Synthesis and characterization of novel poly(amide imide)s based on bis(p‐amidobenzoic acid)‐n‐trimellitylimido‐L‐leucine

N‐Trimellitylimido‐L ‐leucine was reacted with thionyl chloride, and N‐trimellitylimido‐L ‐leucine diacid chloride was obtained in a quantitative yield. The reaction of this diacid chloride with p‐aminobenzoic acid was performed in dry tetrahydrofuran, and bis(p‐amidobenzoic acid)‐N‐trimellitylimido‐L ‐leucine (5) was obtained as a novel optically active aromatic imide–amide diacid monomer in a high yield. The direct polycondensation reaction of the monomer imide–amide diacid 5 with 4,4′‐diaminodiphenylsulfone, 4,4′‐diaminodiphenylether, 1,4‐phenylenediamine, 1,3‐phenylenediamine, 2,4‐diaminotoluene, and benzidine (4,4′‐diaminobiphenyl) was carried out in a medium consisting of triphenyl phosphite, N‐methyl‐2‐pyrolidone, pyridine, and calcium chloride. The resulting novel poly(amide imide)s (PAIs), with inherent viscosities of 0.22–0.52 dL g^?1, were obtained in high yields, were optically active, and had moderate thermal stability. All of the compounds were fully characterized with IR spectroscopy, elemental analyses, and specific rotation. Some structural characterization and physical properties of these new optically active PAIs are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 35–43, 2002; DOI 10.1002/app.10181     

Synthesis and characterization of degradable copoly(ester–amide)s: Poly(trans‐4‐hydroxy‐L‐proline‐co‐ε‐caprolactam)

Novel copolyesteramides were synthesized by reacting trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with ε‐caprolactam (CLM) in the presence of stannous octoate [Sn(II) Oct.] as a catalyst. Various techniques, including ¹H‐NMR, IR, DSC, and viscosity, were used to elucidate structural characteristics and thermal properties of the resulting copolymers. Data showed that the optimal reaction condition for the synthesis of the copolymers was obtained by using 3 wt % Sn(II) Oct. at 170°C for 24 h. The DSC analysis demonstrated amorphous structure for most of the copolymers. The glass‐transition temperature of the copolymers shifts to a higher temperature with increasing Hpr/CLM molar ratio. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐CLM)s was evaluated by weight loss measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1615–1621, 2002     

Synthesis and characterization of new polyureas derived from 4‐(4′‐Methoxyphenyl)urazole

4‐(4′‐Methoxyphenyl)urazole (MPU) was prepared from 4‐methoxybenzoic acid in five steps. The reaction of monomer MPU with n‐isopropylisocyanate was performed at room temperature in N,N‐dimethylformamide solution, and the resulting bis‐urea derivative was obtained in high yield and was finally used as a model for polymerization reaction. The step‐growth polymerization reactions of monomer MPU with hexamethylene diioscyanate, isophorone diioscyanate, and toluene‐2,4‐diioscyanate were performed in N,N‐dimethylacetamide solution in the presence of pyridine as a catalyst. The resulting novel polyureas have an inherent viscosity (η_inh) in a range of 0.07–0.21 dL/g in DMF and sulfuric acid at 25°C. These polyureas were characterized by IR, ¹H‐NMR, elemental analysis, and TGA. Some physical properties and structural characterization of these novel polyureas are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1141–1146, 2002     

Microwave‐assisted synthesis of new optically active poly(ester‐imide)s containing N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine moieties

Pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) (1) was reacted with L‐phenylalanine (2) in a mixture of acetic acid and pyridine (3 : 2) and the resulting imide‐acid [N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid] (4) was obtained in quantitative yield. The compound (4) was converted to the N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid chloride (5) by reaction with thionyl chloride. A new facile and rapid polycondensation reaction of this diacid chloride (5) with several aromatic diols such as phenol phthalein (6a), bisphenol‐A (6b), 4,4′‐hydroquinone (6c), 1,8‐dihydroxyanthraquinone (6d), 4,4‐dihydroxy biphenyl (6e), and 2,4‐dihydroxyacetophenone (6f) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o‐cresol. The polymerization reactions proceeded rapidly and are completed within 20 min, producing a series of optically active poly(ester‐imide)s with good yield and moderate inherent viscosity of 0.10–0.26 dL/g. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐imide)s are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2211–2216, 2002     

Synthesis and properties of high oil‐absorbent 4‐tert‐butylstyrene‐EPDM‐divinylbenzene graft terpolymer

The graft crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto ethylene–propylene–diene (EPDM) was carried out in toluene by using benzoyl peroxide (BPO) as an initiator. The synthesized graft terpolymer, tBS‐EPDM‐DVB (PBED), was extracted with tetrahydrofuran (THF) into gel (called as PBED I) and sol, and then they were identified by infrared (IR) spectroscopy. The effects of solvent amount, molar ratio of DVB to tBS, EPDM content, initiator concentration, reaction temperature, and reaction time on the graft crosslinking polymerization were examined. Among them, solvent amount and molar ratio of DVB to tBS were the important factors for this reaction system. Maximum oil absorbency of PBED I was 84.0 g/g but its oil‐absorption kinetic rate was very low. Sol PBED can be reused as oil absorbent (named as PBED II) through photocrosslinking by ultraviolet light irradiation. Although the oil absorbencies of PBED II were lower than those of PBED I in most cases, their oil absorption kinetic rates were higher than oil absorbencies of PBED I. The highest value of oil absorbency of PBED II was 56.0 g/g. The thermal stability of PBED I was studied by TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2119–2129, 2002     

A novel visible light photo‐induced acid‐generation system

A novel, visible light, photo‐induced acid‐generation system composed of four types of intramolecular charge transfer compound and substituted bis(trichloromethyl) triazine was studied in this work. The photo‐induced electron transfer process between electron donor and electron acceptor was studied by the methods of fluorescence quenching and the change of fluorescence intensity with the time of irradiation. In the acidity measurement, the chemical reaction of acid formation of the studied system can be observed clearly. The acid‐induced cross‐linking reaction of m‐cresol resin and 2,4,6‐tris‐[N,N‐di(methoxymethyl) amino] triazine (HMMM) has also been studied. A clear negative image can be obtained after irradiation and developing by solvent. The possible mechanism of reaction has been discussed before. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 909–915, 2002; DOI 10.1002/app.10103     

Stability constants of polymer‐bound iminodiacetate‐type chelating agents with some transition‐metal ions

A chelating vinyl monomer, glycidyl methacrylate (GMA)–iminodiacetic acid (IDA), was formed by the reaction between GMA and IDA. Three polymeric chelating agents, PGMA–IDA, PGMA–IDA‐co‐methyl acrylate (MA), and PGMA–IDA‐co‐acrylamide (AAm), were also synthesized. Acid dissociation constants and stability constants of these chelating agents with Ni(II), Zn(II), and Co(II) were determined by means of potentiometric titration and ultraviolet–visible spectrophotometry, respectively. The values of K_a1 and K_a2 of all the polymeric chelating agents were smaller than those of GMA–IDA. The stability constants of all the polymeric chelating agents were larger than those of GMA–IDA. Increasing the MA content within PGMA–IDA‐co‐MA affected the stability constant only slightly. A proper molar ratio of AAm in PGMA–IDA‐co‐AAm, stability constants was 30–60 times greater than that of GMA–IDA. However, as the molar content of AAm increased, the stability constant of PGMA–IDA‐co‐AAm decreased. The results obtained in the polymer system are explained in terms of the polymer's stereo and entanglement structure, the neighboring effect, and the hydrophobic/hydrophilic nature of MA or AAm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1986–1994, 2002     

On‐line determination of the conversion in a styrene bulk polymerization batch reactor using near‐infrared spectroscopy

A fast on‐line method for measuring the monomer conversion of a styrene batch polymerization reaction with near‐infrared spectroscopy (NIR) has been developed. Multivariate calibration was performed, using polymer samples having temperatures around the set point of the batch reactor (75–85°C) and monomer conversions up to 35%. The calibration model was built in such a way that the effect of the temperature on the predicted conversion of the sample was minimized. The method was validated in a number of batch runs. In these runs, the batch temperature and molar mass distributions of the polymer were varied. At‐line size‐exclusion chromatography was used as a reference method for measuring the monomer conversion. Results show that on‐line conversion monitoring with NIR offered overall an excellent accuracy (～ 0.32% conversion). For high and low monomer conversions a small bias in the predicted conversion is present. The method proved to be insensitive to both relative large changes (10°C) of the batch temperature and to considerable changes of the molar mass distribution of the polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 90–98, 2002; DOI 10.1002/app.10241     

Synthesis and characterization of 4,5‐bis(4‐fluorobenzoyl)‐1‐methylcyclohexene and its polyethers

A new difluoride 4,5‐bis(4‐fluorobenzoyl)‐1‐methylcyclohexene (DFKK) has been prepared with fumaryl chloride, fluorobenzene, and 2‐methyl‐1,3‐butadiene as starting materials through two steps of reactions. This DFKK monomer undergoes reaction with 2,2‐(p‐hydroxyphenyl)‐iso‐propane (BPA) in the presence of excess anhydrous potassium carbonate in sulfolane to give a high molecular weight reactive poly(ether ketone ketone) (PEKK) that is very soluble in solvents such as chloroform and N,N‐dimethylformamide at room temperature, has glass transition temperature of 182°C, and is easily cast into flexible and bale ivory film with tensile strength of 64 MPa. The 5% weight loss temperature is 407°C. Ring‐closing reaction of PEKK with hydrazine gives cyclized PEKK (CPEKK) with improved thermal stability and reduced solubility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1866–1871, 2002; DOI 10.1002/app.10454     

On‐line optimizing control of bulk polymerization of methyl methacrylate: Some experimental results for heater failure

An experimental unit has been assembled to carry out on‐line optimizing control of the bulk polymerization of methyl methacrylate (MMA). A rheometer‐reactor assembly is used. Temperature and viscosity measurements are used to describe the state of the system. The polymerization is carried out under an off‐line computed optimal temperature history, T_op(t). A planned disturbance (heating system failure) is introduced at time t₁. This disturbance leads to a fall in the temperature of the reaction mass. A new optimal temperature history, T_reop(t), is re‐computed on‐line and is implemented on the reaction mass at time t₂, when the heating is resumed. This procedure helps ‘save the batch’. A genetic algorithm is used to compute this reoptimized temperature history in a short period of ～2 min of real time. The feasibility of the on‐line optimizing control scheme has been demonstrated experimentally. Replicable results for the viscosity history, η(t), of the polymerizing mass under several non‐isothermal conditions have been obtained. These experimental results are quite trustworthy, even though the model predictions are only in approximate agreement with them, perhaps because of the extreme sensitivity of results to the values of the model parameters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2350–2360, 2002     

Nitroxide‐terminated poly(styrene‐co‐diethyl fumarates) and derived block copolymers

Copolymerization of styrene (S) and diethyl fumarate (DEF) at 125°C in the presence of 2,2,6,6‐ tetramethylpiperidin‐1‐yloxyl radical (TEMPO) and initiated with a thermal initiator, 2,2′‐azobisisobutyronitrile (AIBN), was studied. The molar fraction of DEF in the feed, F_DEF, varied within 0.1–0.9. An azeotropic composition, (F_DEF)_A = 0.38, was found for the copolymerization under study. At F_DEF = 0.1–0.4, a quasi‐living process was observed, transforming to a retarded conventional radical copolymerization at a higher content of DEF in the initial mixtures. The obtained TEMPO‐terminated S‐DEF copolymers were used to initiate polymerization of styrene. Poly(styrene‐ co‐diethyl fumarate)‐block‐polystyrene copolymers were prepared with molecular weight distributions depending on the amount of inactive polymer chains in macroinitiators, as indicated by size‐exclusion chromatography. A limited miscibility of the blocks in the synthesized block copolymers was revealed by using differential scanning calorimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2432–2439, 2002     

Dehydration of light oil by pervaporation using poly(vinyl alcohol)–poly(acrylic acid‐co‐maleic acid) membranes

A new blended membrane was prepared and tested by pervaporation of light oil, a mixture of five alcohols plus water. The blended membrane was synthesized by blending poly(vinyl alcohol) and poly(acrylic acid‐co‐maleic acid) sodium salt in the presence of sulfuric acid to dope the reaction. We tested several membranes in order to choose the adequate composition to have the best permselectivity. The PVA(60)–PAA‐co‐maleic acid(40) membrane was selected as it was found to be highly selective. Sorption experiments were performed using binary and ternary water–alcohol solutions. The influence of temperature and feed composition on the selectivity and flux in pervaporation was investigated for two different binary mixtures (water/ethanol, water/isobutanol) and one ternary system (water/ethanol/isobutanol). This membrane presents good permselective properties, high water flux, and good selectivity and can even be used for high‐water activities The performances of this new membrane were compared to those obtained with the PVA(90)–PAA(10) membrane synthesized recently: The fluxes observed for the water–ethanol separation were of the same order of magnitude but the selectivity was found to be much higher. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1709–1716, 2002     

Robust on‐line measurement of conversion and molecular weight using NIR spectroscopy during solution polymerization

Fiber‐optic near‐infrared (NIR) spectroscopy was used to monitor the monomer conversion and the weight‐average molecular weight of the polymer produced during solution polymerization of methyl methacrylate (MMA) carried out in a lab‐scale reactor. NIR spectra were recorded during batch and semi‐continuous reactions using an in situ transmission probe. Off‐line gravimetry and GPC were used as reference methods to provide the conversion and the average molecular weight data set required for the calibration procedure. A statistical model was generated using partial least‐squares regression (PLS) to relate the NIR spectral data to the two polymerization variables of interest. The measurements were then validated for various operating conditions (i.e., different solvent, initiator, MMA, and chain‐transfer agent concentrations) and for both batch and semi‐continuous modes. The conversion was predicted during three validation experiments with an average standard error of prediction (SEP) of 2.1%. The on‐line evaluation of M?_w was obtained with an average relative SEP of 5.7%; such on‐line NIR measurement was thus demonstrated to be robust and accurate, even in the case of versatile use of the polymerization plant. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2510–2520, 2002     

Synthesis of oligo‐ortho‐azomethinephenol and its oligomer–metal complexes: Characterization and application as anti‐microbial agents

The oxidative polycondensation reaction conditions and optimum parameters of o‐phenylazomethinephenol (PAP) with oxygen (air) and NaOCl were determined in an aqueous alkaline solution at 60–98°C. The properties of oligo‐o‐phenylazomethinephenol (OPAP) were studied by chemical and spectra analyses. PAP was converted to dimers and trimers (25–60%) by oxidation in an aqueous alkaline medium. The number average molecular weight (M_n), mass average molecular weight (M_w), and polydispersity index (PDI) values were 1180 g mol^?1, 1930 g mol^?1, and 1.64, respectively. According to these values, 20–33% of PAP turned into OPAP. During the polycondensation reaction, a part of the azomethine (? CH?N? ) groups oxidized to carboxylic (? COOH) group. Thus, a water‐soluble fraction of OPAP was incorporated in the carboxylic (? COOH); (2–20%) group. Also, the structure and properties of oligomer–metal complexes of OPAP with Cu(II), Ni(II), Zn(II), and Co(II) were studied. Antimicrobial activites of the oligomer and its oligomer–metal complexes were tested against B. cereus, L. monocytogenes, B. megaterium, B. subtilis, E. coli, Str. thermophilus, M. smegmatis, B. brevis, E. aeroginesa, P. vulgaris, M. luteus, S. aureus, and B. jeoreseens. Also, according to differential thermal analysis and thermogravimetric analysis, OPAP and its oligomer–metal complexes were stable throughout to temperature and thermo‐oxidative decomposition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2004–2013, 2002     

Kinetics of the solid‐state polymerization of nylon‐6

The kinetics of the thermally induced solid‐state polymerization (SSP) of nylon‐6 were examined in both a fixed‐bed reactor and a rotary reactor. Factors such as the regulator content, the reaction temperature and time, the particle size, the type and geometry of the nylon‐6 prepolymer, the nitrogen gas flow rate, the water content of the nitrogen gas flow, and the polymerization process were studied. The results showed that the regulator content, the reaction temperature and time, and the particle size were the primary factors, and that the others were negligible. Moreover, the SSP rate and number‐average molecular weight (M_n) increased with increasing reaction temperature and time and decreasing particle size. The SSP rate and M_n had maximum values with increasing regulator content in an experimental range of 0.03–0.07 wt %. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 616–621, 2002; DOI 10.1002/app.10341     

Influence of hydrogen donors on peroxide‐initiated melt grafting of vinylsilane to poly(ethylene‐co‐vinyl acetate)

A technique has been examined for reducing the extent of crosslinking resulting from 1,1‐di(t‐butylperoxy)‐3,3,5‐trimethylcyclohexane (L‐231) initiating melt grafting of vinyltriethoxysilane (VTEOS) onto poly(ethylene‐co‐vinyl acetate) (EVA). Using measurements of crosslink density and VTEOS conversion, a standard of selectivity for the EVA/VTEOS/L‐231 system at 145 °C was defined and used to assess the influence of a range of additives (0.25 mol per mole VTEOS). The data indicated that compounds such as 4‐nonene, N,N‐dimethylaniline, and cumene improve reaction selectivity, whereas dodecane and cyclohexyl acetate have no effect. A strong correlation between the minimum C? H bond dissociation energy and the influence of a given compound is evident, suggesting that a labile C? H bond is the key element of an effective additive. A mechanism of additive function on the basis of hydrogen atom donation is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2397–2402, 2002     

Conduction mechanism in H‐type polysiloxane‐polypyrrole block copolymers

Conducting polymers of polysiloxane‐polypyrrole were synthesized by electropolymerization of the pyrrole monomer through pyrrole moieties in N‐pyrrole‐terminated polysiloxanes. Sodium paratoluene sulfonate was used as the electrolyte. Scanning electron microscopy (SEM) was used to determine the surface morphology of the films. The room‐temperature conductivity values of the films were found to be in the range of 1.9–4.4 × 10^?4 (Ω cm)^?1, depending on the supporting electrolyte concentration. The temperature dependence of the dc conductivities of the copolymers having different dopant concentrations was investigated within the temperature range of 100–320 K. The evaluated parameters showed that the electrical transport is dominated by variable range hopping. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 52–56, 2002     

Lifetime predictions for the epoxy system BADGE n=0/m‐XDA using kinetic analysis of thermogravimetry curves

Lifetime of the epoxy system diglycidil ether of Bisphenol A (BADGE n=0)/ m‐xylylenediamine (m‐XDA) was calculated by thermogravimetric analysis. The Flynn‐Wall‐Ozawa method is used to determine the activation energy of the reaction. Experimental lifetimes in the range of 60–300°C vary from 1.41 10⁹ (2682 years) to 3.35 10^?4 min. This isoconversional method is not appropiate to calculate lifetime prediction because of high errors. Scaling factors were determined using the ratio of two reaction rates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1692–1696, 2002     

Investigation of microstructure of the N‐vinyl‐2‐pyrrolidone/methyl methacrylate copolymers by NMR spectroscopy

The copolymers containing N‐vinyl‐2‐pyrrolidone (V) and methyl methacrylate (M) units of different compositions were synthesized by free radical bulk polymerization. The copolymer composition of these copolymers was determined by CHN analysis. The distortionless enhancement by polarization transfer (DEPT) technique was used to resolve the methine, methylene, and methyl resonance signals in the V/M copolymer. Comonomer reactivity ratios were determined by the Kelen–Tudos (KT) and nonlinear least‐square error‐in‐variable (EVM) methods. ¹H–¹³C Heteronuclear shift quantum correlation spectroscopy (HSQC) and ¹H–¹H homonuclear total correlation spectroscopy (TOCSY) spectra were used for the resolution of the proton nuclear magnetic resonance (¹H NMR) spectrum of the V/M copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1328–1336, 2002     

Postpolymerization of vinyl acetate‐containing latexes

The postpolymerization of vinyl acetate (VAc)‐containing latexes with tert‐butyl hydroperoxide (TBH)/ascorbic acid (AsA) as a redox initiation system was investigated. Volatile organic compounds (VOCs) such as acetone and tert‐butyl alcohol were produced in this process. The influence of the TBH/AsA ratio, initiator concentration, reaction temperature, and feeding time on the reduction of residual VAc and VOC formation during the postpolymerization was investigated. A total reduction of residual VAc monomer was achieved, with the formation of VOCs kept within acceptable limits. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 923–928, 2002