Study on the properties of crosslinking of poly(ethylene oxide) and hydroxyapatite–poly(ethylene oxide) composite

This study covers the crosslinking of poly(ethylene oxide) (PEO) and its composite with calcium hydroxyapatite (HA), their mechanical and swelling properties, and morphology. Sheets of the composites of PEO (two different grades with M_v: 5 × 10⁶ and 2 × 10⁵) and HA and neat PEO were prepared by compression molding. The prepared composite and PEO (0.1‐mm‐thick) sheets were crosslinked with exposure of UV‐irradiation in the presence of a photoinitiator, acetophenone (AP). This simple method for crosslinking, induced by UV‐irradiation in the presence of AP, yielded PEO with gel content up to 90%. Gel content, equilibrium swelling ratio, and mechanical and morphological properties of the low molecular weight polyethylene oxide (LMPEO)–HA crosslinked and uncrosslinked composites were evaluated. Although the inclusion of HA into LMPEO inhibits the extent of crosslinking, the LMPEO–HA composite with 20% HA by weight shows the highest gel content, with appreciable equilibrium swelling and mechanical strength. The growth of HA in simulated body fluid solutions on fractured surfaces of LMPEO and also LMPEO–HA was found to be very favorable within short times. The dimensional stability of these samples was found to be satisfactory after swelling and deposition experiments. The good compatibility between the filler hydroxyapatite and poly(ethylene oxide) makes this composite a useful tissue‐adhesive material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 488–496, 2003     

吸水树脂PAA／AM的合成研究

以N，N-亚甲基双丙烯酰胺（Bis）为交联剂，过硫酸钾（KPS）做引发剂，以丙烯酸（AA），丙烯酰胺（AM）为反应单体水溶液聚合法合成了适用于淡水和盐水的吸水膨胀聚合物。采用正交实验法对最佳吸水膨胀配方进行了优选：单体浓度[M]=30％；单体中和度N=75％；引发剂浓度[I]=0．15％；交联剂浓度[C]=0.011％；反应温度为75℃及反应时间3h。对PAA的吸液速率进行了测定，并讨论了它的反复吸液能力。     

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.     

Crosslinking of cotton cellulose in the presence of alkyl diallyl ammonium salts. I. Physical properties and agent distribution

We used three kinds of alkyl diallyl ammonium salts (methyl, ethyl, and propyl) in combination with dimethyloldihydroxyethyleneurea (DMDHEU) as crosslinking agents. The nitrogen content, dry crease recovery angle (DCRA), moisture regain, and wicking height for the DMDHEU/alkyl diallyl ammonium salts were in the order of ? CH₃ > ? C₂H₅ > ? C₃H₇, but the wet crease recovery angle (WCRA) and tensile strength retention (TSR) were in the opposite order at the same resin concentration. For the same DCRA and TSR, the WCRA values for only DMDHEU were lower than those for DMDHEU/alkyl diallyl ammonium salts, and the WCRA values for DMDHEU/alkyl diallyl ammonium salts were in the order of ? C₃H₇ > ? C₂H₅ > ? CH₃. Both the ? OH group of the cellulose and DMDHEU could react with the vinyl or epoxy groups of the alkyl diallyl ammonium salts during the pad–dry–cure process. The surface migration for DMDHEU/alkyl diallyl ammonium salts was in the order of ? CH₃ > ? C₂H₅ > ? C₃H₇. Fabrics treated with DMDHEU/alkyl diallyl ammonium salts showed good antibacterial properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1662–1669, 2003     

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     

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups with reduced environmental impact

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups was prepared by the copolymerization of 4‐styrenesulfonic acid sodium salts (SSS) with N‐phenylmethacrylamide (copolymer A) or p‐hydroxy‐N‐phenylmethacrylamide (copolymer B), and its properties such as solubility changes, photochemical reaction, and photoresist characteristics were studied. The copolymer containing a relatively higher amount of SSS units was soluble in water. Solubility changes of the copolymers in the various buffer solutions of pH 4 ～ 11 and in water upon irradiation were observed by the measurement of insoluble fraction. The copolymers were soluble in water before irradiation, whereas they became insoluble upon irradiation with the UV light of 254 nm. The photochemical reaction of the copolymer studied by the UV and IR absorption spectroscopies indicated that a photo‐Fries rearrangement was favored for copolymer A, whereas a photocrosslinking reaction was predominate for copolymer B. Resist properties of the copolymers were studied by measurement of the normalized thickness and by development of the micropattern. Negative tone images with a resolution of 1 μm were obtained with these materials that have a sensitivity (D) of ～ 1100 mJ/cm² with an aqueous developing process.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1172–1180, 2002     

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。