforementioned spectra based on the contents of literature by Mochel, V. D., in Journal of Polymer Science Part A-1: Polymer Chemistry (1972), Vol. 10, Issue 4, pg. 1009-1018 for polybutadiene, and by Sato H. et al. in Journal of Polymer Science: Polymer Chemistry Edition (1979), Vol. 17, Issue 11, pg. 3551-3558, for polyisoprene.
(15) FT-IR Spectra (Solid StateUATR)
(16) The FT-IR spectra (solid stateUATR) were recorded using a Bruker IFS 48 spectrophotometer equipped with a Thermo Spectra-Tech horizontal ATR connection. The section wherein the samples to be analyzed are placed is a Fresnel ATR accessory (Shelton, Conn., USA) which uses crystals of zirconium selenide (ZrSe) with an angle of incidence of 45 in the horizontal direction.
(17) The FT-IR spectra (solid stateUATR) of the pyridyl iron complexes used for the purpose of the present invention, were obtained by inserting samples of the pyridyl iron (III) complexes to be analyzed into said section.
(18) I.R. Spectra
(19) The I.R. spectra (FT-IR) were recorded through Thermo Nicolet Nexus 670 and Bruker IFS 48 spectrophotometers.
(20) The I.R. spectra (FT-IR) of the ligands used for the purpose of the present invention, were obtained by dispersing the ligand to be analyzed in anhydrous potassium bromide (KBr) (KBr disks), or in nujol solution.
(21) The I.R. spectra (FT-IR) of the polymers were obtained from polymeric films on potassium bromide (KBr) tablets, said films being obtained through the deposition of a solution in hot 1,2-dichlorobenzene of the polymer to be analyzed. The concentration of the polymeric solutions analyzed was equal to 10% by weight with respect to the total weight of the polymeric solution.
(22) Determination of the Molecular Weight
(23) The determination of the molecular weight (MW) of the polymers obtained was carried out through GPC (Gel Permeation Chromatography), using the Waters Alliance GPC/V 2000 System by Waters Corporation which uses two detection lines: Refractive Index (RI) and viscometer operating under the following conditions: two PLgel Mixed-B columns; solvent/eluent: o-dichlorobenzene (Aldrich); flow rate: 0.8 ml/min; temperature: 145 C.; molecular mass calculation: Universal Calibration method.
(24) The weight-average molecular weight (M.sub.w) and the polidispersity index (PDI) are reported, corresponding to the ratio M.sub.w/M.sub.n (M.sub.n=number-average molecular weight).
(25) Mass Spectra
(26) The mass spectra of the ligands used for the purpose of the present invention were carried out with a Trace DSQ single quadrupole mass spectrometer (Thermo ISQ) in Electronic Ionization (EI) mode, operating under the following conditions: scanning: from 35 amu to 600 amu (amu=atomic mass unit); temperature of the source: 250 C.; transfer line temperature: 300 C.; capillary column: MDN-5S (Supelco) (length=30 m; diameter=0.25 mm; stationary phase thickness=0.25 m); carrier gas: helium (He) with constant flow equal to 1 ml/min.
(27) X-Ray Diffraction (XRD) XR SPECTRUM
(28) For that purpose, samples of the powdered polymers obtained (about 100 mg), were analyzed by means of X-ray diffraction (XRD) using a Bruker P4 diffractometer equipped with a HiStar 2D detector using Cu KR monochromatic radiation () (1.54179 ) of graphite and a sample-detector distance of 10 cm.
Example 1
(29) Synthesis of Ligand Having Formula (L1)
(30) ##STR00007##
(31) In a 500 ml flask, 2-pyridinecarboxaldehyde (30 g, 280 mmoles) and some drops of formic acid were added to a solution of aniline (26.1 g, 280 mmoles) in methanol (250 ml): the mixture obtained was maintained, under stirring, at room temperature, for 48 hours. Subsequently, the solvent was removed through vacuum evaporation and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 99/1 (v/v)], obtaining 38 g of a pale yellow solid (yield=74.5%) corresponding to the ligand having formula (L1).
(32) Molecular weight (MW): 182.22.
(33) Elementary analysis [found (calculated for C.sub.12H.sub.10N.sub.2)]: C: 80.00% (79.10%); H: 5.83% (5.53%); N: 15.71% (15.37%).
(34) .sup.1H-NMR (CDCl.sub.3, ppm) 8.70 (m, 1H, HPy), 8.41 (m, 1H, HPy), 8.80 (tds, 1H CHN), 8.19 (d, 1H, HPy), 7.77 (dt, 1H, HPy), 7.23-7.42 (m, 1H, HPy; m, 5H, Ar).
Example 2
(35) Synthesis of Ligand Having Formula (L1A)
(36) ##STR00008##
(37) 13 g (71.3 mmoles) of the ligand having formula (L1) obtained as described in Example 1 and 700 ml of anhydrous methanol were loaded into a 2 liter reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (40 g, 1057 mmoles) was added, in small portions, under stirring. The mixture obtained was maintained, under stirring, at room temperature, all night. Subsequently, the solvent was removed through distillation at reduced pressure and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 9/1 (v/v)], obtaining 9.12 g of a white crystalline solid (yield=69.5%) corresponding to the ligand having formula (L1A).
(38) GC-MS: M.sup.+=m/z 184; [M-C.sub.6H.sub.6].sup.+=m/z 106; [M-C.sub.7H.sub.9N].sup.+=m/z 77.
(39) .sup.1H-NMR (CDCl.sub.3, ppm): 8.60 (dd, 1H, PyH), 7.64 (m, 1H, PyH), 7.35 (d, 1H, PyH), 7.22-7.17 (m, 1H, Py-2H, ArH), 6.75-6.69 (tm, 3H, ArH), 4.8 (s, 1H, NH), 4.48 (s, 2H, Py-CH.sub.2N).
Example 3
(40) Synthesis of Ligand Having Formula (L2)
(41) ##STR00009##
(42) In a 250 ml flask, 2-acetylpyridine (9.1 g, 75 mmoles) and some drops of formic acid were added to a solution of o-toluidine (8 g, 75 mmoles) in methanol (100 ml): the mixture obtained was maintained, under stirring, at room temperature, for 48 hours. Subsequently, the solvent was removed through vacuum evaporation and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 99/1 (v/v)], obtaining 6.5 g of a light yellow oil (yield=40%) corresponding to the ligand having formula (L2).
(43) Molecular weight (MW): 210.28.
(44) Elementary analysis [found (calculated for C.sub.14H.sub.14N.sub.2)]: C: 80.00% (79.97%); H: 6.77% (6.71%); N: 13.41% (13.32%).
(45) .sup.1H-NMR (CDC.sub.3, ppm) 8.70 (m, 1H, HPy), 8.41 (m, 1H HPy), 8.80 (td, 1H, HPy), 7.39 (dt, 1H, HPy), 7.27-7.18 (m, 2H, Ph), 7.02 (m, 1H, Ph), 6.69 (d, 1H, Ph), 2.30 (s, 3H, NCCH.sub.3), 2.10 (s, 3H, Ph-CH.sub.3).
Example 4
(46) Synthesis of Ligand Having Formula (L2A)
(47) ##STR00010##
(48) 8 g (38 mmoles) of the ligand having formula (L2) obtained as described in Example 3 and 150 ml of anhydrous methanol were loaded into a 250 ml reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (21.6 g, 571 mmoles) was added, in small portions, under stirring. The mixture obtained was maintained, under stirring, at room temperature, all night. Subsequently, the solvent was removed through distillation at reduced pressure and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 9/1 (v/v)], obtaining a pale yellow oil: the whole was placed in the refrigerator, all night, obtaining 2.43 g of a white solid (yield=30%) corresponding to the ligand having formula (L2A).
(49) Molecular weight (MW): 212.29.
(50) GC-MS: M.sup.+=m/z 212; [M-CH.sub.3].sup.+=m/z 197; [M-C.sub.5H.sub.4N].sup.+=m/z 134; [M-C.sub.7H.sub.8N].sup.+=m/z 106.
Example 5
(51) Synthesis of Ligand Having Formula (L3)
(52) ##STR00011##
(53) In a 500 ml flask, 2-acetylpyridine (3.78 g; 31.1 mmoles) and p-toluenesulfonic acid monohydrate (0.15 g; 0.81 mmoles) were added to a solution of 2-iso-propylaniline (4.20 g; 31.1 mmoles) in toluene (20 ml): the mixture obtained was heated under reflux, for 2 hours. Subsequently, the solvent was removed through vacuum evaporation and the residue obtained was purified through vacuum distillation, obtaining 5.89 g of an orange oil (yield=79%) corresponding to the ligand having formula (L3).
(54) FT-IR (nujol) (cm.sup.1): 1637 (v.sub.CN).
(55) Molecular weight (MW): 238.
(56) Elementary analysis [found (calculated for C.sub.16H.sub.18N.sub.2)]: C: 80.17% (80.63%); H: 7.804% (7.61%); N: 11.91% (11.75%).
(57) FT-IR (solid state, UATR) (cm.sup.1): 1637 (v.sub.CN).
(58) .sup.1H NMR (400 MHz, 20 C., CDCl.sub.3): =8.71 (d, 1H), 8.37 (d, 1H), 7.81 (t, 1H), 7.38 (m, 2H), 7.22 (t, 1H), 7.15 (t, 1H), 6.67 (d, 1H), 3.05 (sept, 1H), 2.39 (s, 3H), 1.23 (d, 6H).
Example 6
(59) Synthesis of Ligand Having Formula (L4)
(60) ##STR00012##
(61) In a 500 ml flask, 2-acetylpyridine (12.9 g, 106.5 mmoles) and some drops of formic acid were added to a solution of 2-tert-butylaniline (15.89 g, 106.5 mmoles) in methanol (300 ml): the mixture obtained was maintained, under stirring, at room temperature, for 48 hours. Subsequently, the solvent was removed by vacuum evaporation and the residue obtained was crystallized by methanol obtaining 20 g of a yellow crystalline powder (yield=75%) corresponding to the ligand having formula (L4).
(62) Molecular weight (MW): 252.36.
(63) Elementary analysis [found (calculated for C.sub.17H.sub.20N.sub.2)]: C: 81.17% (80.91%); H: 8.14% (7.99%); N: 10.91% (11.10%).
(64) FT-IR (nujol) (cm.sup.1): 1641 (v.sub.CN).
(65) .sup.1H NMR (400 MHz, 20 C., CDCl.sub.3): =8.71 (d, 1H), 8.35 (d, 1H), 7.84 (t, 1H), 7.45 (d, 1H), 7.40 (t, 1H), 7.21 (t, 1H), 7.10 (t, 1H), 6.56 (d, 1H), 2.38 (s, 3H), 1.38 (s, 9H).
Example 7
(66) Synthesis of Ligand Having Formula (L4A)
(67) ##STR00013##
(68) 28 g (38 mmoles) of the ligand having formula (L4) obtained as described in Example 6 and 800 ml of anhydrous methanol were loaded into a 2 liter reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (38 g, 1004 mmoles) was added, in small portions, under stirring. The mixture obtained was maintained, under stirring, at room temperature, all night, and then quenched with brine and extracted with ethyl acetate (3100 ml). Subsequently the solvent was removed by distillation at reduced pressure and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 9/1 (v/v)], and treated with cold ethyl ether, obtaining 11 g of a crystalline white solid (yield=39%) corresponding to the ligand having formula (L4A).
(69) Molecular weight (MW): 254.
(70) Elementary analysis [found (calculated for C.sub.17H.sub.22N.sub.2)]: C: 80.00% (80.27%); H: 9.12% (8.72%); N: 11.31% (11.01%).
(71) GC-MS: M.sup.+=m/z 254; [M-CH.sub.3].sup.+=m/z 239; [M-C.sub.4H.sub.9].sup.+=m/z 197; [m-C.sub.7H.sub.10N.sub.2].sup.+=m/z 132; [M-C.sub.10H.sub.14N].sup.+=m/z 106; [M-C.sub.12H.sub.18N].sup.+=m/z 78.
(72) .sup.1H-NMR (CDCl.sub.3, ppm): 8.64 (d, 1H, HPy), 7.7 (td, 1H, PyH), 7.36 (d, 1H, HPy), 7.25 (d, 1H, ArH), 7.18 (td, 1H, PyH), 6.98 (td, 1H, PyH), 6.98 (td, 1H, PyH), 6.48 (d, 1H, PyH), 5.0 (broad s, 1H, NH), 4.7 (q, 1H, NCH(CH.sub.3)), 1.57 (d, 3H, NCH(CH.sub.3)), 1.5 (s, 9H, C(CH.sub.3).sub.3).
Example 8
(73) Synthesis of Ligand Having Formula (L5)
(74) ##STR00014##
(75) In a 250 ml flask, 2-acetylpyridine (9.1 g, 75 mmoles) and some drops of formic acid were added to a solution of 2,6-di-iso-propylaniline (13.3 g, 75 mmoles) in methanol (100 ml): the mixture obtained was maintained, under stirring, at room temperature, for 48 hours. Subsequently, the precipitate obtained was filtered and vacuum dried, obtaining 14 g of a yellow crystalline powder (yield=67%) corresponding to the ligand having formula (L5).
(76) Molecular weight (MW): 280.41.
(77) Elementary analysis [found (calculated for C.sub.19H.sub.24N.sub.2)]: C: 81.37% (81.38%); H: 8.64% (8.63%); N: 10.01% (9.99%).
(78) .sup.1H-NMR (CDCl.sub.3, ppm) 8.69 (d, 1H, PyH), 8.38 (d, 1H, PyH), 7.82 (t, 1H, PyH), 7.39 (m, 1H, PyH), 7.11-7.20 (m, 3H, ArH), 2.75 (m, 2H, CHMe.sub.2), 2.21 (s, 3H, NCH-Me), 1.15 (d, 12H, CH(CH.sub.3).sub.2).
(79) FT-IR (nujol) (cm.sup.1): 1649 (v.sub.CN).
Example 9
(80) Synthesis of Ligand Having Formula (L5A)
(81) ##STR00015##
(82) 24 g (85.6 mmoles) of the ligand having formula (L5) obtained as described in Example 8 and 900 ml of anhydrous methanol were loaded into a 2 liter reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (48.6 g, 1285 mmoles) was added, in small portions, under stirring: the mixture obtained was maintained, under stirring, at room temperature, all night, and then switched off with brine and extracted with ethyl acetate (3100 ml). Subsequently the solvent was removed by distillation at reduced pressure and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 9/1 (v/v)], and treated with cold ethyl ether, obtaining 11 g of a crystalline white solid (yield=46%) corresponding to the ligand having formula (L5A).
(83) Molecular weight (MW): 282.43.
(84) Elementary analysis [found (calculated for C.sub.19H.sub.26N.sub.2)]: C: 81.03% (80.80%); H: 9.42% (9.28%); N: 10.01% (9.92%).
(85) GC-MS: M.sup.+=m/z 282; [M-C.sub.3H.sub.7].sup.+=m/z 239; [M-C.sub.7H.sub.8N].sup.+=m/z 176; [M-C.sub.12H.sub.18N].sup.+=m/z 106.
(86) .sup.1H-NMR (CDCl.sub.3, ppm): 8.64 (d, 1H, HPy), 7.53 (dt, 1H, HPy), 7.2 (d, 1H, HPy), 7.00-7.12 (m, 1H, HPy; m, 3H, ArH), 4.0-4.2 (m, 1H, NCH(CH.sub.3); m, 1H, NH), 3.30 (sept, 2H, CH(CH.sub.3).sub.2), 1.55 (d, 3H, NCH(CH.sub.3)), 1.10 (s, 12H, CH(CH.sub.3).sub.2).
Example 10
(87) Synthesis of Ligand Having Formula (L6)
(88) ##STR00016##
(89) In a 250 ml flask, 2-pyridinecarboxaldehyde (20 g, 187 mmoles) and some drops of formic acid were added to a solution of 2,4,6-tri-methylaniline (25 g, 187 mmoles) in methanol (60 ml): the mixture obtained was maintained, under stirring, at room temperature, for 48 hours. Subsequently, the precipitate obtained was filtered and the solvent was removed through distillation at reduced pressure. The yellow oily product obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 99/1 (v/v)], and treated with cold ethyl ether, obtaining 30 g of a pale yellow crystalline product (yield=72%) corresponding to the ligand having formula (L6).
(90) Molecular weight (MW): 224.31.
(91) Elementary analysis [found (calculated for C.sub.15H.sub.16N.sub.2)]: C: 80.35% (80.32%); H: 7.64% (7.19%); N: 12.51% (12.49%).
(92) FT-IR (nujol) (cm.sup.1): 1640 (v.sub.CN).
(93) .sup.1H-NMR (CDCl.sub.3, ppm) 8.72 (m, 1H), 8.32 (s, 1H), 8.29 (dt, 1H), 7.84 (m, 1H), 7.41 (m, 1H), 6.91 (s, 2H), 2.31 (s, 3H), 2.18 (s, 6H).
(94) GC-MS: M.sup.+=m/z 224; [M-H].sup.+=m/z 223; [M-CH.sub.3].sup.+=m/z 209; [M-C.sub.5H.sub.4N].sup.+=m/z 146.
Example 11
(95) Synthesis of Ligand Having Formula (L6A)
(96) ##STR00017##
(97) 13 g (58 mmoles) of the ligand having formula (L6) obtained as described in Example 10, 80 ml of anhydrous methanol and 80 ml of chloroform were loaded into a 250 ml reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (2.2 g, 58 mmoles) was added, in small portions, under stirring. The mixture obtained was maintained, under stirring, at room temperature, for 24 hours. Subsequently, the solvent was removed through distillation at reduced pressure and the residue obtained was extracted with ethyl acetate (80 ml) and water (80 ml). The combined organic extracts were washed to neutrality with water, anhydrified on anhydrous sodium sulfate and filtered. Subsequently, the solvent was removed through vacuum evaporation, obtaining a pale yellow oil to which 30 ml of heptane were added: the whole was placed in the refrigerator, all night, obtaining 5.2 g of a white crystalline solid (yield=40%) corresponding to the ligand having formula (L6A).
(98) Molecular weight (MW): 226.
(99) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm) 8.6 (d, 1H, PyH), 7.61-7.56 (m, 1H, PyH), 7.21 (m, 1H, PyH), 7.19 (m, 1H, PyH), 6.8 (s, 2H, (CH3)3C6H2), 4.2 (s, 2H, PyCH2), 4.11 (s, 1H, NH), 2.31 (s, 6H), 2.2 (s, 3H).
(100) GC-MS: M.sup.+=m/z 226; [M-CH.sub.3].sup.+=m/z 211; [M-C.sub.5H.sub.4N].sup.+=m/z 148, [M-C.sub.5H.sub.4NCH.sub.2].sup.+=m/z 134, [M-C.sub.6H.sub.2(CH3)N].sup.+=m/z 93.
Example 12
(101) Synthesis of Ligand Having Formula (L7)
(102) ##STR00018##
(103) In a 500 ml flask, 2-pyridinecarboxaldehyde (16.86 g; 157.5 mmoles) were added to a solution of 2-iso-propylaniline (27.93 g; 157.5 mmoles) in anhydrous ethanol (250 ml): the mixture obtained was heated under reflux, for 3 hours. Subsequently, the mixture was vacuum dried obtaining a yellow oil to which 30 ml of pentane were added: the whole was placed in the refrigerator, for 48 hours, obtaining the formation of yellow crystals that were recovered through filtration and drying under vacuum, obtaining 41.7 g of a yellow crystalline powder (yield 99%) corresponding to the ligand having formula (L7).
(104) Molecular weight (MW): 266.38.
(105) Elementary analysis [found (calculated for C.sub.18H.sub.22N.sub.2)]: C: 81.31% (81.16%); H: 8.21% (8.32%); N: 9.96% (10.52%).
(106) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm): 8.72 (d, 1H, PyH), 8.32 (s, 1H CHN), 8.27 (d, 1H PyH), 7.86 (t, 1H PyH), 7.39 (m, 1H PyH), 7.11-7.20 (m, 3H ArH), 3.00 (sept, 2H CHMe.sub.2), 1.18 (d, 12H C(CH.sub.3).sub.2).
(107) FT-IR (nujol) (cm.sup.1): 1651 (v.sub.CN).
Example 13
(108) Synthesis of Ligand Having Formula (L7A)
(109) ##STR00019##
(110) 28 g (105.1 mmoles) of the ligand having formula (L7) obtained as described in Example 12 and 1800 ml of anhydrous methanol were loaded into a 2 liter reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (70 g, 1850 mmoles) was added, in small portions, under stirring. The mixture obtained was maintained, under stirring, at room temperature, all night, and then quenched with brine and extracted with ethyl acetate (3100 ml). Subsequently, the solvent was removed by distillation at reduced pressure and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 9/1 (v/v)], and treated with cold ethyl ether, obtaining 16.9 g of a crystalline white solid (yield=60%) corresponding to the ligand having formula (L7A).
(111) Molecular weight (MW): 268.403.
(112) Elementary analysis [found (calculated for C.sub.18H.sub.24N.sub.2)]: C: 80.49% (80.55%); H: 8.99% (9.01%); N: 10.37% (10.44%).
(113) FT-IR (solid state, UATR) (cm.sup.1): 3309, 1588, 1570, 1493, 1463, 1435.
(114) .sup.1H-NMR (CDCl.sub.3, ppm): 8.61 (d, 1H, o-PyH), 7.66 (td, 1H, PyH), 7.30 (d, 1H, PyH), 7.21 (m, 1H, PyH), 7.04-7.12 (m, 3H, ArH), 4.20 (s, 2H, CH.sub.2), 4.10 (s, 1H, NH), 3.47 (m, 2H, CH(CH.sub.3).sub.2), 1.42 (d, 12H, CH(CH.sub.3).sub.2).
(115) GC-MS: M.sup.+=m/z 268; [M-C.sub.3H.sub.7].sup.+=m/z 225; [M-C.sub.6H.sub.6N].sup.+=m/z 176; m/z 93 C.sub.6H.sub.7N.
Example 14
(116) Synthesis of Ligand Having Formula (L8)
(117) ##STR00020##
(118) 14.07 g (131.3 mmoles) of 2-pyridinecarboxaldehyde and 50 ml of ethanol were loaded into a 250 ml reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, cyclohexylamine (13 g, 131.1 mmoles) was added, by dripping, under stirring. The mixture obtained was maintained, under stirring, at room temperature, for 1 hour and, subsequently, it was anhydrified on magnesium sulfate and filtered. The solvent was then removed through vacuum evaporation obtaining 23.04 g of a yellow oil (yield=93%) corresponding to the ligand having formula (L8).
(119) Molecular weight (MW): 188.27.
(120) Elementary analysis [found (calculated for C.sub.12H.sub.16N.sub.2)]: C: 76.56% (76.56%); H: 8.31% (8.57%); N: 14.78% (14.88%).
(121) FT-IR (KBr) (cm.sup.1): 1646 (v.sub.CN).
(122) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm): 8.6 (dd, 1H, PyH), 8.48 (s, 1H, PyH), 7.90 (dd, 1H, PyH), 7.64 (ddd, 1H, PyH), 7.30 (m, 1H, CHN), 3.32 (m, 1H, NCH), 1.9-1.2 (broad m, 10H, CH.sub.2).
(123) GC-MS: M.sup.+=m/z 188; [M-NCH.sub.3].sup.+=159; [M-C.sub.5H.sub.4NCH.sub.3].sup.+=145.
Example 15
(124) Synthesis of Ligand Having Formula (L8A)
(125) ##STR00021##
(126) 15 g (79 mmoles) of the ligand having formula (L8) obtained as described in Example 14 and 100 ml of anhydrous methanol were loaded into a 250 ml reactor, equipped with a magnetic stirrer: the whole was cooled to 0 C. with a water bath and ice and, subsequently, sodium borohydride (3 g, 79 mmoles) was added, in small portions, under stirring. The mixture obtained was maintained, under stirring, at room temperature, for 24 hours, and then quenched with brine and extracted with ethyl acetate (3100 ml). The solvent was then removed through distillation at reduced pressure and the residue obtained was purified through elution on a silica gel chromatography column [eluent: mixture of heptane/ethyl acetate in ratio of 8/2 (v/v)], obtaining 6 g of a yellow oil (yield=40%) corresponding to the ligand having formula (L8A).
(127) Molecular weight (MW): 190.29.
(128) Elementary analysis [found (calculated for C.sub.12H.sub.18N.sub.2)]: C: 76.57% (75.74%); H: 9.31% (9.53%); N: 14.68% (14.72%).
(129) FT-IR (solid state, UATR) (cm.sup.1): 3306 (v.sub.NH).
(130) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm): 8.54-8.49 (m, 1H, PyCH), 7.70-7.60 (m, 1H, PyH), 7.35-7.30 (dd, 1H, PyH), 7.18-7.12 (ddd, 1H, PyH), 3.9 (s, 2H, Py-CH.sub.2), 2.5 (m, 1H), 1.9 (s, 2H), 1.75 (m, 3H), 1.6 (m, 1H), 1.3-1.0 (m, 5H).
(131) GC-MS: M.sup.+=m/z 190; [M-C.sub.6H.sub.6N].sup.+=m/z 98; [M-C.sub.6H.sub.12N].sup.+=m/z 93; [M-C.sub.6H.sub.13N].sup.+=m/z 92.
Example 16
(132) Synthesis of FeCl.sub.3(L1) [Sample MG87]
(133) ##STR00022##
(134) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (225 mg; 1.39 mmoles) was added to a solution of the ligand having formula (L1) (253 mg; 1.39 mmoles; molar ratio L1/Fe=1), obtained as described in Example 1, in toluene (20 ml): the mixture obtained was maintained, under stirring, at room temperature, for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 203 mg of a brown solid product corresponding to the complex FeCl.sub.3(L1), equal to a 42% conversion with respect to the iron (II) chloride (FeCl.sub.3) loaded.
(135) Molecular weight (MW): 344.43.
(136) Elementary analysis [found (calculated for C.sub.12H.sub.10Cl.sub.3FeN.sub.2)]: C 41.20 (41.84), H 2.35 (2.92), N 7.88 (8.13), Cl 31.25 (30.88), Fe 15.84 (16.21).
(137)
Example 17
(138) Synthesis of FeCl.sub.3(L2) [Sample MG213]
(139) ##STR00023##
(140) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (225 mg; 1.39 mmoles) was added to a solution of the ligand having formula (L2) (293 mg; 1.39 mmoles; molar ratio L2/Fe=1), obtained as described in Example 3, in toluene (20 ml): the mixture obtained was maintained, under stirring, at room temperature, for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 396 mg of a brown solid product corresponding to the complex FeCl.sub.3(L2), equal to a 76% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(141) Molecular weight (MW): 372.48.
(142) Elementary analysis [found (calculated for C.sub.14H.sub.14Cl.sub.3FeN.sub.2)]: C 45.00 (45.14), H 3.69 (3.79), N 7.69 (7.52), Cl 28.96 (28.55), Fe 15.09 (14.99).
(143)
Example 18
(144) Synthesis of FeCl.sub.3(L3) [Sample MG208]
(145) ##STR00024##
(146) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (350 mg; 2.16 mmoles) was added to a solution of the ligand having formula (L3) (514 mg; 2.16 mmoles; molar ratio L3/Fe=1), obtained as described in Example 5, in toluene (20 ml): the mixture obtained was maintained, under stirring, at room temperature, for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 821 mg of a red solid product corresponding to the complex FeCl.sub.3(L3), equal to a 95% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(147) Molecular weight (MW): 400.35.
(148) Elementary analysis [found (calculated for C.sub.16H.sub.18Cl.sub.3FeN.sub.2)]: C 48.09 (47.97), H 4.71 (4.53), N 6.65 (6.99), Cl 25.96 (26.55), Fe 14.08 (13.94).
(149)
Example 19
(150) Synthesis of FeCl.sub.3(L4) [Sample MG205]
(151) ##STR00025##
(152) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (450 mg; 2.77 mmoles) was added to a solution of the ligand having formula (L4) (699 mg; 2.77 mmoles; molar ratio L4/Fe=1), obtained as described in Example 6, in toluene (20 ml): the mixture obtained was maintained, under stirring, at room temperature, for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 942 mg of an orange solid product corresponding to the complex FeCl.sub.3(L4), equal to an 82% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(153) Molecular weight (MW): 414.56.
(154) Elementary analysis [found (calculated for C.sub.17H.sub.20Cl.sub.3FeN.sub.2)]: C 49.00 (49.25), H 4.69 (4.86), N 6.67 (6.76), Cl 24.96 (25.65), Fe 13.04 (13.47).
(155)
Example 20
(156) Synthesis of FeCl.sub.3(L5) [Sample MG73]
(157) ##STR00026##
(158) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (94 mg; 0.58 mmoles) was added to a solution of the ligand having formula (L5) (163 mg; 0.58 mmoles; molar ratio L5/Fe=1), obtained as described in Example 8, in toluene (15 ml): the mixture obtained was maintained, under stirring, at room temperature, for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 187 mg of an orange solid product corresponding to the complex FeCl.sub.3(L5), equal to a 71% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(159) Molecular weight (MW): 442.61.
(160) Elementary analysis [found (calculated for C.sub.19H.sub.24Cl.sub.3FeN.sub.2)]: C 51.91 (51.56), H 5.36 (5.46), N 6.68 (6.33), Cl 24.26 (24.03), Fe 12.94 (12.62).
(161)
Example 21
(162) Synthesis of FeCl.sub.3(L6) [Sample MG76]
(163) ##STR00027##
(164) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (182 mg; 1.12 mmoles) was added to a solution of the ligand having formula (L6) (251 mg; 1.12 mmoles; molar ratio L6/Fe=1), obtained as described in Example 10, in toluene (15 ml): the mixture obtained was maintained, under stirring, at room temperature, for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 340 mg of an orange-brown solid product corresponding to the complex FeCl.sub.3(L6), equal to a 79% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(165) Molecular weight (MW): 386.50.
(166) Elementary analysis [found (calculated for C.sub.15H.sub.16Cl.sub.3FeN.sub.2)]: C 46.20 (46.61), H 4.35 (4.17), N 7.68 (7.25), Cl 28.05 (27.52), Fe 15.24 (14.44).
(167)
Example 22
(168) Synthesis of FeCl.sub.3(L8) [Sample MG250]
(169) ##STR00028##
(170) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (258 mg; 1.59 mmoles) was added to a solution of the ligand having formula (L8) (299 mg; 1.59 mmoles; molar ratio L8/Fe=1), obtained as described in Example 14, in toluene (20 ml): the mixture obtained was maintained, under stirring, at 100 C., for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 474 mg of a red-brown solid product corresponding to the complex FeCl.sub.3(L8), equal to an 84% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(171) Molecular weight (MW): 350.47.
(172) Elementary analysis [found (calculated for C.sub.12H.sub.16Cl.sub.3FeN.sub.2)]: C 41.95 (41.12), H 4.66 (4.60), N 7.26 (7.99), Cl 29.87 (30.35), Fe 15.55 (15.93).
(173)
Example 23
(174) Synthesis of FeCl.sub.3(L8A) [Sample MG251]
(175) ##STR00029##
(176) In a 100 ml flask, iron (III) chloride (FeCl.sub.3) (213 mg; 1.31 mmoles; molar ratio L8A/Fe=1) was added to a solution of the ligand having formula (L8A) (249 mg; 1.31 mmoles), obtained as described in Example 15, in toluene (20 ml). The mixture obtained was maintained, under stirring, at 100 C., for 3 hours. The supernatant was then removed through evaporation at reduced pressure and the residue obtained was washed with heptane (215 ml) and vacuum dried, at room temperature, obtaining 347 mg of a light brown solid product corresponding to the complex FeCl.sub.3(L8A), equal to a 75% conversion with respect to the iron (III) chloride (FeCl.sub.3) loaded.
(177) Molecular weight (MW): 352.49.
(178) Elementary analysis [found (calculated for C.sub.12H.sub.18Cl.sub.3FeN.sub.2)]: C 40.52 (40.88), H 5.21 (5.15), N 7.87 (7.95), Cl 29.98 (30.17), Fe 15.70 (15.84).
(179)
Example 24 (IP176)
(180) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.7 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L1) complex [sample MG87] (1.7 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.4 mg) obtained as described in Example 16. The whole was maintained, under magnetic stirring, at room temperature, for 5 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(181)
Example 25 (IP176/1)
(182) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 8 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L1) complex [sample MG87] (1.7 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.4 mg) obtained as described in Example 16. The whole was maintained, under magnetic stirring, at room temperature, for 2 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.2 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(183)
Example 26 (IP203)
(184) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L2) complex [sample MG213] (1.86 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.72 mg) obtained as described in Example 17. The whole was maintained, under magnetic stirring, at room temperature, for 2 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.3 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(185)
Example 27 (IP203/1)
(186) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 8 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L2) complex [sample MG213] (1.86 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.72 mg) obtained as described in Example 17. The whole was maintained, under magnetic stirring, at room temperature, for 3 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(187)
Example 28 (IP204)
(188) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.4 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L3) complex [sample MG208] (2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4 mg) obtained as described in Example 18. The whole was maintained, under magnetic stirring, at room temperature, for 2 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 0.765 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(189)
Example 29 (IP204/1)
(190) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 7.7 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.3 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L3) complex [sample MG208] (2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4 mg) obtained as described in Example 18. The whole was maintained, under magnetic stirring, at room temperature, for 30 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.2 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(191)
Example 30 (ZG192)
(192) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.3 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L4) complex [sample MG205] (2.1 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.2 mg) obtained as described in Example 19. The whole was maintained, under magnetic stirring, at room temperature, for 2 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(193)
Example 31 (ZG192/1)
(194) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 7.6 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L4) complex [sample MG205] (2.1 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.2 mg) obtained as described in Example 19. The whole was maintained, under magnetic stirring, at room temperature, for 5 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(195)
Example 32 (IP105)
(196) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 7.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.21 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.42 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at room temperature, for 16 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(197)
(198)
(199)
Example 33 (IP105/1)
(200) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.2 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.21 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.42 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at room temperature, for 16 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(201)
(202)
Example 34 (IP109)
(203) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 7.8 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L6) complex [sample MG76] (1.9 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.8 mg) obtained as described in Example 21. The whole was maintained, under magnetic stirring, at room temperature, for 5 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(204)
(205)
Example 35 (IP109/1)
(206) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L6) complex [sample MG76] (1.9 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.8 mg) obtained as described in Example 21. The whole was maintained, under magnetic stirring, at room temperature, for 60 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.05 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(207)
Example 36 (G1531)
(208) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 7.95 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L8) complex [sample MG250] (1.75 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.5 mg) obtained as described in Example 22. The whole was maintained, under magnetic stirring, at room temperature, for 10 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(209)
Example 37 (G1531/1)
(210) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.6 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L8) complex [sample MG250] (1.75 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.5 mg) obtained as described in Example 22. The whole was maintained, under magnetic stirring, at room temperature, for 30 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.4 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(211)
Example 38 (IP115)
(212) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.) in a 25 ml test tube. Subsequently, 7.94 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L8A) complex [sample MG251] (1.76 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.52 mg) obtained as described in Example 23. The whole was maintained, under magnetic stirring, at room temperature, for 120 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 0.115 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(213)
Example 39 (IP115/1)
(214) 2 ml of 1,3-butadiene equal to about 1.4 g were condensed, cold (20 C.), in a 25 ml test tube. Subsequently, 13.6 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L8A) complex [sample MG251] (1.76 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.52 mg) obtained as described in Example 23. The whole was maintained, under magnetic stirring, at room temperature, for 120 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 0.190 g of polybutadiene having a mixed structure: further characteristics of the process and of the polybutadiene obtained are reported in Table 1.
(215)
Example 40 (IP155)
(216) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.65 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L1) complex [sample MG87] (1.72 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.44 mg) obtained as described in Example 16. The whole was maintained, under magnetic stirring, at room temperature, for 2 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.25 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(217)
Example 41 (IP205)
(218) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L2) complex [sample MG213] (1.87 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.74 mg) obtained as described in Example 17. The whole was maintained, under magnetic stirring, at room temperature, for 4 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(219)
(220)
Example 42 (IP205/1)
(221) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L2) complex [sample MG213] (1.87 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.74 mg) obtained as described in Example 17. The whole was maintained, under magnetic stirring, at room temperature, for 4 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(222)
(223)
Example 43 (IP206)
(224) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.4 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L3) complex [sample MG208] (2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4 mg) obtained as described in Example 18. The whole was maintained, under magnetic stirring, at room temperature, for 4 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(225)
(226)
Example 44 (IP206/1)
(227) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 7.7 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L3) complex [sample MG208] (2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4 mg) obtained as described in Example 18. The whole was maintained, under magnetic stirring, at room temperature, for 9 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(228)
(229)
Example 45 (ZG193)
(230) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.3 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L4) complex [sample MG205] (2.1 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.2 mg) obtained as described in Example 19. The whole was maintained, under magnetic stirring, at room temperature, for 65 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(231)
Example 46 (ZG193/1)
(232) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 7.6 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L4) complex [sample MG205] (2.1 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.2 mg) obtained as described in Example 19. The whole was maintained, under magnetic stirring, at room temperature, for 60 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(233)
(234)
Example 47 (IP108)
(235) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 7.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.4 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at room temperature, for 120 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(236)
(237)
Example 48 (IP108/1)
(238) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 10.65 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (3.15 ml; 510.sup.3 moles, equal to about 0.29 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.4 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at room temperature, for 120 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(239)
(240)
(241)
(242)
Example 49 (IP112)
(243) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.2 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.4 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at room temperature, for 120 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.23 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(244)
(245)
(246)
(247)
Example 50 (IP160)
(248) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.2 ml of toluene were added and the temperature of the solution thus obtained was brought to 0 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.4 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at 0 C., for 240 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 0.887 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(249)
(250)
(251)
Example 51 (IP159)
(252) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.2 ml of toluene were added and the temperature of the solution thus obtained was brought to 30 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L5) complex [sample MG73] (2.2 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 4.4 mg) obtained as described in Example 20. The whole was maintained, under magnetic stirring, at 30 C., for 300 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 0.405 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(253)
(254)
Example 52 (IP110)
(255) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 7.8 ml of toluene were added and the temperature of the solution thus obtained was brought. to 20 C. Then, methylaluminoxane (MAO) in toluene solution (6.3 ml; 110.sup.2 moles, equal to about 0.58 g) was added and, subsequently, the FeCl.sub.3(L6) complex [sample MG76] (1.9 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.8 mg) obtained as described in Example 21. The whole was maintained, under magnetic stirring, at room temperature, for 60 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
(256)
(257)
(258)
(259)
Example 53 (IP111)
(260) 2 ml of isoprene equal to about 1.36 g were placed in a 25 ml test tube. Subsequently, 13.5 ml of toluene were added and the temperature of the solution thus obtained was brought to 20 C. Then, methylaluminoxane (MAO) in toluene solution (0.63 ml; 110.sup.3 moles, equal to about 0.058 g) was added and, subsequently, the FeCl.sub.3(L6) complex [sample MG76] (1.9 ml of toluene solution at a concentration of 2 mg/ml; 110.sup.5, equal to about 3.8 mg) obtained as described in Example 21. The whole was maintained, under magnetic stirring, at room temperature, for 60 minutes. The polymerization was then quenched by adding 2 ml of methanol containing some drops of hydrochloric acid. The polymer obtained was then coagulated by adding 40 ml of a methanol solution containing 4% of Irganox 1076 antioxidant (Ciba) obtaining 1.36 g of polyisoprene having a mixed structure: further characteristics of the process and of the polyisoprene obtained are reported in Table 2.
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(262)
(263)
(264) TABLE-US-00001 TABLE 1 Polymerization of 1,3-butadiene with catalytic systems comprising pyridyl iron (III) complexes Al/Fe Con- 1,4- 1,4- M.sub.w Exam- (molar Time version cis trans 1.2 (g M.sub.w/ ple ratio) (min) (%) (%) (%) (%) mol.sup.1) M.sub.n 24 100 5 100 17.1 17.6 65.3 457000 2.1 25 1000 2 85.7 14.7 17.2 68.1 371400 2.1 26 100 2 92.9 22.6 7.3 70.1 413700 2.3 27 1000 3 100 24.0 6.9 69.3 285700 2.0 28 100 2 54.6 25.8 3.6 70.6 768300 2.3 29 1000 30 85.7 18.6 11.9 69.5 147700 1.9 30 100 2 100 10.8 31.0 58.2 399700 2.1 31 1000 5 100 13.2 30.9 55.9 222400 1.9 32 1000 16 100 13.7 43.4 42.9 166300 2.1 33 100 16 100 11.7 41.2 47.1 138100 1.8 34 1000 5 100 40.9 2.0 57.1 232300 2.2 35 100 60 75.0 38.7 1.7 59.6 129300 1.9 36 1000 10 100 29.2 16.5 54.4 379000 1.7 37 100 30 100 31.1 12.3 56.6 427500 1.8 38 1000 120 8.2 20.3 34.1 45.6 20200 2.6 39 100 120 14.0 19.5 30.8 49.7 25360 1.1
(265) TABLE-US-00002 TABLE 2 Polymerization of isoprene with catalytic systems comprising pyridyl iron complexes Al/Fe Conver- 1,4- 1,4- M.sub.w Exam- (molar Time sion cis trans 3.4 (g M.sub.w/ ple ratio) (min) (%) (%) (%) (%) mol.sup.1) M.sub.n 40 100 2 91.9 34.1 0 65.9 297300 1.8 41 100 4 100 54.1 5.0 40.9 369900 1.9 42 1000 1.5 100 53.0 5.5 41.5 260800 1.8 43 100 4 100 4.6 42.3 355600 2.0 44 1000 9 100 49.8 9.5 40.7 244700 2.0 45 100 65 100 67.8 8.7 23.5 106800 1.7 46 1000 60 100 69.2 10.0 20.8 70000 1.6 47 1000 120 100 18.7 59.6 1.7 29900 1.9 48 500 120 100 17.7 60.0 22.3 34300 1.7 49 100 120 90.4 23.7 66.4 9.9 59500 1.7 50 100 240 65.2 63.7 17.5 18.8 42300 1.6 51 100 300 29.8 66.3 14.5 19.2 57200 1.5 52 1000 60 100 62.0 19.0 19.0 107900 2.3 53 100 60 100 61.4 18.7 19.9 101000 1.8