Hydrogen‐Assisted Unique Incorporation of 1,4‐Divinylbenzene in Copolymerization with Propylene Using an Isospecific Zirconocene Catalyst

Summary: Propylene was copolymerized with 1,4‐divinylbenzene (1,4‐DVB) using rac‐Me₂Si(2‐Me‐4‐Ph‐Ind)₂ZrCl₂ and MAO in the presence of hydrogen. ¹H NMR spectra of the obtained copolymer confirmed the successful incorporation of 1,4‐DVB. ¹³C NMR analysis revealed a unique copolymer structure with the incorporated 1,4‐DVB units predominantly forming 1,4‐substituted phenyl repeating units in the polymer main chain. A plausible mechanism involving spontaneous insertion of terminal styryl into Zr‐H species was proposed to rationalize the unique incorporation of 1,4‐DVB.

Copolymerization of propylene with 1,4‐divinylbenzene in the presence of hydrogen.     

Synthesis and thermal properties of polydimethylsiloxanes modified by decyl and methylundecylenate substituents

A series of polydimethylsiloxanes modified by long-chain hydrocarbon substituents, including those containing terminal ester groups, was synthesized. The structures of the copolymers were confirmed by the data of ¹H and ²⁹Si NMR spectroscopy. The thermal properties of the copolymers were studied by differential scanning calorimetry. The change in the behavior of the copolymers is observed at the content of modifying units is >5 mol.% and the fluidity of the polymers is retained at the content of these units <15 mol.%.     

Micellar behavior of well‐defined polystyrene‐based block copolymers with triethoxysilyl reactive groups and their hydrolysis–condensation

Block copolymers of acryloxy propyl triethoxysilane and styrene were prepared through nitroxide‐mediated polymerization using alkoxyamine initiators based on N‐tert‐butyl‐1‐diethylphosphono‐2,2‐dimethylpropyl nitroxide. The copolymers were characterized by ¹H NMR, size exclusion chromatography and differential scanning calorimetry. Their micellar behavior in dioxane/methanol solutions was examined through static light scattering and transmission electron microscopy (TEM). TEM indicated the successful formation of spherical micelles which were subsequently frozen by the sol–gel process. Hydrolysis–condensation of the reactive ethoxysilyl side groups was followed by FTIR, ¹H NMR, and ²⁹Si NMR. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 784–793, 2010     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

Preparation,characterization, and thermal properties of alt‐copoly[1,9‐decaphenylpentasiloxanylene/1,3‐bis(ethylene)permethyloligosiloxanylene]s

alt‐Copoly[1,9‐decaphenylpentasiloxanylene/1,3‐bis(ethylene)tetramethyldisiloxanylene], alt‐copoly[1,9‐decaphenylpentasiloxanylene/1,5‐bis(ethylene)hexamethyltrisiloxanylene], alt‐copoly[1,9‐decaphenylpentasiloxanylene/1,7‐bis(ethylene)octamethyltetrasiloxanylene], and alt‐copoly[1,9‐decaphenylpentasiloxanylene/1,9‐bis(ethylene)decamethylpentasiloxanylene] were synthesized by Pt‐catalyzed hydrosilylation reactions of 1,9 divinyldecaphenylpentasiloxanes with a series of oligodimethylsiloxanes. The molecular weights of these copolymers were determined by gel permeation chromatography. Their glass‐transition temperatures (T_g's) were obtained by differential scanning calorimetry. The thermal stabilities of the copolymers were measured by thermogravimetric analysis. The structures of the copolymers were verified by ¹H, ¹³C, and ²⁹Si NMR as well as IR and UV spectroscopy. The copolymers displayed high thermal stabilities and a single T_g, indicating that phase separation between the two short blocks did not occur. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6146–6152, 2005     

Functional polysiloxanes. I. Microstructure of poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s obtained by cationic copolymerization

Poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s of various compositions have been prepared by cationic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) and 1,3,5,7‐tetramethylcyclotetrasiloxane (D) in the presence of hexamethyldisiloxane as end‐blocker or by rearrangement of poly(hydrogenmethylsiloxane) in the presence of D₄. These copolymers were examined by high resolution ¹H NMR (500.13 MHz) and ²⁹Si NMR (99.37 MHz) spectroscopies. Triad effects were observed by ¹H and up to heptad effects by ²⁹Si NMR. The chemical shifts were assigned for these stereosequences. The intensities of the triad signals were used to calculate the quantitative parameters describing the microstructure of the copolymer chains: number‐average block length (L̄) and persistence ratio (η). The values of these parameters for copolymers prepared in various experimental conditions show that the time necessary for redistribution reactions (backbiting) is much larger than the time required to establish the equilibrium between linear polymer and cyclic oligomers. However, redistribution is fast enough to prevent the formation of block copolymers even in the case of the rearrangement of poly(hydrogenmethylsiloxane) in the presence of D₄. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 826–836, 2000     

Simple route for synthesis of H‐shaped copolymers

The H‐shaped copolymers, [poly(L ‐lactide)]₂polystyrene [poly(L ‐lactide)]₂, [(PLLA)₂PSt(PLLA)₂] have been synthesized by combination of atom transfer radical polymerization (ATRP) with cationic ring‐opening polymerization (CROP). The first step of the synthesis is ATRP of St using α,α′‐dibromo‐p‐xylene/CuBr/2,2′‐bipyridine as initiating system, and then the PSt with two bromine groups at both chain ends (Br–PSt–Br) were transformed to four terminal hydroxyl groups via the reaction of Br–PSt–Br with diethanolamine in N,N‐dimethylformamide. The H‐shaped copolymers were produced by CROP of LLA, using PSt with four terminal hydroxyl groups as macroinitiator and Sn(Oct)₂ as catalyst. The copolymers obtained were characterized by ¹H NMR spectroscopy and gel permeation chromatography. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2794–2801, 2006     

Modification of polyisoprene‐block‐poly(vinyl trimethylsilane) block copolymers via hydrosilylation and hydrogenation,and their gas transport properties

Polyisoprene‐block‐poly(vinyl trimethylsilane) (PI‐b‐PVTMS) block copolymers having different isoprene contents are successfully chemically modified and characterized by proton nuclear magnetic resonance spectroscopy (¹H‐NMR), Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. Gas transport properties of the initial block copolymers and their derivatives modified via hydrosilylation and hydrogenation are measured. The modified block copolymers show higher permeabilities for O₂ and H₂ than the unmodified block copolymers while maintaining similar O₂/N₂ and H₂/N₂ selectivities. Hydrosilylation and hydrogenation of block copolymers with a low isoprene content result in a permeability increase for O₂ and H₂ of 15 to 40%, respectively. Similarly, for block copolymers with high isoprene contents, increases in permeabilities up to 125% are observed compared to initial PI‐b‐PVTMS. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2013 , 51, 1252–1261     

Reactivity of Extra‐framework Species of USY Zeolites in Alkaline Medium

Zeolites of type USY (ultra‐stable Y) were obtained by steaming of NH₄NaY modification. Samples were modified by subsequent alkaline treatment in KOH solution. USY and USY‐KOH were characterised by chemical element analysis, XRD, IR, ²⁹Al and ²⁹Si MAS NMR spectroscopic measurements. Correct silicon to aluminium ratios (Si/Al) were determined by XRD and IR (double ring vibration w_DR) data whereas values calculated according to data of ²⁹Si MAS NMR and IR spectroscopy (asymmetrical TOT valence vibration w_TOT) appeared to be too high., In the latter case, the signals of the zeolite framework were strongly superimposed by that of extra‐framework silica gel (EFSi) formed during steaming. It was found that alkaline leaching induces desilication of silicon‐rich area of the zeolite framework and partial dissolution of EFSi. Silicate ions of both react with likewise dissolved extra‐framework aluminium (EFAl) to form X‐ray amorphous aluminosilicate. Consequently, the superposition of the ²⁹Si MAS NMR signals of the zeolite framework by silica gel was reduced for Q⁴(0Al) but increased for Q⁴ (2Al) and Q⁴(3Al) structure units. A reinsertion of EFAl into the zeolite framework has not been observed.     

Random propene/4‐methyl‐1‐pentene copolymers synthesized with C2 symmetric highly isospecific metallocenes

Propene (P)/4‐methyl‐1‐pentene (Y) copolymers in a wide range of composition were prepared with isospecific single center catalysts, rac‐Et(IndH₄)₂ZrCl₂ ( EBTHI ), rac‐Me₂Si(2‐Me‐BenzInd)₂ZrCl₂ ( MBI ), and rac‐CH₂(3‐^tBuInd)₂ZrCl₂ ( TBI ). ¹³C NMR analysis of copolymers and statistical elaboration of microstructural data at triad level were performed. Unprecedented and surprising results are here reported. Random P/Y copolymers were prepared with the most isospecific catalyst, TBI , that is known to prepare ethene/propene and ethene/4‐methyl‐1‐pentene copolymers with long homosequences of both comonomers, whereas longer homosequences of both comonomers were observed in copolymers from the less enantioselective metallocenes EBTHI and MBI . These findings, which are against what is acknowledged in the field, can pave the way for the preparation on a large scale of random propene‐based copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2575–2585     

Synthesis and enzymatic degradation of 2‐methylene‐1,3‐dioxepane and methyl acrylate copolymers

Copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and methyl acrylate (MA) containing ester units both in the backbone and as pendant groups were synthesized by free‐radical copolymerization. The influence of reaction conditions such as the polymerization time, temperature, initiator concentration, and comonomer feed ratio on the yield, molecular weight, and copolymer composition was investigated. The structure of the copolymers was confirmed by ¹H NMR, ¹³C NMR, and IR spectroscopy. Differential scanning calorimetry indicated that the copolymers had a random structure. An NMR study showed that hydrogen transfer occurred during the copolymerization. The reactivity ratios of the comonomers were r_MDO = 0.0235 and r_MA = 26.535. The enzymatic degradation of the copolymers obtained was carried out in the presence of proteinase K or a crude enzyme extracted from earthworms. The experimental results showed that the higher ester molar percentage in the backbone caused a faster degradation rate. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2898–2904, 2003     

Synthesis and characterization of poly(diethylsiloxane) and its copolymers with different diorganosiloxane units

Poly(diethylsiloxane) and its copolymers with various kinds of R₁R₂SiO (R₁ = R₂ = methyl or phenyl, or R₁ = methyl and R₂ = phenyl) units have been prepared by the equilibrium polymerization of cyclosiloxanes. All the polymers have been characterized by ¹H and ²⁹Si NMR, gel permeation chromatography, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) measurements. The results indicate that a random distribution of different units has been obtained in the structures of copolymers containing 50 mol % diethylsiloxane units content. DSC and DMA show that the presence of 2.5 mol % diphenylsiloxane units or 5.0 mol % methylphenylsiloxane units in the copolymer can disrupt the crystallinity and lead to noncrystalline copolymers with low glass‐transition temperatures (ranging from ?133 to ?137 °C according to DSC). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2722–2730, 2003     

Preparation of novel cyclic olefin copolymer with high glass transition temperature

A series of novel cyclic olefin copolymers (COCs), including ethylene/tricyclo[4.3.0.1^2,5]deca‐3‐ene (TDE), ethylene/tricyclo[4.4.0.1^2,5]undec‐3‐ene (TUE), and ethylene/tricyclo[6.4.0.1^9,12]tridec‐10‐ene (TTE) copolymers, have been synthesized via effective copolymerizations of ethylene with bulk cyclic olefin comonomers using bis(β‐enaminoketonato) titanium catalysts ( 1a [PhN?C(CH₃)CHC(CF₃)O]₂TiCl₂; 1b : [PhN?C(CF₃)CHC(Ph)O]₂TiCl₂). With modified methylaluminoxane as a cocatalyst, both catalysts exhibit high catalytic activities, producing high molecular weight copolymers with high comonomer incorporations and unimodal molecular weight distributions. The microstructures of obtained ethylene/COCs are established by combination of ¹H, ¹³C NMR, ¹³C DEPT, HSQC ¹H? ¹³C, and ¹H? ¹H COSY NMR spectra. DSC analyses indicate that the glass transition temperature (T_g) increases with the enhancement of comonomer volume (TDE < TUE < TTE). High T_g value up to 180 °C is easily attained in ethylene/TTE copolymer with the low content of 35.8 mol %. TGA analyses reveal that these copolymers all possess high thermal stability with degradation temperatures (T_d) higher than 370 °C in N₂ and air. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3144–3152     

The microstructure determination of ethylene‐styrene‐propylene terpolymers at triad level by high‐temperature two‐dimensional NMR spectra

To further extend temperature range of application and low temperature performance of the ethylene‐styrene copolymers, a series of poly(ethylene‐styrene‐propylene) samples with varying monomer compositions and relatively low glass‐transition temperatures (T_g = −28 – 22 °C) were synthesized by Me₂Si(Me₄Cp)(N‐t‐Bu)TiCl2/MMAO system. Since the ¹³C NMR spectra of the terpolymers were complex and some new resonances were present, 2D‐¹H/¹³C heteronuclear single quantum coherence and heteronuclear multiple bond correlation experiments were conducted. A complete ¹³C NMR characterization of these terpolymers was performed qualitatively and quantitatively, including chemical shifts, triad sequence distributions, and monomer average sequence lengths. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 340–350     

Atom transfer radical copolymerizationof acrylonitrile/n‐butyl acrylate: Microstructure determination by two‐dimensional nuclearmagnetic resonance spectroscopy

Atom transfer radical polymerization conditions were optimized and standardized with different initiator and catalyst systems. Acrylonitrile/n‐butyl acrylate copolymers were synthesized with 2‐bromopropionitrile as the initiator and CuCl/Cu(0)/2,2′‐bipyridine as the catalyst system. Variations of the feed composition led to copolymers with different compositions. The number‐average molecular weight and the polydispersity index were determined by gel permeation chromatography. Quantitative ¹³C{¹H} NMR was employed to determine the copolymer composition. The reactivity ratios calculated with a methodology based on the Mao–Huglin terminal model were r_A = 1.30 and r_B = 0.68 for acrylonitrile and n‐butyl acrylate, respectively. The reactivity ratios determined by the modified Kelen–Tudos method were r_A = 1.29 ± 0.01 and r_B = 0.67 ± 0.01. ¹³C{¹H} NMR and distortionless enhancement by polarization transfer (DEPT‐45, 90, and 135) were used to distinguish methyl, methylene, methine, and quaternary carbon resonance signals. The overlapping and broad signals of the copolymers were assigned completely to various compositional and configurational sequences by the correlation of one‐dimensional (¹H, ¹³C{¹H}, and DEPT) and two‐dimensional (heteronuclear single quantum coherence, total correlation spectroscopy, and heteronuclear multibond correlation) NMR spectral data. The complete spectral assignments of carbonyl and nitrile carbons were performed with the help of heteronuclear multibond correlation spectra. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2810–2825, 2005     

Controlled synthesis of trifluoropropylmethylsiloxane–dimethylsiloxane gradient copolymers by anionic ROP of cyclotrisiloxanes

Kinetics of the anionic ring opening copolymerization of 2,4,6‐tris(3,3,3‐trifluoropropyl)‐2,4,6‐trimethylcyclotrisiloxane (F₃) with hexamethylcyclotrisiloxane (D₃) was studied in THF using BuLi as the initiator. The apparent reactivity ratios were estimated by computer simulation to r = 0.10 ± 0.02, r = 51.8 ± 5.5, which were used to predict the copolymer composition. As a result of so much different reactivities, simultaneous copolymerization leads to copolymers of blocky structure containing a narrow intermediate fragment with gradient distribution of siloxane units. Polymers having more uniform distribution of the trifluoropropyl groups along the chain were obtained by the semibatch process, adding F₃ to the polymerization of less reactive D₃. The resulted copolymers were characterized by SEC chromatography, ²⁹Si NMR, DSC, DMA, and SAXS. Thermal and mechanical properties of the copolymers obtained by simultaneous copolymerization were similar to those of block copolymers. Only the copolymers obtained by semibatch method showed properties typical for gradient copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1204–1216, 2009     

Oxo‐crown‐ethers as comonomers for tuning polyester properties

2‐Oxo‐12‐crown‐4‐ether (OC) was procured in a novel, two‐step procedure in a 37% overall yield. This interesting hydrophilic lactone was effectively polymerized with Novozym 435 as the catalyst: within 10 min, the monomer conversion was greater than 95%. Poly(2‐oxo‐12‐crown‐4‐ether) [poly(OC)] was obtained as a viscous oil with a glass‐transition temperature of approximately ?40 °C, and it was soluble in water. Subsequently, OC was copolymerized with ω‐pentadecanolactone (PDL). A kinetic evaluation of both monomers showed that for OC, the Michaelis–Menten constant (K_M) and the maximal rate of polymerization (V_max) were 2.7 mol/L and 0.24 mol/L min, respectively, whereas for PDL, K_M and V_max were 0.5 mol/L and 0.09 mol/L min, respectively. Although OC polymerized five times faster than PDL, ¹H NMR analysis of the copolymers revealed a random copolymer structure. Differential scanning calorimetry traces of the copolymers showed that they were semicrystalline and that the melting temperature and melting enthalpy of the copolymers linearly decreased with an increasing amount of OC. The melting temperature of the copolymers could be adequately predicted by the Baur equation, and this suggested that poly (OC) was rejected from the poly(ω‐pentadecanolactone) [poly(PDL)] crystals. Solid‐state NMR studies confirmed that the crystalline phase exclusively consisted of poly (PDL), whereas the amorphous phase was a mixture of OC and PDL units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2166–2176, 2006     

Para‐hydrogen induced polarization of Si‐29 NMR resonances as a potentially useful tool for analytical applications

Para‐hydrogen–induced polarization effects have been observed in the ²⁹Si NMR spectra of trimethylsilyl para‐hydrogenated molecules. The high signal enhancements and the long T₁ values observed for the ²⁹Si hyperpolarized resonances point toward the possibility of using ²⁹Si for hyperpolarization applications. A method for the discrimination of multiple compounds and/or complex mixtures of hydroxylic compounds (such as steroids), consisting of the silylization of alcoholic functionalities with an unsaturated silylalkyl moiety and subsequent reaction with para‐H₂, is proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and thermal behavior of new poly(ethylene terephthalate‐imide)s

Copoly(ethylene terephthalate‐imide)s (PETIs) were synthesized by the melt copolycondensation of bis(2‐hydroxyethyl)terephthalate with a new imide monomer, N,N′‐bis[p‐(2‐hydroxyethoxycarbonyl)phenyl]‐biphenyl‐3,3′,4,4′‐tetracarboxydiimide (BHEI). The copolymers were characterized by intrinsic viscosity, Fourier transform infrared, ¹H NMR, differential scanning calorimetry, and thermogravimetric analysis techniques. Although their crystallinities decreased as the content of BHEI units increased, the glass‐transition temperatures (T_g) increased significantly. When 5 or 10 mol % BHEI units were incorporated into poly(ethylene terephthalate), T_g increased by 10 or 24 °C, respectively. The thermal stabilities of PETI copolymers were about the same as the thermal stability of PET, whereas the weight loss of PETIs decreased as the content of BHEI units increased. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 408–415, 2001