Preparation and characterization of inherently heat‐sealable polyimides with high glass transition temperatures

A series of inherently heat‐sealable copolyimides (CPIs) with high glass transition temperatures were synthesized from 2,3,3′,4′‐oxydiphthalic anhydride (aODPA) and bicomponent diamines, 4,4′‐oxydianiline (ODA) and para‐phenylenediamine (PDA). The PI chain rigidity was manipulated by the regulation of the diamine ratio, and its effects on the heat sealability and thermal resistance of the derived CPI films were investigated in detail. The results show that these films are in possession of both good heat sealability and thermal resistance due to the synergetic effect of the asymmetry of aODPA and the rigidity of PDA. It is also found that there exists one critical PDA content that distinguishes the heat‐sealing behaviors of the CPI films, and the relevant mechanism was established. Especially for CPI‐5, the heat‐sealing strength is up to 350 N m^?1 simultaneously with a relatively high T_g of 310°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43058.     

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     

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     

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.     

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.     

Preparation and characterization of high molecular weight novolak resins

Summary High molecular weight novolak resins were prepared from phenol and paraformaldehyde in organic solvents, e.g., 2-propanol, ethyl propionate, 2-methoxyethanol, 4-methyl-2-pentanone, dioxane and acetic acid. The molecular weights were estimated by gel permeation chromatography (GPC) and solution viscosity measurement and it was confirmed that high molecular weight resins were formed in organic solvents. The structure was determined by¹³C-NMR measurements, and it was found that the resin obtained in organic solvent was a random novolak with higher molecular weight than a conventional novolak.     

The effect of the molecular weight on the glass transition temperature in amorphous poly(ethylene terephthalate)

Summary The glass transition temperature of amorphous and fractionated poly(ethylene terephthalate) has been measured by differential scanning calorimetry. The application of the Fox-Flory equation for the range of molecular weights between 37100 and 4500 gives the values of Tg=342.4 K and Kg=51200. The low value of Kg is interpreted by the free volume theory. The flex energy of the chain is evaluated by the Gibbs-Di Marzio theory with a value of 1483 cal/mol. These results are compared with those obtained by other authors for the poly(ethylene adipate) and the poly(diethylene terephthalate).     

Synthesis and characterization of pendent hydroxy fluoroesters of secondary high molecular weight guayule rubber

The epoxidation of secondary high molecular weight guayule rubber (SHMWGR) and subsequent ring opening with fluoroacids to give hydroxyfluoroesters (FGR) is reported. Structural characterization was performed with FTIR; ¹H-, ¹³C-, and ¹⁹F-NMR; and DSC. The percent epoxidation was quantitatively determined by ¹H-NMR. It was noted that the glass transition temperatures (T_g) of the FGR polymers increased with increasing fluoro acid content; however, reactions with longer chain, highly fluorinated acids lowered the T_g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1077–1089, 1997     

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.     

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.     

Preparation and characterization of ultra‐low molecular weight poly(vinyl alcohol) graft copolymer

Graft reaction of acrylamide (AM) and 4‐vinyl pyridine (4‐VP) onto ultra‐low molecular weight poly(vinyl alcohol) by ceric (IV) ion initiation had been systematically investigated; and the graft conditions were optimized by studying the effect of monomer/initiator concentration, solvents composition, reaction time and temperature. At optimized conditions, the maximum grafting efficiency and grafting ratio was ～ 50% and 51%, respectively with the presence of AM, whereas they decreased to 19% and 23%, respectively, without the presence of AM. Thermogravimetric analysis showed that as‐resulted graft copolymer had a lower thermal stability than homopolymer PVA. FTIR and ¹H‐NMR confirmed chemical structure of as‐synthesized graft copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Ionic conductivities and glass transition temperatures in poly(vinyl methyl ether)-salt mixtures

Summary The solubility of a number of salts in poly(vinyl methyl ether) (PVME) was tested, and several gave homogeneous solutions over a range of concentrations. When dissolution of the salts occurred, the glass transition temperature of the mixture tended to rise, reflecting the solvation of the cations by the ether oxygens which also leads to crosslinking. Ionic conductivities (/Scm^–1) were measured for some of the mixtures but the level at room temperature was low. A rise in with increase in temperature was observed reaching 10^–4 Scn^–1 at 430K for PVME/LiClO₄ mixtures at a [Li⁺]/[O] ratio of 0.25.     

Effect of structure on the glass transition temperatures of linear and crosslinked poly(isobornylacrylate-co-isobutylacrylate)

A series of linear acrylic copolymers based on Isobornyl acrylate (IBOA) and isobutyl acrylate (IsoBA) were elaborated by radical photopolymerization. In addition, several photochemically crosslinked poly(IBOA-co-IsoBA) were prepared by introducing small amounts of 1,6-hexanedioldiacrylate as crosslinking agent. The evolution of the glass transition temperature was determined experimentally by differential scanning calorimetry as a function of composition for both linear and crosslinked poly(IBOA-co-IsoBA), yielding T_g values ranging from (~249) to (~315 K). Theoretical modeling was performed applying Fox, Gordon-Taylor and Couchman-Karasz models by simple calculations using experimental data, leading to only fair agreement between theoretical and experimental values, or by applying fitting procedures involving one or two adjustable parameters. Likewise, the Kwei model, known to take into account hydrogen bonding interactions between monomers, could not describe well the evolution of T_g, indicating the existence of other factors influencing T_g. Finally, a thermodynamic approach based on entropy considerations allowed to attribute an explanation of the evolution of T_g.     

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.     

Glass transition temperature — molecular weight relation of a poly(amide-imide)

Summary Several fractions of a poly(amide-imide), prepared from 3,4-dicarboxy-4-chloroformyl biphenyl anhydride and 4,4-methylene dianiline, were studied in order to determine the Tg and K values of Fox-Flory relationship.     

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。     

窄分子量分布端羟基环氧乙烷-四氢呋喃共聚醚的合成及表征

用三氟化硼乙醚络合物(BF3.OEt2)为催化剂,乙二醇(EG)为起始剂,甲苯作溶剂,通过阳离子开环聚合制备出了窄分子量分布(w/n<1.3)的端羟基环氧乙烷-四氢呋喃(TEO)共聚醚,探讨了聚合温度、时间、反应介质、加料方式、起始剂及单体配比对分子量及其分布的影响,采用凝胶渗透色谱-多角度激光散射联用仪(SEC-MALLS)对其分子量及分布进行准确的测定,并用IR和1HNMR对共聚醚结构进行了表征。研究表明:有EG存在时,采用一次加料的方式,以甲苯为溶剂,温度为0℃,单体配比为11,∶反应时间为5 h的条件下制得的共聚醚具有分子量分布较窄的特点。