Synthesis,cationic polymerization and curing reaction with epoxy resin of 3,9‐di(p‐methoxybenzyl)‐1,5,7,11‐tetra‐oxaspiro(5,5)undecane

A new spiro ortho carbonate, 3,9‐di(p‐methoxybenzyl)‐1,5,7,11‐tetra‐oxaspiro(5,5)undecane was prepared by the reaction of 2‐methoxybenzyl‐1,3‐propanediol with di(n‐butyl)tin oxide, following with carbon disulfide. Its cationic polymerization was carried out in dichloromethane using BF₃‐OEt₂ as catalyst. The [¹H], [¹³C]NMR and IR data as well as elementary analysis of the polymers obtained indicated that it underwent double ring‐opening polymerization. The polymerization mechanism is discussed. The curing reaction of bisphenol A type epoxy resin in the presence of the monomer and a curing agent was investigated. DSC measurements were used to follow the curing process. In the case of boron trifluoride‐o‐phenylenediamine (BF₃‐OPDA) as curing agent, two peaks were found on the DSC curves, one of which was attributed to the polymerization of the epoxy group, and the other to the copolymerization of the monomer with the isolated epoxy groups or homopolymerization. However, when BF₃‐H₂NEt was used as curing agent, only one peak was present. IR measurement of the modified epoxy resin with various weight ratios of epoxy resin/monomer was performed in the presence of BF₃‐H₂NEt as curing agent. The results demonstrate that the conversion of epoxy group increases as the content of monomer increases. The curing process and the structure of the epoxy resin network are discussed. © 2000 Society of Chemical Industry     

Copolymerization of styrene and methyl methacrylate with nickel acetylacetonate/methylaluminoxane catalyst system

The present work deals with copolymerization of styrene (STY) and methyl methacrylate (MMA) catalysed by nickel acetylacetonate - Ni(acac) ₂ , employing methylaluminoxane (MAO) as cocatalyst. This catalyst system presented low catalyst activities for STY homopolymerization and very high activities for MMA. It seems that the catalyst system based on Ni(acac) ₂ /MAO is effective for the copolymerization of MMA and STY to give block copolymer but it also produced polystyrene and poly(methyl methacrylate) homopolymers. The polymers were characterized by ¹³ C NMR, GPC and FTIR. The polystyrene homopolymer was identified by IR and NMR analyses of the cyclohexane soluble fraction. The presence of absorption bands correspondent to carbonyl group and aromatic ring was observed in the IR spectrum of the acetic acid soluble part. This result is a clue that STY-MMA copolymer with low molecular weight was produced. The high molecular weight copolymer (acetic acid insoluble fraction) was also characterized by IR analysis which indicated the presence of characteristic absorption bands of carbonyl group and aromatic ring. These results were confirmed by ¹³ C NMR analysis. Received: 6 August 1997/Revised version: 29 December 1997/Accepted: 7 January 1998     

Graft copolymerization of polyacrylonitrile (PAN) onto polyester (PET) and simultaneous homopolymerization: A kinetic study. I

The kinetics of graft copolymerization of polyacrylonitrile (PAN) onto polyester (PET) and the simultaneous homopolymerization initiated by the potassium penoxomonosulfate (PMS)–ascorbic acid (H₂A) redox system were studied separately. Results on the graft copolymerization was adequately explained by a mechanism which also accounts for the reason for simultaneous homopolymerization. The observed homopolymerization results agreed with the proposal. Kinetic chain-length measurements on the graft copolymer and homopolymerization were used to evaluate the kinetic parameters. © 1995 John Wiley & Sons, Inc.     

Curing of unsaturated polyester resins: Effects of comonomer composition. II. High-temperature reactions

The effects of comonomer composition of the curing kinetics of unsaturated polyester (UP) resins at 100–120°C were investigated by differential scanning calorimetry (DSC) and infrared spectroscopy (IR) over the entire conversion range. One commercial UP resin, UP2821, with 6.82 unsaturated C?C bonds per polyester molecule, was used. For styrene/UP2821 reactions, experimental results of the initial and maximum reaction rates by DSC at 100–120°C revealed that the styrene content, as well as the reaction temperature, would affect the formation of microgel structures. As the initial molar ratio of styrene to polyester C?C bonds increased, the styrene swelling effect could enhance the intramicrogel crosslinking reactions, while the styrene dilution effect could diminish the intermicrogel crosslinking reactions. The competition between the two reactions would depend on the reaction temperatures. Finally, a microgel-based reaction mechanism was proposed for the high temperature reactions. © 1993 John Wiley & Sons, Inc.     

Crosslinking of unsaturated polyester resins studied by low-resolution 1H-NMR spectroscopy

The curing behavior of five unsaturated polyester resins with different molar ratios of styrene to the double bonds in the polyester chain (MR) was investigated. The gel time was measured according to a standard method by the Society of the Plastic Industry (SPI) and by low-resolution pulse nuclear magnetic resonance (LRP-NMR). The gel and curing times decreased and the maximum temperature of the reaction increased when the MR was decreased. The proton mobilities and populations were measured by LRP-NMR. Three components could be seen in the crosslinking reaction: styrene (very mobile, T₂ ≅ 3 s), free polyester polymers (less mobile, T₂ ≅ 150 ms), and cured resin (immobile, T₂ ≅ 0.04 ms). The third component, cured resin, could be detected at the gel point. At this point, the proton mobilities of styrene and free polyester polymers were rapidly decreasing and the proton populations of the cured resin started to increase. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 77–83, 1997     

Curing of unsaturated polyester resins—effects of comonomer composition. III. Medium-temperature reactions

The effects of comonomer composition on the curing kinetics of unsaturated polyester (UP) resins at 70–90°C were studied by differential scanning calorimetry (DSC) and infrared (IR) spectroscopy over the whole conversion range. One commercial UP resin, UP2660PF2, with cobalt promoter added and with 8.85 unsaturated C?C bonds per polyester molecule, was used. It was found that a marked shoulder in the initial DSC rate profile, rather than that reported after the peak of rate profile for low-temperature and high-temperature reactions, appeared when the molar ratio of styrene to polyester C?C bonds was greater than 1. With the initiator system accelerated by cobalt promoter, the formation rate of microgel particles would be enhanced at the early stage of reaction, as supported by the much higher conversion of polyester C?C bonds than that of styrene by IR spectroscopy. Those relatively greater number of microgel particles tended to facilitate the intramicrogel crosslinking reactions, which would be independently identified from the initial DSC rate profile as a shoulder. Consequently, the reaction mechanism was elucidated by decomposing the reaction rate profile into two individual profiles accounting for the intramicrogel dominated and the intermicrogel dominated crosslinking reactions, respectively. © 1993 John Wiley & Sons, Inc.     

Cure behavior of unsaturated polyester/modified montmorillonite nanocomposites

Dynamic rheology, differential scanning calorimetry and in situ Fourier transform infrared spectroscopy were used to study the cure behavior of unsaturated polyester/modified montmorillonite nanocomposites. The results showed that their gel times increased markedly at the same cure temperature, and that the activation energy of the nanocomposites was higher than that of the pure unsaturated polyester. Their peak temperatures of enthalpy increased as well. The total exotherm of the cure reaction declined and the cure rate decreased. In the curing process of pure unsaturated polyesters, the conversion of styrene was higher than that of the double bonds on unsaturated polyester macromolecular chains. The cure mechanism of the unsaturated polyester/modified montmorillonite changed because of the presence of double bonds in the layers of modified montmorillonite. However, the conversion of styrene in the nanocomposites was lower than that of double bonds on unsaturated polyester chains during cure at room temperature, and the conversion of styrene was increased after post‐curing and was higher than that of the double bonds on unsaturated polyester chains at the end of the cure reaction. Moreover, the degree of reaction of double bonds on unsaturated polyester chains of the nanocomposites was higher than that of unsaturated polyesters. Copyright © 2006 Society of Chemical Industry     

Synthesis and properties of poly(butylene succinate) with N-hexenyl side branches

N-hexenyl side branches were introduced into poly(butylene succinate) (PBS) by polymerization of succinic acid (SA) with 1,4-butanediol (BD) in the presence of 7-octene-1,2-diol (OD). Thermal properties and biodegradability of the aliphatic polyesters were investigated before and after epoxidation of the pendant double bonds. The glass-transition temperature (T_g) decreased with the branching density to give a minimum at 0.03 mol of branching units per mole of structural units. Thereafter, T_g increased due to the in situ crosslinking of the unsaturated groups during the differential scanning calorimetry (DSC) measurements. N-Hexenyl side branches decreased melting temperature (T_m) more significantly than ethyl side branches, but the effect was on par with that by n-octyl branches. Epoxidation of the double bonds decreased T_m and melting enthalpy (ΔH_m), but increased T_g of the aliphatic polyester. Biodegradability was enhanced to some extent by the presence of n-hexenyl side branches. However, the epoxidation of the unsaturated groups did not notably affect the biodegradability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2219–2226, 2001     

Curing of unsaturated polyester resins—effects of pressure

The effects of pressure ranging from 0.1 to 6.21 MPa (0–900 psig) on the curing of unsaturated polyester resins at 110°c were investigated by an approach of integrated reaction kinetics-rheology-morphology measurements using a pressure differential scanning calorimeter (DSC), an infrared spectrophotometer (IR), a Haake rheometer, and by using scanning electron microscopy (SEM). Increasing pressure was found to delay the gel effect, and a previously unknown plateau of kinetic-controlled region in the initial portion of the DSC rate profile was observed. The plateau region was mainly attributed to the crosslinking of C ? C double bonds inside the microgel particles, as revealed by the conversions of styrene and polyester C ? C bonds measured by IR, gel conversion data and SEM micrographs. The mechanisms of reaction kinetics both at atmospheric pressure and under pressures have also been elucidated by the progress of buildup of microgel structures.     

Kinetic analysis and mechanical properties of nanoclay reinforced unsaturated polyester (UP) resins cured at low temperatures

The reaction between unsaturated polyester (UP) resin and styrene (St) is a heterogeneous free‐radical chain‐growth cross‐linking copolymerization. Curing of the UP/St system in the presence of organically‐modified nanoclay was studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. A mechanistic kinetic model based on the free radical copolymerization mechanism was developed to simulate the reaction rate and conversion profiles of UP/St resin mixtures with various nanoclay contents cured at low temperatures. The model parameters were determined from several DSC experiments under isothermal conditions. The model, in conjunction with heat transfer analysis, was able to successfully predict the temperature and conversion profiles during curing in two vacuum‐infusion liquid composite molding (e.g., the Seemann composite resin infusion molding process [SCRIMP]) experiments. The presence of nanoclay particles enhanced the tensile modulus, but reduced the tensile strength of the UP nanocomposites. The fracture toughness parameter K_IC was improved by 30% with the addition of 5 wt% nanoclay. The system with mixed nanoclay and calcium carbonate was found to possess the highest K_IC without sacrificing the tensile strength. POLYM. ENG. SCI., 45:496–509, 2005. © 2005 Society of Plastics Engineers     

DSC curing study of catalytically synthesized maleic‐acid‐based unsaturated polyesters

Unsaturated polyesters were synthesized based on ethylene glycol and maleic acid as unsaturated dicarboxylic acid, using a variety of saturated acids in the initial acid mixture, without or with different catalysts. The curing of the polyesters produced with styrene was studied using differential scanning calorimetry (DSC) under dynamic‐ and isothermal‐heating conditions. The FTIR spectra of the initial polyesters and cured polyesters were also determined. Curing is not complete at the end of DSC scan and the unreacted bonds were quantitatively determined from the FTIR spectra and by estimation based on literature data. The value of the mean degree of conversion (α) of all double bonds (styrene unit and maleate unit) was approximately α = 0.40. Using an appropriate kinetic model for the curing exotherm of polyesters, the activation energy (E_a), the reaction order (x) and the frequency factor (k_o) were determined. Because the kinetic parameters (ie E_a, k, x) affect the kinetics in various different ways, the curves of degree of conversion versus time at various isothermal conditions are more useful to compare and characterize the curing of polyesters. The kinetic parameters are mainly influenced by the proportion of maleic acid in the polyesterification reaction mixture and secondarily by the residual polyesterification catalyst. The degree of conversion of already crosslinked polyesters is greatly increased by post‐curing them at elevated temperature and for a prolonged time. © 2002 Society of Chemical Industry     

烯丙基醚改性不饱和聚酯树脂的空干性能研究

本文研究了氧气氛围中苯乙烯、烯丙基醚的氧化聚合机理和苯乙烯与烯丙基醚的氧化共聚机理，对烯丙基醚的空干性机理进行较为深入阐述，并应用差热扫描仪、扫描电镜、热谱仪和红外光谱仪等仪器和手段，探讨了不同饱和酸骨架和烯丙基醚含量对树脂性能的影响。     

Microgelation of unsaturated polyester resins by static and dynamic light scattering

The microgelation phenomenon during the curing of unsaturated polyester resin was investigated by both static and dynamic light scattering before gelation. The results of static light scattering revealed that the polymer molecular weight increased with degree of curing. The second virial coefficient, A₂, decreased slowly in the initial stage of curing and decreased dramatically at a conversion around α ∼ 8.7%, indicating a drastic decrease of compatibility between the polyesters and styrene. Two modes of the size distribution of the microgel particles during curing were observed by dynamic light scattering. The small particles consist of primary unsaturated polyester molecules. The large ones consist of microgel particles formed by linking adjacent polyester molecules. The sizes of the microgel particles increased in the initial stage of curing, then decreased slightly at a conversion of α ∼ 8.7%, which was due to the intramolecular crosslink reaction of the microgel particles. The experimental results revealed that the compatibility between polyesters and the styrene monomer became worse as the intramolecular crosslinking reaction inside the microgel particles caused a tight packing of the micro-gel molecules. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 871–878, 1998     

Synthesis and conformation studies of copolypeptides composed of γ-methyl-l-glutamate and ε-N-carbobenzyloxy-l-lysine

Copolypeptides (PMGCL) composed of γ-methyl-l-glutamate(MLG) and $\text{?-N-}\text{carbobenzyloxy-}\text{l}\text{-lysine(CBL)}$ covering the whole range of copolymer composition were synthesized by the N-carboxyanhydride (NCA) method. The experimentally obtained monomer reactivity ratios were r₁(MLG)=2·0±0·4 and r₂(CBL)=0·5±0·1, from which the fractions of monomer dyads and triads in copolymer were plotted against the initial comonomer composition. From experimental results on thermally induced coil-to-helix transition of the copolypeptides in dichloroacetic acid/1,2-dichloroethane (DCA-DCE) systems, it has been found that these copolypeptides can exist in the α-helix conformation in the same manner as homopolypeptides PMLG and PCBL. The van't Hoff heat of transition ΔH showed a minimum against the initial monomer composition. The enthalpy ΔH_res of formation of intramolecular hydrogen bonds per peptide bond also showed a minimum against copolymer composition. Such behaviour on ΔH and ΔH_res was also found for copolypeptide (PBGCL) composed of γ-benzyl-l-glutamate(BLG) and $\text{?-N-}\text{carbobenzyloxy-}\text{l}\text{-lysine(CBL)}$ in DCA-DCE systems reported in a previous paper. The presence of a minimum in these relationships may be attributed to specific interactions between the side chain of one comonomer and that of the other comonomer in a two component copolymer. It is also pointed out that these copolymer molecules can exist in the α-helix conformation in the solid state.     

Crystal Structure and Improved Synthesis of 1‐(2H‐Tetrazol‐5‐yl)guanidium Nitrate

Energetic derivatives of tetrazoles are one of the key areas of research focus in pursuit of novel high energy materials, useful as propellants and explosives. Herein, the crystal structure and an improved synthetic procedure of 1‐(2H‐tetrazol‐5‐yl)guanidine ( 1 ) and its nitrate salt ( 2 ) are reported. The compounds were structurally characterized by spectroscopic (FT‐IR, ¹H NMR, ¹³C NMR) and elemental analysis. The molecular structure of tetrazolyl guanidium nitrate ( 2 ) was solved using low temperature single‐crystal X‐ray diffraction. 2 crystallized as its hemihydrate in the orthorhombic space group Fdd2, with a crystal density of 1.69 g cm⁻³. Thermal behavior and decomposition of the molecules were studied with differential scanning calorimetry (DSC). Molar enthalpy of formation (Δ_fH^m) of compound 2 was back calculated from heat of combustion (Δ_cH⁰) value obtained experimentally using bomb calorimetric measurements. Lattice enthalpy of 1‐(2H‐tetrazol‐5‐yl)guanidium nitrate was directly calculated from measured crystal density using Jenkins equation. Preliminary ballistic parameters of the compound were predicted and compared with reported high nitrogen tetrazole derivatives.     

Some filler effects on cross-linking of unsaturated polyesters

The effect of five fillers on the cross-linking macro-and microcharacteristics of simple unsaturated polyester resins was investigated by differential scanning calorimetry (DSC), reactivity tests, and gel time tests. Glass beads and silica flour appeared to have little influence on the cross-linking reaction of the resin itself, their effect being comparable to mere dilution of the resin. Kaolin presented some interaction with the resin due to its absorption characteristics and acid groups. Reground polyester/glass fiber powder and especially wood flour appeared to present clear chemical interactions with the curing behavior of the resin. Wood flour, in particular, was shown by DSC analysis to strongly co-react with the resin during cross-linking and altered markedly the resin enthalpy change and energy of activation during curing. The wood flour component causing the altered behavior of the resin appears to be lignin. DSC analysis of resins filled with three different types of isolated lignins indicated that this wood flour component reacts in a heterogeneous phase reaction with the resin during cross-linking. It appears that it is the lignin unsaturated carbon–carbon double bonds at the polyester/wood flour and at the polyester/lignin interphases that are likely to co-react by heterogeneous phase radical cross-linking with the polyester resin and styrene unsaturation, markedly changing the resin curing behavior. © 1993 John Wiley & Sons, Inc.     

Styrene–substituted‐styrene copolymerization using diphenylzinc–metallocene–methylaluminoxane systems

Homopolymerization of disubstituted styrenes (2,4‐ and 2,5‐dimethylstyrene) and trisubstituted styrene (2,4,6‐trimethylstyrene) and their copolymerization with styrene were carried out using diphenylzinc–metallocene–methylaluminoxane initiator systems for metallocene (n‐BuCp)₂TiCl₂ and for half‐metallocene CpTiCl₃. The studied comonomers were found to be less reactive than p‐tertbutylstyrene, p‐methylstyrene and styrene. The results indicate that, even though the methyl group has I+ inductive effect, di‐ and tri‐methylstyrenes are reluctant to undergo either homopolymerization or copolymerization. This behavior suggests that the reactivity is regulated not only by the inductive effect of the alkyl group but also by the steric impediment caused by the crowding of the substituents on the benzene ring. Copyright © 2006 Society of Chemical Industry     

The effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin

An experimental study was conducted to investigate the effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin during isothermal cure. For the study a general-purpose unsaturated polyester resin was cured in the presence of t-butyl perbenzoate as Initiator. The curing behavior of the resin was investigated using differential scanning calorimetry (DSC). Three different thermoplastic low-profile additives were used, namely poly(vinyl acetate) (PVAc), poly(styrene-co-butadiene), which is also known as KRATON DX-1300, and dehydrochlorinated Isobutylene/isoprene copolymer, often referred to as conjugated diene butyl (CDB) rubber. Each of the these additives, about 30 weight percent, was first dissolved in styrene. The solution was then mixed with unsaturated polyester resin and CaCO₃. The CaCO₃ particles helped stabilize the emulsions consisting of resin and KRATCN, and of resin and CDB. For each resin formulation, a series of isothermal DSC runs were made at various levels of cure pressure. It was found that for all three low-profile resins investigated, the final degree of cure went through a maximum as cure pressure was increased from atmospheric to 6.21 MPa (900 psi). We have observed evidence that in the presence of an initiator generating free radicals, the unsaturated double bonds in the KRATON and CDB undergo grafting reactions with the styrene monomers and unsaturated polyester resin, increasing the glass transition temperature of KRATON and CDB, to an extent which varies with the cure conditions employed. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer. The rheological measurements indicate that the resin/CaCO₃/KRATON and resin/CaCO₃/CDB systems give rise to gel times shorter than the resin/CaCO₃/PVAc system. It is concluded that both KRATON and CDB are more effective, both for enhancing the rate of cure of unsaturated polyester resin and imparting impact properties to the cured composites, than those thermoplastic low-profile additives that contain neither unsaturated double bonds nor a chemical structure that has rubber-like properties in the solid state.     

Synthesis and characterization of styrene–N-butyl maleimide copolymers using iniferters containing thiyl end groups

The radical homopolymerization of styrene or copolymerization of styrene (S) with N-butyl maleimide (I) initiated by tetraethylthiuram disulfide was used to prepare macroinitiators having thiyl end groups. The S–I copolymers from the feeds containing 30–70 mol % I showed approximately alternating composition. The rate of copolymerization and molecular weights decreased with increasing maleimide derivative concentration in the feed; homopolymerization of I alone did not proceed. The macroinitiators served for synthesis of further S–I copolymers. Using polystyrene macroinitiator and the S–I copolymer with thiyl end groups in the polymerization of S–I mixture and styrene, respectively, the copolymers containing blocks of both polystyrene and alternating S–I copolymer were obtained. The copolymerization of S–I mixture initiated with the S–I copolymer bearing thiyl end groups led to the extension of macroinitiator chains by the blocks of alternating copolymer. The presence of the blocks in the polymer products was corroborated using elemental analysis, size exclusion chromatography, and differential scanning calorimetry. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 755–762, 1998     

Structure and properties of p-carboxysuccinanilic polyester resins

Polyester resins were prepared by the reaction of p-carboxysuccinanilic acid ethyl ester with ethylene glycol and 1,4-butenediol. Also, unsaturated polyester resins were prepared by the copolymerization of p-carboxysuccinanilic acid ethyl ester and maleic anhydride with ethylene glycol, 1,6-hexanediol, 1,4-butenediol, and 2-butyne-1,4-diol. All the polyester resins and the copolyesters have been characterized and were found to cure with styrene, except those prepared in the absence of maleic anhydride. The properties of the cured products in the form of films were determined. Infrared and nuclear magnetic resonance (NMR) spectroscopy were used for both qualitative and quantitative analyses of the polyester resins and their hydrolyzate products after curing with styrene.