Facile synthesis of ethylene–propylene fully alternating copolymer and comparison with random copolymer of similar composition

A precisely sequenced ethylene–propylene (EP) fully alternating copolymer was synthesized via trans‐1,4‐polymerization of isoprene catalyzed by Ziegler–Natta catalyst followed by hydrogenation. This EP copolymer was used as model polymer for studying structure–property relationship. An ethylene–propylene random copolymer (ethylene–propylene rubber [EPR]) with similar ethylene content was also prepared for comparison, and the effect of comonomer sequence distribution on properties was investigated. The copolymer chain structures were monitored by ¹H and ¹³C NMR and Fourier translation infrared. Differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile tests were employed to determine the thermal and mechanical properties. The fully alternating copolymer EP gives a more precise glass transition comparing than EPR. Further understanding on thermal properties and aggregation behavior of ethylene–propylene copolymers is made possible by this comparative study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45816.     

Study of the thermal properties and relaxation transitions in tetrafluoroethene-ethene copolymers

Copolymerization of tetrafluoroethene (TFE) with ethene (E) in water-alcohol medium initiated by 2,2′-azo-bis-izobutyronitrile (AIBN) at 338 K and 4.2 MPa was conducted in an autoclave by employing a semiflow procedure to feed the comonomers. The thermal properties of the copolymers under both the static and dynamic conditions of thermal treatment in air (ageing) were studied. The most pronounced changes in the initial temperature of destruction were observed for the compositions containing more than 42 mol % TFE, which corresponded to the formation of alternating copolymers. The reaction of thermal degradation was found to follow the first order kinetic equation, with the activation energy 174 kJ · mol⁻¹. The higher thermal stability of the alternating TFE-E copolymers was proved by IR spectroscopy and DTA analysis. Both the melting and crystallization DSC scans of copolymers of various compositions were analyzed. Monomodal peak of melting (and respectively, crystallization) was observed in both scans for the alternating copolymer, whereas the second peak appeared for the copolymer fractions with the higher content of ethylene block fragments and 30–40 mol % TFE units. The dynamic-mechanical analysis showed three relaxation transitions (γ, β₁ and β₂, α) in the temperature interval from 173–433 K, related to the mobility of structural units of different type in the copolymers prepared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2626–2632, 2001     

Charge transfer copolymerization and properties of isopropyl methacrylate with acrylonitrile and methacrylonitrile

Isopropyl methacrylate (IPMA) with Acrylonitrile (AN) and Methacrylonitrile (MAN) copolymers of different copositions were prepared at 60°C and 80°C, respectively, using a mixture of n-Butylamine (nBA) and carbon tetrachloride (CCl₄) in dimethyl sulphoxide (DMSO) as a charge transfer (CT) initiator. The percentage composition of the copolymers was established by elemental analysis. The copolymerization reactivity ratios were computed by the Kelen–Tudos method. In both the systems, IPMA was found to be more reactive; the copolymers sequence was random in nature. The copolymers were characterized by IR, ¹H-NMR, ¹³C-NMR spectroscopy and intrinsic viscosity measurements in dimethyl formamide (DMF) at 30±0.1°C. The thermal behavior of the AN-IPMA copolymers was studied by thermogravimetry (TG) in air. The thermal stability increased, with increasing AN content in the copolymer chain. The solubility parameter of AN-IPMA copolymer was evaluated by studying the intrinsic viscosity in different solvents. The solubility parameter of the copolymer was found to be 9.7 (cal/cc)^1/2.     

Synthesis and properties of three kinds of phenylenevinylene copolymers with dialkoxyphenylene units

Two random copolymers, poly(p-phenylenevinylene-co-2,5-didodecyloxy-p-phenylenevinylene) and poly(2,5-dimethoxy-p-phenylenevinylene-co-2,5-didodecyloxy-p-phenylenevinylene), were synthesized via the chlorine precursor route followed by thermal elimination. One alternating copolymer, poly(p-phenylenevinylene-alt-2,5-didodecyloxy-p-phenylenevinylene), was prepared via the Heck coupling reaction. The effects of molar ratio of monomers on yield and composition of the precursor copolymers were studied. The two precursor copolymers and the alternating copolymer were characterized by gel permeation chromatography, differential scanning calorimetry, elemental analysis, and infrared spectroscopy. The UV-visible absorption spectra and photoluminescence spectra, as well as solubility and conductivity of these copolymers, were compared. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 937–946, 1998     

Studies on the microstructure of vinyl/N‐phenylmaleimide copolymers by NMR and their applications

The micro‐ and stereostructures and sequence distribution of methyl methacrylate (MMA)/N‐phenylmaleimide (PMI) and styrene (St)–PMI copolymers were studied in detail with NMR spectroscopy. The MMA–PMI copolymer was in a random sequence distribution and the St–PMI copolymer was alternating in structure. Some micro‐ and stereoinformation of the MMA–PMI copolymers could be obtained from ¹H‐NMR spectra. The average number sequence length obtained from the copolymer triad by ¹³C‐NMR spectra was in agreement with that calculated from the reactivity ratios measured by an elemental analyzer. From the triad fraction of the copolymer measured by ¹³C‐NMR, the copolymer chain of MMA–PMI was proved to be a one‐order Markov chain. More suitable propagation reactions were proposed from the deviation of sequence distribution of the St–PMI copolymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2581–2587, 2000     

Random vs. alternating donor-acceptor copolymers: A comparative study of absorption and field effect mobility

The influence of the arrangement of donor and acceptor units in a conjugated copolymer chain on the absorption and field effect mobilities was studied. We synthesized a target random copolymer and compared it with two structurally relevant alternating copolymers, all consisting of 2,1,3-Benzothiadiazole (BT) as acceptor and 3-Hexylthiophene (Th) as donor units. Especially, bifunctional AB-type monomers were developed to obtain the desired randomly linked copolymer r-BT-2Th. We chose AA/BB-type monomers as well to obtain relevant alternating copolymers a-BT-2Th and a-BT-1Th. The systematic structural variation enables us to compare the copolymers in a precise manner. In dilute solutions r-BT-2Th and a-BT-2Th resemble closely in absorption spectra and have similar oxidation potentials regardless of random or alternating arrangement of donor and acceptor. In thin films, a-BT-2Th shows the lowest optical gap and depicts the highest field effect hole mobility of 1.5 × 10⁻³ cm² V⁻¹ s⁻¹.     

Synthesis,characterization and properties of functionalized styrene–maleimide copolymers

New functionalized styrene–maleimide copolymers were prepared by free radical copolymerization of styrene (St) and N‐4‐carboxybutylmaleimide (NBMI) in chloroform, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator. Monomer and copolymer characterization was carried out by ¹H‐ and ¹³C‐NMR. Copolymer composition was determined by elemental analysis and Fourier‐transform infrared (FTIR) spectroscopy. The glass transition temperature (from DSC) and the thermogravimetric analysis (TGA) of the copolymers were consistent with the thermal behavior and stability observed for alternating St–maleimide copolymers. St–NBMI copolymers crosslinked with divinylbenzene (DVB) were also synthesized and their cation exchange properties evaluated in order to assess the capacity of the new copolymers to bind metallic ions. Copyright © 2005 Society of Chemical Industry     

Photocrosslinkable copolymers based on 4‐acryloyloxyphenyl‐3′‐chlorostyryl ketone and methyl methacrylate: synthesis,comonomer reactivity ratios and UV photosensitivity

A new photosensitive acrylate monomer having a pendant chlorocinnamoyl moiety (APCSK) was copolymerized with methyl methacrylate (MMA) in different feed compositions in ethyl acetate solution at 70°C using benzoyl peroxide as a free‐radical initiator. The newly synthesized copolymers were characterized by FTIR, ¹H and ¹³C nuclear magnetic resonance (NMR) spectral techniques, as well as by size‐exclusion chromatography. Their thermal behaviour was assessed by thermogravimetric analysis in air and differential scanning calorimetry under nitrogen atmosphere. The copolymers exhibit no phase separation since there is only one glass transition temperature (T_g) value in the region of copolymer composition studied. The reactivity ratios of the comonomers were calculated by adopting linearization methods such as the Fineman–Ross (F‐R), Kelen–Tudos (K‐T) and extended Kelen–Tudos (ExtK‐T) methods, and by a non‐linear error‐in‐variables model method (EVM) using a computer program (RREVM). The results suggest that MMA is more reactive than APCSK and that their copolymerization leads to the formation of random copolymers. The photosensitivity of the copolymer samples was studied in solution as well as in thin films through UV irradiation. The influence of different factors, including solvent nature, concentration, temperature, photosensitizer and copolymer composition, on the rate of photocrosslinking of the photoreactive copolymers was investigated for effective industrial application of these polymers as negative photoresists. Copyright © 2004 Society of Chemical Industry     

Radical copolymerization of 2-acetoxyacrylates with nitrile monomers and properties of the copolymers

Radical copolymerization of captodatively (cd) substituted methyl and ethyl 2-acetoxyacrylates (MAA and EAA) with electron-withdrawing olefins including vinylidene cyanide and acrylonitrile is studied using azobisisobutylonitrile as a radical initiator at 60 °C, and the structure of copolymers is examined by ¹³C NMR spectra. It is found that the copolymerization of MAA and EAA with vinylidene cyanide provides a 1:1 alternating copolymer with ε-tacticity of 0.540 and 0.517, respectively, but that with acrylonitrile gives a random copolymer containing a larger amount of acetoxyacrylate unit. Addition of zinc chloride to the copolymerization of MAA and acrylonitrile, however, leads to the increase of acrylonitrile unit contents in the copolymer. Dielectric constant, gas permeability, and deformation by elongation of the copolymer film of MAA and vinylidene cyanide are also examined.     

Thermal behavior of poly(dimethyl itaconate) and poly(di‐n‐butyl itaconate) copolymerized with methyl methacrylate

The thermal degradation behavior of random copolymers of dimethyl itaconate and di‐n‐butyl itaconate with methyl methacrylate was studied. The thennal stability of copolymers depends on the structure of the di‐n‐alkyl itaconate comonomer, and on the copolymer composition. The relative thermal stability increases with the methyl methacrylate copolymer molar fraction, following a trend similar to the glass transition temperature variation. The activation energy was obtained by using MacCallum and Tanner's approach. In addition, the thermal degradation of homopolymers was evaluated in inert atmosphere as well as in thermo‐oxidative conditions, presenting different behaviors.     

Poly[N-(hydroxyethyl)ethyleneimine-co-phenyl succinic anhydride] Synthesis and structure

Summary Five copolymers from N-(hydroxyethyl)ethyleneimine as nucleophilic monomer and phenylsuccinic anhydride (PhSAn) as electrophilic monomer, were synthesized according to the spontaneous copolymerization concept. These copolymers were characterized by elemental analysis, FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopy. The copolymer composition determined from the ¹H-NMR spectra showed that the copolymers are not alternating. According to all the data, it was suggested a copolymer structure which includes ester and anhydride bonds. The molecular weights determined by vapor pressure osmometry ranged between 5.100 and 6.100 g/mol. Received: 12 February 1999/Revised version: 5 October 1999/Accepted: 5 October 1999     

Microstructure analysis and thermal properties of l-lactide/?-caprolactone copolymers obtained with magnesium octoate

A series of copolymers with various compositions were prepared by the ring opening copolymerization of l-lactide (l-LA) and ?-caprolactone (?-CL) using nontoxic magnesium octoate as a catalyst in bulk. The copolymerization process and the influence of transesterification on the chain microstructure were examined by ¹H and ¹³C NMR. A tapered block or gradient copolymer is expected to be formed on the basis of the reactivity difference between l-LA and ?-CL. Two modes of transesterification occurred and played an important role in the redistribution of comonomer sequences but not a completely random distribution. The CLC sequence formed by the second mode of transesterification was observed at the end of reaction. The coefficient of the second mode of transesterification (T_II) increased as the feed mole fraction of ?-CL increased. In terms of the overall feed compositions, the L_LL^r values of lactidyl sequences calculated from the reactivity ratio exceeded the L_LL^e values determined from the product, however, the L_C^r values of caproyl sequences were identical or shorter than the L_C^e values. The thermal properties and crystallinities of the obtained copolymers were investigated by DSC and WAXD. The thermal properties and crystallinities depend on both the composition and the chain microstructure. The l-LA/?-CL copolymer with intermediate composition exhibited some blocky character by DSC. Only single T_g was observed for each copolymer and in agreement with the calculated value from Fox equation, indicating that the amorphous region of the copolymers is miscible. The obtained copolymers can best be described as random copolymers with more or less blocky chain structure.     

How does sequence length heterogeneity affect the dilute solution conformation of copolymers?

Sequence length heterogeneity (SLH) is defined as the change, as a function of copolymer molar mass (M), in the average number of continuous monomers of a given repeat unit. SLH can influence polymeric properties such as thermal stability, mechanical behavior, transparency, and the ability of copolymers to reduce interfacial surface tension. Here, we demonstrate the relation between SLH and the change as a function of molar mass of a dimensionless size parameter, the ratio of the viscometric radius and the radius of gyration, irrespective of chemical heterogeneity or molar mass polydispersity. Multi-detector size-exclusion chromatography (SEC) provides for a convenient method by which to experimentally establish this relation and, consequently, a method by which to determine whether SLH is present in a copolymer, whether the degree of randomness of a copolymer changes across the molar mass distribution (MMD), or whether two copolymers differ from each other in degree of randomness at a given M and/or across their MMDs. Results from our SEC and FT-IR measurements of block, random, alternating, and gradient copolymers of styrene (S) and methyl methacrylate (MMA) and their respective homopolymers agree with results from a probability theory based model of SLH in linear random copolymers. The multi-detector SEC method employs instrumentation available in most polymer separations laboratories and the relations developed should be applicable to copolymers other than the S-MMAs studied here.     

Copolymerization of 4-cyanophenyl methacrylate with methyl methacrylate: Synthesis,characterization and determination of monomer reactivity ratios

Summary A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70±1 °C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r₁=2.524±0.038, r₂=0.502±0.015), Kelen-Tudos (r₁=2.562±0.173, r₂=0.487±0.005) and extended Kelen-Tudos methods (r₁=2.735±0.128, r₂=0.4915±0.007).     

Synthesis and characterization of ABA‐type block copolymers of trimethylene carbonate and ϵ‐caprolactone

This paper describes the synthesis of a series of ABA‐type triblock copolymers of trimethylene carbonate and ?‐caprolactone with various molar ratios and analyses the thermal and mechanical properties of the resulting copolymers. The structures of the triblock copolymers were characterized by ¹H and ¹³C nuclear magnetic resonance spectroscopy, FT‐IR spectroscopy and gel permeation chromatography. Results obtained from the various characterization methods proves the successful synthesis of block copolymers of trimethylene carbonate and ?‐caprolactone. The thermal properties of the block copolymers were investigated by differential scanning calorimetry. The T_m and ΔH_m values of the copolymers decrease with increasing content of trimethylene carbonate units. Two T_gs were found in the copolymers. Furthermore, both of the T_g values increased with increasing content of trimethylene carbonate units. The mechanical properties of the resulting copolymers were studied by using a tensile tester. The results indicated that the mechanical properties of the block copolymers are related to the molar ratio of trimethylene carbonate and ?‐caprolactone in the copolymers, as well as the molecular weights of the resulting copolymers. The block copolymer with a molar composition of 50/50 possessed the highest tensile stress at maximum and modulus of elasticity. Block copolymers possessing different properties could be obtained by adjusting the copolymer compositions. Copyright © 2004 Society of Chemical Industry     

Radical copolymerization of photocrosslinkable cinnamoylphenylmethacrylate and acrylamide

Copolymers of 4-Cinnamoylphenylmethacrylate (4-CPMA) and acrylamide (AA) were prepared in a ethylmethylketone (MEK) solution with benzoylperoxide (BPO) as a radical initiator at 70 °C. They were characterized by IR, ¹H NMR, and ¹³C NMR techniques. Copolymer compositions were determined from ¹H NMR spectra. The monomer reactivity ratios and the copolymer composition were determined by using Finemann–Ross (F–R) and Kelen-Tudos (K–T) methods. Thermogravimetric analysis of copolymers reveals that the thermal stability of the copolymer increases with an increase in the mole fraction of CPMA in the copolymer. The photocrosslinking of the copolymer were studied in solution.     

Syntheses and Properties of Novel Copolymers of Polylactide and Aliphatic Polycarbonate Based on Ketal-Protected Dihydroxyacetone

The novel random copolymers of L-LA and 2, 2-ethylenedioxy-1, 3-propanediol carbonate (EOPDC) were synthesized in bulk using Sn(Oct)₂ as a catalyst. The poly(EOPDC -co- L-LA)s obtained were characterized by FT IR, ¹H NMR, ¹³C NMR, GPC and DSC. The copolymers were obtained with yield of 87.9–95.6%. The number average molecular weight of the copolymer is 1.85–6.18 × 10⁴ with a polydispersity of 1.41–1.73. The properties of the copolymer including the enzymatic degradation by proteinase K and drug-controlled release property were also investigated. The results show that the degradation rate of the copolymers increases with increasing LA content in the copolymers.     

Poly (α-methylstyrene) and α-methylstyrene-maleic anhydride copolymer: an electron beam lithographic study

The electron beam sensitivity and contrast are reported for syndiotactic poly(α-methylstyrene), and random, and alternating copolymers of α-methylstyrene-maleic anhydride. Once again it has been observed that tacticity has a marked effect on the sensitivity of a homopolymer. Comparison of the properties of a random and alternating copolymer, indicate that the sensitivity and contrast are higher, for the alternating copolymer. Similar behaviour has been reported in another copolymer system, supporting this observation.     

Syntheses and properties of novel copolymers of polycaprolactone and aliphatic polycarbonate based on ketal-protected dihydroxyacetone

The random copolymers of ε-caprolactone (CL) and 2,2-ethylenedioxy propane-1,3-diol carbonate (EOPDC) were synthesized in bulk at 120 °C using Sn(Oct)₂ as a catalyst. The poly(EOPDC-co–CL)s obtained were characterized by FT IR, ¹H NMR, ¹³C NMR, GPC and DSC. The copolymers were obtained with yield of 84.2–97.8 %. The number-average molecular weight of the copolymer is 2.75–7.76 × 10⁴ with a polydispersity of 1.52–1.68. The properties of the copolymer including the enzymatic degradation by Pseudomonas Cepacia lipase and drug-controlled release property were also investigated. The results showed that the copolymers are degradable at physiological conditions, and their degradation rate and release of Tegafur in the copolymers increase with increasing CL content in the copolymers.     

Perfectly AB‐alternating copolymers via alternating diene metathesis polymerization: one‐step synthesis,characterization and properties

Perfectly alternating copolymers with functional phosphate groups were synthesized via reacting diacrylates with terminal dienes using alternating diene metathesis polymerization, showing a controllable polymerization characteristic which was evidenced by changing the relative stoichiometry of the two monomers. The compositional analysis and the sequence structural information of the polymers obtained from ¹H NMR spectra demonstrated that the resulting copolymers possessed strictly alternating structure. In addition, the thermal and flame‐retardant properties of the alternating copolymers were investigated, indicating favorable thermal degradation and flame retardancy which is an important feature for future applications. This special combination of the benefits of metathesis polymerization and phosphorus chemistry is a highly versatile system for materials in many applications. © 2013 Society of Chemical Industry