Siloxane copolymers degradation

Another important class of linear polysiloxanes are the siloxane copolymers. The replacement of methyl groups by other organic groups improves the specific physicochemical properties of PDMS, and one such improvement is in the area of resistance to thermal degradation, e.g., phenyl-containing polysiloxanes have superior thermal stability compared to PDMS. 

Silphenylene-Siloxane Copolymers.—The thermal properties vctsus structure for poly(tetramethyl-p-silphenylensesiloxane) and (tetramethyl-p-silphenylene/di-methylsiloxane) block copolymers have been compared. The homopolymer has a m.p. of 160°C, heat of fusion of 54.4 J/g and Tg of —20°C. The Tg of the copolymer varies monotonically with inojeased dimethylsiloxane content, from — 20 to —123 °C. Data have been reported on the crystallization kinetics and morphology of blends of fractionated poly(tetramethyl-p-silphenylenesiloxanes). The chemical degradation of poly(tetramethyl-/ -silphenylenesiloxane/dimethyl-siloxane) block copolymers by HF has been reported. In 48% HF at 30 °C, preferential attack occurs at the Si—O bond, particularly those of the MejSi—O non-crystalline components, in copolymers containing 15, 35, and 52% poly-dimethylsiloxane. - Further data have been reported on the crystal structure and fold conformation of poly(tetramethyl-/>-silphenylenesiloxane)s, obtained from X-ray diffraction studies. ... 

See also PBT degradation structure and properties of, 44-46 synthesis of, 106, 191 Polycaprolactam (PCA), 530, 541 Poly(e-caprolactone) (CAPA, PCL), 28, 42, 86. See also PCL degradation OH-terminated, 98-99 Polycaprolactones, 213 Poly(carbo[dimethyl]silane)s, 450, 451 Polycarbonate glycols, 207 Polycarbonate-polysulfone block copolymer, 360 Polycarbonates, 213 chemical structure of, 5 Polycarbosilanes, 450-456 Poly(chlorocarbosilanes), 454 Polycondensations, 57, 100 Poly(l,4-cyclohexylenedimethylene terephthalate) (PCT), 25 Polydimethyl siloxanes, 4 Poly(dioxanone) (PDO), 27 Poly (4,4 -dipheny lpheny lpho sphine oxide) (PAPO), 347 Polydispersity, 57 Polydispersity index, 444 Poly(D-lactic acid) (PDLA), 41 Poly(DL-lactic acid) (PDLLA), 42 Polyester amides, 18 Polyester-based networks, 58-60 Polyester carbonates, 18 Polyester-ether block copolymers, 20 Polyester-ethers, 26... 

The thermostability of siloxane-silazane copolymers of both random and block structure is found to be much higher (i.e. 100-200°C) with respect to polysiloxanes. This effect is brought about by introducing only a few silazane entities into the polymer chain. The reasons for the effect are not clear and the mechanism of thermal degradation of polysilazoxanes will require further experimental studies. 

For decades I avoided mixtures or copolymers of organic resins with silicones, even abhorred them, because I did not want the pristine properties of my silicone brain children to be degraded or ruined by adulteration. Now, all manner of siloxane-organic copolymers (such as the polyimide block copolymers) with disciplined structures and admirable properties have been developed. 

The thermal and thermo-oxidative degradation of dimethyl siloxane-phenol-phthalein terephthalate block copolymers has also been studied. In inert atmosphere cross-linking occurred in the polyester blocks and changes in the infrared spectrum suggested the invoivement of the Fries rearrangement. In air, degradation was preferentially in the siloxane block. ... 

The TG profiles of vinyl triethoxy silane-methyl methacrylate (VTES-MMA) copolymers in N2 have been reported to be similar to that of PMMA [a.l85]. However, the initial decomposition temperature (IDT) of the copolymers decreased with increasing VTES content in the copolymer. This behaviour was attributed to the decrease in the molecular weight of these copolymers during degradation. A similar tendency for TG was also reported for styrene-siloxane block copolymers synthesised with a living anionic initiator [a.l86]. 

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