WO2022137071A1 - Catalyseurs à base de nanoparticules métalliques fonctionnalisées avec une base de schiff et leur utilisation dans la polymérisation d'oléfines - Google Patents

Catalyseurs à base de nanoparticules métalliques fonctionnalisées avec une base de schiff et leur utilisation dans la polymérisation d'oléfines Download PDF

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WO2022137071A1
WO2022137071A1 PCT/IB2021/062005 IB2021062005W WO2022137071A1 WO 2022137071 A1 WO2022137071 A1 WO 2022137071A1 IB 2021062005 W IB2021062005 W IB 2021062005W WO 2022137071 A1 WO2022137071 A1 WO 2022137071A1
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metal
metal nanoparticle
ligand
polymerization catalyst
substituted
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Rehana MALGAS-ENUS
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Stellenbosch University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings

Definitions

  • This invention relates to novel Schiff base functionalised metal nanoparticles and their use in olefin polymerization.
  • the invention relates the bidentate N,N and N,O Schiff base functionalized metal nanoparticles and their use in the polymerization of olefins.
  • BACKGROUND Salicylaldimine ligands and Ni-complexes, respectively, are known to be active in the facilitation of various polymerization and oligomerization reactions.
  • Ni-complexes are known to be activate in polymerization of norbornene. Modification of the salicylaldimine ligands have proven to be expensive, ineffective and has effectively shown little to no improvement in the catalytic activity of the corresponding complexes. Therefore, said Ni-complexes effectively cannot be improved upon further, utilizing transition metal coordination chemistry. The same holds for other similar transition metal polymerization catalysts. This poses a problem, as the improved activity of any catalytic reaction is desirable and a substantial driving force in both the chemical research and chemical industry arenas.
  • a Schiff base functionalised metal nanoparticle polymerization catalyst wherein the metal nanoparticle is functionalised with a bidentate N,N or N,O donor Schiff base ligand.
  • the metal a transition metal.
  • the metal is selected from the group consisting of nickel, copper, cobalt, chromium, iron or zinc.
  • the bidentate N,N or N,O donor Schiff base ligand is a substituted or unsubstituted imine ligand according to Formula 1 or Formula 2 Formula 1
  • R 1 is selected from substituted or unsubstituted, linear or branched alkyl
  • R 2 and R 3 is one or more groups independently selected from H or substituted or unsubstituted, linear or branched alkyl.
  • R 2 and R 3 is independently selected from H or substituted or unsubstituted, linear or branched C 1 -C 8 alkyl.
  • the bidentate N,N or N,O donor Schiff base ligand is selected from 3-tertbutylsalicylaldimine or 6-me-2-iminopyridine.
  • the nanoparticle has an average diameter in the range of about 1.0 nm to about 100.0 nm.
  • the nanoparticle has an average diameter in the range of about 1.0 nm to about 30.0 nm. Most preferably, the nanoparticle has an average diameter in the range of about 1.0 to about 10 nm, including about 3.1 nm to about 5.4 nm.
  • a method for the polymerization of olefins comprising: a) providing a Schiff base functionalised metal nanoparticle polymerization catalyst, wherein the metal nanoparticle is functionalised with a bidentate N,N or N,O donor Schiff base ligand, in a reaction vessel; b) providing an olefin polymerization catalyst activator; c) providing an olefin substrate; d) optionally heating and/or stirring the reaction mixture; and e) optionally quenching the reaction with an appropriate quenching agent.
  • the olefin polymerization catalyst activator is methylaluminoxane or modified methylaluminoxane.
  • the metal a transition metal.
  • the metal nanoparticle comprises a metal selected from the group consisting of nickel, copper, cobalt, chromium, iron or zinc.
  • the bidentate N,N or N,O donor Schiff base ligand is a substituted or unsubstituted imine ligand according to Formula 1 or Formula 2 wherein R 1 is selected from substituted or unsubstituted, linear or branched alkyl, and wherein R 2 and R 3 is one or more groups independently selected from H or substituted or unsubstituted, linear or branched alkyl.
  • R 2 and R 3 is independently selected from H or substituted or unsubstituted, linear or branched C 1 -C 8 alkyl.
  • the substituted bidentate N,N or N,O donor Schiff base ligand is selected from 3-tertbutylsalicylaldimine or 6-me-2-iminopyridine.
  • the olefin substrate is a cyclic olefin, a linear olefin, or combinations thereof.
  • the olefin substrate is a cyclic olefin selected from the group consisting of functionalised or non-functionalised norbornene, cyclobutene, styrene or cyclopentane.
  • Figure 1 shows TEM micrographs of AZ18 (Left), AZ21 (Middle) and AZ22 (Right) and their respective corresponding size distribution histograms
  • Figure 2 shows FTIR spectra of unreacted salicylaldimine ligand (L1) and NiCl 2 -salicylaldimine nanoparticles (AZ13A)
  • Figure 3 shows FTIR spectra of unreacted salicylaldimine ligand (L1) and Ni(NO 3 )-2-salicyaldimine nanoparticles (AZ14A)
  • Figure 4 shows FTIR spectra of unreacted salicylaldimine ligand (L1) and Ni(NO 3 )-2-salicyaldimine nano
  • the present invention provides for a novel Schiff base functionalised metal nanoparticle catalyst, wherein the metal nanoparticle is functionalised with a bidentate N,N or N,O donor Schiff base ligand.
  • the invention further provides for a method for the polymerization of olefins comprising the use of the functionalised metal nanoparticle catalyst in a polymerization reaction, wherein a co-catalyst or catalyst activator is used to activate the nanoparticle catalyst.
  • the metal in the metal nanoparticle catalyst may be selected from any one or more of the transition metal group of metals, as defined by standard IUPAC nomenclature.
  • the transition metal may be selected from the group consisting of nickel, copper, cobalt, chromium, iron and zinc.
  • the bidentate N,N or N,O donor Schiff base ligand may be a substituted or unsubstituted bidentate N,N or N,O ligand.
  • the bidentate ligand may be a suitable substituted or unsubstituted imine ligand (such as 2-(iminomethyl)phenol or 2-(iminomethyl)pyridineimine) according to Formulas 1 and 2 below, including ligands such as 3-tertbutylsalicylaldimine or 6-me-2- iminopyridine.
  • Formula 1 Formula 2 the bidentate N,N or N,O donor Schiff base ligand may be any other bidentate N,N or N,O donor Schiff base ligand with similar metal binding characteristics or properties.
  • the R 1 substituent may be selected from the group consisting of substituted or unsubstituted, linear or branched alkyl.
  • the R 2 and R 3 substituents as shown in the chemical structures for Formulas 1 and 2 above, may be one or more groups independently selected from the group consisting of H and substituted or unsubstituted, linear or branched alkyl.
  • R 2 and R 3 is independently selected from the group consisting of substituted or unsubstituted, linear or branched C 1 -C 8 alkyl.
  • the metal nanoparticles according to the present invention have an average particle diameter in the range of about 1.0 nm to about 100.0 nm, preferably about 1.0 nm to about 30.0 nm, preferably about 1.0 nm to about 10.0 nm including for example about 3.1 nm to about 5.4 nm. It should be understood the range of about 1.0 nm to about 100.0 nm includes a disclosure of all sub-ranges within this range, for example about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and up to 100 nm as lower or upper ranges within this range.
  • the disclosure should also be understood to include all possibly ranges between 1 and 2, 2 and 3, 3 and 4, 4 and 5, 5 and 6, 6 and 7, 7 and 8, 8 and 9, and 9 and 10 nm, for example 1.5, 2.5, 3.5, 4.5, 5.5, 6.5, 7.5, 8.5, and 9.5 nm.
  • the method according to the present invention provides for the polymerization of olefins comprising the use of the functionalised metal nanoparticle catalyst of the invention, as described above, in an olefin polymerization reaction.
  • the reaction further comprises the use of a co-catalyst or catalyst activator to activate the metal nanoparticle catalyst. Any suitable catalyst activator known to those skilled in the art may be used to activate the metal nanoparticle catalyst.
  • Suitable co-catalysts or catalyst activators are disclosed in Chen et al., Chem. Rev.2000, 100, 1391 ⁇ 1434. While the experiments described below utilised methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), it is envisaged that several other known activators will be suitable. Without thereby wishing to be bound by any particular theory, the data obtained indicate that the polymerization reaction surprisingly proceeds via a radical polymerization mechanism when using MAO as a co-catalyst. When using MMAO as a co-catalyst, the mechanism proceeds via a vinyl polymerization mechanism.
  • MAO methylaluminoxane
  • MMAO modified methylaluminoxane
  • metal nanoparticle catalyst particle according the present invention has been demonstrated in the experiments below through the polymerization of the cyclic olefin norbornene as a model catalytic reaction.
  • the metal nanoparticle catalyst of the present invention will be active in the polymerization of olefins in general, including other cyclic olefins such as cyclobutene, or cyclopentane.
  • L1 Salicylaldimine
  • L2 2-Iminopyridine
  • L3 3-tertbutylsalicylaldimine
  • L4 6-me-2-iminopyridine
  • L1 Salicylaldimine (L1) 20 mL of toluene was added to a 50 mL round-bottom flask. To the toluene using a 1 mL micro-pipette 0.784 mL (7.32 mmol) of salicylaldehyde was added. The solution was stirred for 5 minutes. To the solution 0.802 mL (9.76 mmol) of n-propylamine was added using a 1 mL micro-pipette.
  • the yellow solution was left to stir for 24 hours at ambient conditions at 400 rpm. After 24 hours the toluene was removed via rotary evaporation. The resulting crude oil was redissolved in 15 mL of dichloromethane (DCM) and purified by washing with 15 mL of distilled water in triplicate. The DCM layer was captured and dried with MgSO 4 for 30 min. The purified dry product was vacuum filtered, and the remaining DCM was removed by evaporation. A yield of 69.7 % was obtained for the pure yellow oil.
  • DCM dichloromethane
  • Example 3 3-tertbutyl-salicylaldimine (L3) 20 mL of toluene was added to a 50 mL round-bottom flask. To the toluene 0.936 mL (5.47 mmol) of 3-tertbutyl-salicyaldehyde was added using a 1 mL micro-pipette. The solution was stirred for 5 minutes. To the solution 0.675 mL (12.1 mmol) of n- propylamine was added using a 1 mL micro-pipette. The yellow solution was left to stir for 24 hours at ambient conditions at 400 rpm.
  • L3 3-tertbutyl-salicylaldimine
  • the resulting yellow crude oil was redissolved in 15 mL of DCM and purified by washing with 15 mL of distilled water in triplicate.
  • the DCM layer was captured and dried with MgSO4 for 30 min.
  • the purified dry product was vacuum filtered, and the remaining DCM was removed by rotary evaporation. A yield of 64.3 % was obtained for the pure yellow oil.
  • Example 4 Substituted 6-me-2-iminopyridine (L4) 20 mL of toluene was added to a 50 mL round-bottom flask. To the toluene 0.8752 g (7.23 mmol) of 6-methyl-2-pyridinecarboxaldehyde was added. The solution was stirred for 5 minutes. To the solution 0.891 mL (10.8 mmol) of n-propylamine was added using a 1 mL micro-pipette. The clear solution was left to stir for 24 hours at ambient conditions at 400 rpm. After 24 hours the toluene was removed via rotary evaporation.
  • the resulting yellow crude oil was redissolved in 15 mL of DCM and purified by washing with 15 mL of distilled water in triplicate.
  • the DCM layer was captured and dried with MgSO 4 for 30 min.
  • the purified dry product was vacuum filtered, and the remaining DCM was removed by rotary evaporation.
  • the yield of the pure product was 73.1%.
  • the salicylaldimine functionalized nanoparticles were hydrophobic, whilst the iminopyridine functionalized nanoparticles were hydrophilic, indicating the effect of the various ligands on the nanoparticles.
  • the nickel nanoparticles were characterized UV-Vis spectroscopy, FTIR, Inductively Coupled Atomic Emission Spectroscopy (ICP-AES) and Transmission Electron Microscopy (TEM). The total metal content for the nanoparticle catalysts were determined by ICP-AES analysis. TEM micrographs of selected nanoparticle systems, as well as their respective diameter distribution histograms, are shown in Figure 1 (AZ18, left, AZ21, middle, and AZ22, right).
  • nanoparticles synthesized with NiCl 2 ⁇ 6H 2 O as the precursor generally had larger diameters with visibly less agglomeration than those synthesized with Ni(NO 3 ) 2 ⁇ 6H 2 O. This indicated that the nanoparticles synthesized with NiCl 2 ⁇ 6H 2 O as precursor had a greater stability compared to the nanoparticles with Ni(NO 3 ) 2 ⁇ 6H 2 O as the precursor salt.
  • FTIR spectra of both the ligands as well as the nanoparticle systems were compared to monitor the C-O hydroxyl, C-N imine and C-N aromatic vibrational frequencies for the salicylaldimine- and- iminopyridine ligand variants (results summarised in Table 1 below).
  • Table 1 FTIR vibrational frequencies of the C-O, C-N Imine as well as the C-N aromatic stretches of both the free a nd bound ligands.
  • T he C-N frequency for the iminopyridyl ligands describes that of the nitrogen atom in the pyridine ring
  • the free salicylaldimine ligands had C-O hydroxy and C-N imine vibrational frequencies at ⁇ 1276 cm -1 and 1631 cm -1 , respectively.
  • the free iminopyridine ligands had C-N aromatic and C-N imine vibrational frequencies at 1376 cm -1 and ⁇ 1647 cm -1 , respectively.
  • the blue shift observed in the C-O vibrational frequency indicated coordination to the metal core had occurred via the hydroxyl moiety.
  • the C-N imine vibrational frequency had not undergone a shift for L1, whereas a blue shift was observed for L3. This indicated that L1 was not coordinated to the metal core via the imine moiety, whilst L3 was.
  • red shifts in the vibrational frequencies of both L2 and L4 were observed. This observed red shifting indicated that coordination to the metal core occurred via both the aromatic and imine moieties. From the UV-Vis absorption spectrum a blue shift of the free-ligand absorption bands were observed which indicated that coordination to the nanoparticle surface occurred.
  • Example 5 NiCl 2 -salicylaldimine nanoparticles (AZ13A) To 20 mL of ethanol, 0.1375 g (0.843 mmol, 1.94 eq.) of salicylaldimine (L1) was dissolved.
  • Example 6 Ni(NO 3 )-2-salicyaldimine nanoparticles (AZ14A) To 20 mL of ethanol, 0.1062 g (0.365 mmol, 1.93 eq.) of salicylaldimine (L1) was dissolved. In a separate vial 0.1062 g (0.706 mmol, 1.00 eq.) of Ni(NO 3 ) 2 .6H 2 O was dissolved in 5 mL of distilled water.
  • Example 7 NiCl 2 -3-tertbutylsalicylaldimine nanoparticles (AZ17) To 20 mL of ethanol, 0.1882 g (0.858 mmol, 2.02 eq.) of 3-tertbutylsalicylaldimine (L3) was dissolved. In a separate vial 0.1010 g (0.425 mmol, 1.00 eq.) of NiCl 2 .6H 2 O was dissolved in 5 mL of distilled water. The Ni-salt solution was added to the 3- tertbutylsalicylaldimine solution. The solution stirred for 30 minutes.
  • Example 8 Ni(NO 3 ) 2 -3-tertbutylsalicylaldimine nanoparticles (AZ18) To 20 mL of ethanol, 0.1545 g (0.704 mmol, 2.02 eq.) of 3-tertbutylsalicylaldimine (L3) was dissolved. In a separate vial 0.1012 g (0.348 mmol, 1.00 eq.) of Ni(NO 3 ) 2 .6H 2 O was dissolved in 5 mL of distilled water. The Ni-salt solution was added to the 3- tertbutylsalicylaldimine solution. The solution stirred for 30 minutes.
  • Example 9 NiCl 2 -2-iminopyridine nanoparticles (AZ19) To 20 mL of ethanol, 0.3837 g (2.57 mmol, 2.02 eq.) of 2-iminopyridine (L2) was dissolved. In a separate vial 0.3024 g (1.272 mmol, 1.00 eq.) of NiCl 2 .6H 2 O was dissolved in 5 mL of distilled water. The Ni-salt solution was added to the 2- iminopyridine solution. The solution stirred for 30 minutes. After 30 minutes, 0.816 mL (25.5 mmol, 20.0 eq.) of hydrazine was added dropwise. Once all the hydrazine was added.
  • Example 11 NiCl 2 -6-me-2-iminopyridine nanoparticles (AZ21) To 20 mL of ethanol, 0.1417 g (0.863 mmol, 1.98 eq.) of 6-me-2-iminopyridine (L4) was dissolved. In a separate vial 0.1033 g (0.435 mmol, 1.00 eq.) of NiCl 2 .6H 2 O was dissolved in 5 mL of distilled water. The Ni-salt solution was added to the 6-me-2- iminopyridine solution.
  • Example 12 Ni(NO 3 ) 2 -6-me-2-iminopyridine nanoparticles (AZ22) To 20 mL of ethanol, 0.1166 g (0.704 mmol, 2.02 eq.) of 6-me-2-iminopyridine (L4) was dissolved. In a separate vial 0.1011 g (0.348 mmol, 1.00 eq.) of Ni(NO 3 ) 2 .6H 2 O was dissolved in 5 mL of distilled water. The Ni-salt solution was added to the 6-me-2- iminopyridine solution. The solution stirred for 30 minutes. After 30 minutes, 0.222 mL (6.95 mmol, 20.0 eq.) of hydrazine was added dropwise.
  • Example 13 Olefin polymerization (Norbornene) The eight nickel nanoparticle catalysts were evaluated in a model catalytic reaction to determine their possible activity in the polymerization of norbornene.
  • the general catalytic procedure involved the usage of specialized equipment, including a Parr reactor and a glovebox.
  • the substrate (norbornene) and catalyst activator (10% MAO in toluene) were dissolved in dried toluene and the appropriate nanoparticle catalyst was transferred to the Parr reactor, and subsequently sealed in the glovebox under inert atmosphere. After the reaction time lapsed, the solution was quenched using an appropriate acidified solvent. The solvent was subsequently removed, and the isolated polymeric product was dried in vacuo at room temperature. Due to the hygroscopic nature of the polymeric product an additional freeze-drying procedure was included.
  • the isolated polymeric products isolated were characterized by an array of characterization methods, including: FTIR, 1 H-NMR, UV/Vis, Scanning-Transition Electron Microscopy (STEM), High Temperature Size Exclusion Chromatography (HT- SEC), Thermal Gravimetric Analysis (TGA) and Dynamic Light Scattering (DLS) analysis.
  • Figure 10 represents the FTIR spectrum of entry 11 (Table 2A) before and after freeze- drying. From the FTIR spectrum expected C-H stretching frequencies at ⁇ 2987 and 2901 cm -1 were observed. However, C-O stretching frequencies at ⁇ 1057 and 1076 cm -1 , as well as an O-H stretching frequency at 3675 cm -1 were also observed.
  • hydroxy functionalities are present in the polymer.
  • the 1 H-NMR spectrum contained peaks at ⁇ 3.0 ppm, these correspond to protons adjacent to a hydroxy moiety.
  • An additional surprising outcome was the hydrophilic properties of the polymer, which indicated that functionalization of the polymer occurred for such properties to arise.
  • the molecular weights and therefore the chain lengths of the polymers were determined by HT-SEC (see Table 3).
  • Table 3 Mw and Mn of samples AZ28, AZ32, AZ33 and AZ34 as determined by HT-SEC.
  • the PDI is presented.
  • the HT-SEC results indicated the formation of tetrameric chain lengths.
  • Experiments 1 to 6 were the controls to optimize the subsequent catalytic reactions.
  • the catalyst concentration was varied to investigate the effect of metal loading on the activity.
  • the increased metal loading had a remarkable influence on the observed activity.
  • the trend observed showed direct proportionality between the metal loading and the achieved activity.
  • the observed trend is comparable to the literature and could be due to the increased availability of active sites for polymerization to commence.
  • the effect of ligand variant and metal precursor was investigated through a comparison of experiments 8 and 11 to 16. The first observation was that the nanoparticle catalysts with chlorides bound to the nanoparticle surface tended to exhibit greater activity than its nitrate bound counterparts.
  • the singular outlier to this trend was the nanoparticle catalysts with L3 as ligand. From the TEM size distribution results, the chloride nanoparticles were more stable with larger average diameters in comparison to the nitrate nanoparticles.
  • the TEM observations could be a possible explanation to the observed trend in the activity, as the relatively unstable nature of the nitrate nickel nanoparticles could have resulted in agglomeration. The agglomeration resulted in decreased surface area and resultantly in decreased activity.
  • the second observation was that the steric bulk in the case of the iminopyridine ligands influenced the achieved activity.
  • the salicylaldimine functionalized and iminopyridine functionalized Ni-complexes showed optimum activities of 259 and 283 kg of PNB / molNi / h, respectively.
  • the unsubstituted salicylaldimine variant had an optimum activity of 221 kg of PNB / molNi / h, whilst the substituted variant has an optimum activity of 243 kg of PNB / molNi / h.
  • the unsubstituted iminopyridine variant had an optimum activity of 276 kg of PNB / molNi / h, whilst the substituted variant has an optimum activity of 226 kg of PNB / molNi / h.
  • the expected mechanistic route for the polymerization reaction was vinyl addition polymerization.
  • the inventors surprisingly found that hydrophilic polymers were isolated. Based on FTIR- and- NMR analysis the polymers were functionalized with hydroxyl moieties.
  • This transformation hydroxylates the norbornene monomer at a sp 3 carbon centre, forming monohydroxynorbornane and a radical on the adjacent sp 3 carbon.
  • the radical monohydroxynorbornane remains attached to the nanoparticle catalyst surface.
  • Chain growth is then propagated by the addition of an unfunctionalized norbornene monomer to a radicalized monohydroxynorbornane monomer. Due to the vast number of active sites on the nanoparticle surface, short oligomeric chains are produced as opposed to long chained polymers.
  • the resulting product, or intermediate product is an oligomer stabilized metal nanoparticle composite (see Figure 11). STEM micrographs have shown that the nanoparticles are embedded in the polymeric material.
  • FTIR, UV-Vis and TGA analysis have shown the presence of metal nanoparticles within the polymer, hinting towards the proposed inorganic-polymer composite. Furthermore, upon addition to DMF (for SEC analysis), the metal centre is stabilized by DMF, which cleaves the oligomer from the metal nanoparticle surface, resulting in the monodisperse tetramers observed from the SEC analysis. Representative spectra for FTIR, NMR, UV-Vis, and HT-SEC analysis, as well as STEM images are shown in Figures 12 – 26.
  • the low steric environment means that few of the active sites are blocked by the presence of the ligand, and therefore the activity was high.
  • Increased ligand concentration resulted in a decreased activity independent of the ligand employed. This is due to the increased M:L ratio which increases the steric crowding on the nano-surface.
  • Increased steric crowding results in increased active site blocking by the ligands, making less of the active sites accessible to olefin insertion.
  • the iminopyridine ligand (L2) is a bidentate N,N-donor solely coordinated to the nano-surface and not through covalent bonding.
  • This bidentate nature increases the steric strain on the nano-surface significantly more than for the monodentate salicylaldimine ligand (L1). Therefore, due to its weak coordinating bonds as well as the favorable energetics of releasing the steric strain on the nano-surface at higher M:L ratios, this becomes more favorable because as they dissociate, the available active sites increase, resulting in the increased activity observed.
  • Mw molecular weight
  • NMR nuclear magnetic resonance
  • THF-SEC THF size exclusion chromatography
  • UV-Vis spectroscopy UV-Vis spectroscopy
  • the AZ19.1 nano-catalyst was selected for this investigation due to exhibiting the greatest catalytic activity during the homopolymerization of styrene.
  • the resulting co-polymers were characterized using FT-IR (ATR) spectroscopy, 1 H- and 13 C-NMR spectroscopy, melting point analysis and UV-Vis spectroscopy.
  • ATR FT-IR
  • 1 H- and 13 C-NMR spectroscopy melting point analysis
  • UV-Vis spectroscopy UV-Vis spectroscopy.
  • THF-SEC was performed at room temperature using polystyrene as reference standard. From the SEC analysis it was found that oligomerization was the active mechanism, resulting in chain lengths of ⁇ 2100 g.mol- 1 .

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Abstract

La présente invention concerne de nouveaux catalyseurs de nanoparticules métalliques fonctionnalisées avec une base de Schiff donneuse de N,N ou N,O bidentée et leur utilisation dans un procédé de polymérisation d'oléfines comprenant du norbornène, par exemple. Le procédé de polymérisation d'oléfines selon l'invention comprend l'utilisation des nouveaux nanocatalyseurs conjointement avec un cocatalyseur ou un activateur de catalyseur, qui peut être le méthylaluminoxane ou un méthylaluminoxane modifié. De manière inattendue, les catalyseurs de nanoparticules de l'invention sont efficaces dans des conditions de réaction favorablement douces.
PCT/IB2021/062005 2020-12-21 2021-12-20 Catalyseurs à base de nanoparticules métalliques fonctionnalisées avec une base de schiff et leur utilisation dans la polymérisation d'oléfines WO2022137071A1 (fr)

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