Synthesis,Thermal Properties,and Radiolysis of Poly(Cyclohexyl α-Chloroacrylate)

Cyclohexyl α-chloroacrylate (CCA) was polymerized by radical anionic and γ-radiation initiation. The anionic polymerization of cyclohexyl α-chloroacrylate gave moderately isotactic polymer in toluene and syndiotactic-rich polymer in THF. Poly(cyclohexyl α-chloroacrylate) (PCCA) was found to undergo two-stage weight loss in thermogravimetric analysis, and the first-stage weight loss was attributed to the lactonization reaction. PCCA degraded under γ-radiation, and the radiation yields of crosslinking and scission, G _x and G _s, were 0.6 and 3.8, respectively.     

Polymerization of α-Methylstyrene with Potassium as Initiator. VII. Thermal Decomposition of the Reaction Products

The polymerization of α-methylstyrene, initiated with high concentrations of potassium in tetrahydrofuran and in p-dioxane or with a butyllithium-tetramethylethylenediamine complex in bulk, was carried out at temperatures above 25°C. The resulting products comprising varying proportions of both low (D + A of [Mbar]w = 2.0 to 4.0 × 10³) and high (B + C of [Mbar]W > 20.0 × 10³) molecular weight components were subjected to 50 min isothermal treatments at different temperatures. The poly-α-methylstyrene samples, prepared under the above mentioned solvent-conditions, which had similar proportions of components D + A and B + C, as characterized by gel permeation chromatography and nuclear magnetic resonance showed that their thermal stability decreased with the following order of solvent-conditions: Bulk > p-dioxane > THF. A comparison of the decomposition results obtained with polymers made up of components D + A and B + C and those made up exclusively of component B + C showed that the percent weight-loss and the decrease in molecular weight associated with the latter component B + C is more pronounced when the low molecular weight component D + A is present.     

Copolymerization of α-Methylstyrene and Styrene

In this paper, the effects of temperature from 60 °C to 80 °C and the molar ratios in monomer feed on the copolymerization of α-methylstyrene(AMS) and styrene(St) were studied. The resulting copolymers, designated as PAS, were characterized by FTIR, GPC, NMR and TGA. When the reaction temperature was below 75 °C, the molecular weights increased almost linearly as the evolution of the copolymerization. The phenomenon revealed that AMS could mediate the conventional free radical polymerization having some features of a controlled system. As the AMS/St = 50/50(molar) in feed, the overall fraction of the AMS unit incorporated into the copolymer was as high as 42 mol%, the monomer conversion could be more than 90 wt% and the molecular weights could reach as high as 4400. However, since the styrene is more reactive than AMS, the AMS fraction in copolymer increased with the overall monomer conversion. The 13C-NMR revealed the products were random copolymers which had triads, such as-AMS-AMS-AMS-,-St-AMS-AMS-(-AMS-AMS-St-) and-St-AMS-St-. TGA curves demonstrated that the degradation temperature of the resulting copolymers went down from about 356.9 °C(0 mol% AMS) to 250.2 °C(42 mol% AMS). This behavior demonstrated that there exist weak bonds in the AMScontaining sequences which could be used as potential free radical generators.     

Thermal Degradation of Poly(ε-caprolactone), Poly(L-lactic acid) and their Blends with Poly(3-hydroxy-butyrate) Studied by TGA/FT-IR Spectroscopy

Summary: The thermal degradation behavior of poly(ε-caprolactone) (PCL) and poly(L-lactic acid) (PLA) have been studied in different environment. It was found that these polymers undergo completely different degradation processes in nitrogen and oxygen atmosphere. In oxygen environment PCL and PLA mainly decompose to CO₂, CO, water and short-chain acids. In nitrogen atmosphere PCL releases 5-hexenioc acid, CO₂, CO and ε-caprolactone, whereas PLA decomposes to acetaldehyde, CO₂, CO and lactide. The polymer blends of poly(3-hydroxybutyrate) (PHB) with PCL and PLA decompose similar to the individual homopolymers with crotonic acid as the initial decomposition product of PHB.     

Structural Characterization of Poly(α-Fluoroacrylonitrile) and Poly(Ethyl α-Fluoroacrylate)

Abstract

Monomers α-fluoroacrylonitrile (FAN) and ethyl α-fluoroacrylate (EFA) and homopolymers poly(α-fluoroacrylonitrile) (PFAN) and poly-(ethyl α-fluoroacrylate) (PEFA) have been synthesized and spectroscopi-cally characterized in detail for the first time. The ¹³C- and ¹⁹F-NMR spectroscopic results are reported, and the results are correlated to the tacticity and microstructure of both homopolymers. The major portion of the polymers is atactic. TGA analysis of PFAN indicates that the polymer is stable to about 200°C with subsequent loss of HF. PEFA is stable to 300 °C. Molecular weights determined by intrinsic viscosity (M_v ) are found to be about 130,000 for PFAN, and GPC analysis of PEFA indicates a molecular weight (M_n ) of about 36,000. Dielectric permittivities (ε) for PFAN and PEFA were determined to be 8.9 and 4.0, respectively, at 50 Hz.     

Polylactones. 13. Transesterification of Poly(L-Lactide) with Poly(Glycoude), Poly(β-Propio-Lactone), and Poly[ε -Caprolactone)

Homogeneous blends of poly(L-lactide) (M _n = 30 000 to 40 000) and poly(β-propiolactone) or poly(ε-caprolactone) were prepared in solution. The solvent-free blends were subjected to transesterification catalyzed by means of methyl triflate, triflic acid, boron trifluoride, or tributyltin methoxide at 100 or 150°C. At 100°C, transesterification was barely detectable even after 96 h. When poly(β-propiolactone) was used as the reactant at 150°C, degradation was faster than transesterification regardless of the catalyst. The same negative result was obtained for heterogeneous blends of poly(L-lactide) and poly(glycolide). In the case of poly(ε-caprolactone), copolyesters with slightly blocky sequences were obtained with tributyltin methoxide as catalyst, whereas the acidic catalysts caused rapid degradation. The copolyesters were characterized by means of ¹H-NMR spectroscopy with regard to their molar composition, by means of ¹³C-NMR spectroscopy with regard to their sequences, and by means of differential scanning calorimetry with regard to crystallinity.     

Electrical,Mechanical, and Thermal Properties of Poly(4,4′-Cyclohexylidene Diphenylene-m-Benzene/Toluene-2,4-Disulfonate)

Abstract

The films of poly(4,4′-cyclohexylidene diphenylene-m-benzene disulfonate) (PSBB, 0.610 mm thick) and poly(4,4′-cyclohexylidene diphenylene-toluene-2,4-disulfonate) (PSBT, 0.537 mm thick) showed 8.23 ± 0.25 and 9.6 ± 0.245 kV, respectively, as the dielectric breakdown voltage (ac) in air at room temperature. The same films have 8.8 × 10¹¹ and 7.2 × 10¹⁴ ω°Cm volume resistivity. PSBB (40 μm thick) and PSBT (50 μm thick) films have tensile strengths of 1971 and 1677 kg/cm² and percent elongations of 1.3 and 1.2, respectively. The static hardnesses of PSBB (0.178 mm thick) and PSBT (0.190 mm thick) at three different loads (15–60 g) are 12.8–15.5 and 14.5–16.5 kg/mm², respectively. PSBB and PSBT are thermally stable up to about 355°C in an N₂ atmosphere and involve two-step degradation. DSC and DTA showed T _g at about 125–127 and 138–142°C, respectively, for PSBB and PSBT in N₂. PSBB and PSBT have comparable breakdown voltages and volume resistivity with some useful plastics whereas they have superior T _g and thermal stability with retention of excellent solubility in common solvents over polysulfonates without a cardo group. Thus, the cardo (cyclo-hexyl) group has enhanced thermal and mechanical properties with excellent solubility and easy processing.     

Theoretical Study of the Thermal Decomposition of Chlorofluoromethanol (CHClFOH)

Introduction Hydrochlorofluorocarbons (HCFCs) have been widely used as replacements of chlorofluorcarbons (CFCs). The insertion of O (1D) into the CH bond of HCFC forms the activated alcohol. It has been shown that these hot alcohols play an important role in the degradation mechanism of atmospheric compounds1.Chlorofluoromethanol (CHClFOH) appears in the reaction of O (1D) with CH2ClF (HCFC-31)2. Neither experimental nor theoretical study of this species was available to date. U…     

Free-Radical-Initiated Polymerization of N(p-Phenoxy-phenyl)maleimide and Copolymerization with Styrene, α-Methylstyrene and β–Methylstyrene

Abstract

Synthesis and free-radical-initiated homopolymerization of phenoxy-phenylmaleimide (PhOPhMI) and copolymerization with styrene (St), (α-methylstyrene (αMeSt) and β–methylstyrene (β-MeSt) are described. It was found that alternating copolymers are formed under different monomer-to-monomer ratios in the feed and that the mechanism based on the participation of CT-complex best explains the formation of alternating copolymers. Equilibrium constants of CT-complexes are: K _PhOPhMI/St = 0.20 Lmol^?1; K_{PhOPhMI/αMeSt} = 0.05 Lmol^?1; K_{PhOPhMI/βMeSt} = 0.02 Lmol^?1. Homopolymer and co-polymers are film-forming materials, stable up to 350°C under TGA conditions. T_g s and higher transition temperatures are within the thermally stable region.     

Anionic Polymerization of New Dual-Functionalized Styrene and α-Methylstyrene Derivatives Having Styrene or α-Methylstyrene Moieties

Anionic polymerizations of four new dual-functionalized styrene and α-methylstyrene derivatives, 3-(4-(4-isopropenylphenoxy)butyl)styrene ( 4 ), 3-(4-(2-isopropenylphenoxy)butyl)-α-methylstyrene ( 5 ), 4-(4-(4-isopropenylphenoxy)butyl)-α-methylstyrene ( 6 ), and 4-(4-(2-vinylphenoxy)butyl)styrene ( 7 ), were carried out in THF at -78 °C with sec-BuLi as an initiator. Both 4 and 5 underwent anionic polymerization in a living manner to quantitatively afford functionalized polystyrenes and poly(α-methylstyrene)s having α-methylstyrene moiety in each monomer unit and precisely controlled chain lengths. On the other hand, insoluble polymers were obtained by the anionic polymerization of 6 and 7 under the same conditions. The positional effect of substituent on anionic polymerization was discussed.     

Synthesis, Characterization and Thermal Decomposition Mechanism of Cetyltrimethyl Ammonium Tetrathiotungstate

The synthesis, characterization and thermal decomposition mechanism of cetyltrimethyl ammonium tetrathiotungstate （CTriMATT） were studied herein. The as-synthesized CTriMATT was characterized by Elemental analysis, X-ray diffraction （XRD）, Fourier transform infrared （FT-IR）, Ultraviolet visible （UV-Vis） spectra. The results showed that the as-synthesized CTriMATT had high purity and good crystallinity. The introduction of alkyl groups induced a shift of the stretching vibration band of W-S bond to lower wavenumber, while it had no influence on the position of WS4^2-. Thermogravimetric analysis （TG）, differential thermal analysis （DTA） and in situ XRD characterizations revealed that CTriMATT began to decompose at 423 K in nitrogen and was converted to WS2 eventually. In addition, the decomposition product of CTriMATT at 673 K in nitrogen was characterized by N2 adsorption （BET） and scanning electron microscopy （SEM）. The results demonstrated that WS2 with higher specific surface area, and pore volume could be obtained from the thermal decomposition of CTriMATT in nitrogen.     

Kinetics and Mechanism of Thermal Decomposition of Bis(η3-Allyl)Nickel Complexes

Kinetics and Catalysis - The kinetics of thermal decomposition of bis(η3-allyl) nickel complexes in various media is studied. The specific features of the mechanism are determined, including...     

Synthesis, Characterization, Thermal Decomposition Mechanism and Non-Isothermal Kinetics of the Pyruvic Acid-Salicylhydrazone and Its Complex of Praseodymium(III)

IntroductionHydrazonesactasherbicides,insecticides,nemato cides ,rodenticidesandplantgrowthregulators.Theyshowspasmolyticactivity ,hypotensiveactionandactivityagainstleukaemia,sarcomasandothermalignantneoplasm .1Rareearthelementshavestrongbiologicaleffectandmanycom plexesofrareearthshaveallkindofmedicinalactivities.2 Aseriesof 2 oxopropionyl(pyridine 4 fomyl)hydrazonewithrareearthscomplexeswassynthesizedbyYangandtheEucom plexshowedacertainanticanceractivity .3Therearethreeradicalsinthepyru…     

Thermal Analysis of Poly(AN—co—St) and Poly(AN—St—MMA)

Poly(AN—co—St) (PAS) and poly(AN—St—MMA)(PASM) were synthetized by emulsion polymerisation. The glass transition temperatures (T_g) of the copolymers and the relationship between T_g and the components of the copolymers were investigated by differential scanning calorimetry. The results show that T_g for the AN—St bipolymers has apeak value in the range 115–118°C at a content of 50 mass% St. When methyl methacrylate was added, the T_g of the terpolymer was decreased by about 2–6°C.The thermostability and the activation energy E of degradation were determined by thermogravimetric analysis.This revised version was published online in November 2005 with corrections to the Cover Date.     

Impact of Zn(Ⅱ) Ions on Crystallization and Thermal Properties of Poly(lactic acid)

The issues of low crystallinity and slow crystallization rate of poly(lactic acid) (PLA) have been widely addressed. In this work, we find that doping PLA with Zn(Ⅱ) ions can speed up the process of crystallization of PLA. Three kinds of Zn(Ⅱ) salts (ZnCl\begin{document}$ _2 $\end{document}, ZnSt and ZnOAc) were tested in comparison with some other ions such as Mg(Ⅱ) and Ca(Ⅱ). The increased crystallinity and crystallization rate of PLA doping with Zn(Ⅱ) are reflected in FT-IR and variable temperature Raman spectroscopy. The crystallinity is further confirmed or measured with differential scanning calorimetry and X-ray diffraction. The crystallinity rate of the PLA/ZnSt-0.4 wt% material can reach 22.46% and the crystallinity rate of the PLA/ZnOAc-0.4 wt% material can reach 24.83%, as measured with differential scanning calorimetry.     

Kinetics and Mechanism of Liquid-Phase Thermal Decomposition of β-Cyanoethyl-N-nitramines

Termal decomposition of -cyanoethyl-N-nitramine in melt is preceded by protonation of the amino nitrogen atom and is accompanied by evolution of nitrogen(I) oxide with formation of acrylonitrile. Thermal decomposition of bis(-cyanoethyl)-N-nitramine under similar conditions follows a radical mechanism with initial dissociation of the NÄN bond. The same mechanism is operative in thermal decomposition of both N-nitramines in a dilute dibutyl phthalate solution.     

Synthesis, Crystal Structure and Kinetic Mechanism of Thermal Decomposition of a Zinc(II) Complex with N-Salicylidene-p-toluidine

1 INTRODUCTION Over the past decades, considerable attention has been devoted to the synthesis, characterization and property studies of Schiff bases and their com- plexes because of their potential and developed appli- cations in the fields of conducting and magnetic ma- terials, dyes, non-linear optics, catalysis, analytical chemistry, biochemical research, agriculture and so on[1～7]. A large number of reports are available in the chemistry and biologic activities of transition metal co…     

Effects of Chain Ends on Thermal and Mechanical Properties and Recyclability of Poly(γ-butyrolactone)

This work investigates effects of poly(γ-butyrolactone) (PγBL) with different initiation and termination chain ends on five types of materials properties, including thermal stability, thermal transitions, thermal recyclability, hydrolytic degradation, and dynamic mechanical behavior. Four different chain-end-capped polymers with similar molecular weights, BnO-[C(=O)(CH₂)₃O]_n-R, R = C(=O)Me, C(=O)CH=CH₂, C(=O)Ph, and SiMe₂CMe₃, along with a series of uncapped polymers R′O-[C(=O)(CH₂)₃O]_n-H (R′ = Bn, Ph₂CHCH₂) with M_n ranging from low (4.95 kg mol⁻¹) to high (83.2 kg mol⁻¹), have been synthesized. The termination chain end R showed a large effect on polymer decomposition temperature and hydrolytic degradation, relative to H. Overall, for those properties sensitive to the chain ends, chain-end capping renders R-protected linear PγBL behaving much like cyclic PγBL. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2271–2279     

Dibenzylmagnesium-Initiated Anionic Oligomerizations of trans-Stilbene, 1,1-Diphenylethylene,and α-Methylstyrene in Hexamethylphosphortriamide

trans-Stilbene, 1, 1-diphenylethylene, and α-methylstyrene were allowed to react with dibenzylmagnesium to form their oligomers in hexamethylphosphortriamide (HMPA). One and two molecules of stilbene and 1, 1-diphenylethylene were incorporated into the magnesium carbon bond, and the carbanions obtained in HMPA were stable in analogy with the anionic living polymer having alkali cation as the gegenion in eithers. Intense coloration was observed during the reaction between α-methylstyrene and dibenzylmagnesium as well as in the case of stilbene and 1, 1-diphenylethylene. The low molecular weight products which were formed after a long time in the reaction between α-methylstyrene and dibenzylmagnesium were found to have no magnesium-carbon bond. It was considered that the cleavage of the propagating chain occurred gradually after the rapid propagation had proceeded to consume the monomer.     

Quasiliving Carbocationic Polymerization. VII. Block Polymerization of α-Methylstyrene from Quasiliving Poly(isobutyl Vinyl Ether) Dication

Poly(α-methylstyrene-b-isobutyl vinyl ether-b-α-methylstyrene) triblock polymers have been prepared by blocking α-methyl-styrene (αMeSt) from biheaded quasiliving poly(isobuty1 vinyl ether) (PIBVE) cations generated with the bifunctional p-dicumyl chloride/AgSbF₆ initiating system in methylene chloride solvent at -90°C. The products were fractionated with 2-propanol, a good solvent for PIBVE and a nonsolvent for PaMeSt. The 2-propanol-insoluble fractions had much higher molecular weights (M _n = 30,500–69,100) than the starting PIBVE (M _n =6,600–10,600) and contained 13–29 wt% IBVE together with 87–71 wt% αMeSt units. The 2-propanol-soluble fractions (M _n = 7,300–11,600) contained ～90 wt% IBVE and ～10 wt% αMeSt units.