Gel formation in diimide‐hydrogenated polymers

The hydrogenation of diene‐based polymers via diimide is a very attractive alternative to the conventional catalytic hydrogenation route based on gaseous molecular hydrogen. However, serious crosslinking always accompanies it and limits the end‐use properties of the polymers. Gel formation in polymers that are hydrogenated via diimide has been investigated in detail through an inspection of all the chemical reactions involved in the process. The results indicate that hydrogen peroxide decomposition, some reactions related to oxygen, and the redox reaction between hydrogen peroxide and hydrazine are capable of generating radicals. However, radicals generated in the aqueous phase do not appear to initiate the crosslinking of diene‐based polymers in the latex form. It is proposed that the primary radicals giving rise to crosslinking are generated in the polymer phase in situ, and the step responsible for generating these organic radicals is possibly the diimide disproportionation reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1122–1125, 2005     

Electron beam irradiation of ethylene‐propylene terpolymer: Evaluation of trimethylol propane trimethacrylate as a crosslink promoter

The effect of electron beam irradiation on ethylene‐propylene terpolymer (EPDM) was investigated. A 50‐part oil‐extended EPDM with high termonomer (ENB) content (iodine number of base polymer) 19, was selected for this study. An increase in irradiation dose from 0 to 200 kGy resulted in increased crosslinking, measured by an increase in gel contents and better swelling resistance. The effect of the multifunctional monomer trimethylol propane trimethacrylate (TMPTMA) as a crosslink promoter was studied using IR spectroscopy. The IR studies revealed enhanced peak absorbances at 1725, 1257, and 1023 cm^?1 as a result of the increased concentration of C = O and C‐O‐C groups and reduced absorbance at 1630 cm^?1 due decreased concentration of C = C groups with TMPTMA level in the irradiated samples. The presence of TMPTMA increased the level of crosslinking at a given irradiation dose, which was manifested by improvement in tensile properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 968–975, 2005     

Effect of Ammonia on Silicone Rubber-Glass Adhesion

The adhesion energy between silicone rubber and glass has been obtained from the Johnson, Kendall and Roberts' test. The specific effect of ammonia on the quasi-equilibrium value has been studied as a function of the degree of crosslinking of the elastomer. For PDMS networks with lower molecular weight between crosslinks, the effect is more pronounced but completely reversible. This has been related to the increase in the non-dispersive part of the surface energy of the silicone due to the imbibed ammonia. In incompletely crosslinked hydroxyl-terminated PDMS, ammonia has a catalytic effect and is responsible for chemical bonding between the unreacted hydroxyl groups of the PDMS and the hydroxyl groups on glass.     

Gamma‐ray irradiation effect of polyethylene on dimaleimides as a class of new multifunctional monomers

Multifunctional monomers, m‐xylylenedimaleimide, p‐phenylenedimaleimide, m‐phenylenedimaleimide, and p‐phenylenedinadimide, all of which have maleimide groups, were synthesized to increase thermal and radiation stabilities. The synthesized multifunctional monomers showed good compatibility with low‐density polyethylene (LDPE). Mixtures of LDPE and these multifunctional monomers were irradiated with γ‐rays from a Co‐60 source at room temperature in a nitrogen atmosphere. The absorbed dose ranged from 0 to 160 KGy. Among these multifunctional monomers, m‐xylylenedimaleimide was the best in gel fraction enhancement. Crosslinked LDPE with m‐xylylenedimaleimide displayed a higher modulus than that of crosslinked LDPE with triallyl cyanurate. For the elongation property, LDPE with m‐xylylenedimaleimide as a multifunctional monomer showed better results than that with commercial multifunctional monomers such as triallyl cyanurate (TAC) and trimethylol propane triacrylate (TMPTA). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2339–2345, 2003     

Synthesis and characterization of novel copolymers with acid‐labile ketal moieties derived from camphor

Novel diastereomeric acrylic ketal monomers derived from (+)‐camphor and (±)‐camphor were synthesized. To investigate the applications of the camphor derivatives on positive‐tone photoresists, the acrylic ketal monomers were copolymerized with methyl methacrylate, methacrylic acid, and n‐butyl methacrylate. The optical activities of the chiral monomers and polymers were all evaluated. After UV irradiation and postexposure baking, the optical activity of the polymers decreased because of the decomposition of the acid‐labile pendant chiral groups. The existence of alicyclic camphyl groups increased the etching resistance of the photoresists. The thermogravimetric properties of the copolymers, the exposure curves, the lithographic evaluation of the positive‐tone photoresists, and the effects of alicyclic groups on the plasma etching resistance of the copolymers were all investigated. A resolution of a line‐and‐space pattern of 0.3 μm was achieved. Acid‐catalyzed dehydration crosslinking was also found in this system. Sufficient UV irradiation and heat treatment could cause the acid‐catalyzed dehydration crosslinking of pendant carboxyl groups and thereby increase the efficiency of the thermal resistance of the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2969–2978, 2003     

Interfacial tension measurement between immiscible polymers: improved deformed drop retraction method

This paper describes an improvement of the technique to measure interfacial tension in immiscible polymer blends. Our method is based on the droplet retraction method, in which one relates the kinetics of relaxation of a deformed droplet to the interfacial tension between the matrix and droplet. Previously, the problem with this technique has been the difficulty in preparing axisymmetric ellipsoidal droplets. In our work, we demonstrate that perfect axisymmetric ellipsoidal droplets are produced at a later stage of relaxation of short imbedded fibers. With this technique, we utilize the strengths of both the deformed droplet method and the imbedded fiber retraction method while overcoming their shortcomings. The interfacial tension value thus obtained was compared to that by conventional methods. Additionally, the effect of confinement by external walls on the interfacial tension measurement was studied. Confinement affects interfacial tension measurement when the gap between the walls is less than two times the equilibrium drop size.     

吸收剂量对二甲基硅橡胶与甲基乙烯基硅橡胶分子量和凝胶含量的影响

将ＧＰＣ和特性粘数［η］测定相结合，在室温和－７８℃下，用Ｃｏ~（６０）辐射源辐照，研究了二甲基硅橡胶（ＭＱ，吸收剂量２．０５×１０~３～３．９７×１０~４Ｇｙ）和甲基乙烯基硅橡胶（ＭＶＱ，吸收剂量１０~２～１０~４）分子量和凝胶含量的变化。结果表明，辐照ＭＶＱ较辐照ＭＱ易生成凝胶，在凝胶点前的较低吸收剂量时，溶胶的分子量出现极大值，分子量分布曲线呈单峰；随吸收剂量的增加，分子量分布变窄，分子量降低；出现凝胶的吸收剂量，ＭＱ大约是ＭＶＱ的１０倍。辐照ＭＱ时，凝胶点前的溶胶的分子量分布曲线为双峰，并随吸收剂量的增加，双峰消失，分子量下降；在凝胶点时，分子量出现极大值。     

柔软热收缩材料的研制

总结了经共混和辐射交联制备柔软耐老化的热收缩材料的研制过程。测得了不同乙丙橡胶含量和不同辐照剂量下的共混物的力学性能和凝胶含量，确定了共混物辐射交联的合适剂量。此外，还测试了ＥＰＤＭ和ＰＥ共混物经辐照后的耐油性能。在此基础上，制得了手感柔软的热收缩管材。     

Interfacial polymerization of pyrrole and in situ synthesis of polypyrrole/silver nanocomposites

We present a new synthetic approach leading to the formation of polypyrrole architectures in submicron level and to silver/polypyrrole nanocomposites via an interfacial polymerization in a water/chloroform interface. The oxidizing agent was either Ag(I) or Fe(III). In the first case, silver nanoparticles resulted. The mean diameter of the polypyrrole structures is in the range of 200-300 nm according to the addition or not of various surfactants. The progress of the reaction was studied by UV-visible spectroscopy, which also revealed the formation of a polaron band during the growth of the oligomers. The crystal structure of the polymers was examined by X ray diffractometry and all samples appeared to be amorphous, while the samples were further characterized by thermogravimetric analysis and FT-IR spectroscopy.     

Effects of resin chemistry on redox polymerization of unsaturated polyester resins

Unsaturated polyester resins are the most widely used thermoset resins in the composite industry. In this study, three well‐defined unsaturated polyester resins were used. These resins have similar number‐average molecular weights, and they have different numbers of C?C bonds per molecule. The reaction kinetics of unsaturated polyester resins was studied using a differential scanning calorimeter (DSC) and a Fourier transform infrared (FTIR) spectrometer. The glass transition temperature of the isothermally cured resin was also measured. Trapped radicals were observed in the cured polyester resin from electron spin resonance (ESR) spectroscopy. Considering the diffusion‐limitation effect, a simple kinetic model was developed to simulate the reaction rate and conversion profiles of polyester vinylene and styrene vinyl groups, as well as the total reaction rate and conversion. Experimental results from DSC and FTIR measurements compare favorably with the model prediction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 211–227, 2002; DOI 10.1002/app.10317