PDMS鈥揊luorous Polyoxetane鈥揚DMS Triblock Hybrid Elastomers: Tough and Transparent with Novel Bulk Morphologies

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• 作者：Souvik Chakrabarty ; Mark Nisenholt ; Kenneth J. Wynne
• 刊名：Macromolecules
• 出版年：2012
• 出版时间：October 9, 2012
• 年：2012
• 卷：45
• 期：19
• 页码：7900-7913
• 全文大小：655K
• 年卷期：v.45,no.19(October 9, 2012)
• ISSN：1520-5835

文摘

PDMS-3F-1.1-PDMS and PDMS-3F-4.5-PDMS triblock hybrid elastomers are investigated, wherein (1) 3F-1.1 and 3F-4.5 are poly(3-methyl-3-trifluoroethoxymethyl)-1,3-propylene oxide with Mb>nb> = 1.1 or 4.5 kDa, (2) segments are linked by urethane/urea forming reactions, and (3) the intermediate PDMS-3F-PDMS aminopropyl end segments are end-capped with isocyanatopropyltriethoxysilane. After condensation cure, PDMS-3F-PDMS triblock hybrids (A-1.1 and A-4.5) form robust elastomers. In a second set, bis(triethoxysilylethane), BTESE, was incorporated to probe effects of increased siliceous domain content (B-1.1, B-4.5). All compositions are optically transparent due to nearly identical refractive indexes for 3F and PDMS segments. TM-AFM images for A-4.5, A-1.1, and B-4.5 fracture surfaces reveal microscale bulk phase separation. The A-4.5 triblock hybrid shows a particularly interesting morphology comprised of 2鈥? 渭m ovaloids (low modulus) surrounded by a higher modulus matrix. A model is proposed for this microscale morphology based on the relative rates of physical network formation (PN, H-bonding) and chemical network formation (CN, SiOb>1.5b>) during coating deposition Despite low hard segment weight percents (2.6鈥?.5) the hybrid triblocks have moderate toughness with strain at break ranging from 260 to 492%. Triblock hybrid elastomer B-1.1 has the highest 鈭扴iOb>1.5b> wt % (mostly from BTESE) and lowest 3F wt % (3F-1.1). No sign of microscale phase separation is observed by TM-AFM imaging, and a separate Tb>gb> for the 3F segment is not detected by DMA; these findings are ascribed to network constrained phase separation of that results in 3F being incorporated in an 鈥渋nterphase鈥? The absence of a separate Tb>gb> for 3F leads to a gradual decrease in storage modulus (8 to 1.4 MPa) from 鈭?0 to 150 掳C. In contrast to the complex bulk morphology, TM-AFM imaging shows the hybrid surfaces are devoid of microstructural features attributable to phase separation. Based on contact angle measurements and XPS analysis, the outermost surface for all PDMS-3F-PDMS hybrid triblocks elastomers is dominated by PDMS.