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·1844·                            精细化工   FINE CHEMICALS                                  第 36 卷

            豆油多元醇的分解温度为 334  ℃,脂肪酸链的断裂                            (3)利用小分子醇作为开环剂,该方法合成的
            是质量损失的主要组成部分,总质量损失率达 93%                           大豆油多元醇生产成本相对较低,有望替代部分石
            左右。大豆油多元醇的分解温度比环氧大豆油高,                             化产品成为环保型新材料的原料。
            说明大豆油多元醇的热稳定性明显优于环氧大豆油。
                                                               参考文献:
                                                               [1]   Huang Yuanbo (黄元波), Wang Jiaqiang (王家强), Gu Jiyou (顾继
                                                                   友),  et al.  Research  progress  on  epoxidation  of  vegetable  oil[J].
                                                                   Forest  Chemicals  and  Industry(林产化学与工业),  2013,  33(5):
                                                                   115-120.
                                                               [2]   Firouzabadi  H,  Jafarpour  M.  Some  applications  of  zirconium  (Ⅳ)
                                                                   tetrachloride  (ZrCl 4)  and  zirconium  (Ⅳ)  oxydichloride  octahydrate
                                                                   (ZrOCl 2.  8H 2O)  as  catalysts  or  reagents  in  organic  synthesis[J].
                                                                   Journal of the Iranian Chemical Society, 2008, 5(2): 159-183.
                                                               [3]   Ager  D  J,  Prakash  I,  Schaad  D  R.  1,  2-Amino  alcohols  and  their
                                                                   heterocyclic  derivatives  as  chiral  auxiliaries  in  asymmetric
                                                                   synthesis[J]. Chemical Reviews, 1996, 96(2): 835-876.

                                                               [4]   Corey E J, Zhang F Y. re- and si-face-selective nitroaldol reactions
                  图 9    环氧大豆油和大豆油多元醇的热重图                          catalyzed  by  a  rigid  chiral  quaternary  ammonium  salt:  A  highly
              Fig. 9    TG curves of epoxidized soybean oil and polyols   stereoselective  synthesis  of  the  HIV  protease  inhibitor  amprenavir
                                                                   (Vertex  478)[J].  Angewandte  Chemie  International  Edition,  1999,
            2.9   环氧大豆油和大豆油多元醇的流变性能测定                              38(13/14): 1931-1934.
                                                               [5]   O'Brien  P.  Sharpless  asymmetric  aminohydroxylation:  Scope,
                 图 10 是环氧大豆油和大豆油多元醇的流变曲
                                                                   limitations, and use in synthesis[J]. Angewandte Chemie International
            线。从图中可以看出,随着温度的升高,环氧大豆                                 Edition, 1999, 38(3): 326-329.
            油和大豆油多元醇的黏度呈线性变化,其黏度随着                             [6]   Li G,  Chang  H  T, Sharpless  K  B.  Catalytic asymmetric
            温度的升高逐渐下降。在温度较低时,大豆油多元                                 aminohydroxylation  (AA)  of  olefins[J].  Angewandte  Chemie
                                                                   International Edition in English, 1996, 35(4): 451-454.
            醇的黏度明显低于环氧大豆油的黏度,说明合成的
                                                               [7]   Wang  Jitao  (王积涛). Organic chemistry (有机化学)[M].  2ed.
            大豆油多元醇的低温流动性优于环氧大豆油。                                   Tianjin:Nankai University Press (南开大学出版社), 1995: 324-329.
                                                               [8]   Liu  Yuheng  (刘玉衡),  Zhang  Zhanhui  (张占辉).  Study  on  ring
                                                                   opening  reaction  of  epoxy  compounds[D].  Shijiazhuang:  Hebei
                                                                   Normal University (河北师范大学), 2009.
                                                               [9]   Zeng  Jun  (曾俊),  Liao  Shisheng  (廖石胜), Ren Xiaona (任小娜).
                                                                   The  research  of  lubricant  synthesis  base  oil  prepared  by  vegetable
                                                                   oil[J]. Food Industry (食品工业), 2015, 36(5): 213-216.
                                                               [10]  Miao S, Zhang S, Su Z, et al. Synthesis of bio-based polyurethanes
                                                                   from  epoxidized  soybean  oil  and  isopropanolamine[J].  Journal  of
                                                                   Applied Polymer Science, 2013, 127(3): 1929-1936.
                                                               [11]  Wang  C  S,  Yang  L  T,  Ni  B  L,  et al.  Polyurethane  networks  from
                                                                   different  soy-based  polyols  by  the  ring  opening  of  epoxidized
                                                                   soybean oil with methanol, glycol, and 1, 2-propanediol[J]. Journal
                                                                   of Applied Polymer Science, 2009, 114(1): 125-131.

                图 10    环氧大豆油和大豆油多元醇的流变曲线                      [12]  Ma Huan (马焕), Huang Yuanbo (黄元波), Yang Xiaoqin (杨晓琴),
            Fig.  10    Rheological  spectrum  of  epoxidized  soybean  oil   et al.  Optimization  of  preparation  of  soybean  oil-based  polyols  by
                    and polyols                                    HPW-based  mesoporous  sieve  using  response  surface  methodology
                                                                   [J]. Chinese Fat (中国油脂), 2017, 42(4): 64-68.
                                                               [13]  Cheng  Qulin  (成取林),  Wang  Mingming  (王明明).  Synthesis  of
            3    结论                                                Environment bio-lubricants by ESO using modified montmorillonite
                                                                   catalysts[J].  Guangdong  Chemical  Industry  (广东化工),2016,43(2):
                (1)通过红外谱图和核磁共振氢谱表征可知,                              45-47.
                                                               [14]  Chen R, Zhang C, Kessler M R. Polyols and polyurethanes prepared
            环氧化合物和醇发生了反应且得到了目标产物。
                                                                   from epoxidized soybean oil ring-opened by polyhydroxy fatty acids
                (2)当催化剂用量为总反应物质量的 3%,助                             with varying OH numbers[J]. Journal of Applied Polymer Science,
            催化剂用量为总反应物质量的 4%,反应时间为 8 h,                            2015, 132(1): 41213.
            反应温度为 70  ℃,醇油物质的量比为 28∶1 时,                       [15]  Bortoluzzi M, Evangelisti C, Marchetti F, et al. Synthesis of a highly
                                                                   reactive form of WO 2Cl 2, its conversion into nanocrystalline mono-
            环氧化合物的开环反应效果最好,开环转化率为
                                                                   hydrated WO 3 and coordination compounds with tetramethylurea[J].
            89.13%。                                                Dalton Transactions, 2016, 45(39): 15342-15349.
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