Preparation and properties of high molecular weight poly(1-germa-) or poly(1-sila-cis-pent-3-enes)

High molecular weight poly(1,1-dimethyl-1-germa-cis-pent-3-ene), poly(1,1-diphenyl-1-germa-cis-pent-3-ene), poly(1,1-dimethyl-1-sila-cis-pent-3-ene), and poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) have been prepared. The thermal stability of these polymers is found to increase with their molecular weight.     

Synthesis and characterization of poly(1-sila-cis-pent-3-enes) substituted with pendant pyridinyl groups

Poly[1-methyl-1-[3′-(3″-pyridinyl)propyl]-1-sila-cis-pent-3-ene], poly[1-phenyl-1-[3′-(3″-pyridinyl)propyl)-1-sila-cis-pent-3-ene], and poly[1-phenyl-1-(4′-pyridinyl)-1-sila-cis-pent-3-ene] were synthesized by the anionic ring-opening polymerization of 1-methyl-1-[3′-(3″-pyridinyl)propyl]-1-silacyclopent-3-ene, 1-phenyl-1-[3′-(3″-pyridinyl)propyl]-1-silacyclopent-3-ene, and 1-phenyl-1-(4′-pyridinyl)-1-silacyclopent-3-ene, respectively. These are the first polycarbosilanes which contain heterocyclic pyridine units as side-chain substituents. These polymers were characterized by¹H,¹³C, and²⁹Si NMR as well as by IR and UV spectroscopy. The molecular weight distributions were determined by gel permeation chromatography, glass transition temperatures, by differential seanning calorimetry: (DSC) and thermal behavior, by thermogravimetric analysis. (TGA).     

Synthesis and microstructure of poly(1-phenyl-1-sila-cis-pent-3-ene)

Summary poly(1-Phenyl-1-sila-cis-pent-3-ene) (I) has been prepared by the anionic ring opening polymerization of 1-phenyl-1-sila-cyclopent-3-ene (II). This reaction is co-catalyzed by n-butyl-lithium and HMPA in THF at low temperature. I has been characterized by ¹H, ¹³C and ²⁹Si NMR, IR, UV, GPC and TGA. The low molecular weight of l permits end group analysis. Pyrolysis of l gives significant char yields.     

Stress-strain behavior and dynamic mechanical properties of poly(1,1-dimethyl-1-sila-cis-pent-3-ene), poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) and of these polymers after crosslinking with sulfur

Mechanical properties of polymers can be described by their stress/strain curves and by their behavior under dynamic mechanical thermal analysis (DMTA). The purpose of this paper is to report such mechanical properties for two unsaturated polycarbosilanes: poly(1, 1-dimethyl-1-sila-cis-pent-3-ene) (I) and poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) (II). Tensile strength, elongation at break, modulus, bending modulus, T_g, and tan δ for I, II and for sulfur crosslinked I and II have been measured. The influence of polymer molecular weight, quantity of crosslinking agent, cure time, presence of carbon black filler, the effect of crosshead speed, and frequency on these properties was investigated.     

Preparation of high molecular weight poly(vinyl pivalate) with high yield and high molecular weight poly(vinyl alcohol) by emulsion polymerization of vinyl pivalate and saponification

To prepare high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with high yield and high linearity which is a promising precursor for syndiotactic poly (vinyl alcohol) (PVA), vinyl pivalate (VPi) was emulsion polymerized, using 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH) as an initiator and sodium dodecyl sulfate (SDS) as an emulsifier. The effect of the polymerization conditions on the conversion, molecular weight, and degree of branching was investigated. PVA with maximum number‐average degree of polymerization (P_n) of 6200 could be prepared by complete saponification of PVPi, with P_n of 13,300–16,700 obtained at polymerization temperature of 50°C, using SDS and AAPH concentration of 2.0 × 10^?3 mol/L of water and 1.0 × 10^?3 mol/L of water, respectively, and the maximum conversion was about 90%. From the emulsion polymerization of VPi, spherical PVPi with high yield was effectively prepared, which might be useful for the precursor of syndiotactic PVA micro‐ and nano‐spheres with various surface properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 410–414, 2007     

Partial and complete hydrogenation of poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene)

Summary Poly(1-methyl-1-phenyl-1-silapentane)(II), andblock copoly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene/1-methyl-1-phenyl-1-silapentane) (block-III) have been prepared by catalytic hydrogenation of poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene)(I) over 5% palladium on carbon. These polymers have been characterized by¹H,¹³C and²⁹Si NMR as well as IR spectroscopy. Molecular weight distributions have been evaluated by gel permeation chromatography (GPC). Thermal stabilities have been measured by thermogravimetric analysis (TGA). Glass transition temperatures (T_g's) have been determined by differential scanning calorimetry (DSC).     

Preparation and characterization of high molecular weight poly(hydroxy ethers) with unusually high glass transition temperatures

A series of novel poly(hydroxy ethers) have been prepared via polymerization of the diglycidyl ethers of bisphenol-A ( 4 ), 4,4 ′-tribromotetramethylbiphenol ( 6a ), and 4,4 ′-tetrabromotetramethylbiphenol ( 6b ) with a variety of rigid diols in an effort to systematically modify structural features of the phenoxy repeat unit in order to control the torsional mobility of polymer backbones and produce materials with softening temperatures higher than are typical for the class. The resulting poly(hydroxy ethers) displyed glass transition temperatures ranging from 109 to 242°C. There of the polymers were characterized with respect to tensile and impact properties and were compared to the polymer sythesized from bisphenol-A ( 1 ) and bisphenol-A diglycidyl ether ( 4 ).     

Effect of molecular weight on crystallization isotherms of high molecular weight poly(ethylene oxide) fractions

Dilatometric crystallization isotherms have been determined for a set of poly(ethylene oxide) fractions ranging in molecular weight from 2 × 10⁴ to 1.6 × 10⁶. For a given fraction the isotherms obtained for different crystallization temperatures can be superimposed over most of the crystallization. For a given crystallization temperature the degree of crystallinity obtained in the primary stage of the crystallization varies greatly with molecular weight, and superimposition of the isotherms is not possible. Secondary crystallization processes are pronounced when the molecular weight ($\text{M}\text{?}{}_{\mathrm{v}}$) exceeds 10⁵.     

Birch reduction of the dichlorocarbene adduct of poly(1,1-dimethyl-1-sila-cis-pent-3-ene)(Cl2C-I): synthesis and characterization of poly(1,1-dimethyl-3,4-methylene-1-sila-cis-pent-3-ene) CH2-I)

Summary Birch reduction of the dichlorocarbene adduct of poly(1,1-dimethyl-1-sila-cis-pent-3-ene) (Cl₂C-I) yields poly(1,1-dimethyl-3,4-methylene-1-sila-cis-pent-3-ene) (CH₂-I) which has been characterized by ¹H, ¹³C and ²⁹Si NMR spectroscopy as well as by elemental analysis. The molecular weight distribution of CH₂-I has been determined by GPC and its thermal stability by TGA. Its glass transition temperature was obtained by DSC.     

Preparation and application of low molecular weight poly(vinyl chloride). IV. Preparation and characteristics of poly(vinyl chloride) with broad molecular weight distribution

Poly(vinyl chloride) (PVC) with a broad molecular weight distribution (BMD-PVC) was prepared by suspension polymerization in the presence of PVC with relatively lower molecular weight (LMW-PVC), which was prepared by suspension polymerization in the presence of 2-mercaptoethanol as a chain-transfer agent. It is elucidated using porosity measurement, scanning electron microscopy (SEM), and energy dispersion X-ray microscopy (EDXM) that the resultant BMD-PVC grains have an interesting internal structure at the level of primary particles. Discoloration time and fusion time of the BMD-PVC was studied. Discoloration time and fusion time of BMD-PVC is particularly dependent on the polymerization degree (Pw) of LMW-PVC and LMW-PVC content in the BMD-PVC samples. © 1994 John Wiley & Sons, Inc.     

高分子量聚醋酸乙烯酯的醇解研究

探讨了催化剂浓度、醇解温度和反应时间等对高分子量聚醋酸乙烯酯醇解的影响,得出高分子量聚醋酸乙烯酯醇解的适合条件。     

Synthesis of poly(1-methyl-1-phenyl-1-silapentane) by chemical reduction of poly)1-methyl-1-phenyl-1-sila-cis-pent-3-ene with diimide

Summary Poly(1-methyl-1-phenyl-1-silapentane) (I) has been prepared by the chemical reduction of the carbon-carbon double bonds of poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene (cis-II) with diimide, which was generatedin-situ by the thermal decomposition ofp-toluenesulfonhydrazide in refluxing toluene. At lower temperature (100°C),cis-II is isomerized byp-toluenesulfinic acid to lower molecular weight poly(1-methyl-1-phenyl-1-sila-cis andtrans-pent-3-ene) (cis/trans-II). Protodesilation of I with trifluoromethanesulfonic acid yields poly(1-methyl-1-trifluoromethanesulfonyl-1-silapentane) (III). The structures of I andcis/trans-II have been characterized by¹H,¹³C and²⁹Si NMR, GPC, TGA and elemental analysis. The structure of I has been characterized spectroscopically by¹H,¹³C,¹⁹F and²⁹Si NMR.     

Effect of molecular weight on spherulite growth rates of high molecular weight poly(ethylene oxide) fractions

Spherulite growth rates have been determined for a set of poly(ethylene oxide) fractions ranging in molecular weight from 10⁴ to 10⁶. At a given crystallization temperature the spherulite growth rate as a function of molecular weight passes through a maximum. At a given undercooling (as assessed by the method of Mandelkern) the spherulite growth rate is a monotonically decreasing function of molecular weight, and in the range $\text{6000 <}\text{M}\text{?}{}_{\mathrm{v}}\text{< 50 000}$ varies roughly as $\text{(}\text{M}\text{?}{}_{\mathrm{v}}\text{)}{}^{\mathrm{?3}}$. The free energy of formation of the end interface (as assessed by nucleation theory) also decreases as molecular weight increases.     

Dielectric properties of low molecular weight poly(ethylene glycol)s

This paper reports the measured values of dielectric permittivity ε′ and dielectric loss ε″ of ethylene glycol, diethylene glycol and poly(ethylene glycol)s of average molecular weight 200, 300, 400 and 600 g mol⁻¹ in the pure liquid state. The measurements have been carried out in the frequency range 200 MHz to 20 GHz at four different temperatures of 25, 35, 45 and 55 °C. The complex plane plots (ε″ versus ε′) of these molecules are Cole–Cole arcs. The static dielectric constant ε₀, high‐frequency limiting dielectric constant ε_∞, average relaxation time τ₀ and distribution parameter α have been determined from these plots. The value of the Kirkwood correlation factor g and the dielectric rate free energy of activation ΔF have also been evaluated. The dependence of relaxation time on molecular size and viscosity has been discussed. A comparison has also been made with the dielectric behaviour of these molecules in dilute solutions of non‐polar solvents, which were carried out earlier in this laboratory. The influences of intermolecular hydrogen bonding and molecular chain coiling on the dielectric relaxation of these molecules have been recognized. © 2000 Society of Chemical Industry     

Chemical synthesis and characterization of high molecular weight poly(2,2'-dithiodianiline) (PDTDA)

Summary A high molecular weight poly(2,2'-dithiodianiline) (PDTDA) was chemically synthesized by simple solution polymerization method. The weight average molecular weight was observed to be 424,690 by GPC analysis. The chemical structure of the undoped PDTDA was characterized by UV/VIS spectroscopy. It was confirmed that the S-S bonds within repeating units could be conserved well after chemical polymerization by FTIR spectroscopic analysis. Received: 7 May 2002 / Accepted: 23 May 2002     

Preparation and properties of UV-curable poly(dimethylsiloxane) urethane acrylate. II. Property-structure/molecular weight relationships

A series of UV-curable polyurethane acrylate resins based on hydroxy-terminated polydimethylsiloxane (PDMS) soft segments with different molecular weights and various diisocyanate hard segments were synthesized. The products were obtained by employing direct-addition polymerization techniques in a nonsolvent system. The structures of the final products were elucidated by IR and ¹H-NMR. The fundamental and physical properties of this type of UV-curable material, the effects on properties by varying the molecular weight of PDMS or the type of diisocyanates, and the effect of using various reactive diluents were widely studied. This resin possessed good optical, electrical insulating, and adhesive properties. The mechanical strength of UV-cured films corresponds approximately to the ratio of hard segments within these material and the dielectric insulating properties correspond to the chain length of PDMS.     

Synthesis and characterization of high molecular weight poly(tert.butyl acrylate)

High molecular weight poly(tert. butyl acrylate) s have been synthesized anionically using a technique derived from that of Teyssié et al. It was established that under proper conditions the sites remained living, allowing proper control of the molecular weight and yielding samples with narrow molecular weight distributions.     

In vitro hydrolytic degradation of poly(para-dioxanone) with high molecular weight

The in vitro hydrolytic degradation of high molecular weight poly (para-dioxanone) was studied by examining the changes of weight retention, water absorption, pH value, tensile strength, break elongation, thermal properties, and morphology of high molecular weight PPDO in phosphate buffered saline (PBS) (pH 7.44) at 37°C for 8 weeks. During the degradation, all samples’ weight retention decreased and water absorption increased significantly, whereas hydrolysis rate of PPDO bars varied with molecular weight. Compared with lower molecular weight samples, higher molecular weight PPDO samples exhibited higher hydrolysis rate. The samples’ glass transition temperature (Tg) decreased notably, while the degrees of crystallinity (Dc) increased. The samples almost totally lost their tensile strengths and breaking elongation after 4 weeks of degradation. The results suggested that the stability of PPDO in vitro hydrolytic degradation increased with the increase of molecular weight.     

Influence of molecular weight on some properties of poly(vinyl chloride)

Several fractions obtained from a large-scale fractionation and several unfractionated PVC polymers and blends have been processed both as rigid and plasticized compounds. The latter have been studied by stress–strain, creep, and recovery tests. The recoverable character of the creep results show that a relatively stable network must be present in the samples. The crosslink density is little influenced by molecular weight, as shown by the modulus and compliance results. On the contrary, the ultimate tensile properties depend strongly on molecular weight, which is interpreted as evidence that the stability of the crosslinks increases with increasing chain length of the polymers.     

Effect of molecular weight and molecular weight distribution on the rheological properties of aqueous poly(ethylene oxide) solution

The effect of the molecular weight and the molecular weight distribution on the rheological properties of aqueous poly(ethylene oxide) (PEO) solutions has been investigated with four PEO samples differing in their M_w, M_w/M_n and purity. The main result of this study is that the steady shear viscosity as well as the complex dynamic viscosity of the samples with broad molecular weight distribution greatly differed from the viscosities of the samples having a narrow molecular weight distribution. Furthermore, the samples with broad molecular weight distribution showed a distinct molecular weight dependent non-Newtonian behavior at increasing shear rates and frequencies. This behavior was not observed for the sample with a narrow molecular weight distribution. Both effects are mainly attributed to the influence of the high molecular weight fraction in the PEO samples of broad molecular weight distribution. The often reported degradation of PEO solutions was not observed within the time scale of our experiment.