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超支化多羟基聚合物的合成、改性及应用-袁绪政-2009

2013年06月17日 11:52 袁绪政 点击:[]

 

 作者姓名  袁绪政
 中文论文题名  超支化多羟基聚合物的合成、改性及应用
 外文论文题名  SYNTHESIS, MODIFICATION & APPLICATION OF HYPERBRANCHED POLYMER POLYOLS
 论文提交日期  2009-06-23
 学位年度  2009
 中文论文关键词  超支化多羟基聚合物,合成改性,鞣制,甲醛捕获
 外文论文关键词  hyperbranched polymer polyol, synthesis modification, tanning,formaldehyde capture

 

中文论文文摘


    根据高分子和有机合成理论,分别采取“一步法”及“有核一步法”合成了两种不同类型的超支化多羟基聚合物,即:超支化多羟基聚(酰胺-酯)(HP-I)和超支化多羟基聚(胺-酯)(HP-II)。并根据分子设计理论,对合成出来的超支化多羟基聚合物进行适当功能化改性,为应用于皮革工业中创造条件,从而开拓皮革化学品研发新领域,促进皮革工业的可持续发展。
    采用二乙醇胺(DEA)和丁二酸酐(SA)为单体,由“一步法”,在一定条件下,制得HP-I,再用无水戊二醛改性,制得含醛基和羟基的超支化聚合物皮革复鞣剂(HR-I)。通过大量单因素实验,并对每次实验产物的酸值进行测量,优化出了HP-I的合成条件:n(DEA):n(SA)=1:1;酰胺化反应时间为6h、酯化反应时间为2.5h;最佳反应温度为130℃;对甲苯磺酸(P-TSA)用量为5.0%(基于反应物总质量)。通过IR和GPC等现代仪器,对HP-I结构进行了表征,并根据分析结果估算出其支化度。通过实验考察了HR-I的相关性能,表明其的水溶性、耐酸碱性和耐盐稳定性良好。将HR-I应用于猪二层蓝湿革复鞣工序中,同时与亭江精细化工有限公司生产的酚醛丹宁PF-210复鞣剂作对比试验,结果表明,其有很好的复鞣增强作用,HR-I复鞣后的革撕裂强度比酚醛丹宁PF-210复鞣后的革高30.5%,抗张强度与酚醛丹宁PF-210复鞣后的革基本相当。此外,HR-I复鞣后的革的手感较柔软、丰满。
    以DEA和丙烯酸甲酯(MA)为原料,通过Michael加成反应制得AB2型单体(N,N-二羟乙基-3-胺基丙酸甲酯,Monomer);接着由“有核一步法”使Monomer与核(三羟甲基丙烷,TMP)在P-TSA为催化剂的条件下,通过酯交换反应制得HP-II;最后使用丙二酸二乙酯(DEM),在无水K2CO3作催化剂的条件下,通过酯交换反应对HP-II进行端基改性,从而制备活泼亚甲基类超支化聚合物(HPAM)。通过单因素实验分析方法分别考察了相关因素对上述每步反应的影响,优化出了单体的合成条件为:采用MA滴入DEA的加料方式;以甲醇作溶剂;n(DEA):n(MA)=1:2;反应温度为35℃,反应时间为4h。HP-II的合成条件为:在根据代数严格控制投料比的前提下,采用向核物质中滴加单体的方式;反应温度控制在120℃;催化剂用量为2.0%,反应时间4~5h。利用IR、1H-NMR、GPC、TG和DSC等方法对各步反应产物的分子结构及聚合物性能进行了表征。研究了HP-II的溶解性能、热力学性能及表面活性,并将其应用于绵羊皮蓝湿革的复鞣中考察其对铬鞣革复鞣性能的影响,应用实验表明:G1(第一代HP-II)对皮样漂白作用明显,白度值增幅为19.8%;G3(第三代HP-II)可以显著提高铬鞣革撕裂强度,增幅为23.3%,抗张强度的增幅为11.3%。同时考察了HPAM对游离甲醛的捕获效果,通过应用于醛鞣猪皮的捕获工艺实验,优化出了最佳捕获参数:HPAM用量为2.0%,捕获时间为5h,该条件下捕获率可达56.3%,捕获效果明显。

 

外文论文文摘


    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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