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1.
Qiujin Zhang Weixin Lin Guang Yang Qun Chen 《Journal of Polymer Science.Polymer Physics》2002,40(19):2199-2207
The phase structure of a series of ethylene‐vinyl acetate copolymers has been investigated by solid‐state wide‐line 1H NMR and solid‐state high‐resolution 13C NMR spectroscopy. Not only the degree of crystallinity but the relative contents of the monoclinic and orthorhombic crystals within the crystalline region varied with the vinyl acetate (VA) content. Biexponential 13C NMR spin–lattice relaxation behavior was observed for the crystalline region of all samples. The component with longer 13C NMR spin–lattice relaxation time (T1) was attributed to the internal part of the crystalline region, whereas the component with shorter 13C NMR T1 to the mobile crystalline component was located between the noncrystalline region and the internal part of the crystalline region. The content of the mobile crystalline component relative to the internal part of the crystalline region increased with the VA content, showing that the 13C NMR spin–lattice relaxation behavior is closely related to the crystalline structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2199–2207, 2002 相似文献
2.
Seung‐Yeop Kwak Jun Hyung Kim Jong‐Chan Lee 《Journal of Polymer Science.Polymer Physics》2001,39(10):993-1000
This article establishes the processing–microstructure–motion–property relationship of high‐speed melt‐spun nylon‐6 fibers. From solid‐state 1H NMR T1ρ (spin–lattice relaxation time in the rotating frame) relaxation studies, all nylon‐6 fibers spun at 4500–6100 m/min showed three‐component exponential decay with the time constants T1ρ,I, T1ρ,II, and T1ρ,III, indicating that there existed three different motional phases. These phases were assigned to immobile crystalline, intermediate rigid amorphous, and mobile amorphous regions. The determination of the correlation time (τc) of the respective phases provided information about the local molecular mobility of each phase with respect to the spinning speed. As the spinning speed increased, τc of the crystalline region increased (4500–5200 m/min) and then reached a plateau. However, τc for the rigid amorphous region increased from 5200 m/min onward, indicating that the rigid amorphous chains were more oriented and constrained in the spinning speed range of 5500–6100 m/min. The drastic increase of the maximum thermal stress for all fibers from 5500 to 6100 m/min was coincident with the τc characteristics of the rigid amorphous region. The significant increase in tenacity and Young's modulus and the large decrease in elongation at break at 5500–6100 m/min were also in good agreement with the local molecular motion of the intermediate rigid amorphous phase in the nylon‐6 fibers. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 993–1000, 2001 相似文献
3.
M. Y. Gelfer A. Waddon K. Schmidt‐Rohr R. Gale L. Kleiner R. Berggren 《Journal of Polymer Science.Polymer Physics》2001,39(22):2774-2780
The 50% increased permeability after annealing of semicrystalline poly(ethylene/vinylacetate) containing 3 mol % vinylacetate is linked to increased mobility in the amorphous phase, as identified by line‐narrowing of 1H wideline nuclear magnetic resonance (NMR) spectra and by reduced cross‐polarization efficiency in 13C NMR. Other morphological parameters, such as crystallinity, measured as 30 to 35% by differential scanning calorimetry (DSC) and NMR, are hardly changed by annealing. Small‐angle X‐ray scattering and NMR studies, using spin diffusion as well as T1ρ and T1 relaxation, detected only a small increase in crystallite thickness. The annealing‐induced enhancement in segmental mobility in the amorphous regions corresponds to a temperature shift of about 10 K, from which an increase of the motional rate by a factor of 2 is estimated, and which can account for the enhancement in the permeability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2774–2780, 2001 相似文献
4.
Mariagrazia Napoli Annaluisa Mariconda Ivano Immediata Pasquale Longo 《Journal of polymer science. Part A, Polymer chemistry》2008,46(14):4725-4733
Half titanocenes (CpCH2CH2O)TiCl2 (1), (CpCH2CH2OCH3)TiCl3 (2), and CpTiCl3 (3), activated by methylaluminoxane (MAO) were tested in copolymerization of ethylene with internal olefins such as cyclopentene. All the catalysts were able to give incorporation of cyclopentene in polyethylene matrix. 13C NMR analysis of obtained copolymers showed that the catalytic systems have low regiospecificity. In fact, in ethylene–cyclopentene copolymers, cyclic olefin inserts with both 1,2 and 1,3‐enchainment. X‐ray powder diffraction analysis of these copolymers confirmed that 1,2 inserted cyclopentene units are excluded from crystalline phase, whereas 1,3‐cyclopentene units are included, giving rise to expansion of unit cell of crystalline polyethylene. Titanium‐based catalysts were investigated also in the copolymerization of ethylene with E and Z‐2‐butene. Only complex (1) was able to give copolymers and 13C NMR analysis of products showed 2‐3, 1‐3, and 1‐2 insertion of 2‐butene. Differential scanning calorimetry analysis displayed that ethylene–cyclopentene, as well as ethylene‐2‐butene, copolymers are crystalline and their melting point decreases by increasing the comonomer content. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4725–4733, 2008 相似文献
5.
Qun Chen Takeyoshi Yamada Hiromichi Kurosu Isao Ando Takeshi Shiono Yoshiharu Doi 《Journal of Polymer Science.Polymer Physics》1992,30(6):591-601
The 13C spin-lattice relaxation times T1 of 13C-labeled polyethylene crystallized under different conditions were measured at temperatures from ?120 to 44°C by variable-temperature solid-state high-resolution 13C nuclear magnetic resonance (NMR) spectroscopy, in order to determine accurately the dynamics of the noncrystalline region of the polymer. From these results, it was found that the T1 minimum for the CH2 carbons in the noncrystalline region of solution-crystallized polyethylene with high crystallinity appears at higher temperature by about 20°C than that of melt-quenched polyethylene with low crystallinity. This means that the molecular motion of the CH2 carbons in the noncrystalline regions is more constrained at a given temperature in the material of higher crystallinity. Furthermore, dynamics of the noncrystalline region is discussed in terms of the 13C dipolar dephasing times. 相似文献
6.
Methyl branching in polyethylene from homopolymerization of ethylene with N‐arylcyano‐β‐diketiminate methallyl nickel‐B(C6F5)3
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Oleksandra S. Trofymchuk Griselda Barrera Galland Marcéo A. Milani Rene S. Rojas 《Journal of polymer science. Part A, Polymer chemistry》2015,53(3):452-458
N‐Arylcyano‐β‐diketiminate methallyl nickel complexes activated with B(C6F5)3 were used in the polymerization of ethylene. The microstructure analysis of obtained polyethylene (PE) was done by differential scanning calorimetry and 13C nuclear magnetic resonance (NMR). The branched polymer structures produced by these catalysts were attributed to one step isomerization mechanism of the catalyst along the polymer chain. The ortho or para position of the cyano group with co‐ordinated B(C6F5)3 in both methallyl nickel catalysts influenced the polymer molecular weight, branching, and consequently melting and crystallization temperatures. NMR spectroscopic studies showed predominantly the formation of methyl branches in the obtained PE. Catalysts under study gave linear low‐density PEs with good crystallinities at temperatures of reaction between 50 °C and 70 °C at moderate pressures (12.3 atm). A propylene–ethylene copolymer produced by the metallocene catalyst had the same concentration of branches as the PE synthesized from methallyl nickel/B(C6F5)3. Comparing the two polyolefins with the same degree of branching, it was observed that the polymer obtained with the nickel catalyst proved to be twice more crystalline and had greater Tm. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 452–458 相似文献
7.
H. Y. Chen E. V. Stepanov S. P. Chum A. Hiltner E. Baer 《Journal of Polymer Science.Polymer Physics》1999,37(17):2373-2382
The viscoelastic behavior of amorphous ethylene–styrene interpolymers (ESIs) was studied in the glass transition region. The creep behavior at temperatures from 15°C below the glass transition temperature (Tg) to Tg was determined for three amorphous ESIs. These three copolymers with 62, 69, and 72 wt % styrene had glass transition temperatures of 11, 23, and 33°C, respectively, as determined by DMTA at 1 Hz. Time–temperature superposition master curves were constructed from creep curves for each polymer. The temperature dependence of the shift factors was well described by the WLF equation. Using the Tg determined by DMTA at 1 Hz as a reference temperature, C1 and C2 constants for the Williams, Landel, and Ferry (WLF) equation were calculated as approximately 7 and 40 K, respectively. The master curves were used to obtain the retardation time spectrum and the plateau compliance. The entanglement molecular weight obtained from the plateau compliance increased with increasing styrene content as 1,600, 1,870, and 2,040, respectively. The entanglement molecular weight of the ESIs was much closer to that of polyethylene (1,390) than to that of polystyrene (18,700); this was attributed to the unique chain microstructure of these ESIs with no styrene–styrene dyads. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2373–2382, 1999 相似文献
8.
Blends of two or more ethylene–styrene (ES) copolymers that differed primarily in the comonomer composition of the copolymers were studied. Available thermodynamic models for copolymer–copolymer blends were utilized to determine the criteria for miscibility between two ES copolymers differing in styrene content and also between ES copolymers and the respective homopolymers, polystyrene and linear polyethylene. Model estimations were compared with experimental observations based primarily on melt‐blended ES/ES systems, particularly via the analysis of the glass‐transition (Tg ) behavior from differential scanning calorimetry (DSC) and solid‐state dynamic mechanical spectroscopy. The critical comonomer difference in the styrene content at which phase separation occurred was estimated to be about 10 wt % for ES copolymers with a molecular weight of about 105 and was in general agreement with the experimental observations. The range of ES copolymers that could be produced by the variation of the comonomer content allowed the study of blends with amorphous and semicrystalline components. Crystallinity differences for the blends, as determined by DSC, appeared to be related to the overlapping of the Tg of the amorphous component with the melting range of the semicrystalline component and/or the reduction in the mobility of the amorphous phase due to the presence of the higher Tg of the amorphous blend component. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2976–2987, 2000 相似文献
9.
Masayoshi Ito Tetsuo Kanamoto Koji Tanaka Roger S. Porter 《Journal of Polymer Science.Polymer Physics》1985,23(1):59-71
Proton spin–spin relaxation times and the Weibull coefficient have been measured as functions of temperature for poly(ethylene terephthalate) (PET) drawn at 50°C in both the amorphous and the semicrystalline (50%) states. Two relaxation times T2a (long) and T2c (short) are observed for all samples. They are ascribed, respectively, to the relaxation of the amorphous and of the crystalline components including highly strained noncrystalline segments. Effects of initial morphology are found for chain mobility in the noncrystalline regions and for the crystal perfection, evaluated from T2a and the Weibull coefficient μc of the T2c-component, respectively. For all draw ratios, T2a for extrudates prepared from the semicrystalline polymer (C-50) is short compared to that for preparations from the amorphous (A-50) polymer. In the A-50 samples, the perfection of stress-induced crystals increase with increasing draw ratio. In the C-50 samples, the crystal orientation increases, whereas the perfection decreases with increasing draw ratio. To improve the crystal perfection, annealing at higher temperature or longer time is required for C-50 as compared with A-50. The value of μc correlates well with the change in crystal perfection during deformation and annealing. 相似文献
10.
Min Wei Todd A. Bullions Cristian C. Rusa Xingwu Wang Alan E. Tonelli 《Journal of Polymer Science.Polymer Physics》2004,42(3):386-394
Bulk poly(ethylene terephthalate) PET has been reorganized both morphologically and conformationally by processing from its inclusion complex (IC) formed with γ‐cyclodextrin (CD). In the narrow channels of its γ‐CD‐IC crystals the included guest PET chains are isolated from neighboring PET chains and the ethylene glycol (EG) units adopt the highly extended g±tg? kink conformations, whose cross‐sectional diameters are ~80% of the diameter of the fully extended, all‐trans crystalline PET conformer, though they are nearly (~95%) as extended. When the highly extended, unentangled guest PET chains are coalesced from their γ‐CD‐IC crystals by exposure to hot water, host γ‐CDs are removed and the PET chains are presumably consolidated into a bulk sample with a morphology and constituent chain conformations not normally found in PET samples solidified from their randomly coiling, possibly entangled, disordered melts and solutions. Observations by polarized light and atomic force microscopies provide visual evidence for widely different semicrystalline morphologies developed in coalesced and as‐received PETs when crystallized from their melts, with possibly chain extended, small crystals and spherulitic, chain‐folded, large crystals, respectively. DSC observations reveal that coalesced PET is rapidly crystallizable from the melt, while as‐received PET is slow to crystallize and is easily quenched into a totally amorphous sample. Analyses of 13C‐NMR data strongly indicate that the PET chains in the noncrystalline regions of the coalesced sample remain predominantly in the highly extended kink conformations, with g±tg? EG units, which are required by their inclusion into PET‐γ‐CD‐IC crystals, while the predominantly amorphous PET chains in the as‐received sample have high concentrations of gauche± ? CH2? CH2? and trans ? O? CH2? ,? CH2? O? EG bond conformations. 13C‐NMR T1(13C) and T1ρ(1H) relaxation studies show no evidence of a glass transition for coalesced PET, while the as‐received sample shows abrupt changes in both the MHz [T1(13C)] and kHz [T1ρ(1H)] motions at T ~ Tg. Preliminary observations of differences in their macroscopic properties are attributed to the very different morphologies and conformations of the constituent chains in these PET samples. Apparently the kink conformers in the noncrystalline regions of coalesced PET are at least partially retained for extended periods even in the melt and are rapidly crystallized upon cooling. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 386–394, 2004 相似文献
11.
D. L. Tzou P. Desai A. S. Abhiraman T.-H Huang 《Journal of Polymer Science.Polymer Physics》1991,29(1):49-56
Lineshape simulation of 13C nuclear magnetic resonances was employed to characterize the structural development of poly (ethylene terephthalate) (PET) during fiber formation and subsequent processing. In all spectra the carbonyl (CA) and glycoethylene (GE) resonances can be simulated with two components. The intensity variation of these components has been interpreted quantitatively on the basis of four morphological components in the solid-state structure, with clearly defined differences in order between them. The four components are, in decreasing structural order, (i) crystalline (C), (ii) noncrystalline with order in both CA and GE environments (NC1), (iii) noncrystalline with order only in the GE environment (NC2), and (iv) amorphous (NCA). The crystalline component has been taken here to correspond to the high-density component which has been estimated from flotation and optical density measurements. Such an analysis reveals a smooth pattern of evolution of order within a range of conditions in melt spinning and subsequent thermomechanical processing of PET fibers. Cold drawing at room temperature was seen to induce substantial ordering only in the GE environment. In contrast, annealing at a temperature significantly above glass transition temperature (Tg) for 2 h appears to cause the conversion of amorphous component to crystalline from with little accumulation of the intermediate components. 相似文献
12.
Efficient synthesis of cyclic olefin copolymers with high glass transition temperatures by ethylene copolymerization with tetracyclododecene using (tert‐BuC5H4)TiCl2(N=CtBu2)—MAO catalyst
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Wannida Apisuk Hikaru Ito Kotohiro Nomura 《Journal of polymer science. Part A, Polymer chemistry》2016,54(17):2662-2667
(tBuC5H4)TiCl2(N=CtBu2) ( 1 ) exhibited remarkable catalytic activities (12,000–43,700 kg‐polymer/mol‐Ti·h) and efficient comonomer incorporation in ethylene copolymerization with tetracyclododecene (TCD) in the presence of methylaluminoxane, and the catalytic activity by 1 increased even at 60 °C. The resultant polymers are high molecular weight amorphous poly(ethylene‐co‐TCD)s (Mn = 5.88–7.03 × 105) with uniform compositions (with high Tg values, 108–203 °C); a linear relationship between Tg values and the TCD contents was observed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2662–2667 相似文献
13.
K. R. Doolan 《Journal of Polymer Science.Polymer Physics》2002,40(6):572-584
Nuclear magnetic resonance (NMR) spin–lattice relaxation times (T1) in various polyethylene and polypropylene resins were measured at 20 MHz and at temperatures of 130–490 K. At each temperature and for all resins, only a single value of T1 was found, which was consistent with the occurrence of rapid spin diffusion throughout the protons attached to the polymer chains. The data were analyzed for the estimation of activation energies corresponding to molecular motion causing spin–lattice relaxation. Two well‐defined minima were found for loge(T1) plotted as a function of temperature for all of the polypropylene resins. Single very broad minima were found for all of the polyethylene samples. In contrast, the free induction decay signals from all of the resins following single radio‐frequency pulses were observed to contain a rapidly decaying component followed by a much more slowly decaying signal. These components were used to estimate the amount of rigid component present in the solid resins at room temperature. Samples of one high‐density polyethylene and one low‐density polyethylene were irradiated with γ radiation up to a 500‐kGy dose to examine the effects of crosslinking on the NMR relaxation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 572–584, 2002; DOI 10.1002/polb.10116 相似文献
14.
A. Rawal X.‐W. Fang K. Urman D. Iverson J. U. Otaigbe K. Schmidt‐Rohr 《Journal of Polymer Science.Polymer Physics》2008,46(9):857-860
The effect of tin fluorophosphate‐glass (Pglass) nanoparticles on the polyamide‐6 (PA6) matrix in Pglass/PA6 hybrids has been investigated by 13C solid‐state nuclear magnetic resonance (NMR). The crystallinity determined by direct‐polarization 13C NMR combined with longitudinal relaxation‐time (T1C) filtering varied between 31 and 44%. T1C‐filtered 13C spectra with cross polarization clearly showed resonances of both the α‐ and γ‐crystalline phases of PA6, typically at ratios near 45:55, while the similarly processed neat polymer contained only the α‐phase. This suggests that the Pglass promotes the growth of the γ‐crystalline phase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 857–860, 2008 相似文献
15.
Jingshan Mu Fei Yang Wei Li Dirong Gong Zhongsu Liu Feng Jiang Zhongren Chen 《Journal of polymer science. Part A, Polymer chemistry》2014,52(15):2146-2154
The synthesis of amphiphilic linear‐hyperbranched graft‐copolymers in a grafting‐from approach is reported. The linear polyethylene with terminated hydroxyls, prepared by copolymerization of ethylene and 10‐undecen‐1‐ol, was used as macroinitiator for ring‐opening multibranching polymerization of glycidol by a typical slow monomer addition approach. Successful attachment of the hyperbranched grafts to the linear polyethylene backbone was confirmed by 1H/13C NMR, GPC, and TGA. The degree of polymerization and Mw/Mn of hyperbranched grafts were efficiently controlled by temperature, deprotonation ratio as well as the molar ratio of glycidol/hydroxyl (Nglycidol/NOH). The complicated microstructures caused by unsymmetric glycidol structure were analyzed by DEPT and 2D HSQC spectra, the degree of branching of 0.63–0.66 were calculated, indicating the extent of branch is close to theoretical values. The thermal analysis of linear‐hyperbranched copolymers via TGA and DSC is also presented. To our knowledge, this is the first report of a linear‐hyperbranched graft‐copolymer with a crystalline and nonpolar linear‐polyethylene segment. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2146–2154 相似文献
16.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(3):340-350
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 (Tg = −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 相似文献
17.
Comparison of the mechanical properties of styrene‐based ionomers containing either crown ether or pentaethylene glycol with those of underneutralized ionomers
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Bum‐Kyu Lee Jeong‐A Yu Young‐Wun Kim Joon‐Seop Kim 《Journal of Polymer Science.Polymer Physics》2015,53(19):1358-1367
Dynamic mechanical properties of styrene‐based ionomers containing varying amounts of either 15‐crown‐5 ether (CE) or pentaethylene glycol (PG) are compared with those of ionomers of varying degree of neutralization (ND). The cluster Tg (Tg,c) and ionic modulus of the ionomers decrease with increasing amount of CE or PG or decreasing ND. Thus, we propose that the CE binds Na+ strongly to form a large‐sized complex. Thus, the electrostatic interactions between charges decrease, leading to lower Tg,c. For the PG‐containing ionomers, the PG acts as polar plasticizer, further lowing the Tg,c. In the case of the underneutralized ionomers, the Tg,c is reduced by the existence of both relatively weak hydrogen bonds between carboxylic acid groups and relatively strong ionic bonds between ion pairs in the multiplets. The small‐angle X‐ray scattering results are also supportive of the above interpretations. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1358–1367 相似文献
18.
Liying Wang Pengfei Fang Chaohui Ye Jiwen Feng 《Journal of Polymer Science.Polymer Physics》2006,44(19):2864-2879
Solid‐state nuclear magnetic resonance spectroscopy and relaxation measurements, together with DSC, have been used to elucidate the structures and molecular dynamics in poly(ethylene‐co‐vinyl acetate) (EVA). It has been found that besides immobile orthorhombic and monoclinic crystalline phases, the third mobile crystalline phase (possibly the phase) of a considerable amount (36% of total crystalline phases) appears in the EVA samples, which forms during room‐temperature aging as a result of the secondary crystallization and melts at temperature somewhat higher than room temperature. Such a mobile crystalline phase has not only the well‐defined chemical shift of its own, but also has different molecular mobility from the orthorhombic phase. The mobile crystalline phase is characterized by the rapid relaxation of the longitudinal magnetization, which is caused by conventional spin‐lattice relaxation, while the slow relaxation of the longitudinal magnetization occurring in the orthorhombic phase is originated from the chain diffusion. In addition, the amorphous phase also contains two components: an interfacial amorphous phase and a melt‐like amorphous phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2864–2879, 2006 相似文献
19.
Long‐Cheng Gao Qi‐Wei Pan Chao Wang Yi Yi Xiao‐Fang Chen Xing‐He Fan Qi‐Feng Zhou 《Journal of polymer science. Part A, Polymer chemistry》2007,45(24):5949-5956
We have designed and synthesized rod–coil–rod triblock copolymers of controlled molecular weight by two‐step nitroxide‐mediated radical polymerization, where the rod part consists of “mesogen‐jacketed liquid crystalline polymer” (MJLCP). The MJLCP segment examined in our studies is poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} (MPCS) while the coil part is polyisoprene (PI). Characterization of the triblock copolymers by GPC, 1H and 13C NMR spectroscopies, TGA, DSC confirmed that the triblock copolymers were comprised of microphase‐separated low Tg amorphous PI and high Tg PMPCS blocks. Analysis of POM and 1D, 2D‐WAXD demonstrated that the triblock copolymers formed nematic liquid crystal phase. Morphological studies using TEM indicated the sample formed lamellar structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5949–5956, 2007 相似文献
20.
Ryan C. Nieuwendaal 《Magnetic resonance in chemistry : MRC》2016,54(9):740-747
We outline the details of acquiring quantitative 13C cross‐polarization magic angle spinning (CPMAS) nuclear magnetic resonance on the most ubiquitous polymer for organic electronic applications, poly(3‐hexylthiophene) (P3HT), despite other groups' claims that CPMAS of P3HT is strictly nonquantitative. We lay out the optimal experimental conditions for measuring crystallinity in P3HT, which is a parameter that has proven to be critical in the electrical performance of P3HT‐containing organic photovoltaics but remains difficult to measure by scattering/diffraction and optical methods despite considerable efforts. Herein, we overview the spectral acquisition conditions of the two P3HT films with different crystallinities (0.47 and 0.55) and point out that because of the chemical similarity of P3HT to other alkyl side chain, highly conjugated main chain polymers, our protocol could straightforwardly be extended to other organic electronic materials. Variable temperature 1H NMR results are shown as well, which (i) yield insight into the molecular dynamics of P3HT, (ii) add context for spectral editing techniques as applied to quantifying crystallinity, and (iii) show why T1ρH, the 1H spin–lattice relaxation time in the rotating frame, is a more optimal relaxation filter for distinguishing between crystalline and noncrystalline phases of highly conjugated alkyl side‐chain polymers than other relaxation times such as the 1H spin–spin relaxation time, T2H, and the spin–lattice relaxation time in the toggling frame, T1xzH. A 7 ms T1ρH spin lock filter, prior to CPMAS, allows for spectroscopic separation of crystalline and noncrystalline 13C nuclear magnetic resonance signals. Published 2016. This article is a U.S. Government work and is in the public domain in the USA. 相似文献