脱氢枞酸基ATRP引发剂的合成与表征

doi:10.3969/j.issn.0253-2417.2016.02.013

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (2): 87-93.doi: 10.3969/j.issn.0253-2417.2016.02.013

脱氢枞酸基ATRP引发剂的合成与表征

俞娟^1,2, 王利军^1,2, 刘少峰^1,2, 王春鹏^1,2, 王基夫^1,2, 储富祥^1,2

1. 中国林业科学研究院林产化学工业研究所;生物质化学利用国家工程实验室;国家林业局林产化学工程重点开放性实验室;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2015-03-19 出版日期:2016-04-25 发布日期:2016-04-26
通讯作者: 王基夫,副研究员,博士,主要从事生物质材料研究;E-mail:wjf118@126.com。 E-mail:wjf118@126.com
作者简介:俞娟(1989—),女,河南信阳人,博士生,主要从事生物质材料研究
基金资助:
国家自然科学基金资助项目(31200447)

Synthesis and Characterization of Dehydroabietic Acid Derived ATRP Initiator

YU Juan^1,2, WANG Li-jun^1,2, LIU Shao-feng^1,2, WANG Chun-peng^1,2, WANG Ji-fu^1,2, CHU Fu-xiang^1,2

1. Institute of Chemical Industry of Forestry Products, CAF;National Engineering Lab.for Biomass Chemical Utilization; Key and Open Lab.of Forest Chemical Engineering, SFA, Key Lab.of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2015-03-19 Online:2016-04-25 Published:2016-04-26

摘要/Abstract

摘要： 以脱氢枞酸为原料,通过酰氯化得到脱氢枞酸酰氯(DA-Cl)后与乙二醇(EG)反应合成脱氢枞酸羟乙酯(DA-EH),然后再与2-溴代异丁酰溴(2-BiBr)进行酯化反应,合成了脱氢枞酸基原子转移自由基聚合(ATRP)引发剂——脱氢枞酸(2-溴代异丁酸乙基)酯(DA-2-iBBrEH)。通过单因素试验考察了不同条件对合成DA-EH和DA-2-iBBrEH的影响规律。结果表明,DA-EH合成的优化条件为:催化剂为4-二甲氨基吡啶(DMAP),n(DA-Cl):n(EG):n(DMAP)为1:5:5,反应时间5 h,反应温度50 ℃;DA-2-iBBrEH合成的适宜条件为:催化剂为DMAP,n(DA-EH):n(2-BiBr):n(DMAP)为1:2:2。利用傅里叶红外光谱(FT-IR)、核磁共振氢谱(¹H NMR)和核磁共振碳谱(¹³C NMR)对两者的结构进行了确证。以DA-2-iBBrEH为引发剂,采用ATRP法制备了聚甲基丙烯酸甲酯均聚物(PMMA)。GPC测试结果表明,DA-2-iBBrEH具有良好的ATRP反应引发活性,所制备的PMMA的数均相对分子质量(M_n)为8 500,相对分子质量分布(PDI)为1.3。

关键词: 脱氢枞酸, ATRP引发剂, 合成

Abstract: Dehydroabietic acid derived ATRP initiator, dehydroabietic acid (2-isobutyric acid bromide) ethyl ester of (DA-2-iBBrEH), was synthesized by esterification of 2-bromoisobutyryl bromide (2-BiBr) and dehydroabietic acid 2-hydroxyethyl ester (DA-EH) which was obtained from the reaction of ethylene glycol (EG) and dehydroabietic chloride(DA-Cl) with dehydroabietic acid as raw material. Single-factor experiments were employed to investigate the effects of reaction conditions on the preparation of DA-EH and DA-2-iBBrEH. The results showed that the optimized conditions of DA-EH preparation were summarized as 4-dimethyaminopyridine (DMAP) using for catalyst,n(DA-Cl):n(EG):n(DMAP)=1:5:5, reaction time 5 h and reaction temperature 50 ℃. The optimized reaction ratio and catalyst of the preparation of DA-2-iBBrEH were n(DA-EH):n(2-BiBr):n(DMAP)=1:2:2 and DMAP, respectively. Then the resulting products were characterized by FT-IR, ¹H NMR and ¹³C NMR. Subsequently, poly(methyl methacryalte)(PMMA) was prepared using DA-2-iBBrEH as initiator. The GPC results showed that the molecular weight of PMMA was about 8 500 and PDI was 1.3. This indicated that DA-2-iBBrEH was a good ATRP initiator.

Key words: dehydroabietic acid, ATRP initiator, synthesis

中图分类号:

TQ35

俞娟, 王利军, 刘少峰, 王春鹏, 王基夫, 储富祥. 脱氢枞酸基ATRP引发剂的合成与表征[J]. 林产化学与工业, 2016, 36(2): 87-93.

YU Juan, WANG Li-jun, LIU Shao-feng, WANG Chun-peng, WANG Ji-fu, CHU Fu-xiang. Synthesis and Characterization of Dehydroabietic Acid Derived ATRP Initiator[J]. Chemistry and Industry of Forest Products, 2016, 36(2): 87-93.

参考文献

[1] 宋湛谦.松香的精细化工利用(Ⅰ)——松香的组成与性质[J].林产化工通讯,2002,36(4):29-33. SONG Zhan-qian.Fine chemical use of rosin (Ⅰ):Composition and properties of rosin[J].Journal of Chemical Industry of Forest Products,2002,36(4):29-33.
[2] 崔国友,莫炳荣,陈文纳.脱氢枞酸的应用研究进展[J].精细与专用化学品,2006,14(20):6-8,17. CUI Guo-you,MO Bing-rong,CHEN Wen-na.Progress on application of dehydroabietic acid[J].Fine and Specialty Chemicals,2006,14(20):6-8,17.
[3] ZHENG Yi-jun,YAO Ke-jian,LEE J,et al.Well-defined renewable polymers derived from gum rosin[J].Macromolecules,2010,43(14):5922-5924.
[4] 高宏,陈姗姗,宋湛谦,等.脱氢枞酸芳胺化合物的结构优化及溶致变色行为[J].林产化学与工业,2014,34(3):1-6. GAO Hong,CHEN Shan-shan,SONG Zhan-qian,et al.Structure optimization by DFT and solvatochromism of series of dehydroabietic acid-based arylamines[J].Chemistry and Industry of Forest Products,2014,34(3):1-6.
[5] 刘超祥,林中祥.脱氢枞胺衍生物及功能性研究[J].安徽农业科学,2014,42(6):1595-1597. LIU Chao-xiang,LIN Zhong-xiang.Dehydroabietylamine derivatives and functional studies[J].Journal of Anhui Agricultural Sciences,2014,42(6):1595-1597.
[6] 蒋丽华,龙先文,黄伟杰,等.手性7-氨基脱氢枞酸乙酯的合成及表征[J].精细化工,2014,31(6):807-811. JIANG Li-hua,LONG Xian-wen,HUANG Wei-jie,et al.Synthesis and characterization of chiral ethyl 7-amino-dehydroabietate[J].Fine Chemicals,2014,31(6):807-811.
[7] 王娟,王丹,商士斌,等.N-乙基甲基丙烯基脱氢枞酰胺的合成及表征[J].化学试剂,2014,36(7):585-588. WANG Juan,WANG Dan,SHANG Shi-bin,et al.Synthesis and characterization of N-ethylo2-methyi pro-penyl-dehydroabietylamide[J].Chemical Reagents,2014,36(7):585-588.
[8] 王基夫,林明涛,储富祥,等.脱氢枞酸(β-丙烯酰氧基乙基)酯的合成和表征[J].精细化工,2008,25(11):1135-1139. WANG Ji-fu,LIN Ming-tao,CHU Fu-xiang,et al.Synthesis and characterization of (2-acryloyloxy) ethyl ester of dehydroabietic acid[J].Fine Chemicals,2008,25(11):1135-1139.
[9] 王静波,窦强.脱氢枞酸型成核剂制备高透明高光泽聚丙烯研究[J].塑料,2007,36(3):54-57,62. WANG Jing-bo,DOU Qiang.Transparent polypropylene with high clarity and excellent gloss prepared by dehydroabietate-based nucleator[J].Plastics,2007,36(3):54-57,62.
[10] 毛新军,唐世华,王军,等.脱氢枞酸乙二醇双酯的合成[J].广西民族大学学报:自然科学版,2013,19(2):88-92. MAO Xin-jun,TANG Shi-hua,WANG Jun.The synthesis of dehydroabietic acid glycol diabietale[J].Journal of Guangxi University for Nationalities:Natural Science Edition,2013,19(2):88-92.
[11] 左振宇,雷福厚,段文贵.马来松香丙烯醇酯聚合物的制备及表征[J].广西民族大学学报:自然科学版,2007,13(1):88-92,103. ZUO Zhen-yu,LEI Fu-hou,DUAN Wen-gui.Preparation and characterization of polymer of allyl maleated rosin ester[J].Journal of Guangxi University for Nationalities:Natural Science Edition,2007,13(1):88-92,103.
[12] 徐建峰,胡惠仁.以松香为功能单体的苯乙烯丙烯酸酯乳液(SAE)表面施胶剂的制备及表征[J].高分子材料科学与工程,2012,28(2):132-136. XU Jian-feng,HU Hui-ren.Preparation and characterization of styrene acrylate emulsion(SAE) surface sizing agent with rosin as functional monomer[J].Polymer Materials Science and Engineering,2012,28(2):132-136.
[13] 李光华,赵治巨,覃柳妹,等.聚去氢枞酸丙烯酸乙二醇酯的合成与表征[J].化学研究与应用,2010,22(8):999-1003. LI Guang-hua,ZHAO Zhi-ju,QIN Liu-mei,et al.Synthesis and characterization of poly(dehydroabietic acid acrylic glycol ester)[J].Chemical Research and Application,2010,22(8):999-1003.
[14] 聂园梅,汪影,申利群,等.脱氢枞酸与二甲亚砜反应产物表征及反应机理研究[J].林产化学与工业,2013,33(6):25-28. NIE Yuan-mei,WANG Ying,SHEN Li-qun,et al.Structural characterization of reaction product of dehydroabietic acid and DMSO and its reaction mechanism[J].Chemistry and Industry of Forest Products,2013,33(6):25-28.
[15] MATYJASZEWSKI K.Atom transfer radical polymerization (ATRP):Current status and future perspectives[J].Macromolecules,2012,45(10):4015-4039.
[16] WANG Ji-fu,YAO Ke-jian,KORICH A L,et al.Combining renewable gum rosin and lignin:Towards hydrophobic polymer composites by controlled polymerization[J].Journal of Polymer Science Part A:Polymer Chemistry,2011,49(17):3728-3738.
[17] YU Juan,WANG Ji-fu,WANG Chun-peng,et al.UV-absorbent lignin-based multi-arm star thermoplastic elastomers[J].Macromolecular Rapid Communications,2015,36(4):398-404.
[18] YU Juan,LIU Yu-peng,LIU Xiao-huan,et al.Integration of renewable cellulose and rosin towards sustainable copolymers by 'grafting from’ ATRP[J].Green Chemistry,2014,16(4):1854-1864.
[19] YAO Ke-jian,TANG Chuan-bing.Controlled polymerization of next-generation renewable monomers and beyond[J].Macromolecules,2013,46(5):1689-1712.
[20] YAO Ke-jian,WANG Ji-fu,ZHANG Wu-jie,et al.Degradable rosin-ester-caprolactone graft copolymers[J].Biomacromolecules,2011,12(6):2171-2177.
[21] MATYJASZEWSKI K,XIA Jian-hui.Atom transfer radical polymerization[J].Chemical Reviews,2001,101(9):2921-2990.

脱氢枞酸基ATRP引发剂的合成与表征

Synthesis and Characterization of Dehydroabietic Acid Derived ATRP Initiator

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