Synthesis,photodegradation, and energy transfer in a series of poly(ethylene terephthalate–co–4,4′-biphenyldicarboxylate) copolymers

Poly(ethylene terephthalate) (PET) filament yarns were photostabilized by addition of 0.5–4.0 mole % dimethyl 4,4′-biphenyldicarboxylate (4,4′-BPDC) to the polymerization feed. The mechanism of photostabilization is proposed to be a triplet–triplet energy transfer from excited terephthalate units to ground-state biphenyldicarboxylate units. The mechanism of transfer is reported to be via an electron exchange mechanism, with the “quenching sphere” calculated to be 14.9 Å. Kinetic studies show the “pseudo” zero-order rate constant of initial photodegradation to decrease from 3.4 × 10^?19 for the PET homopolymer to 2.0 × 10^?19% breaking strength loss/quantum exposure/cm² for the copolyester containing 4.0 mole % of the 4,4′-biphenyldicarboxyl moieties. The photophysical processes available to the dimethyl 4,4′-biphenyldicarboxylate monomer were characterized by absorption and luminescence studies. In solution, dimethyl 4,4′-biphenyldicarboxylate was shown to emit an intense fluorescence from a ²(π,π*) state and a weaker (～10^?2×) phosphorescence from a ¹(π,π*) state derived from the ¹A→supn1L_b absorption. The copolymer yarns were shown to exhibit both fluorescence and phosphorescence from the biphenyldicarboxylate units: the fluorescence from direct excitation, the phosphorescence by sensitized transfer.     

Synthesis of and photodegradation in a series of poly(ethylene terephthalate)–co–4,4′-sulfonyldibenzoate yarns

Phototendering studies of poly(ethylene terephthalate) homopolymer yarn and a series of poly(ethylene terephthalate–co–4, 4′-sulfonyldibenzoate) copolymer yarns have shown that photosensitized degradation occurs more readily in the copolymers than in the homopolymer. A photo-oxidative mechanism involving the second monomer, dibutyl 4, 4′-sulfonyldibenzoate, has been proposed to account for the photosensitization. The photophysical processes in the second monomer, dibutyl 4, 4′-sulfonyldibenzoate, were studied by absorption and luminescence techniques. The lowest excited singlet and triplet in this compound were identified as the ¹(π, π^*) and ₃(π, π^*) states, respectively. The energy levels in the second monomer have been assigned as follows: ¹S₁ ～ 33,000 cm^?1, ¹S₂ ～ 42,000 cm^?1, and ³T₁ ～ 26,000 cm^?1.     

Photophysical processes and interactions between poly(ethylene terephthalate) and 1-amino-2-(2-methoxyethoxy)-4-hydroxy-9,10-anthraquinone

The effect of 1-amino-2-(2-methoxyethoxy)-4-hydroxy-9,10-anthraquinone (C. I. Disperse Red 59) on the phototendering of poly(ethylene terephthalate) (PET) was assessed. The photophysical processes occurring in the polymer, the dye, and the dyed polymer were determined. The energy and nature of the dye and polymer electronic excited states were assigned on the basis of absorption and luminescence properties. Irradiation failed to produce dye-sensitized phototendering of PET; however, the titanium dioxide delusterant in commercial PET did function as a sensitizer in the presence of moist air. The phototendering of blank-dyed PET yarn was found to obey (pseudo-) zero-order kinetics k = 1.69 × 10^?19 per cent breaking strength loss/quantum absorbed/cm². The dye exhibited fluorescence from a lowest, ～51.5 kcal/mole, singlet charge-transfer (C-T) excited state but did not phosphoresce. The PET possessed a complex fluorescence spectrum attributed to similar ¹(n,π^*)₁ excited states, ～78.1 kcal/mole, while its phosphorescence derives from a proposed ³(π,π^*) state, ～69.8 kcal/mole, populated by intersystem crossing from a ¹(π,π^*) state, ～92.3 kcal/mole. The dyed polymer exhibited a PET-sensitized delayed fluorescence from the dyestuff involving triplet–singlet transfer by a dipole–dipole (Coulumbic) long-range resonance excitation mechanism. The transfer process was characterized by an experimentally determined critical transfer distance, R₀, of approximately 40 Å.     

Poly(ethylene-2,6-naphthalenedicarboxylate) fiber for industrial applications

Poly(ethylene-2,6-naphthalenedicarboxylate) (PEN) has been prepared from commercial dimethyl-2,6-naphthalenedicarboxylate (DM-2,6-NDC) and ethylene glycol (EG) according to the well-known transesterification/polycondensation route. PEN fibers, intended for industrial yarn applications, were obtained by melt spinning and drawing high molecular weight PEN. The properties of these yarns were measured in detail and compared with those of PET industrial yarns. The development of molecular orientation in the spinline is more pronounced for PEN than for PET. Because the yield stress is lower, PEN yarns can more easily be drawn. Breaking tenacities of PEN yarns are comparable with those of PET yarns, but the modulus is much higher and the thermal shrinkage is lower. Therefore, PEN yarns have a better dimensional stability than PET yarns. In addition, it was demonstrated that the thermal resistance of PEN yarns is better. © 1995 John Wiley & Sons, Inc.     

Melt polymerization of copoly(ethylene terephthalate–imide)s and thermal properties

Copoly(ethylene terephthalate–imide)s (PETI) were prepared by melt polycondensation of bis(2-hydroxyethyl)terephthalate (BHET) and imide containing oligomer, i.e., 4,4′-bis[(4-carbo-2-hydroxyethoxy)phthalimido]diphenylmethane(BHEI). The apparent rate of poly-condensation reaction was faster than that of homo poly(ethylene terephthalate) (PET) due to the presence of imide units. The PETI copolymers with up to 10 mol % of BHEI unit in the copolymer showed about the same molecular weight and carboxyl end group content as homo PET prepared under similar reaction conditions. The increase in T_g of copolymer was more dependent on molar substitution of BHEI than on substitution of BHEN, reaching 91°C with 8 mol % BHEI units in the copolymer from T_g = 78.9°C of homo PET. In the case of PETN copolymer, 32 mol % of bis(2-Hydroxyethyl)naphthalate (BHEN) units gave T_g of 90°C. The maximum decomposition temperature of PETI copolymer was about the same as that of homo PET by TGA analysis. The char yield at 800°C was higher than that of homo PET. © 1996 John Wiley & Sons, Inc.     

Sequence length determination in poly(ethylene terephthalate)–bisphenol-A polycarbonate random copolymers by application of selective degradation

Poly(ethylene terephthalate) (PET) and bisphenol-A polycarbonate (PC) are melt-mixed in equimolar ratios under various conditions to get a series of PET–PC copolymers. Samples from each copolymer are characterized by differential scanning calorimetry, ¹H and ¹³C nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), and polarizing light microscopy. The lengths of the PET sequences are determined in different copolymer samples by NMR sequential analysis before and after removal of the PC segments by selective degradation. In the former case, rather unusual results are obtained, suggesting predominant alternating order of single PET and PC repeating units. After selective elimination of the PC units, however, the NMR techniques show evidence of consecutively bonded dyads or triads of PET and PC units, which corresponds to the theoretical values in random copolymers obeying the statistics of Bernoulli. Considering the ¹H-NMR and SEC results after selective elimination of the PC sequences, a possible structure of the residual PET containing segments is proposed for the first time. It is concluded that in the PET/PC copolymers studied, when sequence distribution approaches the random one, determination of the PET block lengths after elimination of the PC sequences is more reliable as compared to the cases when selective degradation is not applied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 429–440, 1998     

Phosphorescence of Large Polycyclic Aromatic Ketones

Phosphorescence measurements were performed for 6H-benzo[cd]-pyren-6-one (l), 2-nitro-benzo[hi]chrysen- 13-one (2), 2-bromo-di-benzo[a, de]anthracen- 13-one (3), and 7H-benzo[hi]chrysen-7-one (4) in an ethanol-ether-toluene mixed solution and the character of their lowest excited triplet (T₁) states were investigated. The phos horescence of the compounds appears at about 5,200 – 6,000 cm^?1 to the red of their fluorescence, indicating that the T, states have ππ^* character. On the other hand, the short phosphorescence lifetimes, 10 – 60 ms, suggest nπ^* transitions. Such a duality of the T₁ state seems to be characteristic of large polycyclic aromatic ketones. The polarized emission study revealed that the duality is ascribed to strong mixing of ππ^* and nπ^* natures.     

Poly(ethylene terephthalate)–poly(caprolactone) block copolymer. I. Synthesis,reactive extrusion,and fiber morphology

A novel poly(ethylene terephthalate)–poly(caprolactone) block copolymer (PET–PCL) is synthesized in a reactive twin‐screw extrusion process. In the presence of stannous octoate, ring‐opening polymerization of ϵ‐caprolactone is initiated by the hydroxyl end groups of molten PET to form polycaprolactone blocks. A block copolymer with minimal transesterification is obtained in a twin‐screw extruder as a consequence of the fast distributive mixing of ϵ‐caprolactone into high melt viscosity PET and the short reaction time. The PET–PCL structure is characterized by IV, GPC, ¹H‐NMR, and DSC. Fully drawn and partially relaxed fibers spun from PET–PCL are characterized by WAXD and SAXS. A substantial decrease in the oriented amorphous fraction appears to be the major structural change in the relaxed fiber that provides the fiber with the desired stress–strain characteristics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1858–1867, 1999     

Study of segmented ethylene terephthalate–caprolactone copolymer by differential refractometry and light scattering

A segmented ethylene terephthalate (ET)–caprolactone (CL) copolymer was characterized by light scattering in chloroform tetrahydrofuran and butanone. The flexibility of the copolymer chain is comparable with that of typical flexible chains, such as polystyrene. In the process of applying the Bushuk–Benoit light scattering theory to the segmented PET–PCL copolymer, we encountered not only the problem of finding three solvents with different refractive index but also the problem of determining the specific refractive index increments for the PET and PCL segments in the copolymer, i.e., ν_PET and ν_PCL . In principle, the approximate values of ν_PET and ν_PCL can be obtained from the PET and PCL homopolymers, respectively. In reality, it involves many practical problems, e.g., to find three solvents not only for copolymer but also for the PET and PCL homopolymers. In this study, a different method was used to find both ν_PET and ν_PCL , wherein the ν values of at least two segmented PET–PCL copolymers with different PET compositions were used. With ν_PET , ν_PCL , and ν, we characterized the absolute molecular weight. Further, we show that the composition of an unknown segmented PET–PCL copolymer can be estimated from ν_PET , ν_PCL , and ν. © 1994 John Wiley & Sons, Inc.     

Synthesis,structural characterization,opto-electrical properties of Ir(III) complexes with imidazolium-based carbene ligands

A series of Ir(III) complexes with N–heterocyclic carbenes (NHC) ligands (1–3) were synthesized and characterized. The opto-electrical properties of these complexes were investigated spectroscopically, electrochemically and theoretically. All complexes exhibit ligand-based ¹π,π* transitions in the UV region, ¹MLCT absorption in the UV region, and weak low energy ³π, π* transition in visible region. These complexes all exhibit blue phosphorescence at both room temperature and 77 K, which is dominated by ³π,π* character. DFT calculation results indicate their lowest unoccupied molecular orbitals (LUMO) from − 0.47 to − 0.33 eV and the highest occupied molecular orbitals (HOMO) from − 4.97 to − 5.33 eV. The opto-electrical properties can be influenced drastically by NHC ligands, which would be useful for rational design of optical functional materials.     

Thermal,rheological, mechanical,and dyeing property studies of poly(ethylene‐co‐trimethylene terephthalate) copolymer filaments

The thermal and rheological properties of poly(ethylene‐co‐trimethylene terephthalate) (PETT) copolymer are investigated. The thermal behavior of PETT copolymers is dependent on the composition. The PETT‐15 and PETT‐85 copolymers can crystallize, whereas the PETT‐30 copolymer cannot crystallize at 5°C/min cooling rate. The copolymers have a good thermal stability, even though the addition of poly(trimethylene terephthalate) (PTT) chain causes a disadvantage to the thermal stability of the copolymers. Moreover, the PETT copolymers are a typical pseudoplastic fluid exhibiting shear thinning. With increasing the shear rate or the content of PTT units, the flow activation energy decreases and the sensitivity of the shear viscosity to the melt temperature declines. The PETT copolymer filaments have intermediate elastic recovery and dyeability between poly(ethylene terephthalate) (PET) and PTT filaments. With increasing the PTT content, the elastic recovery and dyeability of PETT copolymer filaments increase. That is to say, introducing PTT units as a minor component into the macromolecular chains is an available means to improve the properties of PET filament. The obtained PETT copolymer filaments blend the advantage of the mechanical property of PET and the elastic and dyeability of PTT filament together into one polymer and possess a softer feeling and a higher extension. POLYM. ENG. SCI., 50:1689–1695, 2010. © 2010 Society of Plastics Engineers     

Insights into process–structure–property relationships of poly(ethylene terephthalate) industrial yarns by synchrotron radiation WAXD and SAXS

Synchrotron radiation wide angle X‐ray diffraction (WAXD) and small angle X‐ray scattering (SAXS) were performed to study the structures of four typical types of poly(ethylene terephthalate) (PET) industrial yarns. Three‐dimensional structural models of the yarns and comprehensive insights into the process–structure–property relationships were gained. High spinning speed, low draw ratio, and high heat‐setting temperatures lead to HMLS yarns with high crystallinity, high amorphous orientation, densely packed lamellar stacks, and a small tilting angle of crystalline lamellae. High draw ratio tends to result in PET industrial yarns with large long period and a large tilting angle of lamellae. Heat‐setting process has a significant influence on the amorphous orientation and crystalline structures, such as crystallinity, crystallite size, as well as crystal grain number. Compared with other structure characteristics, amorphous orientation plays a more important role in determining the tenacity, initial modulus, part load elongation, ultimate elongation, as well as shrinkage of PET industrial yarns. The crystal grain number seems to have an effect on the initial modulus, while the long period influences the elongation of the yarns to some extent. In addition, the small tilting angle of crystalline lamellae may relate to the dimensional stability of PET yarns. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42512.     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Synthesis and characterization of a poly(ether–ester) copolymer from poly(2,6 dimethyl‐1,4‐phenylene oxide) and poly(ethylene terephthalate)

A series of poly(ether–ester) copolymers were synthesized from poly(2,6 dimethyl‐1,4‐phenylene oxide) (PPO) and poly(ethylene terephthalate) (PET). The synthesis was carried out by two‐step solution polymerization process. PET oligomers were synthesized via glycolysis and subsequently used in the copolymerization reaction. FTIR spectroscopy analysis shows the coexistence of spectral contributions of PPO and PET on the spectra of their ether–ester copolymers. The composition of the poly(ether–ester)s was calculated via ¹H NMR spectroscopy. A single glass transition temperature was detected for all synthesized poly(ether–ester)s. T_g behavior as a function of poly(ether–ester) composition is well represented by the Gordon‐Taylor equation. The molar masses of the copolymers synthesized were calculated by viscosimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis,characterization, and rheological studies of methacrylic acid–ethyl acrylate–diallyl phthalate copolymers

Copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was performed by the emulsion polymerization technique in the presence of a mixture of ionic and nonionic emulsifiers, at 85°C, using potassium persulfate as initiator (0.16 wt % of monomer). The molar ratio of MAA : EA varied between 44 : 56 and 54 : 46 in the monomer feed. Copolymers of MAA and EA were synthesized by incorporating diallyl phthalate (DAP) with varying concentrations (0–1.7 mol % of total monomer) in the feed. A copolymer latex of MAA, EA, and DAP was also prepared by the variable feed process. The intrinsic viscosity and gel content were determined. Copolymers were characterized by IR and NMR spectroscopic techniques. The composition of copolymers was determined by ¹H‐NMR spectra and sequential distribution from ¹³C{¹H}‐NMR spectra. The pH of the copolymer emulsion varied between 3 and 10 by addition of aqueous ammonia (23% w/w) and its effect on Brookfield viscosity was studied. The effects of copolymer composition, crosslinking agent concentration in the feed, monomer feed process, polymer solid contents, and shear rate on Brookfield viscosity were studied at pH ～ 8. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1430–1441, 2003     

Untersuchungen zum UV/Vis-Spektralverhalten von Azofarbstoffen. XVIII. Substituenteneinflüsse auf die Absorptionsmaxima der n → π*– und π → π*-Banden von 4-N,N-Diethylaminoazobenzenen

Studies on UV/Vis Absorption Spectra of Azo Dyes. XVIII. Substituent Effects on the Absorption Maxima of the n → π^* and π → π^* Bands of 4-N,N-Diethylaminoazobenzenes The spectra of 27 substituted 4-N.N-diethylaminoazobenzenes are determined. The band systems can be separated by deconvolution into two Gaussian curves. The results so obtained show that the effects of substituents on n → π^* and π → π^* transitions are similar and that electron withdrawing substituents in the phenylazo residue cause a bathochromic shift of both the n → π^* and the π → π^* bands.     

Styrene–butyl acrylate–N,N-dimethyl N-butyl N-methacrylamidino propyl ammonium bromide emulsifier–free emulsion copolymerization

Emulsifier-free emulsion copolymerization of styrene (St) and butyl acrylate (BA) in the presence of cationic functional comonomer N,N-dimethyl N-butyl N-methacrylamidino propyl ammonium bromide (DBMPAB) was carried out using azobis(isobutylamidine hydrochloride) (AIBA) as initiator. The surface properties of particles were studied by testing the actual value of -N⁺ and -C⁺(NH₂)₂ (Publisher's note: for graphical representations please see printed journal or the Acrobat PDF version on this website.) on the surface of particles and the surface charge density. The copolymer particles were characterized by transmission electron microscopy (TEM). The effects of reaction temperature, DBMPAB content, AIBA content, and ionic strength on conversion of monomer, average diameter D _w) and number (N_p) of copolymer particles were investigated. Under constant ionic strength the average diameter of copolymer particles (D_w) decreased with increasing AIBA and DBMPAB concentration, and decreased with rising reaction temperature. At constant concentration of comonomer and initiator and constant monomer composition, D_w showed an increase–decrease–increase with ionic strength plot. The polymerization rate increased with increasing DBMPAB content, AIBA content and rising temperature. The surface charge properties of particles were mainly decided by DBMPAB content, AIBA content, and ionic strength. ©1997 SCI     

Graft copolymers of cellulose and vinylic ketones. I. Preparation of poly(methyl vinyl ketone)–cotton cellulose copolymers

The graft copolymerization reaction of methyl vinyl ketone from several solvents with fibrous cotton cellulose, preirradiated to a dosage of 5.2 × 10¹⁹ eV/g with γ-radiation from ⁶⁰Co, was investigated. Solvents included water, methanol, N,N-dimethyl formamide, and several combinations of these solvents. From water a maximum yield of copolymer product was obtained after 2 hr at 25°C. The addition of methanol to aqueous solutions of methyl vinyl ketone, in all concentrations, inhibited the graft copolymerization reaction. The addition of a small amount of N,N-dimethylformamide to aqueous solutions of the monomer increased the rate of the copolymerization reaction; however, the addition of large amounts of N,N-dimethylformamide to these solutions also inhibited the reaction. From solutions of methanol or N,N-dimethylformamide and monomer, little or no copolymerization of monomer with irradiated cellulose occurred. The copolymer products exhibited a strong infrared absorption band at 5.85 μ which is characteristic of the ? C?O group of the grafted poly(methyl vinyl ketone). Fibrous copolymer yarns exhibited increased yarn number and decreased breaking strength and average stiffness, as compared with unmodified cotton yarns.     

Preparation of hydrophilic woven fabrics: Surface modification of poly(ethylene terephthalate) by grafting of poly(vinyl alcohol) and poly(vinyl alcohol)-g-(N-vinyl-2-pyrrolidone)

One of the most industrially important synthetic textile materials, woven poly(ethylene terephthalate) (PET) fabrics, have limitations in the usage of casual apparel applications due to their unwanted hydrophobicity. For that reason, in this study, to impart permanent hydrophilicity to the PET fabrics, hydrophilic poly(vinyl alcohol) (PVA) and a PVA-based copolymer were introduced to the alkaline hydrolysis pretreated PET surface by graft copolymerization for the first time. The graft modification of PET fabric surface was performed with an industrial-adaptable approach. The synthesis of a novel PVA-g-(N-vinyl-2-pyrrolidone) copolymer was achieved by the introduction of glycidyl methacrylate monomer to the PVA backbone. The structure of the copolymer was evidenced by attenuated total reflection–Fourier transform infrared spectroscopy and ¹H-NMR techniques. The introduction of PVA and copolymer structures with desired functional groups to the PET fabric surface was confirmed with the X-ray photoelectron spectroscopy technique. It was obtained that the contact angle–wetting time of PET fabric (145° and 98 s) could be dropped to 37° and 0.1 s and 64° and 0.7 s after PVA and copolymer grafting, respectively. This suggests that the graft-modified PET fabrics may find the potential of use in the textile applications as the alternative hydrophilic materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48584.