Synthesis and properties of alternating copolymers of acrylics and olefins

The free radical copolymerization and terpolymerization of acrylic monomers with olefins in the presence of Lewis acid complexing agent for the acrylic monomer has been investigated. The course of the polyreaction is in agreement with the features of a radical chain growth reaction, and the polymer properties can be varied by changing the composition of the reaction mixture and the reaction conditions. The alternating copolymers are usually amorphous materials, and only the alternating ethylene/acrylonitrile copolymer can be obtained as a material of relatively high crystallinity. The degree of crystallinity can be varied through terpolymerization of complexed acrylonitrile with ethylene/propylene comonomers. The basic features of the polyreaction and the polymer structures as well as some of the physical and material properties of the copolymers have been studied.     

1:1 alternating copolymers of 1-bicyclobutanecarbonitrile with styrene

High molecular weight, 1:1 alternating copolymers of 1-bicyclobutanecarbonitrile with styrene were prepared in tetramethylenesulfone solution by complexing the electron-poor bicyclobutane monomer with zinc chloride. Methyl 1-bicyclobutanecarboxylate under these conditions gave copolymers containing a slight excess of styrene units (ratio 1:1.3 to 1:1.8). High molecular weight homopolymers of 1-bicyclobutanecarbonitrile and of methyl 1-bicyclobutanecarboxylate were prepared similarly. The tendency of the bicyclobutane nitrile to form 1:1 alternating copolymers is as great as that of its vinyl analog, acrylonitrile, and the synthesis of other alternating copolymers from this monomer should be possible.     

Linear nano-templates of styrene and maleic anhydride alternating copolymers

Poly(styrene-alt-maleic anhydride) (SMA) self-assembles in aqueous solution to form nanotube structures. These can be used as templates to linearly guide the growth of a secondary polymeric or inorganic material. Templates are made starting from a basic SMA solution, followed by slow pH decrease by dialysis against deionized water, until a 50% degree of protonation is reached. The nanotube structure is composed of multiple polymer chains, associating sideways by π-stacking to form the nanotube walls. The SMA templates were used to grow linear composites, which shows the applicability of the template properties and also confirms the nanotube association mechanism. Linear polymer composites were formed using this SMA template: pyrrole was polymerized, silver nitrate was reduced to silver and silver cyanide nanowires were grown.     

Mechanical and thermal properties of ternary alternating copolymers of carbon monoxide with olefins

Thermal properties and the deformational behavior of ternary alternating copolymers of carbon monoxide with ethylene and other olefins (propylene, 1-butene, styrene) with molecular masses of M _n = 1000–35000 and molar fraction of the third comonomer in the polymer chain from 0.02 to 0.70 were investigated. Temperatures of melting and glass transition are significantly affected by the composition of the products. Varying the nature of the third comonomer or the content of its units in the polymer chain and the molecular masses of terpolymers makes it possible to obtain materials with Young’s moduli of 0.003–3.090 GPa and elongations at break of 5–2000%.     

Palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups in scCO2

Product control of palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups can be achieved through modifying reaction conditions. When the oxidant, such as CuCl₂/O₂, benzoquinone/O₂ or O₂, was present in scCO₂, aerobic oxidation of terminal olefins goes smoothly. With enough MeOH and sufficient oxygen, acetalization preponderated over cyclotrimerization, while with little MeOH as co-solvent in scCO₂ or no MeOH in DMF and an appropriate pressure of O₂, cyclotrimerization of terminal olefins became the dominated reaction. When oxygen is absent and triethylamine was added into the reaction system, palladium-catalyzed C-N bond formation occurs to produce β-amino acid derivatives as the sole product.     

Unperturbed dimensions of random and alternating styrene/n-alkyl methacrylate copolymers

The steric factors σ of homopolymers of ethyl, n-butyl, and n-octyl methacrylate, of equimolar random and alternating copolymers of these monomers with styrene, and of polystyrene, were determined by measuring intrinsic viscosities in a good solvent (butanone, 25°C) and extrapolating the data thus obtained to zero molecular weight of the polymer. For all comonomeric pairs under investigation, the σ² of an equimolar random copolymer and, particularly, of an alternating copolymer, is higher than the arithmetic mean (σ + σ)/2 of the σ² values of the parent homopolymers. The positive deviation from the linear dependence of σ² on the copolymer composition, expressed as an increment of σ², is proportional to the mole fraction of alternating dyads in the copolymer chain with in the limits of experimental error. The effect of copolymer microstructure on the unperturbed dimensions of the chains has been compared for equimolar copolymers of styrene with methyl, ethyl, n-butyl, and n-octyl methacrylate by using a relative increment ξ defined as the ratio of σ² of the alternating copolymer to (σ + σ)/2. The dependence of ξ on the number of carbon atoms in the alcohol substituent of the methacrylate component of the copolymer seems to exhibit a maximum for ethyl methacrylate.     

Effect of chirality on pi-stacking in styrene and maleimide alternating copolymers

The effect of different chiral sequences in alternating copolymers of styrene and maleimide, poly(styrene-alt-dimethyl-N,N-propylamide) (SMI) was studied. The methods used for the SMI also applied to the general class of alternating copolymers of styrene and various maleimides. Only racemo-diisotactic polymers can associate into complexes because of the symmetrically distributed phenyl groups and maleimide monomers. This polymer is isotactic with respect to the chiral site of the styrene monomers (R, S) and isotactic with respect to the chirality of the maleimide [racemo (RR, SS)]. The maleimide, racemo (SS or RR) chirality, and the complementary S or R chirality in the styrene moiety form the repeating unit of racemo-diisotactic SMI. Structural deviations from the isotactic configurations induces an asymmetry in the distribution of styrene monomers and introduce bends in the polymer backbone, which prevent association through pi-stacking interactions. Semiempirical PM3 calculations on the SMI polymer have shown that this pi-stacking occurs when the polymers are separated by a distance about 10 A, and each pi-stacking pair formed from the styrene monomers has a stabilization energy of about 12 kJ/mol.     

Initiated chemical vapor deposition of alternating copolymers of styrene and maleic anhydride

Initiated chemical vapor deposition (iCVD) of alternating copolymer thin films has been achieved for the first time. Copolymerization is desirable for maleic anhydride (Ma) since this monomer does not homopolymerize to an appreciable extent. At conditions where the observed deposition rates for styrene (S) and Ma homopolymers were only 0 and 5.5 nm/min, respectively, combining the two monomers resulted in a much higher deposition rate of 75.4 nm/min. iCVD processes utilize low energy (<30 W) to generate peroxy radicals from initiator molecules while avoiding degradation of functional groups in the monomers. Indeed, full retention of the anhydride functionality from the Ma monomer and avoidance of undesirable side reactions was observed in iCVD of poly(styrene-alt-maleic anhydride) (PSMa) copolymer films. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and 13C nuclear magnetic resonance (NMR) conclusively demonstrate that all of the copolymer films contain 50% styrene and 50% Ma (within experimental error), irrespective of gas feed ratios employed during the deposition. The 13C NMR signal in the 136-140 ppm region from the quaternary carbon in styrene and additional distortionless enhancement polarization transfer experiments confirmed that the copolymers are strictly alternating. Varying the gas feed ratio of Ma to styrene provided control over deposition rates and number-average molecular weights. Number-average molecular weights varied from 1380 to 4680 g/mol, and deposition rates varied from 6.3 to 75.4 nm/min.     

4-PEG接枝苯乙烯-马来酸酐交替共聚物的合成及功能化

采用普通自由基聚合和可逆加成一断裂链转移（RAFT）自由基聚合方法合成了对位PEG取代苯乙烯（PEG-g-St）和马来酸酐的交替共聚物（P（（PEG—g—St）-alt-MA））,”CNMR分析表明PEG-g-St和马来酸酐单元采取交替的序列结构．利用反应性基团-马来酸酐单元的水解以及胺解可以制备功能性的PEG聚合物．以月桂胺为模型小分子研究了该聚合物的胺解,得到4-PEG-苯乙烯与羧酸基团以及疏水烷烃的交替序列聚合物,该双亲聚合物在水溶液中形成组装体．     

Synthesis and photochemical properties of high-impact styrene copolymers containing keto groups

A method for the preparation by suspension polymerization of high-impact styrene copolymers containing built-in keto groups is described. Some of the features of the process are described. Photolysis of these copolymers on irradiation with polychromatic and monochromatic light (λ = 313 and 366 nm) has been investigated. The quantum yields of cleavage of the main chain (ø_cs) in film or solution have been shown to be concentration dependent. It has been concluded that the photoprocesses in these two-phase polymeric systems proceed independently in the polymer matrix and in the dimethylformamide insoluble fraction.     

Pd(II)-catalyzed acetalization of terminal olefins with electron-withdrawing groups in supercritical carbon dioxide: selective control and mechanism

Pd(II)-catalyzed acetalization of terminal olefins with electron-withdrawing groups was carried out smoothly in supercritical carbon dioxide under oxygen atmosphere when polystyrene-supported benzoquinone (PS-BQ) or Cu^II (Cu^I) chloride was employed as cocatalyst. The higher selectivity was achieved, without any chlorinated by-product detected, when using PS-BQ instead of Cu^II (or Cu^I) chloride. PS-BQ could be recycled with excellent catalytic activity remaining after each simple filtration. Chlorine ion was demonstrated to be a promoter. The different acetalization mechanisms were revealed by the subtle relationship of chlorine ion and benzoquinone (BQ) to the catalytic activity of PdCl₂/PS-BQ, Pd^II-CuCl₂ or Pd(OAc)₂/PS-BQ.     

Photooxidation of copolymers of fluorinated olefins and allyl or vinyl ethers

This article reports the results on the photooxidation mechanisms of two copolymers of fluorinated olefins and allyl or vinyl ethers. It is shown that the presence of the fluorine atoms influences strongly both the orientation of the reaction and the photooxidation kinetics. Due to the neighbouring fluorine atoms, the methylene groups in α-position of the oxygen of the ether groups are not equivalent regarding oxidation and the secondary carbon becomes more oxidable than the tertiary one. Because these unexpected results were obtained, the study has been extended to non fluorinated polyethers. On the basis of the results obtained, a general mechanism of the primary oxidation of polyethers is given, and the role played by the fluorine atoms on the orientation of the reactions is discussed.     

Effect of electron-withdrawing groups on photovoltaic performance of thiophene-vinyl-thiophene derivative and benzochalcogenadiazole based copolymers: A computational study

We report a density functional theory study of the effect of electron-withdrawing groups such as –F, –CN, –NO₂ on the geometrical, optoelectronic, intramolecular charge transfer (ICT), and photovoltaic properties of (E)-1,2-bis(5-alkyl-[2,3′-bithiophene]-2′-yl)ethene (TVT-T) based donor-acceptor (D-A) copolymers with different acceptor units, that is, benzo[c][1,2,5]thiadiazole, benzo[c][1,2,5]oxadiazole, and benzo[c][1,2,5]selenadiazole. The computed optical absorption spectra of the designed compounds lie in the visible and near-infrared regions. Of all the studied copolymers, -CN substituted and Se-based compound displays the lowest HOMO-LUMO (E _{H - L}) gap and optical band gap (E _opt). The exciton binding energy (E _b) is found to be smaller for O-incorporated compounds and -CN substituted copolymer as well, inferring more ICT. The electron-hole coherence concentrated over the D-A units is nearly the same for -CN and -NO₂ substituted compounds, but larger in -F derivatives, indicating weak electron-hole coupling in the formers. Comparatively larger dipole moment (6.421 Debye-9.829 Debye) and charge transfer length (D _CT) (1.976 Å-3.122 Å) for -CN derivatives lead to enhanced ICT properties. The designed donors yield good hole mobilities (0.127-6.61 cm² V⁻¹ s⁻¹) and the predicted power conversion efficiencies are calculated to be as high as ~6%-7% for –CN and –NO₂ substituted compounds.     

Copolymerization of styrene. III. Physical and mechanical properties of copolymers with styrene derivatives containing nitrile groups in the side chain

Copolymers of styrene with cinnamonitrile (I), ethyl benzylidenecyanoacetate (II), and benzylidenemalononitrile (III) were prepared in bulk, in suspension, and in emulsion up to high conversion. Their softening points, flexural properties, impact resistance, hardness, and volumetric shrinkage due to polymerization were studied. All three copolymers show improved thermal resistance in comparison to polystyrene, but whereas copolymers styrene–I and styrene–III are inferior to polystyrene in flexural strength and the impact resistance, the copolymer styrene–II is about equal to polystyrene in its flexural properties and impact resistance.     

Esters of alternating copolymers of maleic or 2,3-dimethylmaleic anhydride with alkyl vinyl ethers

Maleic anhydride or 2,3-dimethylmaleic anhydride was copolymerized with a number of alkyl vinyl ethers, with AIBN as the initiator. The comonomers were always alternating and were obtained in yields ranging from 15 to 99%. The acid anhydride group in both series of copolymers was converted to the corresponding methyl esters in a two-step reaction. The structure of these polymers was established by elemental analysis and by infrared, ¹H-and ¹³C-NMR spectroscopy. Addtional characterization of these copolymers were carried out by viscosity measurements, differential scanning calorimetry for the determination of glass transition temperatures, and thermal degradation for the determination of the thermal stability of the copolymers.     

Polymerization of coordinated monomers. XV. 13C-NMR study on the alternating copolymers of methyl methacrylate with styrene

By the use of various metal halides methyl methacrylate and styrene were copolymerized to produce equimolar alternating sequences and different cotacticities. The ¹³C-NMR spectra of these copolymers were simple in comparison to those of random copolymers because of the fixed monomer sequence which yielded sharply split triplets for carbonyl, methoxy, and quaternary carbons. The relative intensities in these split peaks varied according to the metal halide used. A comparison of the intensities made it possible to obtain clear-cut and quantitative information on the methyl methacrylate-centered triad cotacticity of the copolymers. The spectral assignment with respect to the methoxy carbon was definitely justified by the combined use of partly relaxed Fourier transform and selective decoupling techniques. The spectrum of aromatic C₁ carbon in styrene units also split into three main peaks. From their relative intensities the splitting was attributed to styrene-centered triad cotacticity. The assignment of this carbon was compared with two other assignments made for random copolymers of methyl methacrylate with styrene; they were contradictory, however. Furthermore, an apparent discrepancy was observed between methyl methacrylate-and styrene-centered tactic triads of these alternating copolymers. The origin of this discrepancy suggests a close relationship with the copolymerization mechanism.     

Regioselective and stereoselective alternating copolymerization of carbon monoxide with functional olefins

Enantioselective, alternating copolymerizations of carbon monoxide with ω‐undecylenic acid, ethyl acrylate, and butyl acrylate were carried out for the first time with a palladium catalyst modified by 1,4:3,6‐dianhydro‐2,5‐dideoxy‐2,5‐bis(diphenylphosphino)‐L ‐iditol. Optical rotation, elemental analysis, and ¹H NMR,¹³C NMR, and IR spectra showed that the copolymers were optically active, isotactic, alternating poly(1,4‐ketone) or poly(spiroketal) structures. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2027–2036, 2001     

Regio- and stereocontrol in the alternating copolymerization of olefins with carbon monoxide

Strictly alternating copolymers between olefins and carbon monoxide are synthesized using cationic palladium catalysts modified by phosphorus or nitrogen ligands. Basic chelate diphosphines as the ligand allow the regioregular copolymerization of aliphatic olefins thus affording, e.g. in the case of propene, poly(1-oxo-2-methyltrimethylene). Steric control of the copolymerization process towards the production of overwhelmingly isotactic copolymers is possible particularly when using atropisomeric ligands. In the case of styrene as the substrate and for all ligands employed the copolymerization process is regioregular. Prevailing syndiotactic structure is obtained with 1,10-phenanthroline or 2,2′-bipyridine as the ligand. Chelate thioether ligands allow the preparation of a completely atactic material. For 4-tert-butylstyrene an isotactic structure became accessible by using chiral bisoxazolidines. The prevailing structure of the copolymers of cyclopentene corresponds to a 1,3-enchainment of the olefin units most probably associated with a prevailing diisotactic structure