Syntheses and properties of tetramethyl-p-silphenylenesiloxanealkenylmethyl-siloxane copolymers and their derivatives

$\text{Tetramethyl}\text{-p-}\text{silphenylenesiloxane}\text{alkenylmethylsiloxane}$ (TMPS/AMS) copolymers were snyhtesized from p-bis-dimethylhydroxysilylbenzene and a series of alkenylmethyldichlorosilanes as the starting materials. The alkenyl groups of the copolymers were vinyl, allyl, 2-(3-cyclohexenyl)ethyl, methacryloxypropyl and 3-bicycloheptenyl groups. The composition ranged from TMPS/AMS mole% ratio of $\text{92}\text{8}$ to $\text{83}\text{17}$ and the molecular weights were in the range 10⁴ to 10⁵. These copolymers were confirmed to have two compositions, one a certain length of TMPS segment and the other an AMS monomer unit, and that they could form films on the basis of the crystallization character of the TMPS segment. The melting temperatures of these copolymers decreased as the TMPS mole content decreased and as the alkenyl group contents were increased. The epoxidation reactions of these copolymers with m-chloroperbenzoic acid were carried out and the proportions of conversions of the alkenyl groups into epoxy groups varied depending upon the types of alkenyl groups involved. Cyclic olefin groups such as the 2-(3-cyclohexenyl)ethyl or the 3-bicycloheptenyl group were more easily epoxidized than the vinyl or allyl groups. The TMPS/dimethylsiloxane (DMS) graft copolymer could also be synthesized by the reaction of TMPS/vinylmethylsiloxane copolymer with dimethylhydrosilyl-terminated DMS oligomer in the presence of chloroplatinic acid acting as the catalyst.     

Effect of vinylacetate content on crystallinity and second-order transitions in ethylene—vinylacetate copolymers

Thermal characteristics of ethylene—vinylacetate (EVA) copolymers having vinylacetate contents ranging from 5 to 40 w/w % are studied by differential scanning calorimetry. It is first shown that EVA copolymers having a vinylacetate content lower than 30 w/w % obey the Flory and Burfield theories of copolymer crystallisation. The minimum sequence length of CH₂ ethylenic entities required to participate in a crystalline lamella is also deduced. One can conclude that EVA copolymers represent cases of “total exclusion” of the noncrystallizable comonomer. Moreover, it is observed that when the vinylacetate content is increased, the relative quantity of polyethylene amorphous phase increases and the degree of crystallinity decreases; whereas the β transition temperature of a characteristic-oriented amorphous phase is kept constant. A phase model of ethylene-vinylacetate copolymers, based on an enrichment process of the interlamellar amorphous phase by polyethylene segments originating from the crystalline phase, at increasing vinylacetate content, is proposed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1903–1912, 1997     

Physical properties of model graft copolymers and their use as blend compatibilizers

The present investigation pertains to the structure–property relationships of highly structured graft copolymers. The specific model graft copolymers are based on an elastomeric backbone, i.e., poly(ethyl acrylate), and monodisperse thermoplastic grafts, i.e., polystyrene. The synthesis of these graft copolymers is based on the free-radical polymerization of ethyl acrylate and an anionically polymerized polystyrene macromonomer. It is clearly demonstrated that grafts significantly enhance tensile properties. The level of improvement is directly related to the graft level, i.e., number of grafts/chain, and graft molecular weight. In addition, blending these graft copolymers into their respective homopolymer mixture results in a mechanical performance strikingly dependent on the molecular characteristics of the graft copolymer. For example, tensile strength is maximized at a level between one and two grafts per chain. This result parallels observations noted in blend compatibilization using diblock and triblock copolymers. It is also demonstrated that using mutually grafted copolymers produces an interesting variety of compatibilized ternary (or higher) component blends. © 1994 John Wiley & Sons, Inc.     

Physical properties of vinyl chloride-propylene copolymers

The polymerization conditions that control the physical properties of vinyl chloride-propylene copolymers have been examined, and the interaction between these polymerization conditions and the melt rheology, intrinsic viscosity, and bound propylene level of the copolymer have been quantified into a series of process control relationships. The interaction between primary and secondary suspension systems have been optimized for these copolymers to maximize the resin porosity. Binary initiator systems have been identified to overcome the degradative polymer kinetics associated with propylene comonomer.     

Physical properties of isobutylene based block copolymers

Physical, mechanical and thermal properties of a new class of isobutylene based model block copolymers are studied and contrasted with those of traditional thermoplastic elastomers based on polydienes and saturated polydienes (polyolefins) such as Kraton (or Vector) and Kraton G block copolymers. Melt state rheological and dynamic mechanical measurements confirm that thermodynamic interactions between polystyrene (S) and polyisobutylene (iB) or poly‐p‐tert‐butylstyrene (tbS) and iB are comparable to, if not larger than, those between S and polybutadiene (B) or S and ethylene/butene‐1 copolymer (EB). Physical properties for the S‐iB‐S and tbS‐iB‐tbS block copolymers, particularly the injection‐moldability and cut‐growth characteristics, are found to be considerably different from those found for the S‐B‐S and S‐EB‐S systems. We attribute this behavior to the longer entanglement chain length of iB compared with those for B and EB.     

含硅聚酰亚胺的合成及性能研究

合成了一类含硅二胺双氨丙基四甲基二硅氧烷,并将其与芳族二胺和芳族四酸二酐共聚,得到了一系列不同配比的含硅聚酰亚胺。通过差热分析(DSC)和热重分析(TGA),表明引入有机硅链段能有效地改善聚酰亚胺的性能。共聚物的玻璃化转变温度(Tg)符合Kwei方程。     

国内外EVA树脂的生产技术及市场对比

介绍了乙烯一醋酸乙烯酯共聚树脂（EVA树脂）的生产工艺,分析了我国EVA树脂的生产消费现状及发展前景,提出今后的发展建议。     

Mechanical properties of vinyl alcohol—ethylene copolymers

The stress‐strain behavior of vinyl alcohol‐ethylene copolymers, with vinyl alcohol as main component, was studied. Films of the copolymer samples, either quenched or slowly cooled from the melt, were stretched at 23, 40 and 80°C. The two former temperatures are below the glass transition (T_g) and the latter is well above the T_g of the studied samples. The drawing process was carried out at different strain rates, and the influence of the stretching parameters (temperature, strain rate) as well as the thermal history and composition of the copolymer samples are discussed in relation to the corresponding homopolymers, poly(vinyl alcohol) and polyethylene. The copolymer with the highest vinyl alcohol content exhibited a critical strain rate, showing maximum values of Young's modulus at a deformation rate around 0.66/min.     

Structure-mechanical property relationships in ethylene methacrylic acid copolymers and their salts

A dynamic mechanical study has been made of an ethylenemethacrylic acid copolymer containing 4.1 mole per cent of methacrylic acid units and its sodium, lithium and calcium salts. On the basis of the results and related physical chemical studies it is proposed that the structures of the ionized copolymers consist of three distinct phases—a crystalline polyethylene phase, an amorphous polyethylene phase, and an ionic phase consisting of ionic domains. It is further proposed that the unionized acid copolymer consists of two phases—a crystalline polyethylene phase and an amorphous phase consisting of polyethylene crosslined with hydrogen bonded, carboxylic acid dimers.     

Conducting copolymers of polytetrahydrofuran and their electrochromic properties

Living polytetrahydrofuran (PTHF) was terminated with sodium thiophene methonate to yield a polymer with a thiophene group at one end. Copolymerizations of PTHF with pyrrole and thiophene were achieved in water‐p‐toluene sulfonic acid and acetonitrile‐tetrabutylammonium tetrafluoroborate (TBAFB) solvent‐electrolyte couples via constant potential electrolyses. Characterizations of the samples were performed by NMR, cyclic voltammetry, FT‐IR, thermal analyses, and scanning electron microscopy. Electrical conductivities were measured by the four‐probe technique. PTHF/PTh film that was deposited on ITO‐glass in a dichloromethane‐TBAFB solvent‐electrolyte couple was found to exhibit electrochromic behavior and it electrochemically switches between blue oxidized and red reduced states. Optical analyses were carried out to investigate the electronic structure of PTHF/PTh electrochromic copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1014–1023, 2005     

Physical properties of block copolymers of polydimethyl siloxane and polycarbonate

A detailed study of the physical properties of alternating block copolymers of polydimethyl siloxane and bisphenol-A polycarbonate is presented. The results suggest that the mechanical and optical properties of such materials are dependent upon the presence of associated regions as well as the nature of the chain between such regions. Dielectric, infrared, and DSC data as well as the stress and birefringence strain behavior are presented.     

Synthesis and properties of some fluorescent 1,8‐naphthalimide derivatives and their copolymers with methyl methacrylate

Six new fluorescent derivatives of 1,8‐naphthalimide were synthesized. Three were dyes, and three were fluorescent whitening agents (FWAs) containing a tetramethylpiperidine (TMP) stabilizer fragment. The FWAs were obtained under phase‐transfer catalysis conditions. Five of the compounds were copolymerized with methyl methacrylate, so copolymers with an intense color and/or fluorescence stable against solvents were obtained. The chemical bonding of the synthesized monomers in the polymers was confirmed spectrophotometrically. The participation of the monomer compounds did not significantly affect the process of copolymerization or the molecular masses of the obtained copolymers. The quantity of chemically bonded naphthalimide monomer in the copolymers was determined to be over 60%. The spectral properties of the compounds and their photostability in solution and in the copolymers were studied. The influence of the compounds on the photostability of the copolymers was determined. The compounds, especially those containing a stabilizer (TMP) fragment in their molecules, showed a positive stabilizing effect on the photodegradation of poly(methyl methacrylate). Polyamide fabrics with 2‐allyl‐6‐hydrazino‐benzo[de]isoquinoline‐1,3‐dione, 2‐allyl‐6‐(2‐amino‐ethylamino)‐benzo[de]isoquinoline‐1,3‐dione, and 2‐chloro‐N′‐(2‐methyl)‐1,3‐dioxo‐2,3‐dihydro‐1H‐benzo[de] isoquinoline‐6‐yl) acetohydrazide were dyed, and materials with an intense yellow color and fluorescence were obtained. Cotton fabrics were whitened with 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐methoxy‐benzo[de]isoquinoline‐1,3‐dione, 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐allyloxybenzo[de]isoquinoline‐1, 3‐dione, and 2‐[2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐1,3‐dioxo‐2,3‐dihidro‐1H benzo [de]isoquinoline‐6‐oxy]ethyl‐2‐methacrylate, and materials with bright whiteness and intense bluish fluorescence were obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic mechanical and rheological properties of metallocene-catalyzed long-chain-branched ethylene/propylene copolymers

The dynamic mechanical and rheological properties of five long-chain branched (LCB) and three linear ethylene/propylene (EP) copolymers were investigated and compared using a dynamic mechanical analyzer (DMA) and an oscillatory rheometer. The novel series of LCB EP copolymers were synthesized with a constrained geometry catalyst (CGC), [C₅Me₄(SiMe₂N^tBu)]TiMe₂, and had various propylene molar fractions of 0.01-0.11 and long-chain branch frequencies (LCBF) of 0.05-0.22. The linear EP copolymers were synthesized with an ansa-zirconocene catalyst, rac-Et(Ind)₂ZrCl₂ (EBI), and contained similar levels of propylene incorporation as the CGC copolymers, but no LCB. In dynamic mechanical analysis, the dynamic storage moduli (G′) and loss moduli (G″) of the copolymers decreased with an increase of propylene molar fraction. The α- and β-transitions of the CGC copolymers were overlaid with each other. High damping (tan δ) values were found with the CGC copolymers at temperatures below 0 °C. In oscillatory rheological analysis, compared to the linear EBI counterparts, the LCB CGC copolymer melts showed higher zero shear activation energies, broader plateaus of δ and larger elastic contributions, which are essential characteristics of LCB polymers. It was found that the long chain branching was the determining factor in controlling rheological properties of the polymer melts while the short chain branching from propylene incorporation played a decisive role in affecting dynamic mechanical properties. This work represents the first rheological evidence of LCB in EP copolymers synthesized with CGC.     

Synthesis and properties of ethylene/styrene copolymers produced by metallocene catalysts

Ethylene/styrene copolymers were synthesized under constant polymerization conditions using six different metallocene catalysts activated with methylaluminoxane. For all the catalysts used, the activity and molecular weight of the copolymers produced decreased with the amount of styrene in the reactor feed, but the styrene content of the copolymers increased. Catalysts with carbon bridges and bulky ligands gave rise to copolymers with higher styrene content. As a result of the increased styrene content of the copolymer, the melting temperature decreased. This effect was ascribed to a decrease in the crystallinity of the copolymers. It was also found that lamellar thickness could be significantly diminished by the incorporation of comonomers. The copolymers showed a broad spectrum of mechanical properties as a function of the comonomer ratio. At low styrene contents, they behaved like typical semicrystalline thermoplastics, and at higher styrene contents, they exhibited the properties typical of elastomers. Of the catalysts tested, [rac‐ethylenebis(4,5,6,7‐tetrahydro‐1‐indenyl)]zirconium dichloride emerged as the most promising for the production of ethylene/styrene copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3420–3429, 2006     

Correlation between microstructure and physical properties in styrene–ethylene copolymers

The structural organization and the physical properties of a new copolymer styrene–ethylene have been analyzed. The composition was 80% of ethylene units, corresponding to 52% in weight, with a distribution of styrene units in the chain implying the absence of styrene–styrene sequences. The length of the polyethylene chains, limited by the insertion of the phenyl group, is not sufficient to allow good crystallization, and in fact the copolymer shows a very low crystailinity, of the order of 5–10%, and a broad melting range, with a peak centered at 120°C. The small crystalline domains are segregated into an amorphous matrix, producing a thermoplastic elastomer. The mechanical properties at large deformation were analyzed at different temperatures. The copolymer shows good elastic properties, in terms of deformation reversibility as well as of energy dissipation in the hysteresis cycles. Also the stress level and the elastic recovery are very good, if compared with others thermoplastic elastomers. © 1995 John Wiley & Sons, Inc.     

Characterization of ethylene homo- and copolymers

Summary For (norbornene ethylene) copolymers with a preferably alternating structure two methods for the determination of chemical composition were tested: the differential refractometry (DR) and the differential scanning calorimetry (DSC). It was found, that the refractive index increments measured by DR in 1,2,4-trichlorobenzene can be calculated by adding the refractive index increments of the homopolymers with regard to the composition of the copolymers. This was proved by comparing with results obtained by 1H-NMR-measurements. The temperatures of the glass transition determined by DSC yield a straight line correlation to the chemical composition. Errors of both methods due to the influence of molecular masses are negligible and of significance only in the range of low molecular masses.Part V: Polymer Bull. 15, 551 (1986)     

Characterization of ethylene homo- and copolymers

Summary For the estimation of molecular mass distribution and average molecular masses of (norbornene ethylene) copolymers a size exclusion chromatography method is described. The validity of the universal calibration function of Benoit et al. based on polystyrene molecular mass standards was confirmed by comparing with the number average molecular masses obtained by osmometry. The constants of the Mark-Houwink equation are a = 0.535, K = 1.00·10^–1 (Xylene, 90 °C) and a=0.589, K=4.93·10^–2 (diethylbenzene, 120°C,[] in cm³g^–1).Part IV: Plaste u. Kautschuk 32, 12, 444 (1985)     

Optical and electroluminescent properties of polyfluorene copolymers and their blends

Light emitting properties of several polyfluorene (PF) copolymers (P1-P4) and their blends have been investigated. Light emitting diodes were fabricated with the configuration of ITO/PEDOT:PSS/polymer/Ca/Al. The EL peak wavelengths were 421 nm (violet), 505, 513 nm (green) and 570 nm (yellow) for PF copolymers and 510, 535 nm (green) for P1/P2 and P1/P3 blends, respectively. Förster energy transfer in the photoluminescence and electroluminescence of the polymer blends P1/P2 and P1/P3 was studied. The LED using the polymer blend P1/P2 showed a turn-on voltage of 2.5 V and a brightness of 5×10⁴ cd/m² at 7 V. The highest external quantum efficiency was observed to be 3.71% at 5 V. Upon addition of 20 wt% of the green emitter P2 to the violet emitter P1, the device efficiency increased from 1.18 to 3.71%.     

Dynamic mechanical analysis of polyethylene and ethylene vinylacetate copolymer blends irradiated by electron beam

Dynamic mechanical properties of nonirradiated and irradiated blends of polyethylene (PE) and ethylene vinylacetate (EVA) copolymer have been determined. Effect of addition of EVA and radiational crosslinking on loss and storage modulus, tan δ, and transition temperatures were determined. Increase in transition temperatures on exposure to radiation and decrease in transition temperatures with addition of EVA is observed. Peak broadening is observed on exposure to radiation. Values of the storage modulus increase while that of loss modulus and tan δ decrease on crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2429–2434, 2002     

Morphology and properties of nanocomposites formed from ethylene/methacrylic acid copolymers and organoclays

Nanocomposites were prepared by melt mixing ethylene/methacrylic acid copolymers and organoclays, which were compared to equivalent composites prepared from low-density polyethylene (LDPE) and a sodium ionomer of poly(ethylene-co-methacrylic acid). The effects of matrix modification and organoclay structure on the morphology and properties of these nanocomposites were evaluated using stress-strain analysis, wide-angle X-ray scattering (WAXS), and transmission electron microscopy coupled with particle analysis. With all four polymers, the use of a two-tailed organoclay, M₂(HT)₂, led to the formation of more exfoliated nanocomposites than a one-tailed organoclay, M₃(HT)₁. Nanocomposites prepared from ethylene/methacrylic acid copolymers revealed better exfoliation compared to similar composites prepared from LDPE. It seems that the presence of relatively small quantities (1.3-3.1 mol%) of the polar methacrylic acid monomer aids in improving the organoclay exfoliation efficiency of these polymers. Nanocomposites prepared from the sodium ionomer of poly(ethylene-co-methacrylic acid) exhibited the highest levels of organoclay exfoliation compared to all other polymers examined in this study. However, from the observations made in this study, it was not possible to determine conclusively the relative interaction of carboxyl acid groups versus the salt form with the organoclay and, thus, their influence on exfoliation; additional studies will be needed to reach a conclusion on this important point.