| As the super softening agent, amino-silicone oil was known to all, however, amino-silicone oil had someproblems such as floating oil of its emulsion, hydrophobic and yellowing easily of finished fabric. Introductionof hydrophilic groups can effectively improve the floating oil of amino silicone emulsion and hydrophobic ofits finished fabric. Hydrophilic modified amino-silicone oil generally started from epoxy modifiedpolysiloxane, but most of epoxy modified polysiloxane was epoxy alkyl modified polysiloxane at present, theepoxy group of which had low reactivity, it was not beneficial to synthesize large molecular weight and goodfilm-forming hydrophilic amino-s ilicone oil. Therefore, in this article, a strong reactivity of linearpolydimethylsiloxane double-terminated with epoxy-carbonyl was synthesized, using the electronic absorptioneffect of ortho carbonyl of epoxy group, to improve the reactivity of epoxy group, then two different kinds ofstructure of amino modified polysiloxane were synthesized with it——block polyether amino modifiedpolysiloxane and hyperbranched amino modified polysiloxane. These two different kinds of structure ofmodified polysiloxane emuls ion and its finished fabric properties were studied and compared. The followingwas the specific contents and results of the research:Part1: The synthesis and characterization of linear polydimethylsiloxane double-terminated with epoxy-carbonyl. Linear polydimethyls iloxane double-terminated with epoxy-carbonyl was synthetized byhydrosilication reaction with polydimethylsioxane terminated with hydrogen (Mn≈4300) and glycidylmethacrylate (GMA) as raw materials. the effect of reaction factors on double bond conversion rate werestudied, the reactive conditions of synthesis were optimized, and the epoxy value of product was determined.The chemical structure of synthetic product was characterized by FT-IR and1H-NMR. The results showed thatthe optimal conditions of the synthesis of linear polydimethyls iloxane double-terminated with epoxy-carbonylwere that the dosage of catalyst was50ppm, the reaction temperature was100℃, the reaction time was3.5h.The epoxy value of synthetic product was4.3810-2mol/100g, the analysis result of FT-IR and1H-NMRproved that the structure of synthetic product was the same of linear polydimethylsiloxane double-terminatedwith epoxy-carbonyl.Part2: Study on the synthesis and application of block polyether amino modified polys iloxane. The blockpolyether amino modified polys iloxane was synthesized by nucleophilic ring-opening reaction of epoxy andamino with polydimethylsiloxane double-terminated with epoxy-carbonyl and polyether terminated with aminopropyl (ED-600) as raw materials. The effect of different reaction factors on the conversion ratio ofepoxy and intrinsic viscosity of synthetic product were researched, the effects of molecular weight ofpolysiloxane of polydimethyls iloxane double-terminated with epoxy on the properties of emulsion and itsfinished fabric were studied, the reactive conditions were optimized, and the chemical structure of syntheticproduct was characterized by1H-NMR and GPC. The results indicated that: as the molecular weight ofpolysiloxane was4300, the molar ratio of polydimethylsiloxane double-terminated with epoxy-carbonyl topolyether terminated with aminopropyl (ED-600) was1:1.1, the temperature of reaction was85℃, the time ofreaction was5h, and the dissolvant was35%wt, the epoxy conversion rate was89.27%, the intrinsic viscosityof product16.83mL/g, the Mn of modified polysiloxane was1.73104, which had a narrow molecular weightdistribution, the analys is result of1H-NMR proved that the structure of synthetic product was the same as thatof block polyether amino modified polysiloxane. Over this basis, the block polyether amino modifiedpolysiloxane was used to finish fabric for softness. The influences of finishing factors of block polyetheramino modified polysiloxane on the properties of finished fabric were studied, the finishing conditions wereoptimized, the properties of the emulsion of modified polysiloxane and its finished fabric were measured, andcompared with commercially available amino-silicone oil and side-chained polyether modified amino-siliconeoil. The results indicated that: as the dosage of block polyether amino modified polysiloxane (solid contentwas30%) was14g/L, the curing temperature was140℃, the curing time was40s, the integral area value offabric finished by the modified polysiloxane was0.504, the wetting time of the finished fabric was10.9s.Compared with the emulsion of amino silicone, the emulsion of modified polysiloxane had stable property andno floating oil, the average particle s ize of the emuls ion was small; compared with the fabric finished byamino-silicone oil, the fabric finished by modified polysiloxane had poor softness and washing resistance, buthad better hydrophilicity and whiteness. Compared with the fabric finished by side-chained polyether modifiedamino-silicone oil, the fabric finished by block polyether amino modified polysiloxane had about the samehydrophilicity and whiteness, and its softness and washing resistance were obviously improved.Part3: Study on the synthesis and application of hyperbranched amino modified polys iloxane. Thehyperbranched amino modified polysiloxane was synthesized by nucleophilic ring-opening reaction of epoxyand amino with polydimethylsiloxane double-terminated with epoxy-carbonyl and diethylenetriamine as rawmaterials. The effect of different reaction factors on the conversion ratio of epoxy were researched, the effectsof molecular weight of polysiloxane of polydimethylsiloxane double-terminated with epoxy-carbonyl on theproperties of emulsion of modified polysiloxane and its finished fabric were studied, the reactive conditions were optimized, and the structures of synthetic product were determined by FT-IR. The results indicated that:as the molecular weight of polysiloxane was3100, the molar ratio of polydimethyls iloxane double-terminatedwith epoxy-carbonyl to diethylenetriamine was1.5:1, the temperature of reaction was80℃, the time ofreaction was3h, and the dissolvant was30%wt, the epoxy conversion rate was93.25%, the result analsis ofFT-IR proved that the structure of synthetic product was the same as that of hyperbranched amino modifiedpolysiloxane. On this basis, the hyperbranched amino modified polysiloxane was used to finish fabric forsoftness. The influences of finishing factors of hyperbranched amino modified polysiloxane on the propertiesof finished fabric were studied, the finishing conditions were optimized, the properties of the emulsion ofmodified polysiloxane and its finished fabric were measured, and compared with commercially availableamino-silicone oil and block polyether modified amino-silicone oil. The results indicated that: as the dosage ofhyperbranched amino modified polysiloxane (solid content was30%) was12g/L, the curing temperature was130℃, the curing time was60s, the integral area value of fabric finished by the modified polys iloxane was0.483, the wetting time of the finished fabric was12.6s. Compared with the emulsion of amino-silicone oil, theemulsion of hyperbranched amino modified polys iloxane had stable property and no floating oil, the averageparticle size of the emulsion was small; compared with the fabric finished by amino-silicone oil, the fabricfinished by hyperbranched amino modified polysiloxane had about the same softness and washing resistance,and the hydrophilicity and whiteness were obviously improved. Compared with the fabric finished by blockpolyether modified amino-silicone oil, the fabric finished by hyperbranched amino modified polysiloxane hadabout the same hydrophilic ity and whiteness, and its softness and washing resistance were obviously improved.Finally, by comparing the synthesis and application properties of the above two different kinds ofstructures of modified polys iloxane, compared with the self-made block polyether modified amino-silicone oil,the self-made hyperbranched amino modified polys iloxane had some advantages such as higher epoxyconversion rate, short synthesis time, and the cost is decreased obviously; compared with the fabric finished byblock polyether modified amino-silicone oil, the fabric finished by hyperbranched amino modifiedpolysiloxane had about the same hydrophilicity and whiteness, and its softness and washing resistance wereobviously improved. Therefore, the self-made hyperbranched amino modified polysiloxane could beconsidered as a better soft and hydrophilic finishing agent of organosilicone. |
PDF Full Text Request