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1.
In this article, copolymer macroinitiators prepared with styrene and iso‐octyl acrylate by reversible additional‐fragmental chain transfer polymerization were used to prepare polymer‐dispersed liquid crystals (PDLCs) with methyl acrylate. The electro‐optical properties of the PDLCs were investigated. The results showed that the glass transition temperature (Tg) of the macroinitiator has a great influence on the memory effect of the resulting PDLCs. Low driving voltage and low memory effect PDLCs could easily be obtained with copolymer macroinitiators. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

2.
Glass transition temperature (Tg), an important parameter of polymer, was reported to have great influence on the electro-optical properties of polymer dispersed liquid crystals (PDLCs). In this study, macroinitiators with different Tg were synthesised by reversible addition fragmentation chain transfer polymerisation, and used to prepare PDLCs with different Tg block chains. The effect of different Tg of the block chains on response times was investigated. It was found that rise time decreased and decay time increased with the decrease of the block chain’s Tg. We proposed a possible mechanism by which Tg of the block chains influence response times.  相似文献   

3.
The continuous‐multilayer model introduced in our previous study for the Tg behavior of thin films is adapted to nanocomposite systems. Tg enhancement in both thin films and nanocomposites with attractive interfacial interactions can be explained by the same model. Various shapes of nanoparticles are proposed to rationalize the adaptation of the one‐dimensional model for the Tg behavior of thin film to three‐dimensional system such as nanocomposite. The tendency of predicted Tg enhancements in poly(methyl methacrylate) and P2VP nanocomposites with silica particles are qualitatively fit to experimental data in literatures. For the further quantitative fitting, the model is partially modified with the consideration for other factors affecting Tg deviation in nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2281–2287, 2009  相似文献   

4.
Diffusion of gases in polymers below the glass transition temperature, Tg, is strongly modulated by local chain dynamics. For this reason, an analysis of pulsed field gradient (PFG) nuclear magnetic resonance (NMR) diffusion measurements considering the viscoelastic behavior of polymers is proposed. Carbon‐13 PFG NMR measurements of [13C]O2 diffusion in polymer films at 298 K are performed. Data obtained in polymers with Tg above (polycarbonate) and below (polyethylene) the temperature set for diffusion measurements are analyzed with a stretched exponential. The results show that the distribution of diffusion coefficients in amorphous phases below Tg is wider than that above it. Moreover, from a PFG NMR perspective, full randomization of the dynamic processes in polymers below Tg requires long diffusion times, which suggests fluctuations of local chain density on a macroscopic scale may occur. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 231–235, 2010  相似文献   

5.
We used neutron reflectivity to measure the interfacial width in the immiscible system polystyrene/poly(n‐butyl methacrylate) (PS/PnBMA). Measurements were made on the same samples at temperatures ranging from below the glass‐transition temperature (Tg) of PS to slightly above. We observed significant broadening of the interface at temperatures below the Tg of PS, indicating chain mobility below the bulk Tg value. The interfacial width exhibited a plateau at a value of 20 Å in the temperature range of 365 K < T < 377 K. A control experiment involving hydrogenated and deuterated PS films (hPS/dPS) showed no such broadening over the same temperature region. The results are consistent with a reduction of the Tg of PS in the interfacial region of ~20 K. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2664–2670, 2001  相似文献   

6.
In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (Tg) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine Tg in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. Tg is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007  相似文献   

7.
Compared with linear polymers, more factors may affect the glass‐transition temperature (Tg) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. Tg's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of Tg to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. Tg's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. Tg values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. Tg values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of Tg versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that Tg increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004  相似文献   

8.
In this work, by adopting the united atom model of cis‐1,4‐poly(butadiene) (PB), we systemically investigate the effect of the chain structure on the glass transition temperature (Tg) and the viscoelastic property of PB system. First, we analyze the atom translational mobility, bond reorientation dynamics, torsional dynamics, conformational transition rate, and dynamic heterogeneity of the PB chains with different chain structures in detail by determining the corresponding Tg. In addition, our results clearly indicate that with the decrease of the amount of the free end atoms of PB via the end‐linking method, the mobility of the PB chains quickly decreases. As a result, the Tg of the PB chains gradually increases. Depending on the chain structure and the calculation method, the Tg of the PB chains varies from 154 to 240 K. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below Tg. The calculated activation energy varies from 7.37 to 16.37 KJ/mol for different chain structures above Tg, which can be compared with those for other polymers. In addition, through the end‐linking approach the strong interaction between the PB chains improves the storage modulus G′ and the loss modulus . Meanwhile, the immobility of the free end atoms effectively reduces the friction loss of the chains under the shear field, which is reflected by the low loss factor . In summary, this work can further help to understand the effect of the chain structure on the dynamic properties of the PB chains. Meanwhile, it provides an effective approach to reduce the energy loss during the dynamic periodic deformation, which can cut the fuel consumption via the end‐linking method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1005–1016  相似文献   

9.
The calorimetric glass‐transition temperature (Tg) and transition width were measured over the full composition range for solvent–solvent mixtures of o‐terphenyl with tricresyl phosphate and with dibutyl phthalate and for polymer–solvent mixtures of polystyrene with three dialkyl phthalates. Tg shifted smoothly to higher temperatures with the addition of the component with the higher Tg for both sets of solvent–solvent mixtures. The superposition of the differential scanning calorimetry traces showed almost no composition dependence for the width of the transition region. In contrast, the composition dependence of Tg in polymer–solvent mixtures was different at high and low polymer concentrations, and two distinct Tg's were observed at intermediate compositions. These results were interpreted in terms of the local length scale and associated local composition variations affecting Tg. The possible implications of these results for the dynamics of miscible polymer blends were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1155–1163, 2004  相似文献   

10.
New ether dimer (ED‐Eh) and diester (EHDE) derivatives of α‐(hydroxymethyl)acrylate, each having two 2‐ethylhexyl side chains, and an amine‐linked di(2‐ethylhexyl)acrylate (AL‐Eh), having three 2‐ethylhexyl side chains, were synthesized and (co)polymerized to evaluate the effects of differences in the structures of the monomers on final (co)polymer properties, particularly glass transition temperature, Tg. The free radical polymerizations of these monomers yielded high‐molecular–weight polymers. Cyclopolymer formation of ED‐Eh and AL‐Eh was confirmed by 13C NMR analysis and the cyclization efficiencies were found to be very high (~100%). Copolymers of ED‐Eh, EHDE, and AL‐Eh with methyl methacrylate (MMA) showed significant Tg decreases over poly(methyl methacrylate) (PMMA) due to 2‐ethylhexyl side groups causing “internal” plasticization. Comparison of the Tg's of the copolymers of 2‐ethylhexyl methacrylate, ED‐Eh, EHDE, and AL‐Eh with MMA revealed that the impacts of these monomers on depression of Tg's are identical with respect to the total concentration of the pendent groups. This is consistent with an earlier study involving copolymers of monomers comprising one and two octadecyl side groups with MMA. That is, the magnitude of decrease in Tg's was quantitatively related to the number of the 2‐ethylhexyl pendent groups in the copolymers rather than their placement on the same or randomly incorporated repeat units. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2302–2310, 2010  相似文献   

11.
The prediction of chemical structures that possess higher glass‐transition temperatures (Tg's) is crucial for designing polyimides. Because of a lack of suitable parameters, several estimation methods cannot be used for this purpose. In this study, therefore, we used molecular dynamic simulation with the DREIDING II force field to predict Tg's for polyimides. Simulated results indicated a good agreement with experimental observations. A barrier analysis of the bridging bonds between moieties along the main‐chain backbone showed a correlation between Tg and the barrier height. This proved to be helpful in a preliminary selection before the molecular dynamic simulation for accelerating the process of research and development on new polyimides. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2243–2251, 2001  相似文献   

12.
Positron annihilation lifetime spectroscopy (PALS), density, and differential scanning calorimetric (DSC) measurements were used to study systematically the variation of the glass‐transition temperature (Tg) and the size v and number density Nh of local free volumes in n‐alkyl‐branched polypropylenes. The samples were metallocene‐catalyzed propylene copolymers with different α‐olefins (from C4 to C16) and a different α‐olefin content (between 0 and 20 mol %). From the total specific volume and crystallinity the specific volume of the amorphous phase Va was estimated and used to calculate the fractional free (hole) volume h and value of Nh. The variations of Tg, v, Va, h, and Nh were related to the degree (number and length) of branching. Tg decreases and v increases linearly with the number and length of n‐alkyl branches. This behavior was attributed to an increased segmental mobility caused by branching. Both values, Tg and v, follow linear master curves as a function of the degree of branching (DB) if this is defined as the number of all side‐chain carbons with respect to a total of 1000 (main‐chain and side‐chain) carbons. Only propylene/1‐butene copolymers deviated from these relations. A linear relation between v and Tg was also found. The number density of holes was estimated to be Nh = 0.49(±0.07) nm?3 and Nh′ = 0.58(±0.11) × 1021 g?1, respectively. It shows a slight variation with the DB, which is also seen in the behavior of the specific volume Va. This variation was explained by the appearance of sterical hindrances resulting from short‐chain branches that may prevent an efficient packing of the chains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 434–453, 2002; DOI 10.1002/polb.10108  相似文献   

13.
Glass transition of core/shell capsules consisting of calcium carbonate whisker as a core and crosslinked polystyrene as a shell was studied by differential scanning calorimetry. The thickness of the crosslinked shell was in the range of 26–81 nm. The crosslinked shells were revealed to show higher glass transition temperatures (Tg) than the corresponding bulk values. It was revealed that a thicker shell exhibits a lower Tg than a thinner shell, and that capsules without core (hollow capsules) exhibit lower Tg's than the corresponding core/shell capsules. These results suggest that the interfacial molecular interaction plays a role in the segmental relaxation, which is responsible for the glass transition. The difference in Tg between the core/shell and hollow samples was reduced when a coupling agent, methacrylic acid 3‐(trimethoxysilyl)propyl ester, was not included. This also suggests the interfacial effect on Tg. However, the results still suggest that the enhancement of Tg for the present crosslinked shells is not only due to the interfacial effect but also to the effects of chain configuration and heterogeneous crosslink. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2475–2485, 2006  相似文献   

14.
Solution and dispersion copolymerizations of N‐phenylmaleimide (PMI) with either styrenics or alkyl vinyl ethers (AVEs), systems with a tendency to give alternating polymers, were investigated with the goal of producing high glass transition particles. Equimolar solution copolymerization of PMI with styrenics gave alternating copolymers, whereas AVEs gave PMI‐rich copolymers (~65:35) except for t‐butyl vinyl ether, which gave copolymers with only a slight excess of PMI. These copolymers had glass transition temperatures (Tgs) ranging from 115 to 225 °C depending on comonomer(s). Dispersion copolymerization in ethanol‐based solvents in the presence of poly(vinylpyrrolidone) as steric stabilizer led to narrow‐disperse microspheres for many copolymers studied. Dispersion copolymeriations of PMI with styrenics required good cosolvents such as acetonitrile or methyl ethyl ketone as plasticizers during particle initiation and growth. Dispersion copolymerizations generally resulted in copolymer particles with compositions and Tgs very similar to those of the corresponding copolymers formed by solution polymerization, with the exception of t‐butyl vinyl ether (tBVE), which now behaved like the other AVEs. Dispersion terpolymerizations of PMI (50 mol %) with different ratios of either n‐butylstyrene and t‐butylstyrene or n‐butyl vinyl ether and tBVE led to polymer particles with Tgs that depended on the ratio of the two butyl monomers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

15.
Nanostructured amorphous bulk polymer samples were produced by processing them with small molecule hosts. Urea (U) and gamma‐cyclodextrin (γ‐CD) were utilized to form crystalline inclusion compounds (ICs) with low and high molecular weight as‐received (asr‐) poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), and their blends as included guests. Upon careful removal of the host crystalline U and γ‐CD lattices, nanostructured coalesced (c‐) bulk PVAc, PMMA, and PVAc/PMMA blend samples were obtained, and their glass‐transition temperatures, Tgs, measured. In addition, non‐stoichiometric (n‐s)‐IC samples of each were formed with γ‐CD as the host. The Tgs of the un‐threaded, un‐included portions of their chains were observed as a function of their degree of inclusion. In all the cases, these nanostructured PVAc and PMMA samples exhibited Tgs elevated above those of their as‐received and solution‐cast samples. Based on their comparison, several conclusions were reached concerning how their molecular weights, the organization of chains in their coalesced samples, and the degree of constraint experienced by un‐included portions of their chains in (n‐s)‐γ‐CD‐IC samples with different stoichiometries affect their chain mobilities and resultant Tgs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1041–1050  相似文献   

16.
Repeating sequence copolymers of poly(lactic‐co‐caprolactic acid) (PLCA), poly(glycolic‐co‐caprolactic acid) (PGCA), and poly(lactic‐co‐glycolic‐co‐caprolactic acid) (PLGCA) have been synthesized by polymerizing segmers with a known sequence in yields of 50–85% with Mns ranging from 18–49 kDa. The copolymers exhibited well‐resolved NMR resonances indicating that the sequence encoded in the segmers used in their preparation is retained and that transesterification is minimal. The exact sequences allowed for unambiguous assignment of the NMR spectra, and these standards were compared with the data previously reported for random copolymers. The glass transition temperatures (Tgs) of the PLCA and PGCA copolymers were found to depend primarily on monomer ratio rather than sequence. Sequence dependent Tgs were, however, noted for the PLGCA polymers with 1:1:1 L:G:C ratios; poly LGC and poly GLC exhibited Tgs that differed by nearly 8 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

17.
Polystyrene‐based ionomers possessing sodium methacrylate (MA) and sodium styrenesulfonate (SS) units in each polymer chain [poly(styrene‐co‐methacrylate‐co‐styrenesulfonate) (PSMA‐SS)] were synthesized. The dynamic mechanical properties of PSMA‐SS ionomers were studied and compared with those of styrene ionomers containing only MA (PSMA ionomer) or SS (PSS ionomer) units. It was observed that the ionic moduli of PSMA‐SS ionomers depended directly on the total ion content and that the ionic modulus was highest for the PSMA ionomer and lowest for the PSMA‐SS ionomer. The matrix Tgs of the three ionomer systems were found to be similar to each other; the cluster Tg of PSMA‐SS ionomer was higher than that of PSS ionomer at low SS contents but became closer to each other at high SS contents. In addition, the small‐angle X‐ray scattering study revealed that the multiplet size might be in the following order: PSMA‐SS > PSS > PSMA. This implied that at the same ion content, the fractions of cluster regions were smallest for PSMA‐SS ionomer in comparison with those of PSS or PSMA ionomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

18.
Poly(styrene‐co‐ethyl acrylate) [P(St‐co‐EA)] with different ratios of St/EA was mixed with the small molecule 4,4′‐thio‐bis(6‐tert‐butyl‐m‐methyl phenol) (AO300) to investigate the influence of hydrogen bonding strength on the glass transition behavior. The glass transition temperature (Tg) linearly increased after adding AO300, and the slope value decreased with increased St/EA ratio. All lines could be extended to 62 °C, demonstrating that Tg of the small molecule in situ detected by the polymer chain was much higher than that by small molecule itself (29 °C). Fourier transform infrared spectroscopy analysis showed that the small molecules began to be self‐associated at a concentration where the hydrogen bonded carbonyl ratio of the bulk polymer was approximately 0.5 and irrespective of the St/EA ratio. Above the critical loading, the mixture's Tg negatively deviated from the linearly extended lines because of self‐association of the small molecules. The apparent Tg of AO300 was found to strongly depend on intermolecular hydrogen bonding number and strength. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 400–408  相似文献   

19.
We investigate the morphology, segmental dynamics, and conductivity of 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate (EMI‐Tf) swollen short side chain perfluorosulfonate ionomer (Aquivion) over a broad uptake range using small angle X‐ray scattering (SAXS), dielectric relaxation spectroscopy, and transient current measurement. The SAXS data indicate that the absorbed EMI‐Tf is mainly bounded in the ionic region of Aquivion. At low uptakes, EMI‐Tf acts as an effective plasticizer lowering the cluster Tg and markedly shifting the segmental relaxation to a high frequency; however, at high uptakes, the additional EMI‐Tf acts like a filler instead. A time–domain model was employed to quantify the conductivity of these membranes containing two mobile ion species, that is, cations and anions. The conductivity of both neat EMI‐Tf and EMI‐Tf swollen membranes exhibits Vogel‐Fulcher‐Tamman relation, revealing different activation parameters for ionic conduction. Furthermore, membranes containing different EMI‐Tf uptakes have similar conductivity over the reduced Tg/T axis and also follow Debye‐Stokes‐Einstein relation. Therefore, despite the abrupt change in conductivity near the critical uptake (29 wt %), both cluster Tg and segmental motion remain the key factors for the ionic conduction in these EMI‐Tf swollen membranes. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1273–1280  相似文献   

20.
Melt polycondensation was used to prepare a systematic series of random and amorphous copolyesters using the following cycloaliphatic diesters: dimethyl‐1,4‐cyclohexane dicarboxylate (DMCD), dimethyl bicyclo[2.2.1]heptane‐1,4‐dicarboxylate (DMCD‐1), dimethyl bicyclo[2.2.2]octane‐1,4‐dicarboxylate (DMCD‐2), dimethyl bicyclo[3.2.2]nonane‐1,5‐dicarboxylate (DMCD‐3), 1,4‐dimethoxycarbonyl‐1,4‐dimethylcyclohexane (DMCD‐M) and the aliphatic diols: ethylene glycol (EG) and 1,4‐cyclohexane dimethanol (CHDM). The polymer compositions were determined by nuclear magnetic resonance (NMR) and the molecular weights were determined using size exclusion chromatography (SEC). The polyesters were characterized by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The copolyester based on DMCD‐2 was observed to have a higher glass transition temperature (Tg up to 115 °C) than the other copolyesters of this study. For poly[x(DMCD‐2)y(DMCD) 30(EG)70(CHDM)], Tg increases linearly with increase of DMCD‐2 mole content. DMA showed that all of the cycloaliphatic copolyesters have secondary relaxations, resulting from the conformational transitions of the cyclohexylene rings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2162–2169, 2010  相似文献   

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