Amino-functionalized polysiloxanes, prepared through the base-catalyzed copolymerization of amino-containing γ-substituted silane coupling agents (γ-SCAs) and hydroxy-terminated polysiloxanes, have wide applications including textile finishing agents, resin modifiers and personal care products. However, the generation of cyclic by-products resulting from the base-catalyzed backbiting reaction of Si-O-Si chains has been a long-standing problem. To address this issue, herein we present an environmentally friendly synthetic route which overcomes the aforementioned problems. Two α-SCAs with ethylene diamine and piperazine substituents were synthesized, whose Si-OC bonds showed self-catalyzed reactivity toward silanol groups. Benefiting from this unique property, two types of α-amino functionalized polysiloxanes were obtained via dealcoholization between α-SCAs and hydroxy-grafted polysiloxanes. The self-catalyzed mechanism of amino-functionalized α-SCAs was revealed for the first time. The film-forming capability of these α-substituted amino polysiloxanes was confirmed by treatment of cellulose membranes with isopropanol solutions, leading to the lowering of the roughness of the membrane accompanied a simultaneous improvement of the hydrophobicity. Further, microemulsions were prepared based on these α-substituted amino polysiloxanes, with which the finishing of real fabrics (cotton fiber and polyester) was tested. The results showed that these newly-developed amino-functionalized polysiloxanes are potentially applicable as a new generation of fabric softener.
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