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Abstract: A novel polysiloxane (RCAS) bearing dodecyl and carboxyl side groups was synthesized by reaction of a dodecyl/amino functionalized polysiloxane with maleic anhydride. Film morphology, molecular orientation and performance of the synthesized polysiloxane on cotton substrates were investigated by field emission scanning electron microscope (FESEM), atomic force microscope (AFM), X-ray photoelectron microscope (XPS) and so on. Affected by the dodecyl and polar carboxyl side groups, RCAS formed a semi hydrophilic, macroscopic smooth but actually uneven siloxane film with many pillar-likes or small humps on the treated substrate surfaces. On the natural cotton surface, RCAS may take such an orientation to form its film that the Si-CH3, Si-C12H25 groups projected outward into air, while the carboxyl groups pointed inward to the substrate, interacting with the hydroxyls of the cotton substrates in ester and hydrogen bonds or twisted away from the negatively charged cotton fiber surface. As a result of such a film-formation, RCAS provided the treated fabric with not only a good wettability of about 22.96s and a whiteness of 88.44°, but also an improved softness as well as thickening handle. [Copyright &y& Elsevier]