Photopolymeritation of Methyl Methacrylate and Styrene by Sulfur Ylides

The photoinitiating ability of some sulfur ylides was studied. Diphenylsulfonium bis (methoxycarbony1)methylide (DPSY) could photoinitiate methyl methacrylate and styrene. A free radical mechanism was confirmed by a kinetic study, the inhibiting effect of benzoquinone, and the copolymer composition. From an analysis of the photodecomposition products it is suggested that the phenyl radical generated from the bond fission between the sulfur atom and the phenyl group participates in the initiation of this free radical polymerization. Methylphenylsulfonium bis (methoxycarbonyl) methylide, as well as DPSY, served as a photoinitiator, but dimethylsulfonium bis (methoxycarbony1)methylide did not. The differences are explained based on UV spectra.     

Study on Biological Safety of Polyvinyl Alcohol/Collagen Hydrogel as a Tissue Substitute (II)

Physically crosslinked polyvinyl alcohol/collagen composite hydrogels were prepared by a cyclic freezing-drying technique. The biological properties of the hydrogels, including hemolysis, anaphylaxis, pyrogen and acute systemic toxicity tests and implantation in-vivo, were investigated. The hemolysis test suggested that the polyvinyl alcohol/collagen, with a hemolysis index of 1.19%, did not have an obvious hemolysis reaction. There was no toxicosis or death cases observed in the acute systemic toxicity test, and the hydrogel showed no anaphylaxis or pyrogen response. The composite hydrogel showed a good histological compatibility in the in-vivo study. The results indicated that the polyvinyl alcohol/collagen composite hydrogels have promising applications for pharmaceutical and biomedical fields.     

Synthesis and Characterization of N‐methylenephenyl Phosphonic Chitosan

Chitosan is a natural based polymer obtained by alkaline deacetylation of chitin, exhibiting excellent properties such as non‐toxicity, biocompatibility and biodegradability. N‐Methylenephenyl phosphonic chitosan (NMPPC) is synthesized from chitosan by reacting with phenyl phosphonic acid using formaldehyde. The NMPPC was characterized by FTIR, ³¹P‐NMR, X‐ray diffraction, scanning electron microscopy, thermogravimeteric analysis and solubility studies. A significant decrease of molecular weight was observed in the NMPPC. The TGA studies suggested that NMPPC has less thermal stability than chitosan. The X‐ray diffraction analysis showed that NMPPC was amorphous in nature. The solubility property of the polymer was improved after the incorporation of a phenyl phosphonic group.     

Elastomeric Properties of Polysiloxane Networks. Bimodal Elastomers that are Spatially Inhomogeneous and Others that are Very Broadly Multimodal

End‐linking poly(dimethylsiloxane) was used to prepare bimodal elastomers networks so as to have inhomogeneous nanostructures, and also to prepare others having very broadly multimodal chain‐length distributions. Macroscopic phase separation, probably high crosslink density clusters, was observed to occur in some of the bimodal networks. The mechanical properties in simple extension and in equilibrium swelling were measured. The bimodal elastomers that were not obviously inhomogeneous showed very good mechanical properties, but the macroscopically phase‐separated networks, and the broadly multimodal network were weak. Analysis of the Mooney‐Rivlin profiles suggests that the reinforcing mechanism could have a structural component in addition to that from the limited extensibilities of the short chains. The mechanical properties and the extents of swelling support the cluster conjecture, in accord with previous morphological studies on spatially‐inhomogeneous polysiloxane elastomers.     

Application Properties of Stimuli-Responsive Polyglycerol Hydrogels

Transient state swelling behavior and swelling kinetics of novel stimuli-responsive polyglycerol hydrogels were studied at 293, 310 and 333 K. Depending on temperature, Fickian or anomalous diffusion behavior was observed. Mechanical properties of the hydrogels in the swollen and dry states were investigated and the average molecular weight between crosslinks was calculated. To assess the potential for biodegradation of hydrogels, initial swelling behavior in phosphate buffered saline (PBS) solution and mass loss profiles as a function of degradation time were investigated over a period of 30 days. All swelling behavior, mechanical properties and degradations were clearly affected by the degree of cross-linking. The hydrophilicity and biodegradability of polyglycerol hydrogels make them suitable for pharmaceutical, biomedical and biotechnological applications. They could potentially serve as a substitute for common fossil-based hydrogels such as poly(ethylene glycol) and poly(vinyl alcohol) hydrogels.     

Polymer Composites with Plasma-Treated Fillers

A Large-volume Microwave Plasma (LMP) generator has been used to irradiate mica and ground-wood fibers in inert and active gas environments. Irradiated fillers were subsequently incorporated in a polypropylene matrix at solids levels of 10 and 20%. Calorimetrically measured heats of immersion showed that substantial changes in surface properties of fillers were effected by irradiation in ethylene, ammonia, and similar active gases. These surface changes are reflected In ultimate tensile and elongation properties of composites which show marked improvement over controls based on unirradiated fillers. Although no appreciable response in melt viscosity has been observed, surface treatment of fillers does seem to increase significantly melt elasticity of filled composites. The implications of improved performance motivate a more detailed study of the use potential of LMP in the fomulation of polymer composites.     

Synthesis and Properties of Poly(Aryl Ether Ketone) Copolymers with Trifluoromethyl‐Substituted Benzene in the Side Chain

The new monomer (4‐(4′‐trifluoromethyl)phenoxyphenyl)hydroquinone (TFPOPH) was synthesized in a three‐step synthesis. A series of poly(aryl ether ketone) copolymers were prepared by the reaction of (4‐(4′‐Trifluoromethyl)phenoxyphenyl)hydroquinone and hydroquinone (HQ) with 4,4′‐difluorobenzophenone (DFB) in the presence of potassium carbonate in tretramethylene sulfone (TMS). Thermal analyses of the fluorinated copolymers showed that the glass transition temperature and 5.0% weight loss temperature are similar with that of PEEK, and the crystallinity decreased with increasing of TFPOPH. For the copolymer synthesized with the molar fraction of TFPOPH in the diphenol monomers (TFPOPH, HQ) being over 0.2, no cold crystallization temperature and melting temperature were detected, indicating that these copolymers are almost amorphous. The crystal structure of the copolymers with the molar fraction of TFPOPH being not higher than 0.2 is rhombic. The solubility in polar aprotic solvents of poly(aryl ether ketone)s copolymers increases and dielectric constant decreases step by step.     

Relationship between Reactivity Ratios and Configuration for Donor—Acceptor Type Copolymers

For binary copolymers from an acrylic monomer (acceptor type, M¹) and an aromatic-substituted monomer (donor type, M₂) a linear relation between log (r₂/r¹) and the probability of “coisotactic” alternating addition is observed. This can be a proof for the influence of monomer polarity on the copolymer configuration.     

Thermal Properties of Copoly(L‐lactic acid/glycolic acid) by Direct Melt Polycondensation

Poly(L‐lactic acid‐co‐glycolic acid) (PLGA) was prepared from hydroxy‐acids with melt polymerization. In this way, the copoly(L‐LA/GA) (PLGA) was synthesized directly using a binary catalyst (tin chloride dihydrate/p‐toluenesulfonic acid). The thermal properties of PLGA were studied by differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). The results show that the melting point of PLGA decreases with increasing mole fraction of GA units in the copolymer. In addition, the melting point of polymer also decreases with increasing degree of racemization of the polymer.     

A Grafting Study on Partially Dehydrochlorinated Poly(vinyl chloride) by Atom Transfer Radical Polymerization

HCl elimination in low ratio was first carried out from poly(vinyl chloride) to increase allylic chlorines. Partially dehydrochlorinated poly(vinyl chloride), having a macroinitiator effect, was grafted with tert‐butyl methacrylate via atom transfer radical polymerization in the presence of CuBr/2,2′‐bipyridine at 64°C in tetrahydrofuran. Original poly(vinyl chloride) was also grafted with tert‐butyl methacrylate under the same conditions to compare with that of partially dehydrochlorinated poly(vinyl chloride). The graft copolymers were characterized by elemental analysis, FTIR, ¹H and ¹³C‐NMR, differential scanning calorimetry, and gel permeation chromatography (GPC). Thermal stabilities of the graft copolymers were investigated by thermogravimetric analysis as compared with those of the macroinitiators.