Synthesis and properties of polyimides based on isomeric (4, 4′-methylenediphenoxyl) bis (phthalic anhydride)s (BPFDAs)

Isomeric (4, 4′-methylenediphenoxyl) bis (phthalic anhydride)s (BPFDAs)were synthesized and their structures were determined via IR spectra and ¹H NMR. Polyimides were then prepared from isomeric BPFDAs and aromatic diamines in N, N-Dimethylacetamide (DMAc) via the conventional two-step method. Polyimides based on 3, 3′-BPFDA are soluble in common organic solvents at room temperature, while polyimides based on 4, 4′-BPFDA were only partially soluble in high-boiling-point solvent even upon heating. The 5% weight-loss temperatures (T _5% ) of these polyimides were in the range of 430–500 °C in air. Dynamic mechanical thermal analysis (DMTA) indicated that the glass-transition temperatures of polyimides from 3, 3′-BPFDA are around 10–20 °C higher than those of polyimides from 4, 4′-BPFDA. The wide-angle X-ray diffraction showed that all polyimides are amorphous.     

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Synthesis and characterization of poly(11-(4′-cyano-trans-4-stilbenyloxy)undecanyl vinyl ether)

Summary Polymers based on 11-(4-cyano-trans-4-stilbenyloxy)undecanyl vinyl ether have been synthesized by living cationic polymerization, photo-initiated cationic polymerization using onium salts and thermal initiated cationic polymerization using onium salts. The polymers have been characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy, differential scanning calorimetry and polarized light microscopy. Living cationic polymerization resulted in a polymer of low molecular mass M_n3 600, with a uniformity index (D) of 1.2 displaying a focal conic texture indicative of smectic A (s_A) phase with preserved cyanogroup and trans-configuration. Photo-initiation using 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and diphenyliodonium hexafluorophosphate resulted in an insoluble polymer exhibiting only vague liquid crystalline textures. Initiation with phenothiazine and phenacyltetramethylenesulfonium hexafluoroantimonate also yielded a partly insoluble polymer with a disturbed s_A phase. It is suggested that the monomer and polymer are sensitive towards radicals leading to cross-linking and branching. The thermal initiation on systems with -methylbenzyltetramethylenesulfonium hexafluorophosphate and p-methoxybenzyltetramethylenesulfonium hexafluorophosphate resulted in completely soluble mesomorphic polymers of M_n13 000, D=1.7 and M_n26 000, D=2.8 respectively, in both cases with a preserved cyanogroup and a transconfiguration. Polarized light microscopy revealed a distinct focal conic structure indicative of s_A in both cases.     

New optically active poly(amide-imide)s based on N,N′-(pyromellitoyl)-bis-L-amino acid and 1,3-bis(4-aminophenoxy) propane: Synthesis and characterization

Five new poly(amide-imide)s 8a–e were synthesized through the direct polycondensation reaction of five chiral N,N′-(pyromellitoyl)-bis-L -amino acids 3a–e with 1,3-bis(4-aminophenoxy) propane 7 in a medium consisting of N-methyl-2-pyrrolidone, triphenyl phosfite, calcium chloride, and pyridine. The polycondensation reaction produced a series of novel poly(amide-imide)s containing trimethylene moiety in the main chain in high yield with inherent viscosities between 0.34 and 0.65 dL/g. The resulted polymers were fully characterized by means of FTIR spectroscopy, elemental analyses, inherent viscosity, and solubility tests. Thermal properties of these polymers were investigated by using thermal gravimetric analysis (TGA) and differential thermal gravimetric (DTG). All of the polymers were soluble at room temperature in polar solvents such as N,N-dimethyl acetamide, N,N-dimethyl formamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. N,N′-(pyromellitoyl)-bis-L -amino acids 3a–e were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic acid 1,2,4,5-dianhydide) 1 with L -alanine 2a , L -valine 2b , L -leucine 2c , L -isoleucine 2d , and L -phenyl alanine 2e in acetic acid. Also 1,3-bis(4-aminophenoxy) propane 7 was synthesized by using a two-step reaction. At first 1,3-bis(4-nitrophenoxy) propane 6 was prepared from the reaction of 4-nitrophenol 4 with 1,3-dibromoprapane 5 in NaOH solution. Then, dinitro compound 6 was reduced by using Na₂S. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polymers from β-propiolactone and poly(ethylene glycol)s

Uncatalysed polymerizations of β-propiolactone with low-molecular-weight poly(ethylene glycol)s were carried out in bulk, at temperatures in the range of 70 to 120°C. ¹H nuclear magnetic resonance (n.m.r.) and differential scanning calorimetry (d.s.c.) measurements on the resulting products indicated a block copolymer structure. Gel permeation chromatography (g.p.c.) and d.s.c. analyses showed that in some cases the copolymerization is accompanied by homopolymerization of β-propiolactone, probably due to the presence of residual water in the poly(ethylene glycol). N.m.r. and infra-red (i.r.) spectra of copolymers revealed the presence of hydroxyl and carboxyl end groups. The copolymerization reaction may be visualized as a two-step process, in which the ring opening of β-propiolactone takes place on both the hydroxyl groups of poly(ethylene glycol), followed by repetitive monomer addition forming an ester-ether-ester triblock copolymer.     

Microhardness and DSC measurements on liquid crystalline poly(diethylene glycolp,p′-bibenzoate) as a function of the ageing time

Summary The ageing process of the liquid crystalline glass of poly(diethylene glycolp,p-bibenzoate), PDEB, has been studied by differential scanning calorimetry and microhardness measurements. The experiments have been performed on a sample of PDEB aged at 36±C during different times. The process was found to be rather fast at that temperature, and the results from both techniques are compared.     

Synthesis and liquid crystalline behavior of phosphorus-containing aliphatic–aromatic copoly(ester-imide)s

A series of phosphorus-containing copoly(ester-imide)s was prepared by polycondensation reaction of 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-1,4-naphthalene diol, 1, or of various mixtures of 1 and 1,12-dodecanediol, 3, with an aromatic diacid chloride containing preformed imide rings, 2, namely 4-chloroformyl-N-(p-chloroformylphenyl)-phthalimide. The polymers exhibited thermotropic liquid crystalline behavior, as was observed by means of polarized light microscopy, differential scanning calorimetry, and X-ray investigations. The copoly(ester-imide)s showed good thermal stability having the temperature of 5% weight loss above 365–408 °C and char yield at 700 °C in the range 8.8–48%.     

Synthesis and characterization of poly(ester-urethane-imide)s by Diels–Alder polyaddition

Poly(ester-urethane-imide)s were prepared by Diels–Alder polyaddition of 1,6-hexamethylene-bis(2-furanylmethylcarbamate) with various bismaleimides containing ester groups in the backbone. The Diels–Alder reaction was carried out in m-cresol, at 110°C, followed by thermal and chemical aromatization of tetrahydrophthalimide intermediates. The monomers and polymers were characterized by IR, ¹H-NMR spectroscopy and elemental analysis. Thermal properties of the polymers were investigated by differential scanning calorimetry and dynamic thermogravimetric analysis.     

Synthesis and characterization of epoxy resin of 9,9′-bis-(3,5-dibromo-4-hydroxyphenyl) anthrone-10 and its jute composite

Epoxy resin of 9,9′-bis-(3,5-dibromo-4-hydroxyphenyl) anthrone-10 (EANBr, EEW 490) was synthesized and was characterized by IR and ¹HNMR . EANBr and EPK3251 cured resin (EANBrC) were characterized by DSC and TGA at 10°Cmin^?1 under nitrogen atmosphere. Broad DSC endothermic transitions of EANBr (265.3 °C) and EANBrC (291.4 °C) are due to some physical change and further confirmed by no weight loss in their TG thermograms. EANBr and EANBrC are thermally stable up to 340 °C and 310 °C, respectively. EANBr has followed single step degradation kinetics, while EANBrC has followed two step degradation kinetics. EANBr followed apparently zero order kinetics, while EANBrC followed apparently second order (1.80) and first order (0.89) degradation kinetics, respectively. Ea and A values of EANBrC (299.7 kJmol^?1 and 6.32?×?10²⁰ s^?1) were found higher than that of EANBr (201 kJmol^?1 and 2.45?×?1013 s^?1) due to more rigid nature of EANBrC. The ΔS^* value of the first step degradation of EANBrC (146.3 JK^?1 mol^?1) was found much more than that of EANBr (4.6 JK^?1 mol^?1). Jute – EANBr composite (J-EANBr) was prepared by compression molding technique at 120 °C for 5 h and under 20 Bar pressure. The observed tensile strength, flexural strength, electric strength and volume resistivity of J-EANBr are 24.7 MPa, 19.0 MPa, 1.8 kVmm^?1 and 3.5?×?10¹² ohm cm, respectively. Water absorption in J-EANBr was carried out at 30 ± 2 °C against distilled water, 10% NaCl, 10% HCl, 10% HNO₃, 10% H₂SO₄, 10% NaOH, and 10% KOH and also in boiling water. The equilibrium time and equilibrium water content for J-EANBr in different environments are 384–432 h; 12.7–15.2%, respectively. The observed equilibrium water content and diffusivity trends of J-EANBr are KOH>H₂SO₄>HCl>NaOH>H₂O>NaCl and H₂O>NaCl>NaOH>H₂SO₄>HCl>KOH, respectively. Good thermo-mechanical, electrical properties and excellent hydrolytic stability of J-EANBr may be useful for high temperature applications in diverse fields.     

Synthesis and characterization of polyrotaxanes comprising α-cyclodextrins and poly(ε-caprolactone) end-capped with poly(N-isopropylacrylamide)s

Biodegradable polyrotaxane (PR)-based triblock copolymers were synthesized via the atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAAm) initiated with polypseudorotaxanes (PPRs) consisting of a distal 2-bromopropiomyl bromide end-capping poly(ε-caprolactone) (Br-PCL-Br) and a varying amount of α-cyclodextrins (α-CDs) in the presence of Cu(I)Br/PMDETA at 25 °C in aqueous solution. The copolymers were featured by relatively higher yields from 46.0% to 82.8% as compared with previous reports. Their structure was characterized in detail by using ¹H NMR, ¹³C CP/MAS NMR, GPC, WXRD, DSC and TGA analyses. When a feed molar ratio of NIPAAm to Br-PCL-Br was changed from 50 to 200, the degree of polymerization of PNIPAAm blocks attached to two ends of PPRs was in a range of 158–500. About one third of the added α-CDs were still entrapped on the central PCL chain after the ATRP process. Attaching PNIPAAm rendered the copolymers soluble in aqueous solution showing the thermo-responsibility as evidenced by turbidity measurements.     

Novel nanocomposites based on reactive organoclay of l-tyrosine and amine end-capped poly(amide–imide): Synthesis and characterization

In the present study, a series of nanocomposite materials were successfully prepared using a poly(amide–imide) (PAI) matrix and novel reactive organoclay as a reinforcing agent. The organoclay was synthesized from Cloisite Na⁺ and protonated form of l-tyrosine amino acid via ion-exchange reaction. It was confirmed by Fourier transform infrared spectroscopy, X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy and thermogravimetry analysis techniques. An optically active PAI was synthesized via solution polycondensation reaction of N,N′-(pyromellitoyl)-bis-phenylalanine diacid chloride and 4,4′-diaminodiphenylether. Then it was end-capped with amine end groups near the completion of the reaction to interact chemically with organoclay. Organoclay/PAI nanocomposite films containing different amounts of organoclay were prepared via solution intercalation method through blending of organoclay with the PAI solution. The nanostructures and properties of the organoclay/PAI hybrids were investigated using different techniques. Thermogravimetry analysis results indicated that the addition of organoclay into the PAI matrix increased the thermal decomposition temperatures of the resulting hybrid materials. The presence of amino acids as a biodegradable segment in both novel organoclay and optically active PAI, made the resulting nanostructure materials susceptible for biodegradation.     

Liquid crystalline polymers VIII: thermotropic liquid crystalline poly(hydrazone–ether)s containing bis-thiophene linked to the main chain through spacers of various lengths

A new series of poly(hydrazone–ether)s was synthesized from 3,4-dimethylthieno [2,3-b] thiophene-2, 5-dicarbohydrazide, II and 4,4′-diformyl-α, ω-diphenoxyalkanes or 4,4′-diformyl -2,2′-dimethoxy -α, ω-diphenoxyalkanes. The inherent viscosities of the polymers were in the range 0.22 – 0.56 dIg^?1. Majority of the polymers were soluble in concentrated H₂SO₄. Their thermotropic liquid crystalline properties were examined by DSC, an optical polarizing microscopy using a hot stage and thermogravimetric analyses. The polymers exhibited almost thermotropic liquid crystalline properties. In most cases, the mesophases extended up to 430°C, where thermal decomposition prevented further observation.

Preparation and thermotropic properties of copoly(4,4′-biphenylene sebacate-co-eicosanedioate)s

Summary A series of thermotropic copoly(4,4-biphenylene sebacate-co-eicosanedioate)s were prepared by melt polycondensation of 4,4-biphenylene diacetate, sebacic acid and eicosanedioic acid. Their thermal transitions and liquid crystalline properties were investigated by DSC and polarized micrrocope. The copolyesters were found to exhibit a smectic phase, but no nematic phase was observed upon cooling. The smectic-isotropic transition temperature decreased as the content of eicosanedioate unit increased, and the corresponding transition heat did not change to a great extent. However, the crystalline-smectic transition temperature showed an eutectic behavior, and the crystalline-smectic transition heat was depressed considerably after copolymerization. The X-ray diffraction data of the copolyesters after thermal treatment were measured and compared with the thermal properties measured by DSC.     

Synthesis and characterization of a novel graft copolymer with poly(n-octylallene-co-styrene) backbone and poly(?-caprolactone) side chain

A novel graft copolymer consisting of poly(n-octylallene-co-styrene) (PALST) as backbone and poly(?-caprolactone) (PCL) as side chains was synthesized with the combination of coordination copolymerization of n-octylallene and styrene and the ring-opening polymerization (ROP) of ?-caprolactone. Poly(n-octylallene-co-styrene) (PALST) backbone was prepared from the copolymerization of n-octylallene and styrene with high yield by using the coordination catalyst system composed of bis[N,N-(3,5-di-tert-butylsalicylidene)anilinato]titanium(IV) dichloride (Ti(Salen)₂Cl₂) and tri-isobutyl aluminum(Al(i-Bu)₃). The molar ratio of each segment in the copolymer, and the molecular weight of the copolymer as well as the microstructure of the copolymer could be adjusted by varying the feeding ratio of both styrene and n-octylallene. The hydroxyl functionalized copolymer PALST-OH was prepared by the reaction of mercaptoethanol with the pendant double bond of PALST in the presence of radical initiator azobisisbutyronitrile (AIBN). The target graft copolymer [poly(n-octylallene-co-styrene)-g-polycaprolactone] (PALST-g-PCL) was synthesized through a grafting-from strategy via the ring-opening polymerization using PALST-OH as macroinitiator and Sn(Oct)₂ as catalyst. Structures of resulting copolymer were characterized by means of gel permeation chromatography (GPC) with multi-angle laser light scattering (MALLS), ¹³C NMR, ¹H NMR, DSC, polarized optical microscope (POM) and contact angle measurements.     

Synthesis and characterization of poly(ethyl vinyl ether) containing the NLO-phore 4′-oxy-4-nitrostilbene in the side chain

Summary 4-(2-Vinyloxyethoxy)-4-nitrostilbene 2 was prepared by the reaction of 4-hydroxy-4-nitrostilbene 1 with 2-iodoethyl vinyl ether. Monomer 2 was polymerized with cationic initiators to obtain a poly(ethyl vinyl ether) with the NLO-phore 4-oxy-4-nitrostilbene in the side chain. The resulting polymer 3 was soluble in common solvents such as chloroform and DMSO. The inherent viscosities of polymer 3 were in the range of 0.25–0.30 dL/g in chloroform. Polymer 3 showed a good thermal stability in TGA thermogram. Solution-cast films were cloudy and brittle with a T_g of 63°C.     

Synthesis and characterization of new poly(ether–ester–imide)s as a generation of soluble and thermally stable polymers

A new-type of dicarboxylic acid 6 was synthesized from the reaction of 1,4-bis[4-aminophenoxy]butane 4 with trimellitic anhydride 5 in a solution of glacial acetic acid/pyridine (Py) at refluxing temperature. 1,4-Bis[4-nitrophenoxy]butane 3 was prepared by reaction of 4-nitrophenol 1 with 1,4-dibromo butane 2 in N,N-dimethylformamide (DMF) solution. Then dinitro 3 was reduced to 1,4-bis[4-aminophenoxy]butane 4 by using 10% Pd–C, ethanol, and hydrazine monohydrate. So six new thermally stable and organosoluble poly(ether–ester–imide)s (PEEIs) 8a–f with good inherent viscosities were synthesized by the direct polycondensation reaction of new 1,4-bis[4-(trimellitimido)phenoxy]butane 6 with several aromatic diols 7a–f through direct polycondensation using tosyl chloride (TsCl)/pyridine (Py)/DMF system as condensing agent. The resulted polymers were fully characterized by means of FTIR and ¹H NMR spectroscopy, elemental analyses, inherent viscosity, solubility tests, differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and derivative of thermogravimetric (DTG).     

Synthesis and X-ray diffraction of ferroelectric liquid crystalline polysiloxanes containing 4′-(2-chloro-3-methylpentanoyloxy)-4-alkanyloxybiphenyl side groups

Summary The synthesis and characterization of side-chain liquid crystalline polysiloxanes containing (2S,3S)-4-(2-chloro-3-methylpentanoyloxy)-4-alkanyloxybiphenyl side groups are presented. All the obtained polymers exhibit smectic mesomorphism. Those polymers containing a spacer length longer than 8 methylene units reveal respectively enantiotropic S_A, S _* ^C and S_B phases. The result demonstrates that the tendency toward the S _* ^C phase increases with increasing the spacer length.     

Photo- and bio-degradation of poly(ester-urethane)s films based on poly[(R)-3-Hydroxybutyrate] and poly(ε-Caprolactone) blocks

Biodegradable segmented poly(ester-urethane)s derived from telechelic dihydroxy-poly[(R)-3-hydroxybutyrate], acting as hard segments, and poly(ε-caprolactone)-diols, acting as soft segments, using 1,6-hexamethylene diisocyanate, as non toxic connecting agent, were synthesized. The copolymers were characterized with regard to their molecular weight by GPC and their main thermal transitions by DSC. These copolymers as well as PHB were exposed to UV-irradiation for different time intervals and the changes in the chemical structure were analyzed by FTIR spectroscopy. Under our experimental conditions, it was found that the increase of irradiation time was accompanied by increase of the proportion of the gel fraction and the decrease of the intrinsic viscosity of the soluble fraction of the investigated copolymers. The biodegradability of PHB and poly(ester-urethane) sample containing ~40 wt% PHB before and after UV-irradiation was investigated under soil burial. The results showed that the photolysis in air prior to biodegradation increased the rate of degradation.     

Synthesis and characterization of ferrocene end-capped poly(ε-caprolactone)s by a combination of ring-opening polymerization and “click” chemistry techniques

Ferrocene (Fc) end-capped linear and star-shaped poly(ε-caprolactone)s (PCLs) with different numbers of arms were synthesized by a combination of ring-opening polymerization (ROP) and “click” chemistry techniques in a four-step reaction procedure. In the first step, the polymer backbones were prepared via ROP of the ε-caprolactone (ε-CL) monomer in bulk by employing the compounds with different numbers of hydroxyl groups as the multisite initiators and stannous octoate (Sn(Oct)₂) as the coordination-insertion catalyst. The hydroxyl end-groups of the obtained PCLs were then converted into a bromides and azides consecutively. In the final step, the Fc moiety was attached to the termini of the PCLs using a Cu(I)-catalyzed 1,3-dipolar cycloaddition reaction between the azide end-groups of the PCLs and the acetylene group of ethynylferrocene under ambient conditions. In all cases, the FT-IR and ¹H NMR spectra indicated a successful and quantitative transformation of the desired end-functional groups. The electrochemical properties of the Fc end-capped PCLs were also investigated via cyclic voltammetry (CV).     

Synthesis and characterization of alternating poly(amide urethane)s from ε-caprolactone, diamines and diphenyl carbonate

The synthesis of alternating poly(amide urethane)s 5a-d was performed in three steps using ε-caprolactone, diamines, and diphenyl carbonate as starting materials. The microstructure and nature of the end groups of the poly(amide urethane)s were determined by means of ¹H NMR spectroscopy, which reveals an alternating sequence of amide and urethane linkages in a linear chain with hydroxy and phenyl urethane end groups. The molecular weight and polydispersity of the polymers obtained (, ) were determined by means of gel permeation chromatography. The thermal properties determined by means of DSC show that the poly(amide urethane)s 5a-d are semicrystalline materials having one or two endothermic transitions similar to the poly(amide urethane)s 10a-d prepared from ε-caprolactam, amino alcohols, and diphenyl carbonate. Thermogravimetric analysis of poly(amide urethane)s 5a-b shows a single step decomposition, while poly(amide urethane)s 10a-c decompose in two steps indicating that different degradation mechanisms are operating.