由1,4-丁二醇和癸二酸合成聚酯型表面活性剂
蔡国星
学位类型硕士
导师吾满江•艾力
2008-06-09
学位授予单位中国科学院研究生院
学位授予地点北京
学位专业有机化学
关键词聚酯 Ti(Obu)4/ Tio2-al2o3 1 负载催化剂 4-丁二醇 表面活性剂
摘要

脂肪族聚酯是由脂肪族二元羧酸和二元醇聚合而成,是性能良好的材料,其分子量不同,用途也不同。由于脂肪族聚酯具有良好的生物降解能力,从而受到广泛的关注。由于我国目前1,4-丁二醇的产量过剩,造成其出口价值低廉等一些问题,将1,4-丁二醇和癸二酸聚合生成脂肪族聚酯,用氨基磺酸或油酸将聚合物端基进行修饰,生成一种聚酯型的两性大分子表面活性剂,这对于1,4-丁二醇附加值的提高和聚酯型表面活性剂的研究开发具有一定的现实意义 本文由1,4-丁二醇和癸二酸为原料,聚合生成聚酯,选用适宜催化剂,优化反应条件,研究证明:无需溶剂时Ti(OBu)4/ TiO2-Al2O3催化剂效果最佳。n(癸二酸):n(1,4-丁二醇)= 1.0:1.2,催化剂用量为1.2wt%左右,反应温度为140~160℃,反应时间为6h,反应羧基转化率最高为92.8%,Mn=3114,Mw/Mn=1.328。用氨基磺酸对聚酯端羟基硫酸化,采用尿素作催化剂,聚酯型表面活性剂的最佳反应条件:羧基转化率为87%左右的聚酯, n(聚酯):n(氨基磺酸):n(尿素)=1:1.2:1.2,反应温度120℃左右,反应时间2.5h,得聚(癸二酸-1,4-丁二醇)酯硫酸酯盐型表面活性剂,Mn=3080,Mw/Mn= 1.0665,分子量分布范围窄,乳化效果较好。同时研究了以Ti(OBu)4/ TiO2-Al2O3为催化剂,应用于己二酸和1,4-丁二醇的聚合反应研究以及其他脂肪族的醇酸酯化反应中,研究证明Ti(OBu)4/ TiO2-Al2O3催化剂对脂肪族二元羧酸和二元醇的酯化反应效果明显,且可反复使用,易分离和回收,符合绿色化学发展的要求。

其他摘要

The research and development of series esters of lubricants were carried out based on neopentyl polyol, dicarboxylic acid, fatty acid, acrylic acid and acrylate. The esterification process of solvent-free was investigated. A series of neopentyl polyol esters, complex compound esters, acrylic polyol polyester and molecular weight controllable viscosity index improver with anti-wear function of polyacrylic esters were designed and synthesized. The physicochemical properties, such as viscosity, viscosity index, flash point and pour point were tested, and the oxidation stability and thermal oxidation stability of the products were investigated. The anti-wear property and shear stability of viscosity index improver with anti-wear function were tested. Results suggested that these synthetic esters can be used as lubricants base oil or base oil additives with excellent properties. The main content and conclusions of this thesis are as follows: ⑴ A series of esters as lubricant base oils were synthesized under solvent free conditions over toluene sulfonic acid catalyst, with neopentyl glycol, trimethylolpropane, pentaerythritol, fatty acid (heptanoic acid, octanoic acid, octanoic acid, azelaic acid, decanoic acid, oleic acid) as the main materials, and the esterification process were further optimized. The data of Fourier Transforminfrared Spectroscopy (FT-IR) confirmed that the structures of the products were in agreement with the structures of esters designed. The physicochemical properties analysis demonstrated that these synthetic esters have excellent performance and could be used as lubricant base oil. The major conclusions are as follows: the performance of ester is affected by molecular structure of acids used when polyol structure was same. The carboxylic ester, which has odd number of carbon atoms, has better low temperature fluidity than those that have adjacent even carbon carboxylic esters. The viscosity index could be improved and pour point could be lower with the branched carbon chain. When esterificated with the same fatty acid, the order of the viscosity of neopentyl polyol esters is as followed: pentaerythritol ester > three trimethylolpropane ester > neopentyl glycol ester, and the low temperature fluidity variation is the opposite. ⑵Using trimethylolpropane, fatty acid and dicarboxylic acid as the main materials, a series of compound esters were synthesized via two-step esterification reaction under solvent free conditions, with toluene sulfonic acid as catalyst. The results of Fourier Transform infrared Spectroscopy (FT-IR) confirmed that the structures of these esters synthesized were in agreement with the structures of targeted products. The physicochemical properties analysis demonstrated that when the carbon chain of fatty acid material increases, the viscosity and flash point of compound ester products improved; The esters, which obtained from fatty acid that have odd number of carbon atoms, have superial low temperature fluidity and viscosity index than those of adjacent even carboxylic esters; When chain length of dicarboxylic acid in raw material was increased, the viscosity, viscosity index and flash point of products were improved, while the pour point was decreased and oxidative stability changed a little. When double bond is prezented in the molecular structure of the synthesized ester, the oxidation stabilitydecreased. ⑶ Using trimethylolpropane,heptanoic acid and acrylic acid as raw materials, TMP-diheptanoate- acrylate was synthesized via two-step esterification under the solvent free condition, with toluene sulfonic acid as catalyst, the esterification process were optimized. The polymerization was carried out in ethyl acetate. Results of Fourier Transform infrared Spectroscopy (FT-IR) of raw material and product confirmed that the polymerization reaction went to complete. RBOT (Rotary Oxygen Bomb Time) and Shear rate declining of the polyester suggested that the polyester has good oxi

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/3531
专题新疆维吾尔自治区精细化工工程技术研究中心
作者单位中国科学院新疆理化技术研究所
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蔡国星. 由1,4-丁二醇和癸二酸合成聚酯型表面活性剂[D]. 北京. 中国科学院研究生院,2008.
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