Thermotropic liquid crystalline copolyesters. II. Synthesis and thermal characterization of copolyesters of terephthalic acid,methyl hydroquinone and 1,4-butane diol

The synthesis and thermodynamic evaluations of a series of random copolyesters based on terephthalic acid, methyl hydroquinone and 1,4-butane diol are presented. The copolyester composition was varied by altering the relative concentrations of methyl hydroquinone and 1,4-butane diol. The copolyesters display thermotropic transitions. The enthalpy changes during mesophasic transition display a minimum corresponding to equimolar composition. The copolyester with 75 mol% of spacer diol exhibited the lowest nematic transition temperature (190-6°C). At this composition the nematic mesophase was most stable (δT_N = 115-6°C). ΔH_N-1 and ΔS_N-1 decrease with increasing rigid diol content. The isotropization temperatures were almost comparable since the largest mesogenic residues are similar in aspect ratio. These residues are required to melt prior to isotropization.     

New thermoplastic segmented polyurethanes with hard segments derived from 4,4′‐diphenylmethane diisocyanate and methylenebis(1,4‐phenylenemethylenethio)dialcanols

New thermoplastic poly(ether–urethane)s and poly(carbonate–urethane)s were synthesized by a one‐step melt polymerization from poly(oxytetramethylene) diol (PTMO) and poly(hexane‐1,6‐diyl carbonate) diol (PHCD) as soft segments, 4,4′‐diphenylmethane diisocyanate, and 2,2′‐[methylenebis(1,4‐phenylenemethylenethio)]diethanol, 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol or 6,6′‐[methylenebis(1,4‐phenylenemethylenethio)]dihexan‐1‐ol as unconventional chain extenders. The effects of the kind and amount of the polymer diol and chain extender used on the structure and properties of the polymers were studied. The polymers were examined by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction analysis, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), TGA coupled with FTIR spectroscopy, and Shore hardness and tensile testing. The obtained high‐molecular‐weight polymers showed elastomeric or plastic properties. Generally, the PTMO‐based polymers exhibited significantly lower glass‐transition temperatures (up to ?48.1 vs ?1.4°C), a higher degree of microphase separation, and ordering in hard‐segment domains in comparison with the corresponding PHCD‐based ones. Moreover, it was observed that the polymers with the PTMO soft segments showed poorer tensile strengths (up to 36.5 vs 59.6 MPa) but higher elongations at break. All of the polymers exhibited a relatively good thermal stability. Their temperatures of 1% mass loss were in the range 270–320°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Application of thermogravimetric analysis to the thermal decomposition of polybutadiene

Thermogravimetric analysis (TGA) has been used extensively to determine the thermal stability of polymers. The present study indicates that the isothermal decomposition of polybutadienes (PBDs) is significantly different from that in the heat mode. The isothermal decomposition of PBDs is an exothermic reaction occurring at 350°–375°C. This decomposition is shown to be rapid and temperature specific. It appears to be related to the cyclization reaction reported previously by several investigators. Decomposition of PBDs in the heat mode (10°C/min) occurs at 447°–461°C. This is about 100°C higher than that observed in the isothermal mode. Further TGA experiments indicate that a period of slow heating stabilizes PBD and can eliminate the exothermic decomposition at about 360°C. This stabilization appears to be related to the ease with which both 1,2- and 1,4-PBDs thermally crosslink. Heating 1,4-PBD for 6 min at 270°C gives rise to 92% gel. 1,2-PBD is shown to crosslink more extensively. It is shown that polymers which do not thermally crosslink or cyclize, such as polystyrene, decompose similarly in the two modes of heating.     

Depolymerization of waste polybutylene terephthalate in hot compressed water in a fused silica capillary reactor and an autoclave reactor: Monomer phase behavior,stability, and mechanism

Depolymerization is a potentially viable means of recycling waste polymers, converting them back into monomers or other useful compounds. Terephthalic acid (TPA) and 1,4‐butanediol (1,4‐BD) are the depolymerization monomer products of polybutylene terephthalate. Their yields from depolymerization in hot compressed water (HCW) were previously found to be lower than reported theoretical values. Thus, the phase behavior, stability, and mechanism of monomers in HCW were investigated in a fused silica capillary reactor (FSCR) and a stainless steel autoclave reactor. Phase change observations showed that TPA was completely dissolved in water at 300°C, was relatively stable at 320 to 350°C, and that its recovery significantly decreased at temperatures above 350°C. The decomposition of TPA increased with increasing heating time. However, the recovery of 1,4‐BD decreased rapidly with increasing temperature or heating time. A mechanism for the stability of TPA and 1,4‐BD is proposed based on their depolymerization products. The products were quantified by Fourier transform‐infrared spectroscopy, high‐performance liquid chromatography, and gas chromatography coupled with mass spectrometry. The wall effect of the stainless steel autoclave promoted the decomposition of TPA and 1,4‐BD in HCW. POLYM. ENG. SCI., 57:544–549, 2017. © 2016 Society of Plastics Engineers     

Thermo-optical and differential scanning calorimetric observations of mobility transitions in polystyrene-poly(2,6-dimethyl-1,4-phenylene oxide) blends

Transition temperatures by thermo-optical analysis (TOA) and by DSC were measured on films of polystyrene (PS), poly(2,6-dimethyl-1,4-phenylene oxide) (PPO resin) and nine homogeneous blends of these polymers. The TOA procedure consists of automatically monitoring light transmission through birefringent scratches in a film during heating at constant rate in a microscope hot stage between crossed (90°) plane polarizers. The T_TOA transition temperature, defined as the temperature of birefringence disappearance in the scratches, increased monotonically from 113°C for pure PS to 222°C for pure PPO resin at a 10°/min heating rate. The T_g (DSC) similarly ranged from 99°C to 212°C at a 20°/min heating rate. The TOA technique as described should be a useful addition to thermomechanical studies of transparent polymers and polymer blends.     

Synthesis and characterization of new aromatic polyesters and poly(ester-imide)s containing phosphorous cyclic bulky groups

New phosphorous-containing polyesters were prepared by polycondensation of 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-1,4-naphthalene diol, 1, with different aromatic dicarboxylic acids using a SOCl₂/pyridine condensing agent. Two poly(ester-imide)s were prepared by polycondensation in solution at high temperature of the same aromatic bisphenol 1, with diacid chlorides containing preformed imide rings. The most of the polymers were easily soluble in polar organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide and chloroform. They showed high thermal stability, the decomposition temperature being in the range of 330-442 °C and glass transition in the temperature range of 193-226 °C. One of these polymers exhibited thermotropic liquid crystalline behavior. Due to the presence of phosphorus the polymers gave high char yield in termogravimetric analysis, hence good flame retardant properties.     

Syntheses and properties of cross‐linked polymers from functionalized triglycerides

A number of functionalized triglycerides were synthesized from glyceryl trioleoate via epoxidation followed by reduction to give glyceryl tris(9‐hydroxy)trioleoate (a triol) or hydrolytic ring opening to obtain glyceryl tris(9,10‐dihydroxy)trioleoate (a hexaol). A selective monoepoxidation reaction of glyceryl trioleoate was also carried out and the resulting monoepoxide was hydrolyzed to give glyceryl 9,10‐dihydroxytrioleoate (a diol). Glyceryl tris(9‐hydroxy)trioleoate was brominated followed by displacement with sodium azide and reduction to give glyceryl tris(9‐amino)trioleoate (a triamine) and glyceryl tris[9‐(N‐isopropylamino)]trioleoate. These functionalized triglycerides were crosslinked with 1,4‐phenylene diisocyanate. The crosslinked polymers exhibit thermoset characteristics. Thermal analysis results suggest that the polymers are in amorphous states, and their thermal stability was significantly affected by crosslink degree. The crosslinked polymer derived from the diol retained 56% of its weight at 408°C, whereas the polymers derived from the aforementioned hexaol with higher crosslink degree retained only 36% of the original weight. Glass transition temperatures of these polymers range from ?1.0°C to 10.2°C. The thermal stable polymer, 12 , derived from the aforementioned diol exhibits a linear viscoelastic character and can be used as thermoplastics. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,thermal, and mechanical characterization of liquid-crystalline polyhydroxyethers

High molecular weight liquid-crystalline polyhydroxyethers, containing functional hydroxy groups, were synthesized from an aromatic diol and the diglycidylether of an aromatic diol. The polymers showed a liquid-crystalline melt when about 70% or more of the aromatic units in the chain were biphenyl units. Tensile modulus values varied from 3 GPa for as-cast films to 6 GPa for drawn films. These polymers are potentially suitable candidates to reinforce common thermoplastics by reactive blending. For this purpose polyhydroxyethers have been prepared, having a liquid-crystalline melt in the processing range of PET, viz. 260–290°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1971–1978, 1997     

Synthesis and characterization of biodegradable poly(1,4-butanediol succinate)

Biodegradable poly(1,4-butanediol succinate) was synthesized from 1,4-butanediol and succinic anhydride. The synthesized polymer was identified by ¹H-NMR spectrometer and FT-IR spectrophotometer. The weight average molecular weights were between 4,600 and 29,000, and molecular weight distributions were in the range of 1.7 and 1.9. The glass transition temperature of poly(1,4-butanediol succinate) was revealed at 73°C. The crystallization and cold crystallization of the polymers were investigated as a function of heating rate, cooling rate, reheating rate, and molecular weight. The biodegradation behavior of poly(1,4-butanediol succinate) in micro-organisms such as fungi, actinomycetes, and bacteria was studied by using modified ASTM method. Based upon visual observation, the crystalline structure of films composed of larger molecular weight polymers retained their crystallinity longer than similar structures in low molecular weight samples. © 1995 John Wiley & Sons, Inc.     

Synthesis and Spectral Characterization of Cross Linked Rigid Structured Schiff Base Polymers: Effect of Substituent Position Changes on Optical,Electrical, and Thermal Properties

Three Schiff base diol monomers were oxidatively polymerized with NaOCl as an oxidant. The structures of the monomers and polymers were confirmed by various spectroscopic techniques. Conductivity of the iodine doped polymers measured was compared based on the total charges on imine nitrogen calculated by Huckel method. The polymers were having quite lower band gap than the monomers. Fluorescence spectra of monomers and polymers showed that the excitation and emission maxima centered in the region 362–400 nm and 467–513 nm with large stokes shift. High carbine residue, around 50% at 800°C confirmed that the polymers were having good thermal stability.     

Solvent‐free cyanoethylation of selected alcohols using amberlyst A‐21 polymer resin

Solvent‐free cyanoethylation of selected alcohols with acrylonitrile (AN) using a weakly basic polymer resin, Amberlyst A‐21 (AA‐21) was studied at 75°C. The conversion of primary alcohols, 1‐octadecanol, hexane‐1,6‐diol, pentaerythritol, but‐2‐yne‐1,4‐diol, N‐methyldiethanolamine, triethanolamine and diethanolamine is higher than secondary alcohols, isopropanol and glycerol in the presence of polymer resin. Of various alcohols, but‐2‐yne‐1,4‐diol gave the product in high conversion (87%) in cyanoethylation with a polymer resin/AN weight ratio of 0.04. The polymer resin showed recycling ability only in two cycles to produce cyanoethylated product from diethanolamine. In case of 1‐octadecanol, hexane‐1,6‐diol, and N‐methyldiethanolamine with AN under similar conditions, no recycling ability was observed. Thermally treated polymer resin at 75°C afforded the product in lower conversion (55%) whereas the same product was obtained in 69% when fresh polymer resin was used in cyanoethylation of 1‐octadecanol. No catalytic effect was observed for polymer resin treated at 100°C. Fourier transform infrared (FTIR) spectra showed CN stretching at 2248 cm^?1 for the polymer resin collected after the reaction which was caused by the AN binding on polymer resin during the reaction. As per thermogravimetric curves, 5% weight loss was observed at 201°C for recovered resin and at 161°C for polymer resin treated at 100°C. Scanning electron microscope images confirmed the AN binding on polymer beads after catalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of new aromatic copolyesters containing phosphorous cyclic bulky groups

A series of phosphorus‐containing copolyesters was prepared by polycondensation of 2‐(6‐oxido‐6H‐dibenz<c,e><1,2>oxaphosphorin‐6‐yl)‐1,4‐naphthalene diol, 1 , or of an equimolecular amount of 1 and different bisphenols 2 , such as 4,4′‐isopropylidenediphenol, 4,4′‐(hexafluoroisopropylidene)diphenol and 2,7‐dihydroxynaphthalene, with an aromatic diacid chloride containing two preformed ester groups 3 , namely, terephthaloyl‐bis‐(4‐oxybenzoyl‐chloride). The copolyesters exhibited good thermal stability having the temperature of 5% weight loss above 380°C and char yield at 700°C in the range of 20–31.2%. The glass transition temperature was in the range of 136–147°C. The polymers exhibited thermotropic liquid crystalline behavior, as was observed with polarized optical microscopy, differential scanning calorimetry, and X‐ray experiments. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Amorphous copolyesters based on 1,3/1,4‐cyclohexanedimethanol: Synthesis,characterization and properties

Two series of amorphous copolyesters, PETGN and PETGS, were synthesized by the copolymerization of 2,6‐naphthalene dicarboxylic acid (NDA) (0–40%), succinic acid (SA) (0–40%), 1,3/1,4‐cyclohexanedimethanol (1,3/1,4‐CHDM) (10–50%), ethylene glycol (EG), and terephthalic acid (TPA). The compositions and molecular weights of the copolyesters were determined by ¹H NMR spectroscopy and viscometry, respectively. The thermal behaviors were studied over the entire range of copolymer compositions, using DSC and TGA. The optical characteristics, heat‐shrinkable effects and tensile properties of these polymers were also determined. Experimental results indicated that the thermal, optical, tensile, and shrinkage properties of PETGN and PETGS were functions of NDA or SA content. DSC and X‐ray analysis demonstrated that both PETGN and PETGS series were amorphous. Incorporating NDA and SA influenced the T_g values of those polymers, from about 37°C for PETG₃₀S₄₀ to 89°C for PETG₃₀N₄₀. Furthermore, the shrinkage of these amorphous copolyesters was more than 40% when the heating temperature was higher than the corresponding T_g. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of melt stability on the crystallization of bis(4-aminophenoxy)benzene-oxydiphthalic anhydride based polyimides

Novel high performance semicrystalline polyimides, based on controlled molecular weight phthalic anhydride (PA) endcapped 1,4-bis(4-aminophenoxy)benzene (TPEQ diamine) and oxydiphthalic dianhydride (ODPA), were synthesized. They exhibited excellent thermal stability in nitrogen and air atmospheres as determined by thermogravimetric analysis (TGA). The glass transition temperatures (T_g) for these polymers ranged from 225°C for the 10,000 M_n (10K) polymer, to 238°C for the 30,000 (30K) M_n material. The observed melting temperatures for all the polymers were ∼420°C. The crystallization behavior of these polymers showed a strong molecular weight dependence, as illustrated by the observation that the 10K and 12.5K polymers crystallized with relative ease, whereas the 15K, 20K, and 30K polymers showed little or no ability to undergo thermal recrystallization. The thermal stability of these polymers above T_m was investigated by studying the effect of time and temperature in the melt on the cold crystallization and melting of these polymers. Increased time and temperature in the melt resulted in lower crystallinity because of melt state degradation, such as crosslinking and branching, as evidenced by an increase in melt viscosity, which was more prominent for the higher molecular weight polymers.     

Reaction of thiol to diene polymer in the presence of various catalysts

The addition reaction of benzylmercaptan to diene polymer (natural rubber, and cis-1,4-polyisoprene) by various optically active catalysts such as d-camphorsulphonic acid, d-percamphoric acid, and active-amylalcoholate (sodium and barium) were carried out in benzene or anisole at room temperature to 100°C. The optically active adduct polymer was only obtained from the reaction of benzylmercaptan to natural rubber and cis-1,4-polyisoprene by active-amylalcoholate (barium), but was not obtained by the other catalysts. The [α]²⁵ value of optically active adduct polymer was ?0·1°C～?0·6°C (in benzene), and the optical rotatory dispersion curves were found to fit the simple Drude equation. The reaction of benzylmercaptan to cis-1,4-polybutadiene, various styrene-butadiene copolymers, and alternating butadiene-acrylonitrile copolymer were carried out, but the optically active adduct polymers were not obtained by these catalysts.     

Water‐soluble poly(vinyl alcohol) grafted with propylene oxide and epichlorohydrin: Characterization,mechanical properties,and model reactions

Poly(vinyl alcohol) (PVA) prepared by full hydrolysis of poly(vinyl acetate) was etherified with propylene oxide and epichlorohydrin. The reaction was done in water with sulfuric acid or sodium hydroxide. Previously, model reactions were carried out on propan‐2‐ol, pentan‐3‐ol, and pentan‐2,4‐diol in order to make the NMR characterization of grafted PVA easier. The new materials were also characterized by DSC and mechanical tests. A determination of their solubility in cold water was done as well. Generally, the prepared polymers showed excellent solubility in water at 10°C and a very low glass‐transition temperature. Consequently, the properties of tension, elongation, elasticity, and resistance were improved. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2868–2874, 2001     

Synthesis and decomposition performance of a polymeric foaming agent containing a sulfonyl hydrazide moiety

A new monomer, methacryloyloxybis(benzenesulfonyl hydrazide) (MAOBSH) containing a foamable sulfonyl hydrazide functional group after decomposition by heating, was synthesized from 4,4′‐oxybis(benzenesulfonyl hydrazide) (OBSH) with methacryloyl chloride, and used to obtain poly(MAOBSH) as a polymeric foaming agent (PFA) in dry tetrahydrofuran at 70 °C using azobisisobutyronitrile as an initiator. The structures of the synthesized MAOBSH and poly(MAOBSH) were identified using Fourier transform infrared and ¹ H NMR spectroscopies. The decomposition temperature of poly(MAOBSH) was determined to be 245 °C and this temperature was decreased to around 160 °C by adding an activator such as surface‐treated urea to the polymer. The exothermic temperature and heat determined by the decomposition of the polymer were 256 °C and 287 J g^?1. The amount of gas evolution for poly(MAOBSH) measured at the decomposition temperature was 74 mL g^?1. Furthermore, polymers incorporating the PFA showed better skin and finer cell structure as well as better mechanical properties such as elongation and compression set than polymers with added OBSH due to the better compatibility of the developed PFA with polymers. © 2012 Society of Chemical Industry     

Biodegradable polymers based on renewable resources VIII. Environmental and enzymatic degradability of copolycarbonates containing 1,4 : 3,6‐dianhydrohexitols

Environmental and enzymatic degradations were investigated on a series of copolycarbonates consisting of equimolar amounts of 1,4 : 3,6‐dianhydrohexitols (1,4 : 3,6‐dianhydro‐D ‐glucitol (1a) and 1,4 : 3,6‐dianhydro‐D ‐mannitol (1b)) and alkylene diols (1,4‐butanediol, 1,6‐hexanediol, 1,8‐octanediol, and 1,10‐decanediol) or oligo(ethylene glycol)s (di‐, tri‐, and tetraethylene glycols). Fourteen different copolycarbonates with number average molecular weights in the range of 1.1–4.2 × 10⁴ were prepared by solution polycondensation as described in our previous article. Biodegradability of the copolycarbonates was assessed by soil burial degradation tests in composted soil at 27 °C and by enzymatic degradation tests in a phosphate buffer solution at 37 °C. In general, biodegradability of the copolycarbonates increased with increasing chain lengths of the methylene groups of alkylene diols or of the oxyethylene groups of the oligo(ethylene glycol)s. SEM observations of the film surfaces of polymers recovered from soil burial indicated that the copolycarbonates were degraded by microorganisms in soil. In enzymatic degradation, the copolycarbonates containing alkylene diol components showed high degradability with Pseudomonas sp. lipase, whereas the copolycarbonates containing oligo(ethylene glycol) components were not degraded at all. The enzymatic degradability of the copolycarbonates is discussed with reference to the geometrical structure around the carbonate linkages and the microstructure and hydrophobicity of the polymer chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1679–1687, 2005     

Differential scanning calorimetry analysis of morphological changes in segmented elastomers

Investigations of morphological changes which are induced in segmented elastomers by annealing and quenching are reported. Four different polymers were studied each based on the same soft segment—1000 or 2000 molecular weight poly(tetramethylene oxide). The hard segments were 4,4′-diphenylmethane diisocyanate (MDI) chain extended with 1,4-butane diol (ET series), piperazine coupled with 1,4-butane diol bischloroformate (BN-1,4), or dimethyl terephthalate condensed with 1,4-butane diol (H-50). Following annealing at various temperatures (120, 150, 170, or 190°C), the polymers were quenched to ambient conditions, and their properties measured by differential scanning calorimetry (DSC) as a function of time following the quench. DSC measurements taken immediately after the quench show that the soft segment T_g is higher than that of the control, suggesting that the applied thermal history promoted increased mixing of hard and soft segments. As time passes after quenching, the T_g values decrease and approach an equilibrium value. This effect is much smaller for those samples having crystalline hard segments. Endotherms attributed to the disruption of long range ordering in the hard segment domains resulted from the annealing process. These endotherms appeared at higher temperatures for higher annealing temperatures. The positions of crystalline melting endotherms were independent of the annealing/quenching conditions investigated.     

The morphology,properties, and shape memory behavior of polylactic acid/thermoplastic polyurethane blends

Biodegradable polylactic acid (PLA) was compounded with thermoplastic polyurethane (TPU) by twin‐screw extrusion at weight ratios of 90/10, 80/20, 70/30, and 60/40. The blends were investigated based on their phase morphology, thermal and mechanical properties, and shape memory properties. The tensile results showed that PLA was successfully toughened by TPU. When the TPU content was 40%, the elongation‐at‐break increased to 400%. The SEM morphology showed that TPU was dispersed uniformly in the PLA matrix; DMA and DSC results indicated that the two polymers were immiscible. Most interestingly, it was found that the blends exhibited a shape memory behavior and, unlike most of the existing shape memory polymers (SMPs), the PLA/TPU blends could be deformed at room temperature without an extra heating and cooling step. During the deformation process, TPU acted as a toughening agent that prevented the PLA/TPU blends from breaking; thus, the temporary shape could be kept and internal stress was stored in the blends. Upon heating to above the glass transition temperature of PLA (about 60°C), the deformed parts regained their original shapes quickly along with the release of the stress. POLYM. ENG. SCI., 55:70–80, 2015. © 2014 Society of Plastics Engineers