| According to the theory of macromolecule and organic synthesis, two kinds of hyperbranched polymer polyols were prepared by"one step method"and"one step method with core"respectively. These polymers as follows: hyperbranched poly(acylamide-ester) polyol (HP-I) and hyperbranched poly(amide-ester) polyol (HP-II). According to the theory of molecular design, the synthesized hyperbranched polymer polyols were modified properly which created condition for its use in leather industry. As a result, the novel research field of leather chemicals is widened and the development of leather industry is sustainable.Using diethanolamine (DEA) and succinic anhydride (SA) as monomers, HP-I was synthesized in appropriate conditions via"one step method". Then it was modified with glutaraldehyde to obtain a hyperbranched polymer leather retanning agent with terminal aldehyde and hydroxyl (HR-I). On the basis of Single-factor experimental, the optimum synthesis conditions for HP-I were determined as follows: n(DEA):n(SA)=1:1, amidation reaction time was 6h, esterification reaction time was 2.5h, at 130℃, and dosage of catalyst is 5.0% (based on the total weight of reactants). HP-I was tested by IR and GPC; the degree of branch was also estimated. Experiments indicated that HR-I possessed good water-solubility, and were stable in acid, alkaline and salt solutions. Contrast experiments were done between HR-I and phenolic tannin PF-210 produced by Tingjiang Fine Chemicals limitied, by applicating to chromme-tanned pig split. It indicated that the tearing resistance of the leather retanned by HR-I was 30.5% higher than retanned by phenolic tannin PF-210, and both have similar tensile strength. Otherwise, the leather retanned by HR-I was softer and fuller.The divergent synthesis of a series of hyperbranched poly(amine-ester)s (HP-II) based on trimethylolpropane(as a core molecule) and N,N-diethylol-3-amine-methylpropionate (as AB2 type monomer) synthesized via Michael addition action of methyl acrylate (MA) and diethanolamine, proceeding in one-step procedure in the melt using P-TSA as catalyst. At last hyperbranched polymer with active methylene (HPAM) has been synthesized by transesterification of HP-II with diethyl malonate (DEM) in the presence of catalyst (anhydrous K2CO3). By the method of Single-factor experimental design, some correlative factors how to influence the action were investigated, the appropriate action conditions were optimized. For monomer was: dripping methyl acrylate to diethanolamine, methyl alcohol as solvent, the molar feed ratio of DEA and MA was 1:2, reaction time was 4h and temperature was 35℃; and for HP-II was: dripping monomer to core material, catalyst amount is 2.0%, reaction time was 4~5h and temperature was 120℃. The monomer and polymers were characterized by IR, 1H-NMR, GPC, TG, and DSC and so on. The thermal property, deliquescent property and surface activity of HP-II were also estimated, It was applied to retan wet blue leather of sheepskin, results indicated that: G1 (the first generation of polymer) obtained good bleaching effect on sample, the white degree increased by 19.8%; G3 (the third generation of polymer) could improve tearing resistance of chrome tanned leather obviously, increased by 23.3%, and had some help to tensile strength, increased by 11.3%, at the same time.The capture effect of HPAM on free formaldehyde was investigated at last. The best capture parameters were optimized through application to capturing experiments of aldehyde-tanned pigskin: the dosage of HPAM was 2.0%, capture time was 5h. In this condition, the capture yield could exceed to 56.3%, the capture effect was obvious. |
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