Polymerization of lactams, 48. Autocopolymerization of 6-caprolactam with 12-dodecanelactam

The homo- and copolymerization of 6-caprolactam and 12-dodecanelactam was studied in the absence of an intentionally added initator. Both the polymerization and the copolymerization of an equimolar mixture of the monomers exhibited an induction period, the length of which was reduced with increasing temperature. Above 260°C, the polymers and copolymers of 6-caprolactam were not stable and their intrinsic viscosities as well as the polymer content decreased during long polymerization periods. On the other hand, insoluble products were formed in the homopolymerization of 12-dodecanelactam at temperatures of 300°C and higher. As much as 35 wt.-% of oligomers, predominantly cyclic ones, were formed in the initial stage of polymerization and copolymerization.     

Alternating copolymerization of methyl α-phenylacrylate and methyl methacrylate by n-BuLi

The copolymerization of methyl α-phenylacrylate (MPhA) and methyl methacrylate by n-BuLi was carried out in toluene at various temperatures with an initial monomer ratio of 1:1. At ?78°C the product was a homopolymer of MPhA. The copolymer obtained at ?40°C was a mixture of poly(methyl α-phenylacrylate) and poly(methyl methacrylate) containing a small amount of alternating copolymer of both monomers. With further increase in the polymerization temperature the fraction of alternating copolymer increased and above 30°C all the copolymers obtained were alternate. With varying composition of feed monomers the copolymerization was carried out at 30°C and the alternating copolymer was obtained over a wide range of monomer feed ratios. In tetrahydrofuran the alternate sequence began to form at a lower temperature than in toluene, and all the copolymers obtained above 0°C were alternating ones. The mechanism of the copolymerization is discussed in some detail.     

Die polymerisation der lactame XI. Die copolymerisation von 6-caprolactam mit 12-laurolactam

The course of the incorporation of 6-caprolactam and 12-laurolactam into polymer chains during the hydrolytic, cationic and anionic copolymerization for an equimolar ratio of the monomers was studied. During the hydrolytic copolymerization 6-caprolactam is incorporated more rapidly at 260, 230 or 200°C at the beginning of the polymerization process; the differences between incorporation rates of the lactams into the copolymer increase with decreasing temperature. During the cationic copolymerization the incorporation of 12-laurolactam is more rapid by orders of magnitude for the above temperatures at the beginning of the process. Changes in the composition of cationic copolymers as compared to the hydrolytic copolymers are independent of the temperature during the copolymerization. The anionic copolymerization is characterized by a more rapid incorporation of 6-caprolactam into the polymer chain. The differences in the polymerization activity of the two lactams decrease with increasing temperature of the anionic copolymerization. The described course of incorporation of individual monomers, with the various mechanisms of the polymerization, also corresponds to melting points of copolymers in accordance with their composition.     

Die polymerisation der lactame VI. Die copolymerisation von 6-caprolactam und 8-capryllactam

The process of incorporating 6-caprolactam and 8-capryllactam into polymer chains was studied during the hydrolytic, cationic, and anionic copolymerization in the case of equimolar ratio of the above mentioned monomers. At the beginning of the hydrolytic copolymerization at temperatures between 200 and 260°C, 6-caprolactam was more rapidly incorporated into the chains. Decreasing temperature led to a decrease in the total rate of polymerization with increasing difference between rates of incorporating the two components. Contrary to this, at the initial stage of the cationic copolymerization, the incorporation of 8-capryllactam was faster by orders of magnitude than that of 6-caprolactam, the changes of the copolymer composition being independent of temperature. Under the conditions of interest, in the course of the anionic copolymerization the two monomers were characterized with the same rates of incorporation into the polymer chains. Different melting points of products separated at various stages of the copolymerization process corresponded to the above mentioned differences in rates of incorporating individual monomers into polymer chains when different reaction mechanisms were employed.     

The structure and physical properties of copolymers of lactams

Copolymers of caprolactam with caprylolactam and laurolactam were prepared by activated anionic copolymerization under adiabatic conditions, at an initial polymerization temperature of T₀ = 130°C. The drop of the crystalline phase content and changes of the copolymer morphological structure depending on the content of comonomers result in increasing toughness and deformability due to enhanced yielding ability. The dependences of the copolymer structure and properties on the concentration of comonomers are different for the two series of copolymers. This results from different courses of the polymerization and crystallization history as a consequence of a large difference between polymerization rates of caprylolactam and laurolactam.     

Dispersion polymerization of styrene and methyl methacrylate initiated by macromonomeric azoinitiator

The free radical dispersion polymerization of styrene (St) and methyl methacrylate (MMA) initiated by poly(oxyethylene) (PEO) macroazoinimer (MIM-400) in water/ethanol, was investigated at three different temperatures (50, 60 and 80°C) for seven polymerization times (3, 6, 9, 12, 24, 36 and 48 h). PSt-PEO and PMMA-PEO networks were obtained. In each case, polymer gel fractions depend on the polymerization temperature and polymerization time. With the same initial concentration of MIM-400, maximum gel fraction was found at 80 wt.-% with St copolymerization while 100 wt.-% in case of copolymerization with MMA at 80°C for 48 h.     

Preparation of thermosensitive cellophane-graft-N-isopropylacrylamide copolymer membranes and permeation of solutes through the membranes

Thermosensitive membranes with high mechanical strength were prepared by heterogeneous graft copolymerization of N-isopropylacrylamide (NIPAAm) onto cellophane in a nitric acid solution using cerium ammonium nitrate as an initiator, and the permeation behavior of solutes such as lithium chloride and poly(ethylene glycol)s (PEGs) through the membranes at various temperatures was investigated. The degree of graft copolymerization of NIPAAm on cellophane depended on temperature, time, initiator concentration, and so on. The copolymer membranes having a high content of the NIPAAm moiety could be obtained at 25°C for 24 h. The permeation of Li⁺ through the membranes was affected by temperature, i.e., the permeation rate of Li⁺ increased with increasing temperature up to 32°C and then decreased rapidly above 35°C. The permeation rate of Li⁺ through the copolymer membranes at 40°C decreased considerably, but that at 20°C decreased slightly with an increasing amount of the NIPAAm moiety in the membranes. The permeation rate of PEGs with a molecular weight more than 1000 through the cellophane-g-NIPPAm copolymer membranes was considerably suppressed and only the permeation rate of PEG300 increased with increasing temperature up to 35°C and then decreased at 40°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 209–216, 1997     

Polymerization of lactams, 49. Hydrolytic polymerization of 6-caprolactam in the presence of its cyclic dimer

The hydrolytic polymerization of 6-caprolactam has been studied at 260–280°C in the presence of 5, 10 and 15 mol-% of cyclic dimer of 6-caprolactam and 2 mol-% of 6-aminocaproic acid as an initiator. The content of monomer and cyclic oligomers, including pentamer, was determined by HPLC. It has been proved that the rate of polymerization decreases with increasing content of cyclic dimer in the initial mixture and the time required to attain the equilibrium content of polymer increases as much as by an order of magnitude. The cyclic dimer is incorporated into the polymer above all in the final reaction stage.     

Study of Vinyl Acetate Partitioning in Emulsion Copolymerization of Vinyl Chloride-Vinyl Acetate by FTIR and HNMR Spectroscopy

Emulsion copolymerization of vinyl chloride with vinyl acetate comonomer was performed. Potassium persulfate, a mixture of stearyl alcohol and sodium lauryl sulfate, was used and reactions were performed at 55 °C in a pressurized reactor. By sampling during the reaction in different intervals copolymer composition was investigated using FTIR and NMR spectroscopy. The results showed that the partitioning of vinyl acetate in the copolymerization in general follows the Mayo-Lewis copolymerization equation with some discrepancy. This was attributed to the gaseous nature of vinyl chloride monomer and the differences between polymerization in heterogeneous and homogeneous systems. Both FTIR and NMR spectroscopy showed two peaks in vinyl acetate content of copolymer beyond 65% conversion which was attributed to the elimination of vinyl chloride droplets in the media and replacing them with vinyl acetate monomer. The first increase is related to the consumption of vinyl chloride droplets and the second is related to the consumption of gaseous vinyl chloride; in both instances vinyl acetate governs the polymerization.     

Die Polymerisation von Lactamen. IV. Die anionische Copolymerisation von 6-Caprolactam mit 8-Caprylolactam

Conditions were defined for preparing homogeneous castings based on copolymers of 6-caprolactam and 8-caprylolactam under conditions of the low-temperature adiabatic copolymerization of the two lactams below the melting point of polymeric products (catalyst: sodium salt of lactams, activator: N-acetyl-6-caprolactam). The content of 8-caprylolactam in the copolymer cannot exceed 30 mole-% owing to its high polymerization heat and to the dependence of the copolymer melting point on the concentrations of the two lactams; the homopolymerization of the 8-caprylolactam cannot be accomplished under these conditions. The copolymer melting point exhibits a minimum in the region of the equimolar ratio of the two lactams. Further, the temperature dependence of the 8-caprylolactam specific heat was determined over an interval of 100 to 226°C (C_p = 0.2543 + 0.0007 T). The copolymerization rate of the anionic process increases with increasing content of 8-caprylolactarn, in accordance with differences of several orders existing between homopolymerization rates of the two lactams. The content of water extractable portions in the copolymers drops proportionally to increasing content of 8-caprylolactam, similarly as in equilibrium copolymers prepared by the hydrolytic copolymerization.     

Degradation kinetics of acrylonitrile/ammonium acrylate copolymers

acrylonitrile (AN)/ammonium acrylate (AAT) copolymers were prepared by H₂O/dimethyl formamide suspension polymerization technique. Differential scanning calorimetry results of the degradation of AN/AAT copolymers in air are presented. The apparent activation energy of degradation of the copolymer was calculated by using Kissinger method. Effects of copolymerization conditions on the apparent activation energy of copolymer were studied. It has been found that increasing dimethyl formamide concentration in the solvent mixture leads to a rapid increase in the degradation apparent activation energy of AN/AAT copolymer. The value of the degradation apparent activation energy of the copolymer synthesized in dimethyl formamide solvent increases up to 141.7 kJ mol^?1. The apparent activation energy decreases quickly, along with increase in AAT concentration, and this change becomes less prominent as the weight ratio of AAT/AN goes beyond 6/94. The apparent activation energy shows a trend of increase with increasing copolymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4649–4653, 2006     

Network copolyesters from benzenepolycarboxylic acids and 1,6-hexanediol

Network copolyesters were prepared from trimesic (Y), pyromellitic (X) or mellitic (Y_H) acids and 1,6-hexanediol (6G). Prepolymers prepared by meltpolycondensation were cast from dimethylformamide solution and postpolymerized at 260°C for 6h to form a network. The resultant films were transparent, flexible and insoluble in any organic solvents. Degree of reaction estimated from the infrared absorbance of ester and methylene groups was almost the same for all films, 94–96%. X-ray diffraction intensity curves and densities showed that the ordering of networks was decreased by the copolymerization, which was remarkable for 6G–X/Y_H copolymer films and was consistent with the higher decreases of heat-distortion temperature for these copolymer films. The copolymerization also caused decrease of thermal stability, tensile properties and alkali resistance and increase of dye absorption.     

Degradation of acrylonitrile–ammonium itaconate copolymers

Acrylonitrile–ammonium itaconate copolymers were prepared by H₂O/dimethyl formamide suspension polymerization technique. Differential scanning calorimetry results of the degradation of acrylonitrile–ammonium itaconate copolymers in air are presented. The apparent activation energy of degradation of the copolymer was calculated using the Kissinger method. Effects of copolymerization conditions on the apparent activation energy of copolymer were studied. Increasing the dimethyl formamide concentration in the solvent mixture leads to a rapid increase in the degradation apparent activation energy of acrylonitrile–ammonium itaconate copolymer. The value of the degradation apparent activation energy of the copolymer synthesized in dimethyl formamide solvent increases up to 168.3 kJ mol^?1. The apparent activation energy decreases quickly along with an increase in ammonium itaconate concentration, and this change becomes less prominent as the weight ratio of ammonium itaconate/acrylonitrile goes beyond 6/94, ΔE_a = 89.4 ± 2.0 kJ mol^?1. The apparent activation energy shows a trend of increase with increasing copolymerization temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1708–1711, 2005     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

Synthesis and Characterization of Poly(glycidyl nitrate‐block‐caprolactone‐block‐glycidyl nitrate) (PGN‐PCL‐PGN) Tri‐Block Copolymer as a Novel Energetic Binder

An energetic binder was synthesized through ring opening copolymerization of glycidyl nitrate (GLYN) with polycaprolactone (PCL) as a macroinitiator to form tri‐block copolymer PGN‐PCL‐PGN. Effect of monomer concentration, catalyst, reaction time and solvent was investigated in polymerization. Resulting tri‐block copolymer was characterized by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The DSC result shows that glass transition temperature of tri‐block copolymer (T_g=−56.2 °C) is lower than PGN (T_g=−35 °C). In optimal condition, the M_w of this polymer was obtained 2900 g/mol.     

On the copolymerization of epichlorohydrin and glycidol

The boron trifluoride-catalyzed cationic copolymerization of epichlorohydrin and glycidol is examined in some detail, with reference to the effect of various reaction variables such as temperature, water content, and stirring rate on the polymerization process and the copolymer product. The reaction temperature does not have a strong effect on the molecular weight of the copolymer, but the water content of the reaction mixture is inversely related to the molecular weight. The stirring rate strongly affects the exotherm associated with the initial stages of the reaction: improved stirring diminishes the exotherm. Based on the relative rates of monomer consumption and other observations, a reaction mechanism is proposed for the formation of the copolymer, in which glycidol polymerizes via what is known as the activated monomer (AM) mechanism rather than by the standard cationic ring-opening polymerization mechanism. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1897–1904, 1997     

Alternierende copolymerisation von butadien und ethen

The copolymerization of butadiene and ethene in the presence of the catalyst dineopentyloxyvanadiumoxychloride/triisobutylaluminum was investigated. Basic reaction parameters, such as the [A1]/[V] ratio, the composition of monomer mixture and the polymerization temperature result in a significant influence on the progress of reaction, the conversion of monomers and on the molecular weight and polydispersity of copolymers obtained. NMR measurements demonstrate a high degree of alternation. A maximum of conversion and molecular weight was found by variation of the ratio of catalyst components at [A1]/[V] ≈? 7. An increase of ethene content in the monomer mixture also results in a maximum of conversion but, in contrast, in a continuous decrease in molecular weight. The increase of polymerization temperature from ?25°C up to +40°C results in different effects on the yield of copolymers and appropriate data of molecular weight. The microstructure of products with a high content of trans-butadiene units exhibits an increase of 1,2-addition of butadiene and the beginning of crosslinking reactions at temperatures above 20°C.     

A tough noncombustible material prepared by grafting of poly(2‐ethylhexyl acrylate) with vinyl chloride

A noncombustible tough poly(vinyl chloride) (tPVC) was prepared by suspension‐grafted copolymerization of poly(2‐ethylhexyl acrylate) (poly‐EHA; elastomer) with vinyl chloride (VC). Elastomer (poly‐EHA) was prepared by emulsion, mainly homopolymerization of 2‐ethylhexyl acrylate at a temperature of 30 ± 0.1°C in the presence of a redox system and with the advantage of dosing the monomer into two portions. Grafted‐suspension copolymerization of poly‐EHA with VC was carried out at 54 ± 0.1°C, keeping other reaction conditions only slightly modified in comparison with those for the polymerization of pure VC. An optimum content of the incorporated poly‐EHA in PVC was found to be in the range 7.5–8.5 wt %, whereas notched toughness of 85–87 kJ m^?2 was reached. Both below and above the found range of the content of poly‐EHA, the toughness decreases. A copolymer prepared by a direct‐emulsion copolymerization of 2‐EHA and VC (poly‐EHA‐co‐VC) exhibited worse mechanical properties than the copolymer prepared by two polymerization steps. On the basis of experimental results, effects of the reaction procedure on the properties of resulting material are described. In addition to good mechanical properties, tPVC also shows its noncombustibly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2355–2362, 2002     

Synthesis of poly(ester amide)s composed of lactic acid and glycolic acid units by the bulk polycondensation of metal halide salts

Thermal polycondensation of the potassium salt of N‐methylchloroacetyl‐6‐aminohexanoic acid (LAHK) was found to be effective in the preparation of a new poly(ester amide) based on lactic acid units with a high yield and a moderate molecular weight. The reaction started in the solid state and proceeded through the formation of potassium chloride salt as the driving force. The use of a monomer having an amide linkage diminished the secondary reactions previously found in the synthesis of polylactide from 2‐halogenopropionates. The polymerization of potassium salt of N‐chloroacetyl‐6‐aminohexanoic acid (GAHK) took place in a similar temperature range as that of the 2‐chloropropionyl derivative; in this way, it was possible to conduct the copolymerization processes. The polymerization kinetics of LAHK and its mixture with GAHK was studied by Fourier transform infrared spectroscopy. The bulk polycondensation reaction was faster for GAHK than for LAHK, but the kinetic differences were not significant enough to prevent copolymerization at a temperature close to 160°C. Therefore, new degradable materials with tuned properties according to the glycolic acid/lactic acid content were obtained. ¹H‐NMR spectroscopy was useful for following the time evolution of the copolymerization process and for determining the final composition. Calorimetric data showed that all of the samples were thermally stable and that decreases in the melting temperature and enthalpy were observed at intermediate compositions. The existence of an eutectic point became proof that effective copolymerization was achieved in the thermal polycondensation process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43197.     

The radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate in an engineering flow system

A flow reactor system was used to study the radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate. The emulsion was recirculated from a stirred vessel through transfer lines to a tubular reactor located within a high-intensity Co-60 source. The effects of physical chemical variables such as soap concentration, phase ratio, reaction temperature and residence time distribution on the molecular weight properties were investigated. The rate of copolymerization was found to be proportional to the 0.17 power of the soap concentration. Variation of the monomer-water ratio produced no significant change in rate. The rate increased with an increase in temperature over the range 5–50°C, while the average molecular weights of the copolymer increased with decreasing polymerization temperature. The molecular weight distribution in this engineering system was found to be essentially similar to those produced in a batch system.