Polymerization Catalysis in Liquid Propylene: High Activities and Molecular Weights in Propylene/CO Copolymerization Reactions

Summary: The dicationic [(dppp)Pd(NCCH₃)₂](BF₄)₂ catalyst (dppp = 1,3‐bis(diphenylphosphino)propane) was applied in a liquid monomer, two phase process for the CO/propene copolymerization reaction. For the first time it was possible to synthesize propene/CO copolymers with an activity up to 7 500 g/(mol · h) and molecular weights of 500 000 g/mol. Activities up to 40 000 g/(mol · h) could be obtained with the use of the unsymmetric catalyst [(CF₃‐dppp)Pd(NCCH₃)](BF₄)₂ (CF₃‐dppp = 1‐diphenylphosphino‐3‐bis[3,5‐di(trifluormethyl)phenyl]phosphinopropane) in homogeneous liquid propene solution.

Granules found after copolymerization.     

New polymer synthesis. XXX. Synthesis and thermal behavior of new organometallic polyketones and copolyketones based on diferrocenylidenecycloheptanone

A new interesting category of organometallic polyketones and copolyketones was synthesized via Friedel–Crafts reactions through the polymerization of 2,7‐bis[(2‐ferrocenyl)methylene] cycloheptanone ( II ) with different diacid chlorides. The model compound was synthesized by reacting monomer II with benzoyl chloride and characterized by ¹H‐NMR, IR, and elemental analyses. The polyketones and copolyketones were insoluble in most organic solvents but easily soluble in concentrated H₂SO₄. The thermal properties of these polyketones and copolyketones were evaluated and correlated to their structural units by TGA and DTG measurements and had inherent viscosity of 0.32–0.65 dI g^?1. Moreover, the electrical conductivity of polyketone Va and copolyketone VI was investigated above the temperature range (300–500 K) and followed an Arrhenius equation with activation energy 2.09 eV. Also, the morphological properties of selected example of polyketones were detected by scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2394–2401, 2005     

Thermal degradation of ethylene–carbon monoxide alternating copolymer under inert atmosphere

This work aims to understand the mechanism of the thermal degradation of the ethylene–carbon monoxide (E-CO) alternating copolymer under mild conditions. The copolymer was subjected to accelerated ageing in an oven at different temperatures below the copolymer melting point, under argon atmosphere, and in the absence of light. The properties of the aged samples were compared with the properties of the untreated copolymer. Untreated and aged samples were analysed by mass spectroscopy (MS) with the direct introduction probe (DIP) and pyrolysis (Py) techniques. The accelerated ageing experiments showed that the thermal degradation of the E-CO alternating copolymer under inert atmosphere is characterized by chain cross-linking, loss of water, and changes in the UV absorption spectrum. The IR spectrum shows modifications only for highly degraded samples in which O−H and C=C groups are present. The experiments performed with the DIP-MS technique have confirmed that the E-CO alternating copolymer loses water during its thermal ageing. The pyrolysis products of the copolymer are linear molecules with 1,4-diketonic structure, 2-cyclopentenone derivatives, alkyl furans, and aromatic compounds. These results suggest that during the thermal degradation of the E-CO alternating copolymer under inert atmosphere, and at low temperatures, aldol condensations and/or dehydration to furan rings probably occur. © 1998 SCI.     

Polymeric amines by chemical modifications of alternating aliphatic polyketones

Alternating, aliphatic polyketones were chemically modified by using di‐amines to obtain polymeric products having pendant amino groups. The used reaction, Paal‐Knorr, involves the formation of pyrrole rings along the polyketone backbone. The corresponding kinetics and final conversions are clearly dependent, among others, on statistical factors (two adjacent carbonyls must react in order to obtain ring formation) as well as on the steric hindrance (sterically hindered amino groups react very slow). The corresponding reaction products (polymeric amines) display very interesting physical properties in aqueous solution. These have been characterized by using dynamic light scattering, Cryo‐electron microscopy, fluorescence techniques, etc. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of high‐strength fibers from aliphatic polyketones by melt spinning and drawing

We have investigated the formation of high‐strength, high‐modulus fibers from four aliphatic polyketone resins. One resin was a perfectly alternating copolymer of ethylene and carbon monoxide, while the other three were terpolymers containing up to 6 mol % propylene. The mechanical properties were measured as a function of processing conditions, and the structures of the filaments were characterized using birefringence, WAXS, SAXS, SEM, and thermal analysis. Fibers formed from all resins develop very high molecular orientations and a microfibrillar structure. Fibers having room temperature tenacities as high as 10 gpd (～1.1 GPa) were obtained. Tensile moduli reached values as high as 120 gpd (～13 GPa). The melting point of the fibers was primarily dependent on the composition of the resin, while the maximum strength and modulus were largely determined by the maximum draw ratio achieved. The maximum draw ratio achieved in the present experiments was greater for the terpolymers than for the copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1794–1815, 2001     

Alternating copolymerization and terpolymerization of vinyl‐substituted phenolic antioxidants with propene and carbon monoxide by a palladium(II)‐based catalyst: polyketones containing intramolecular stabilizers

The copolymerization and terpolymerization reactions of the vinyl‐substituted phenolic stabilizers, 6‐tert‐butyl‐2‐(1,1‐dimethylhept‐6‐enyl)‐4‐methylphenol, o‐allylphenol, 4‐methylstyrene‐2,6‐di‐tert‐butylphenol and 2,6‐di‐tert‐butyl‐4‐allylphenol, with propene and carbon monoxide, by using the solvent‐stabilized palladium(II ) phosphine complex [Pd(dppp)(NCCH₃)₂](BF₄)₂ (dppp, 1,3‐bis(diphenylphosphino)propane) as a catalyst precursor and methanol as a co‐catalyst, is described. The influence of functional α‐olefins/CO units, distributed statistically along the propene/carbon monoxide (P/CO) copolymer backbone, on the molecular weight, glass transition temperature (T_g), elastic behavior and stability of the high‐molecular‐weight P/CO copolymer has been investigated. Loss of both elasticity and transparency were observed upon incorporating o‐allylphenol as a termonomer. The terpolymers, which contain phenolic stabilizers, were shown to be more stable when compared to the stabilizer‐free polyketones. In contrast to the propene/carbon monoxide copolymer, no degradation was observed for the 2,6‐di‐tert‐butyl‐4‐allylphenol/P/CO terpolymer; instead, the molar masses increased. Copyright © 2004 Society of Chemical Industry     

On the effect of the nature of the side chain over the crystalline structure in aliphatic polyketones

The crystalline structure of a number of random polymers of perfectly alternating l-olefins/carbon monoxide aliphatic polyketones has been studied by wide angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) and Raman spectroscopy. From previous studies, WAXS, Raman and DSC have shown to be suitable techniques for the characterisation of the two crystalline polymorphs, α (denser) and β, detected in ethene/carbon monoxide (ECO) and in ethene/propene/carbon monoxide (EPCO) polymers. In this paper for the first time, polyketones with butene and hexene as the second olefin are reported. It was found that the ethene/propene/carbon monoxide polymers and ethene/butene/carbon monoxide (EBCO) polymers, predominately contain the β-rich crystalline phase. The crystalline density of this phase drops with increasing second olefin content, albeit at a faster pace for propene polymers. From the latter results, and from the behaviour of the melting point, crystallinity, and crystal thickness across composition, inclusion of methyl and ethyl side chains into the crystals as defects was inferred. Ethene/hexene/carbon monoxide (EHCO) polymers do seem to behave differently: they show lower crystallinity, the presence of a larger quantity of the denser α crystals and a relatively high and constant crystalline density for the β phase throughout composition; observations that unambiguously support the exclusion argument for the butyl branches. The above behaviour is surprising since for instance in polyethylene copolymers it is considered that only methyl branches can enter the crystal lattice. The relative presence of α crystals was found to decrease with increasing the concentration of branches and in the order EHCO>EBCO>EPCO.     

Acyclic diene metathesis polymerization: The synthesis of unsaturated polyketones

The first acyclic diene metathesis (ADMET) polymerization of unsaturated ketone containing monomers using the molybdenum catalyst, Mo(CHCMe₂Ph)(N-2,6-C₆H₃-i-Pr₂)[OCCH₃(CF₃)₂]₂ is reported. 6,6,8,8-Tetramethyl-1,12-tridecadiene-7-one undergoes homopolymerization; copoly-merizations are carried out with 1,9-decadiene and 2,12-dimethyl-2,12-dipentenylcyclododecan-1-one, 2,12-diallylcyclododecan-1-one, and trans-2,12-diallyl-2,12-dimethylcyclododecan-1-one These polymerizations are initiated under bulk conditions and are continued in solution. No evidence of Wittig chemistry is observed between the carbonyl functional group and the catalyst when a high degree of steric hindrance exists around the carbonyl moiety. Polymer structures were characterized by IR, ¹H NMR, and ¹³C NMR spectroscopy. Molecular weights were determined by endgroup analysis and gel permeation chromatography.     

New polymer syntheses XXVIII. Synthesis and thermal behavior of new organometallic polyketones and copolyketones based on diferrocenylidenecyclohexanone

A new interesting category of organometallic polyketones and copolyketones were synthesized via the Friedel–Crafts reaction through the polymerization of 2,6‐[bis (2‐ferrocenyl)methylene] cyclohexanone (II) with different diacid chlorides. The model compound was synthesized by reacting the monomer (II) with benzoyl chloride and characterized by ¹H‐NMR, IR, and elemental analyses. The polyketones and copolyketones were insoluble in most organic solvents but easily soluble in protic solvents. The thermal properties of these polyketones and copolyketones were evaluated and correlated to their structural units by thermogravimetric analysis and DSC measurements, and they had inherent viscosity of 0.29–0.52 dI g^?1. Moreover, the electrical conductivity of one of the polyketones, as a selected example, namely poly [carbonyl‐terephthaloyloxy‐ (2‐oxo‐1,3‐cyclohexanediylidene)methylidyne‐ferrocenyl], Va , and copolyketone, VI , was investigated above the temperature range (300–500 K) and it followed an Arrhenius equation with activation energy 2.09 eV. The morphological properties of selected example of polyketones were determined by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1440–1448, 2004     

Melting and crystallization behavior of aliphatic polyketones

The basic crystallization and melting behavior of three aliphatic polyketones were studied using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and optical microscopy. One resin was a perfectly alternating copolymer of ethylene and carbon monoxide, while the other two resins were terpolymers in which 6 mol % propylene was substituted for ethylene. Small decreases in the melting point and percent crystallinity of these materials were displayed with repeated melting. This behavior was attributed to light crosslinking as a result of condensation reactions occurring at temperatures in the melting range. WAXS showed that, after cooling to room temperature, the crystalline form in the copolymer was the α‐phase, while that in the terpolymers was the β‐phase. Optical microscopy revealed that the materials produce both negative and mixed birefringence spherulites under the conditions studied. SAXS measurements showed that the lamella thickness was largely a function of the temperature of crystallization. Attempts were made to measure the equilibrium melting temperature of these resins using several available techniques. The best value of the equilibrium melting temperature was concluded to be 278 ± 2°C for the copolymer. The results varied over a wide range for the terpolymers, but it is suggested that appropriate values are of order 252°C for the terpolymers. Crystallization kinetics studies, carried out under isothermal conditions using DSC, were evaluated using the Avrami equation. Results showed the Avrami exponent to lie in the range of 2–3. Spherulite growth rates were interpreted in terms of the secondary nucleation theory of Lauritzen and Hoffman. A transition from regime II to regime III was discovered. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2124–2142, 2002