Heterochain model for simultaneous long‐chain branching and crosslinking. III. Multicomponent polymerization

The matrix formula developed in the context of heterochain theory, M?_w = M?_wp + WF ( I ? M )^?1 S , was applied to describe the molecular weight development during free‐radical multicomponent polymerization. All of the required probabilistic parameters are expressed in terms of the kinetic‐rate constants and the various concentrations associated with them. In free‐radical polymerization, the number of heterochain types, N, needs to be extrapolated to infinity, and such extrapolation is conducted with only three different N values. This matrix formula can be used as a benchmark test if other approximate approaches can give reasonable estimates of the weight‐average molecular weights. The moment equations with the average pseudo‐kinetic‐rate constants for branching and crosslinking reactions may provide poor estimates when the copolymer composition drift during polymerization is very significant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2801–2812, 2004     

Effect of photoinitiator on photopolymerization of inorganic–organic hybrid polymers (ORMOCER®)

Inorganic–organic hybrid polymers have been developed and tested for evaluation in optical and electrical applications. Although hybrid inorganic–organic polymers can be synthesized by sol–gel chemistry at first, the physical properties of hybrid inorganic–organic polymers are changed during thin film-making processes, that is, photocuring and thermal curing. To investigate the effect of photoinitiator on the material properties during processing, a model system containing methacrylic groups as organically polymerizable units was selected. The conversion of CC double bond of methacrylic groups depending on some kinds of photoinitiator quantities was characterized by Fourier transform infrared spectroscopy. It was confirmed to correlate the degree of CC double bond conversion with the refractive indices. Thermodynamically, the enthalpy of the photopolymerization of hybrid polymer was investigated by UV–DSC. UV–DSC spectra showed the exothermic nature of photopolymerization of ORMOCER® to be in dependence of photoinitiator quantities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1979–1986, 2004     

Fracture mechanism of liquid‐crystalline epoxy resin systems with different phase structures

A liquid‐crystalline epoxy resin was cured at two different temperatures. The phases of the cured systems clearly showed isotropic and nematic polydomain structures, which depended on the curing temperature. The fracture toughness of the systems was measured, and the fracture mechanism was investigated with polarized IR measurements. The nematic polydomain structure system showed considerably higher fracture toughness than the isotropic structure. Moreover, both systems exhibited a reorientation of the network chains near the fracture surface during the fracture process, and the region of the network reorientation in the nematic polydomain structure system was larger than that in the isotropic structure system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4044–4052, 2004     

Physical properties of glycosaminoglycan hydrogels

The chemical composition of glycosaminoglycan (GAG) hydrogels was found to have a profound effect on the physical properties of gels. Hyaluronan (HA) and chondroitin sulfate (CS) were each modified with adipic dihydrazide (ADH) with carbodiimide chemistry. The resulting polymer was crosslinked with various concentrations of poly(ethylene glycol) dialdehyde (PEG‐diald) to produce a series of hydrogels. The physical properties of these GAG hydrogels varied in a concentration‐dependent fashion. Maximal crosslinking was observed at a theoretical crosslinking of 50% for the HA‐ADH‐PEG‐diald hydrogels and 75% for the CS‐ADH‐PEG‐diald hydrogels. Adding PEG‐diald beyond the optimum for crosslinking prolonged the in vitro enzymatic degradation time of the hydrogels. The swelling of the crosslinked GAG hydrogels was correlated with the amount of PEG‐diald used rather than with the crosslinking density. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4344–4356, 2004     

Stability control of the electrooptic effect with new maleimide copolymers containing photoreactive tricyanopyrrolidene‐based chromophores

New photocrosslinkable maleimide copolymers have been synthesized by the attachment of a tricyanopyrrolidene‐based chromophore. The 2‐(3‐cyano‐4‐(2‐{4‐[hexyl‐(6‐hydroxy‐hexyl)‐amino]‐phenyl}‐vinyl)‐5‐oxo‐1‐{4‐[4‐(3‐oxo‐3‐phenyl‐propenyl)‐ phenoxy]‐butyl}‐1,5‐dihydro‐pyrrol‐2‐ylidene)‐malononitrile chromophore exhibits nonlinear optical activity and contains a chalcone moiety that is sensitive to UV light (λ = 330–360 nm) for crosslink formation. The maleimide monomers have also been functionalized with chalcone moieties. The resultant copolymers exhibit great processability, and one of them shows a maximum electrooptic coefficient of 90 pm/V at 1300 nm. We could control the thermal stability of the electrooptic coefficient with the newly synthesized photoreactive copolymers successfully. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 531–542, 2007     

Synthesis and thermal crosslinking of oxazolidine‐functionalized polyurethanes

A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (M_w ～ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007     

Investigation on crosslinking behaviors of NBR/PVC filled with anhydrous copper sulfate particles by dynamic mechanical analysis

Crosslinking behaviors of acrylonitrile butadiene rubber (NBR)/poly (vinyl chloride) (PVC) alloy, filled with anhydrous copper sulfate (CuSO₄) particles, were investigated for the first time by dynamic mechanical analysis (DMA) under hetero and isothermal modes, respectively. In the heterothermal testing, (NBR/PVC)/CuSO₄ compound showed two marked increases in the storage modulus (E′), corresponding to coordination crosslinking of NBR-CuSO₄ and self-crosslinking of NBR and PVC respectively. During the isothermal testing, a dramatic increase in E′ was found at the initial stage while that of original NBR/PVC alloy was not detected. The marked increase in E′ of (NBR/PVC)/CuSO₄ compound was mainly due to the crosslinking induced by coordination between  CN and Cu²⁺. The increasing extent of E′ increased with the rise of CuSO₄ content, suggesting the formation of a greater number of crosslinks. Moreover, the activation energy (E_a) of crosslinking process was about 139 kJ/mol. In this work, fourier transform infrared spectrum (FT-IR) and equilibrium swelling method were also performed for the characterization of the compound. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 41–51, 2007     

Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004     

Dialdehyde starch‐crosslinked chitosan films and their antimicrobial effects

For improved mechanical and water‐swelling properties of chitosan films, a series of transparent films were prepared with dialdehyde starch as a crosslinking agent. Fourier transform infrared and X‐ray analysis results demonstrated that the formation of Schiff's base disturbed the crystallization of chitosan. The mechanical properties and water‐swelling properties of the films were significantly improved. The best values of the tensile strength and breaking elongation were 113.1 MPa and 27.0%, respectively, when the dialdehyde starch content was 5%. All the crosslinked films still retained obvious antimicrobial effects toward S. aureus and E. coli, and they showed potential for biomedical applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 993–997, 2003