Polymorphism in alternating polyketones studied by x-ray diffraction and calorimetry

Differential scanning calorimetry and high temperature x-ray diffraction were used to study the perfectly alternating copolymer of ethene and carbon monoxide (polyketone; POKC2). It was found that oriented POK-C2 fibers show a crystalline phase transition at a temperature between 110–125°C with a 10% change in crystalline density. At this temperature, the crystal structure reported recently (POK-α) is transformed to a crystal structure that was reported in the past for room temperature imperfectly alternating polyketone. The latter structure will be designated as POK-β. The influence of chain defects on the crystal structure was studied by synthesizing terpolymers (POK-C2/C3), in which small amounts of propylene-CO units are incorporated into the polymer backbone. The resulting terpolymers differ from the copolymer by the presence of methyl groups randomly distributed along the polyketone backbone chain. Evidence is presented that indicates that the methyl groups are built into the crystal lattice as defects. With more than 5 mole-% propene the terpolymer fibers crystallize exclusively in the β-modification. Below this level the α/β ratio (at room temperature) increases with decreasing amounts of propene. Both as-synthesized and as-spun POK-C2 were found to consist of both POK-α and POK-β; the α/β ratio depends on the method of preparation. Because the drawn POK-C2 fibers studied here consist exclusively of POK-α, the process of spinning and drawing leads to the transformation of unoriented β-rich material into oriented POK-α. © 1995 John Wiley & Sons, Inc.     

Alternating copolymerizations of styrene derivatives and carbon monoxide in the presence of a palladium (II) catalyst

A series of styrene derivatives were synthesized from aromatic substances by Friedel-Crafts acylation, reduction, and dehydration. Alternating copolymers of styrene derivatives and carbon monoxide were prepared in the presence of a palladium(II) catalyst. The characterization of the polyketones produced was performed by use of ¹H-NMR, IR, WXRD, and EA methods. The thermal degradation of the regular alternating copolymer of carbon monoxide and styrene (STCO) has been studied by thermal gravimetry (TG). The TG spectra of solid samples were recorded both in nitrogen and in air. The degradation reaction order and activation energy were determined. The photodegradation of STCO was investigated. In addition, the block copolymerization of STCO with methyl methacrylate under UV irradiations was also studied. It is found that the tertiary amine can promote this photopolymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1283–1291, 1997     

Thermal Phase Transitions of Carbon Monoxide–Ethylene Alternating Copolymer: An FT/IR Study

In this study an analysis of the changes that occur in the infared spectrum of the ethylene–carbon monoxide alternating copolymer as a function of the temperature is presented. This copolymer can assume two polymorphic crystalline states, named POK-α and POK-β. Fourier transform infrared spectroscopy seems to be a good technique to observe the transition between these two forms, which occurs between 120 and 140°C in an undrawn sample. The IR results have been supported by differential scanning calorimetry measurements. The data obtained have, also, clarified that in the solid state the structure of the ethylene–carbon monoxide copolymer is extended by strong intermolecular interactions that weaken its intrinsic resistance and aid its thermal degradation. These interactions are absent or at least less strong in the melt or in the amorphous state. © 1997 John Wiley & Sons, Ltd.     

Influence of the physical characteristics of the polymer on the glass transition of various chemically modified PVCs

Vinylchloride–vinylthiocresol and vinylchloride–vinylthionaphthol copolymers of various compositions were prepared by the substitution reaction of PVC with sodium thiocresol and sodium thionaphthol, respectively, in different solvents and at different temperatures. The variation of the glass transition temperature of these copolymers with chemical com-position does not follow the Flory–Fox equation, but is found to depend on the solvent and the temperature at which the copolymer is obtained. The comonomer sequence distribution and stereosequence content of the above copolymers, and those of vinylchloride–vinyl-thiobenzene copolymer, were determined by ¹H- and ¹³C-NMR spectroscopy. The depen-dence of comonomer distribution and stereoregularity content with chemical composition for the three series of copolymers, prepared in different solvents and temperatures, are similar. The T_g deviations for the three series of copolymers were attributed to the con-tribution of physical characteristics of the PVC structure, originating from polymer–solvent interactions. © 1995 John Wiley & Sons, Inc.     

An NMR study of mobility in a crystalline side‐chain comblike polymer

Carbon‐13 spin–lattice relaxation times are measured for poly(octadecyl acrylate) above and below the melting point of the crystalline side chains. The chain backbone has long spin–lattice relaxation times below the melting point that shorten by more than an order of magnitude as the melting point range is traversed. Below the melting point, the backbone is nearly immobilized with spin–lattice relaxation changing very slowly with temperature. Above the melting point, the shorter spin–lattice relaxation times are typical of a rubber above the glass transition and decrease with increasing temperature. The methylene groups in the side chain are quite mobile well below the melting point, indicating fairly rapid anisotropic motion within the crystal. The methyl group at the end of the chain and the adjacent methylene group have longer spin–lattice relaxation times, indicating the greatest side‐chain mobility at the end, which is in the middle of the crystal structure. The side‐chain carbon adjacent to the carbonyl group is as mobile as the majority of the side‐chain carbon, indicating side‐chain mobility extends to all of the side‐chain CH₂ groups. The abrupt transition in the mobility of the backbone is not typical of the amorphous phase in a semicrystalline polymer where the backbone units can crystallize. The close proximity of every backbone segment to the crystalline domain locks backbone segmental motion below the melting point. Melting and crystallization of the side chains switch segmental motion of the backbone on and off. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1548–1552, 2001     

Synthesis of new fluorinated aromatic poly (ether ketone amide)s containing cardo structures by a heterogeneous palladium‐catalyzed carbonylative polycondensation

New fluorinated aromatic poly (ether ketone amide)s containing cardo structures were prepared by a heterogeneous palladium‐catalyzed polycondensation of fluorinated aromatic diiodides with ether ketone units, aromatic diamines containing cardo groups, and CO. Polymerizations were conducted in N,N‐dimethylacetamide at 120°C using 6 mol% of magnetic nanoparticles‐supported bidentate phosphine palladium (II) complex [Fe₃O₄@SiO₂‐2P‐PdCl₂] as catalyst and 1,8‐diazabicyclo[5,4,0]‐7‐undecene as base and resulted in fluorinated cardo poly (ether ketone amide)s with inherent viscosities up to 0.75 dL/g. All the polymers were readily soluble in many organic solvents and could afford transparent, flexible, and strong films by solution casting. These polymers showed good thermal stability with the glass transition temperature of 237°C–258°C, the temperature at 5% weight loss of 462°C–477°C in nitrogen. These polymer films also exhibited good mechanical properties, excellent electrical and dielectric performance, and high optical transparency. The incorporation of bulky fluorinated groups and cardo structures into polymer backbone has played an important role in the improvement of solubility, dielectric performance, and optical properties. Importantly, the heterogeneous palladium catalyst can easily be recovered from the reaction mixture by simply applying an external magnet and recycled up to 7 times without significant loss of catalytic activity.     

Copolymerization of carbon monoxide and 4-vinylcyclohexene with a palladium catalyst

In this work, carbon monoxide (CO) and 4-vinylcyclohexene (VCH) with [Pd(CH₃CN)₄](BF₄)₂ were copolymerized under various conditions at 60°C. Elemental analysis and infrared, UV, and NMR spectra indicated that copolymers containing a ketone and a cyclic structure of cyclohexyl and norbornane groups are produced. Bidentate nitrogen ligands proved to be more effective at stabilizing catalytic activity than monodentate phosphorus or nitrogen ligands. Also, the bulk substituent on the bidentate ligand led to inactive catalysts. Methanol served as the coinitiator and chain transfer agent. Increasing the concentration of 4-vinylcyclohexene caused the copolymer's CO content to be enhanced. TGA revealed that the copolymer's mass loss starts at 120°C and the maximum peak of decomposition occurs at 450°C. Moreover, X-ray diffraction analysis demonstrated the copolymer to be partially crystalline. Furthermore, reduction of 4-vinylcyclohexene/CO copolymer with LiAlH₄ in THF yields a hydroxyl-containing polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2759–2768, 1997     

Thermodynamic properties of an alternating copolymer of bicyclo[2.2.1]hepta-2,5-diene and carbon monoxide in a region from <Emphasis Type="Italic">T</Emphasis> → 0 to 550 K

The temperature dependence of the heat capacity of an alternating copolymer of bicyclo[2.2.1]hepta-2,5-diene and carbon monoxide in the temperature range 6–550 K (with an error of 0.2–0.5% at 6–350 K and 0.5–1.5% at 330–550 K) was studied by the adiabatic vacuum and dynamic calorimetry. Physical transformations of the copolymer in the studied temperature region were identified, and their thermodynamic characteristics were determined. The combustion energy of the copolymer at 298.15 K was measured in a calorimeter with a static bomb and isothermal jacket. The thermodynamic functions for a region of 0–550 K, enthalpy of combustion, and thermodynamic parameters of copolymer formation from simple substances at T = 298.15 K and p = 101.325 kPa were calculated from the obtained experimental data. The new results and earlier published data were used for the calculation of the thermodynamic characteristics of the alternate copolymerization of bicyclo[2.2.1]hepta-2,5-diene and CO under standard pressure for a region of 0–350 K for the bulk reaction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1483–1487, June, 2005.     

“Click” coupling between alkyne‐decorated multiwalled carbon nanotubes and reactive PDMA‐PNIPAM micelles

Covalent functionalization of alkyne‐decorated multiwalled carbon nanotubes (MWNTs) with a well‐defined, azide‐derivatized, thermoresponsive diblock copolymer, poly(N,N‐dimethylacrylamide)‐poly(N‐isopropylacrylamide) (PDMA‐PNIPAM) was accomplished by the Cu(I)‐catalyzed [3 + 2] Huisgen cycloaddition. It was found that this reaction could simultaneously increase the molecular size and bonding density of grafted polymers when PDMA‐PNIPAM micelles were employed in the coupling system. On the other hand, attachment of molecularly dissolved unimers of high‐molecular weight onto the nanotube resulted in low‐graft density. The block copolymer bearing azide groups at the PDMA end was prepared by reversible addition–fragmentation transfer polymerization, which formed micelles with a diameter of ～40 nm at temperatures above its critical micelle temperature. Scanning electron microscopy was utilized to demonstrate that the coupling reaction was successfully carried out between copolymer micelles and alkyne‐bearing MWNTs. FTIR spectroscopy was utilized to follow the introduction and consumption of alkyne groups on the MWNTs. Thermogravimetric analysis indicated that the functionalized MWNTs consisted of about 45% polymer. Transmission electron microscopy was utilized to image polymer‐functionalized MWNTs, showing relatively uniform polymer coatings present on the surface of nanotubes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7187–7199, 2008     

Asymmetric polymerization using C1 resources

Two examples of asymmetric alternating copolymerization, (1) the alternating copolymerization of α‐olefins (monosubstituted ethenes) with carbon monoxide and (2) the alternating copolymerization of meso‐epoxide with carbon dioxide, are described, and the meaning of chirality in polymer synthesis is emphasized. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 215–221, 2004     

Novel organotin-containing diblock copolymer with tunable nanostructures: Synthesis, self-assembly and morphological change

Interesting self-assembly behavior and morphological change of a novel organotin-containing diblock copolymer were firstly reported. The organotin-containing diblock copolymer, poly(methyl methacrylate)-block-poly(acetoxydibutyltin methacrylate) (PMMA-b-PADBTMA), was prepared via RAFT polymerization of ADBTMA with PMMA as the macroCTA and AIBN as the initiator in toluene. Both the FT-IR and TG analysis revealed an incorporation of both co-monomers in the resulted polymer backbone. The ratio of two segments was determined indirectly by TG analysis, gravimetric method and derivative process. All results from the different methods were well matched. And it was found that the morphology of the diblock copolymer could be changed easily from vesicles to nano-particle or cross-linked nano-composite under the ultrasonication or additional Ph₂SnCl₂, respectively. All the morphologies were analyzed by SEM, TEM and DLS. The self-assembly and the morphological change attributed to the strong coordination action between tin atoms and the carbonyl groups among PADBTMA segments.     

A successive route to amphiphilic graft copolymers with a hydrophilic poly(3‐hydroxypropyl methacrylate) backbone and hydrophobic polystyrene side chains

A successive method for preparing novel amphiphilic graft copolymers with a hydrophilic backbone and hydrophobic side chains was developed. An anionic copolymerization of two bifunctional monomers, namely, allyl methacrylate (AMA) and a small amount of glycidyl methacrylate (GMA), was carried out in tetrahydrofuran (THF) with 1,1‐diphenylhexyllithium (DPHL) as the initiator in the presence of LiCl ([LiCl]/[DPHL]₀ = 2), at −50 °C. The copolymer poly(AMA‐co‐GMA) thus obtained possessed a controlled molecular weight and a narrow molecular weight distribution (M_w /M_n = 1.08–1.17). Without termination and polymer separation, a coupling reaction between the epoxy groups of this copolymer and anionic living polystyrene [poly(St)] at −40 °C generated a graft copolymer with a poly(AMA‐co‐GMA) backbone and poly(St) side chains. This graft copolymer was free of its precursors, and its molecular weight as well as its composition could be well controlled. To the completed coupling reaction solution, a THF solution of 9‐borabicyclo[3.3.1]nonane was added, and this was followed by the addition of sodium hydroxide and hydrogen peroxide. This hydroboration changed the AMA units of the backbone to 3‐hydroxypropyl methacrylate, and an amphiphilic graft copolymer with a hydrophilic poly(3‐hydroxypropyl methacrylate) backbone and hydrophobic poly(St) side chains was obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1195–1202, 2000     

2H NMR spin relaxation study of the soft segment motion in alternating ethylene–propylene copolymers

We synthesized three partially deuterated polymer samples, namely a poly(ethylene‐alt‐propylene) (EP) alternating copolymer, a poly(styrene‐b‐EP) diblock copolymer (SEP) and a poly(styrene‐b‐EP‐b‐styrene) triblock copolymer (SEPS). The ²H spin–lattice relaxation time, T₁, of EP soft segments above their glass transition temperature was measured by solid‐state ²H NMR spectroscopy. It was found that the block copolymers had a fast and a slow T₁ component whereas EP copolymer had only a fast component. The fast T₁ components for SEP and SEPS are similar to the T₁ value of EP above ca 20°C. The slow T₁ component for SEP and SEPS exhibited a minimum at 60°C and approached the value of the fast component near the T_g of polystyrene. The motional behavior of the EP units for SEP is similar to that of SEPS over the entire range of temperature. Copyright © 2001 John Wiley & Sons, Ltd.     

Synthesis of a polyester macromonomer via the cobalt-catalyzed alternating copolymerization of propylene oxide and carbon monoxide

The alternating copolymerization of propylene oxide and carbon monoxide was investigated with cobalt complexes. The NaCo(CO)₄/amine catalyst system selectively yielded oligo(3-hydroxybutyrate)s bearing a polymerizable crotonate end group, whereas the use of Co₂(CO)₈ as a cobalt source resulted in a smaller concentration of the crotonate end group and a high degree of polymerization. The high selectivity for the oligoesters with the crotonate end group with the NaCo(CO)₄/amine system was attributed to its more basic reaction condition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4666–4670, 2004     

Thermal properties of nylons containing carbonyl groups

Nylons containing carbonyl groups in backbone chains were prepared and their response to heat was studied. The carbonyl groups were introduced using either HOOC(CH₂)₄CO(CH₂)₄COOH or H₂N(CH₂)₅CO(CH₂)₅NH₂ in the initial monomer compositions. In addition to pyrolysis of these polyamides, the progress of chemical and physical changes as a function of temperature was continuously monitored and analyzed by FT–IR spectroscopy on cast films placed in an environmental chamber. Introduction of the carbonyl groups into the polymer backbone resulted in a significant reduction of the thermal stability of the corresponding polyamide. Possible mechanisms for the thermal degradation entailing these carbonyl groups and N-acylamide compounds are discussed.     

Thermodynamics of alternating copolymer of ethylene and carbon monoxide in the 0–600 K region

The temperature dependence of the heat capacity of the alternating copolymer (ACP) of carbon monoxide with ethylene was studied, and temperatures and enthalpies of its phase transformations were measured by adiabatic vacuum, dynamic, and isothermal calorimetry in the temperature range from 8 to 600 K. The energy of burning of ACP was measured at 298.15 K in a calorimeter with the static bomb and isothermal shell. The thermodynamic parameters of transformation of the α-form of ACP crystals into the β-form and fusion of the β-form were determined. The thermodynamic functions for the 0–507 K range and thermodynamic characteristics atT=298.15 K andp=101.325 kPa were calculated. The thermodynamic parameters of the alternating copolymerization of ethylene and CO at 0–507 K and standard pressure were calculated for the bulk reaction. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 284–288, February, 1998.     

Alternating copolymerization of carbon dioxide and epoxide catalyzed by an aluminum Schiff base–ammonium salt system

The alternating copolymerization of carbon dioxide (CO₂) and cyclohexene oxide (CHO) with an aluminum Schiff base complex in conjunction with an appropriate additive as a novel initiator is demonstrated. A typical example is the copolymerization of CO₂ and CHO with the (Salophen)AlMe ( 1a )–tetraethylammonium acetate (Et₄NOAc) system. When a mixture of the 1a –Et₄NOAc system and CHO was pressurized by CO₂ (50 atm) at 80 °C in CH₂Cl₂, the copolymerization of CO₂ and CHO took place smoothly and produced a high polymer yield in 24 h. From the IR and NMR spectra, the product was characterized to be a copolymer of CO₂ and CHO with an almost perfect alternating structure. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis indicated that an unfavorable reaction between Et₄NOAc and CH₂Cl₂ and a possible chain‐transfer reaction with concomitant water occurred, and this resulted in the bimodal distribution of the obtained copolymer. With carefully predried reagents and apparatus, the alternating copolymerization in toluene gave a copolymer with a unimodal and narrower molecular weight distribution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4172–4186, 2005     

Pulsed‐EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative

A key intermediate in the electroconversion of carbon dioxide to carbon monoxide, catalyzed by a manganese tris(carbonyl) complex, is characterized. Different catalytic pathways and their potential reaction mechanisms are investigated using a large range of experimental and computational techniques. Sophisticated spectroscopic methods including UV/Vis absorption and pulsed‐EPR techniques (2P‐ESEEM and HYSCORE) were combined together with DFT calculations to successfully identify a key intermediate in the catalytic cycle of CO₂ reduction. The results directly show the formation of a metal–carboxylic acid–CO₂ adduct after oxidative addition of CO₂ and H⁺ to a Mn⁰ carbonyl dimer, an unexpected intermediate.     

Fully Borylated Methane and Ethane by Ruthenium‐Mediated Cleavage and Coupling of CO

Many transition‐metal complexes and some metal‐free compounds are able to bind carbon monoxide, a molecule which has the strongest chemical bond in nature. However, very few of them have been shown to induce the cleavage of its C?O bond and even fewer are those that are able to transform CO into organic reagents with potential in organic synthesis. This work shows that bis(pinacolato)diboron, B₂pin₂, reacts with ruthenium carbonyl to give metallic complexes containing borylmethylidyne (CBpin) and diborylethyne (pinBC≡CBpin) ligands and also metal‐free perborylated C₁ and C₂ products, such as C(Bpin)₄ and C₂(Bpin)₆, respectively, which have great potential as building blocks for Suzuki–Miyaura cross‐coupling and other reactions. The use of ¹³CO‐enriched ruthenium carbonyl has demonstrated that the boron‐bound carbon atoms of all of these reaction products arise from CO ligands.     

Copolymerization of carbon monoxide with 1,3-cyclopentadiene by palladium complexes

Copolymerization of carbon monoxide with 1,3-cyclopentadiene (CPD) by palladium complexes, [Pd(CH₃CN)_4?n (PPh₃)n] (BF₄)₂, n = 1–3 (especially n = 1), was studied at 60°C. Results of elementary analysis, infrared spectra, and NMR spectra showed that copolymers containing ketone and ring structures were produced. Phosphorus compounds such as PPh₃ were found to be more effective stabilizing ligands for the catalytic activity compared to arsenic or nitric ligands. A higher activity of the catalyst for the copolymerization of CPD with carbon monoxide was observed in noncoordinating solvents such as CHCl₃ even at a pressure as low as 300 psi. The amount of 1,2 structure for the CPD-CO copolymer increased as the polarity of solvent increased. The copolymer was confirmed to be partially crystalline by the x-ray diffraction. TGA shows that weight loss of copolymer starts at 120°C and the maximum peak of decomposition occurs at 469°C. © 1993 John Wiley & Sons, Inc.