Terpolymerization of carbon monoxide, ethylene and styrene in the presence of supported palladium catalyst

Terpolymers of carbon monoxide with ethylene and styrene are synthesized in the presence of supported palladium catalyst in toluene and heptane medium for the first time. The terpolymerization rate exceeds the rate of carbon monoxide and ethylene copolymerization. The maximum terpolymer yield amounts 7.9 g per g of supported catalyst per hour or 321 g per g of palladium per hour. The influence of reaction temperature, pressure, 1.4-benzoquinone amount and co-monomers mole ratio on the yield and the composition of terpolymer have been studied. The NMR ¹³C data obtained testify to a distribution of ethylene and styrene units in terpolymer with the predominance of short blocks at equal contents of comonomer units.     

Synthesis of phosphonated copolymers with tailored architecture by reversible addition‐fragmentation chain transfer polymerization (RAFT)

The synthesis by reversible addition‐fragmentation chain transfer (RAFT) polymerization of three phosphonated terpolymers with tailored architecture has been studied. A phosphonated methacrylate (MAUPHOS) was copolymerized with vinylidene chloride (VC₂) and methyl acrylate (MA) to prepare a gradient terpolymer poly(VC₂‐co‐MA‐co‐MAUPHOS). Besides, hydroxyethyl acrylate (HEA) was used as a functional monomer in RAFT polymerization to prepare a statistical poly(VC₂‐co‐MA‐co‐HEA) terpolymer and a diblock poly(VC₂‐co‐MA)‐b‐poly(HEA) terpolymer. The HEA‐containing polymers were then modified with a phosphonated epoxide to introduce the phosphonated group. The control of the polymerization was proven by kinetic studies (evolution of molecular weight vs. conversion) and by a successful block copolymerization. The architecture of the terpolymers was determined by the reactivity ratios of the monomers: terpolymerization of VC₂, MA, and HEA leading to an ideal statistical terpolymer (no composition drift) whereas terpolymerization of VC₂, MA, and the phosphonated methacrylate led to a gradient terpolymer. These terpolymers were characterized by size exclusion chromatography, ³¹P NMR and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 13–24, 2006     

Terpolymerization of maleic anhydride, trans-stilbene and acrylic monomers

The results of radical terpolymerization of maleic anhydride (MA), trans-stilbene (Stb) and acrylic monomers (n-butyl methacrylate (BMA) and acrylonitrile (AN)) as acceptor-donor-acceptor monomer systems are discussed. The structure and composition of terpolymers are determined by chemical (acid number for MA units) and elemental (content of N for AN units and O for BMA units) analyses, as well as by FTIR spectroscopy through recorded analytical absorption bands for MA (1770 and 1845 cm⁻¹), Stb (864 cm⁻¹) and BMA (1730 cm⁻¹) units, respectively. The considerable change in the terpolymer compositions is observed when a strong acceptor MA is substituted with BMA (or AN), having comparatively low acceptor character in the system studied. Copolymerization constants for the MA ? Stb complex and acrylic comonomers pairs are determined according to the modified Kelen-Tüdös equation. Obtained results show that at the chosen ratios of comonomers, radical terpolymerization proceeded mainly by a true “complex” mechanism in the stage of near binary copolymerization of MA ? Stb complexed monomers with free BMA (or AN). The kinetics of terpolymerization and terpolymer compositions are studied in the low and high conversion stages. It is shown that for the MA-Stb-BMA system the dependence of R_p on the concentration of individual comonomers has extreme character, while for BMA-Stb-AN this dependence does not have similar character. This fact indicated that terpolymerization in the BMA-Stb-AN system proceeds according to a classical statistical copolymerization mechanism. The terpolymer composition-thermal behaviour relationships are also studied by differential scanning calorimetry and thermogravimetric analysis methods.     

Template‐free anion‐controlled synthesis of Pd (II) nano‐aggregates for the antifouling polymerization of CO and ethylene

The reaction of [(domppp) Pd (OAc)₂] [domppp = 1,3‐bis (di‐o‐methoxyphenylphosphino)propane] and imidazolium‐functionalized carboxylic acids containing various anions (Br^?, PF₆^?, SbF₆^? and BF₄^?) resulted in the formation of nano‐sized Pd (II) aggregates under template‐free conditions. The rate of formation of aggregates can be modulated by changing the anion, affecting the rate of polymerization of CO and olefins without fouling. Herein, we describe the analysis of Pd (II) catalysts by dynamic light scattering, atomic force microscopy, X‐ray photoelectron spectroscopy and X‐ray crystallography, and co‐ and terpolymerization results including the catalytic activity, and bulk density and molecular weight of polymers.     

Synthesis and characterization of norbornene–ethylene–styrene terpolymers with a substituted ansa‐fluorenylamidodimethyltitanium‐based catalyst

This article reports a synthetic method for a norbornene–ethylene–styrene (N‐E‐S) terpolymer, which has not been well investigated so far, via incorporation of styrene (S) into vinyl‐type norbornene–ethylene (N‐E) copolymers catalyzed by a substituted ansa‐fluorenylamidodimethyltitanium [Me₂Si(3,6‐tBu₂Flu)(tBuN)]TiMe₂ catalyst ( I ) activated with a [Ph₃C][B(C₆F₅)₄]/Al(iBu)₃ cocatalyst at room temperature in toluene. The resulting terpolymerization product contained the targeted N‐E‐S terpolymer and the contaminated homopolymers, which were then able to be completely removed by solvent fractionation techniques. While homopolystyrene was easily extracted by fractionation with methylethylketone as a soluble part, homopolyethylene and a trace amount of homopolynorbornene could be perfectly separated by fractionation with chloroform as insoluble parts. The detail characterizations of a chloroform‐soluble polymer with gel permeation chromatography, nuclear magnetic resonance, and differential scanning calorimetry analyses proved that it contained a true N‐E‐S terpolymer with long N‐E sequences incorporated with isolated or short styrene sequences. The homogeneity of the morphology together with a single glass transition temperature that proportionally decreased with the increase of the styrene contents indicated that the N‐E‐S terpolymer obtained in this work is a random polymer with an amorphous structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2765–2773, 2007     

Metallocene-catalyzed ethene/styrene co- and terpolymerization with olefinic termonomers

Ethene was co- and terpolymerized with 1-octene and styrene using the methylalumoxane (MAO) activated halfsandwich metallocene Me₂Si(Me₄Cp)(N-t.-butyl)TiCl₂(Cp = cyclopentadienyl, Me = methyl) as catalyst. At temperatures of 40 and 60°C styrene concentration was varied in order to investigate the influence of the comonomers. Despite decreasing the overall activity with respect to ethene/1-octene copolymerization, polymerization activity was found to exibit a relative maximum with increasing styrene concentration. An explanation is given taking two different comonomer effects into account. Low styrene concentration promoted higher 1-octene incorporation compared to ethene/1-octene copolymerization but significantly lowered the molecular weight of the terpolymers. With constant ethene and 1-octene concentration it was possible to produce ethene/1-octene/styrene terpolymers with styrene content varying from 0 to 25 mol % and 1-octene content varying from 8 to 21 mol %. All terpolymers were amorphous. With constant ethene content it was found possible to vary their glass transition temperature with 1-octene/styrene molar ratio incorporated in the terpolymer. ¹³C-NMR spectroscopic microstructure analysis showed that no styrene/1-octene sequences were found in the terpolymer backbone. Furthermore terpolymerizations were conducted successfully incorporating norbornene, 1,5-hexadiene and propene as monomers in terpolymertization with ethene and styrene. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2549–2560, 1997     

Sequence Control in Asymmetric Terpolymerizations of meso-Epoxides,CO2, and Phthalic Anhydride: Unprecedented Statistical Ester–Carbonate Distributions

The statistical terpolymerization of epoxides, CO₂ and cyclic anhydrides remains challenging, mainly because epoxide/CO₂ and epoxide/anhydride copolymerizations typically proceed at considerably different rates. Herein, we report the syntheses of novel chiral terpolymers with unprecedented statistical distributions of carbonate and ester units (up to 50 % junction units) via the one-pot reaction of cyclohexene oxide, phthalic anhydride, and CO₂ under mild conditions using enantiopure bimetallic aluminum-complex-based catalyst systems. Notably, all resulting terpolymers exhibited excellent enantioselectivities (≥96 % ee) that were independent of the carbonate–ester distribution. The statistical compositions of the carbonate and ester units in the resulting terpolymers were determined via ¹H and ¹³C NMR spectroscopies. Furthermore, thermal properties were tuned by altering the ester content of the chiral terpolymer without influencing the enantioselective ring-opening step involving the meso-epoxide. This asymmetric terpolymerization methodology is also compatible with a variety of meso-epoxides to afford the corresponding terpolymers with 17 %–25 % junction units and excellent enantioselectivities (94 %–99 % ee). The present study is expected to provide new guidelines for preparing a broad range of biodegradable polymers with excellent enantioselectivities and adjustable properties.     

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     

Course of the terpolymerization of ethylene,propylene, and dicyclopentadiene. I. Single initial addition of dicyclopentadiene

Detailed studies were made of the course of the terpolymerization of ethylene, propylene, and dicyclopentadiene to form unsaturated elastomers. All the dicyclopentadiene was added at the start of a polymerization, but the monoolefins were added continuously throughout the run. Under these conditions, unsaturation of the initial polymer is fairly high but decreases steadily as the reaction progresses. From analyses of the initial samples from each run, the catalyst of VCl₄ (with Al₂Et₃Cl₃ cocatalyst), with heptane as the polymerization solvent, was most efficient for introducing unsaturation into terpolymer. This system also produces gel in the terpolymer in the latter stages of reaction, however. Catalysts of VCl₄, VOCl₃, or V(C₅H₇O₂)₃, with Al₂Et₃Cl₃ cocatalyst, in benzene solvent gave terpolymers of quite similar unsaturations. With all systems, terpolymer yield increases very rapidly in the first few minutes of reaction, then very slowly for the remainder of the 30-min. reaction time, reflecting the rapid loss of activity of the vanadium catalysts. Molecular weight growth of the terpolymer prepared in heptane was extremely rapid, reaching a high value in a few minutes. When prepared in benzene, the terpolymers showed a steady increase in molecular weight throughout the reaction but reached only a moderate final value (as expressed by inherent viscosity).     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. III. Synthesis and chain‐microstructure analysis of terpolymer obtained from L‐lactide,glycolide, and ϵ‐caprolactone initiated by zirconium(IV) acetylacetonate

Zirconium(IV) acetylacetonate [Zr(acac)₄] is a very good initiator for the terpolymerization of glycolide with L‐lactide and ?‐caprolactone. The microstructure of the obtained terpolymer was determined by NMR spectroscopy and then compared with terpolymers obtained in the presence of stanous(II) octoate [Sn(oct)₂]. Samples obtained with Zr(acac)₄ were characterized by a segmental‐chain microstructure. Apart from relatively long lactidyl microblocks, there were also segments made of random copolymer of glycolide with lactide. Such a structure is formed as a result of strong transesterification caused by active caproyl chain endings attacking the glycolidyl groups. Domination of this type of transestrification is shown. The growth of terpolymer chains and the influence of transesterification on gradual changes of the microstructure of the forming terpolymer chain were examined. Significant differences among glycolide, lactide, and the least reactive caprolactone were observed. The results of differential scanning calorimetric examinations of the obtained terpolymers are presented. Differences between the structures of random terpolymers obtained during terpolymerization initiated by Sn(oct)₂ and those obtained by Zr(acac)₄ influence their thermal properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3129–3143, 2002     

Preparation of H‐shaped ABCAB terpolymers by atom transfer radical coupling

H‐shaped ABCAB terpolymers composed of polystyrene (PS) (A), poly(ethylene oxide) (PEO) (B), and poly(tert‐butyl acrylate) (PtBA) (C) were prepared by atom transfer radical coupling reaction using ABC star terpolymers as precursors, CuBr and N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalysts, and nanosize copper as the reducing agent. The synthesis of 3‐miktoarm star terpolymer PS‐PEO‐(PtBA‐Br) involved following steps: (1) the preparation of PS with an active and an ethoxyethyl‐ptotected hydroxyl group at the same end; (2) the preparation of diblock copolymer PS‐b‐PEO with ethoxyethyl‐protected group at the junction point through the ring‐opening polymerization (ROP) of EO; (3) after de‐protection of ethoxyethyl group and further modification of hydroxyl group, tBA was polymerized by atom transfer radical polymerization using PS‐b‐PEO with 2‐bromoisobutyryl functional group as macroinitiator. The H‐shaped terpolymer could be successfully formed by atom transfer radical coupling reaction in the presence of small quantity of styrene, CuBr/PMDETA, and Cu at 90 °C. The copolymers were characterized by SEC, ¹H NMR, and FTIR in detail. The optimized coupling temperature is 90 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 59–68, 2009     

稀土配位催化马来酸酐-苯乙烯-N-苯基马来酰亚胺三元共聚合

采用稀土配位催化剂研究了马来酸酐、苯乙烯和N 苯基马来酰亚胺的三元共聚合反应 .考察了Al La物质的量的比、不同稀土元素、催化剂浓度、聚合反应时间、单体配比等因素对共聚合反应的影响 .利用核磁、红外、热分析等方法对共聚物进行了初步的表征     

Terpolymerization of ethyl methacrylate,N‐phenylmaleimide,and itaconic acid

The terpolymerization of ethyl methacrylate (EMA), N‐phenylmaleimide (NPMI), and itaconic acid (IA) was investigated. The terpolymer composition was determined by elemental analysis and ¹H NMR spectroscopy. The reactivity ratios of the three binary systems (EMA/NPMI, EMA/IA, and NPMI/IA) were calculated and used for the calculation of the terpolymer composition with the terminal model equations. A comparison between the experimental and theoretical compositions was made. The rate of the terpolymerization process was measured dilatometrically at two total monomer concentrations; this was done to establish the presence of intermolecular interactions between the investigated monomers. The thermal analysis of the obtained terpolymers was performed by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3180–3187, 2003     

Selective and efficient oxidation of ethylene to ethylene glycol acetates with H2O2 catalyzed by Pd(OAc)2-di(2-pyridyl)ketone-di(2-pyridyl)methanesulfonate system

Novel systems for palladium-catalyzed selective oxidation of ethylene to a mixture of ethylene glycol mono- and di-acetates as the major reaction products (90-95% selectivity) with H₂O₂ in acetic acid solution at ambient pressure and 20 °C were developed. The catalytic reaction is very efficient with up to 90% combined yield of glycol acetates with H₂O₂ as a limiting reagent and 1 mol% catalyst loading. The catalytic systems developed are comprised of a mixture of Pd(OAc)₂, and 6-methyl substituted (2-pyridyl)methanesulfonate and/or di(6-pyridyl)ketone ligands. Compositions of the binary, Pd(OAc)₂-dpk, Pd(OAc)₂-Me-dpms, and ternary, Pd(OAc)₂-dpk-Me-dpms, systems have been studied by means of ¹H NMR spectroscopy and ESI mass spectrometry. Kinetics studies were performed as well and plausible reaction mechanism was suggested, which features facially chelating ligand-enabled facile oxidation of Pd^IIC₂H₄OAc intermediates with H₂O₂ to form Pd^IVC₂H₄OAc transients.     

Ethylene‐Norbornene Terpolymerization with 5‐Vinyl‐2‐norbornene Using Single‐Site Catalysts

The incorporation of 5‐vinyl‐2‐norbornene (VNB) into ethylene‐norbornene copolymer was investigated with catalysts [Ph₂C(Fluo)(Cp)]ZrCl₂ ( 1 ), rac‐[Et(Ind)₂]ZrCl₂ ( 2 ), and [Me₂Si(Me₄Cp)^tBuN]TiCl₂ ( 3 ) in the presence of MAO by terpolymerizing different amounts of 5‐vinyl‐2‐norbornene with constant amounts of ethylene and norbornene at 60°C. The highest cycloolefin incorporations and highest activity in terpolymerizations were achieved with 1 . The distribution of the monomers in the terpolymer chain was determined by NMR spectroscopy. As confirmed by XRD and DSC analysis, catalysts 1 and 3 produced amorphous terpolymer, whereas 2 yielded terpolymer with crystalline fragments of long ethylene sequences. When compared with poly‐(ethylene‐co‐norbornene), VNB increased both the glass transition temperatures and molar masses of terpolymers produced with the constrained geometry catalyst whereas decreased those for the metallocenes.     

Effect of the co‐catalyst on the polymerization of ethylene and styrene by nickel‐diimine complexes

The attempt to copolymerize ethylene and styrene using η³‐methallyl‐nickel‐diimine {[η³‐2‐MeC₃H₄]Ni[1,4‐bis(2,6‐diisopropylphenyl)C₂H₂N₂][PF₆]} ( 1 ) associated with MAO or TMA produces polystyrene, polyethylene and polyethylene with styrene end groups. Characteristics of the formed polymer depend on the reaction conditions. The presence of styrene in the medium reduces the polymerization productivity and the molecular weight of polyethylene. Incorporation of styrene into polyethylene is favored by a 1 /ethylene/MAO pre‐contact time and depends on the amount of styrene. Maximum incorporation was 4.4 wt.‐%. If styrene is introduced after the pre‐contact time, a bimodal product distribution is observed, suggesting the occurrence of two different catalytic species. If the co‐catalyst is changed from MAO to TMA, no copolymer is formed but the presence of styrene leads to higher amounts of branched polyethylene.     

Preparations of Saturated N‐P‐N Type Secondary Phosphine Oxides and their Applications in Cross‐Coupling Reactions

A series of cyclohexane‐1,2‐diamine ( 3a – 3d ) and benzene‐1,2‐diamine derivatives ( 3e – 3h ) were pre‐ pared. Followed by hydrolysis, the reaction of 3a – 3c with PCl₃ successfully led to the formation of cor‐ responding metastable saturated heteroatom‐substituted secondary phosphine oxides (HASPO 4a – 4c ), a tautomer of the saturated heteroatom‐substituted phosphinous acid (HAPA). Whereas ambient‐stable diamine‐coordinated palladium complexes were obtained, HAPA‐coordinated palladium complexes were not successfully synthesized. The molecular structures of HASPO 4c , Pd(OAc)₂(3a) , PdBr₂(3b) and Pd(OAc)₂(3c) and [Cu(NO₃)(3d)⁺][NO₃ ^? ] were determined by single‐crystal X‐ray diffraction method. Catalysis of in‐situ Suzuki‐Miyaura cross‐coupling reactions for aryl bromides and phenylboronic acid using diamine 3a as ancillary ligand showed that the optimized reaction condition at 60 °C is the combination of 2 mmol % 3a /3.0 mmol KOH/1.0 mL 1,4‐dioxane/1 mmol % Pd(OAc)₂. Moreover, moderate reactivity was observed when using aryl chlorides as substrates (supporting infor‐ mation). When diamine 3d was employed in Heck reaction, good tolerance of functional groups of aryl bromides were observed while using 4‐bromoanisole and styrene as substrates. The optimized condi‐ tion for Heck reaction at 100 °C is 3 mmol % 3d /3.0 mmol CsF/1.0 mL toluene/3 mmol % Pd(OAc)₂. In general, cyclohexane‐1,2‐diamine derivatives exhibited better catalytic properties than those of benzene‐1,2‐diamines.     

Quasiliving Carbocationic Polymerization. XVI. Forced Ideal Terpolymerization of Styrene-α-Methylstyrene-lsobutylene

Forced ideal carbocationic terpolymerization of styrene/α-methylstyrene/isobutylene systems has been achieved by continuous addition of mixed monomer feeds to 2-chloro-2,4,4-trimethylpentane/TiCl₄ initiator/coinitiator charges dissolved in n-hexane/methylene chloride solvent mixtures. The compositions of terpolymers were uniform and identical to those of the feeds in the concentration ranges studied. The number-average molecular weights increased monotonously with the amounts of monomers consumed; however, pronounced chain transfer to monomer was evident. The microstructure of the products was investigated ¹³C-NMR spectroscopy. According to dual detector GPC, ¹³C-NMR and DSC data true terpolymers have formed.     

Copper(I)-anilide complex [Na(phen)3][Cu(NPh2)2]: an intermediate in the copper-catalyzed N-arylation of N-phenylaniline

Complex [Na(phen)₃][Cu(NPh₂)₂] ( 2 ), containing a linear bis(N‐phenylanilide)copper(I) anion and a distorted octahedral tris(1,10‐phenanthroline)sodium counter cation, has been isolated from the catalytic C? N cross‐coupling reaction with the CuI/phen/tBuONa (phen=1,10‐phenanthroline) catalytic system. Complex 2 can react with 4‐iodotoluene to produce 4‐methyl‐N,N‐diphenylaniline ( 3 a ) with 70.6 % yield. In addition, 2 can work as an effective catalyst for C? N coupling under the same reaction conditions, thus indicating that 2 is the intermediate of the catalytic system. Both [Cu(NPh₂)₂]^? and [Cu(NPh₂)I]^? have been observed by in situ electron ionization mass spectrometry (ESI‐MS) under catalytic reaction conditions, thus confirming that they are intermediates in the reaction. A catalytic cycle has been proposed based on these observations. The molecular structure of 2 has been determined by single‐crystal X‐ray diffraction analysis.     

Terpolymerization of acrylonitrile,styrene, and 2,4,6-tribromophenyl acrylate

Acrylonitrile was terpolymerized with styrene and 2,4,6-tribromophenyl acrylate in aqueous emulsion and dimethylformamide solution. Experimental terpolymerization data agreed well with calculations based on the Alfrey–Goldfinger equation. Triangular coordinate graphs show the feed/terpolymer relationships; the lines of unique and binary azeotropic compositions were identified. No points of true azeotropic composition were found but a “pseudo-azeotropic” region was recognized. The experimental data of the emulsion terpolymerization experiment agreed well with the theoretical curves over a wide range of monomer compositions up to high conversions. Incorporation of 2,4,6-tribromophenyl acrylate in the terpolymer decreased the thermal stability but improved the flame retardancy of the terpolymers.