咔唑功能化等规聚丙烯的合成及性能研究

商睿凝; 高欢; 李玉莲; 王彬; 马哲; 潘莉; 李悦生

doi:10.11777/j.issn1000-3304.2019.19081

您当前的位置：

首页 >

文章列表页 >

咔唑功能化等规聚丙烯的合成及性能研究

研究论文 | 更新时间：2021-01-26

- 咔唑功能化等规聚丙烯的合成及性能研究
- Synthesis and Properties of Carbazole-functionalized Isotactic Polypropylenes
- 高分子学报 2019年50卷第11期页码：1187-1195
- 作者机构：
  
  天津大学材料科学与工程学院　天津 300350
- 作者简介：
  
  E-mail: lilypan@tju.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21574097)资助项目()
- DOI：10.11777/j.issn1000-3304.2019.19081
  中图分类号：
- 纸质出版日期：2019-11，
  
  网络出版日期：2019-5-27，
  
  收稿日期：2019-4-18，
  
  修回日期：2019-5-6，
扫描看全文
商睿凝, 高欢, 李玉莲, 王彬, 马哲, 潘莉, 李悦生. 咔唑功能化等规聚丙烯的合成及性能研究[J]. 高分子学报, 2019,50(11):1187-1195.

Rui-ning Shang, Huan Gao, Yu-lian Li, Bin Wang, Zhe Ma, Li Pan, Yue-sheng Li. Synthesis and Properties of Carbazole-functionalized Isotactic Polypropylenes[J]. Acta Polymerica Sinica, 2019,50(11):1187-1195.
商睿凝, 高欢, 李玉莲, 王彬, 马哲, 潘莉, 李悦生. 咔唑功能化等规聚丙烯的合成及性能研究[J]. 高分子学报, 2019,50(11):1187-1195. DOI： 10.11777/j.issn1000-3304.2019.19081.

Rui-ning Shang, Huan Gao, Yu-lian Li, Bin Wang, Zhe Ma, Li Pan, Yue-sheng Li. Synthesis and Properties of Carbazole-functionalized Isotactic Polypropylenes[J]. Acta Polymerica Sinica, 2019,50(11):1187-1195. DOI： 10.11777/j.issn1000-3304.2019.19081.

摘要

通过丙烯与带有咔唑功能基团的

-烯烃的直接共聚合得到了一系列具有高分子量、高插入率的新型功能化等规聚丙烯. 高效的均相非茂金属催化剂体系，二甲基吡啶胺铪/[Ph

C][B(C

)

]/Al

，对于咔唑基团表现出很好的耐受性和共聚能力，在温和的反应条件下高效地实现了丙烯与11-咔唑-1-十一碳烯的共聚反应，并且聚合反应活性较高(最高可达4.08 × 10

polymer

mol

Cat.

−1

). 共聚所得功能化聚合物具有高分子量(最高可达7.02 × 10

)、高插入率(最高可达13.5 mol%)和高立构规整度([mmmm]

99%). 大多数共聚物都表现出高熔融温度和良好的热稳定性(

约为450 °C)，同时共聚物的表面性能有了十分明显的改善，并且其力学性能也得到了明显的提高，断裂伸长率最高达727%. 此外咔唑基团的引入赋予了共聚物独特的荧光性质，使该类功能聚丙烯材料在光电器件方面具有潜在的应用价值和广阔的应用空间.

Abstract

A series of novel amino-functionalized isotactic polypropylenes with high molecular weight and satisfying functional comonomer incorporation were prepared by direct copolymerization of propylene and

-olefins carrying carbazole functional groups. The homogeneous non-metallocene catalyst system consisting of dimethyl(pyridylamido)Hf(IV) complex

[Ph

C][B(C

)

]

and Al

showed good tolerance to carbazole groups and promoted the copolymerization of propylene with 11-carbazole-1-undecene effectively under mild reaction conditions

in which very high catalytic activity (up to 4.08 × 10

polymer

mol

Cat.

−1

) was achieved. The functional copolymers obtained possessed high molecular weight (up to 7.02 × 10

) and tacticity ([mmmm]

99%)

as well as decent incorporation of carbazole functional groups (up to 13.5 mol%). Besides

DSC and TGA results verified the excellent thermostability of most copolymer products by giving decomposition temperatures around 450 °C as well as high melting points. Representative physical properties such as hydrophilicity

mechanical performance

and fluorescent characteristics of these

PPs functionalized by carbazole groups have also been explored. The increased incorporation of 11-carbazole-1-undecene monomer could reduce the water contact angle gradually and thus make significant improvement in surface properties; the copolymers became hydrophilic when comonomer incorporation exceeded 4.1 mol%. In terms of the mechanical properties

elongation at break of the copolymer barely increased at low incorporation (1.2 mol%)

and the material still showed typical attributes of rigidity and brittleness. As more 11-carbazole-1-undecene monomer was incorporated (

6.2 mol%)

toughness of the materials was dramatically enhanced yet their stiffness was inevitably sacrificed. In addition

the introduction of carbazole group endowed the copolymers with unique fluorescent characteristics—they could emit purple fluorescence under 365 nm UV light in both solution and film states

thereby making this kind of functional polypropylene materials valuable and promising for the extensive applications in optoelectronic devices.

关键词

功能化聚丙烯荧光性热稳定性亲水性能力学性能过渡金属催化剂

Keywords

Functional polypropyleneFluorescent propertyThermostabilityHydrophilicityMechanical propertyTransition metal catalyst

references

Chung T C. Macromolecules , 2013 . 46 6671 - 6698 . DOI:10.1021/ma401244thttp://doi.org/10.1021/ma401244t .

Franssen N M, Reek J N, de Bruin B. Chem Soc Rev , 2013 . 42 5809 - 5832 . DOI:10.1039/c3cs60032ghttp://doi.org/10.1039/c3cs60032g .

Nakano R, Nozaki K. J Am Chem Soc , 2015 . 137 10934 - 10937 . DOI:10.1021/jacs.5b06948http://doi.org/10.1021/jacs.5b06948 .

Resconi L, Cavallo L, Fait A, Piemontesi F. Chem Rev , 2000 . 100 1253 - 1346 . DOI:10.1021/cr9804691http://doi.org/10.1021/cr9804691 .

Wang X, Wang Y, Shi X, Liu J, Chen C, Li Y. Macromolecules , 2014 . 47 552 - 559 . DOI:10.1021/ma4022696http://doi.org/10.1021/ma4022696 .

Wang X, Wang Y, Li Y, Pan L. Macromolecules , 2015 . 48 1991 - 1998 . DOI:10.1021/acs.macromol.5b00128http://doi.org/10.1021/acs.macromol.5b00128 .

Wang X, Li Y, Mu H, Pan L, Li Y. Polym Chem-UK , 2015 . 6 1150 - 1158 . DOI:10.1039/C4PY01350Fhttp://doi.org/10.1039/C4PY01350F .

Chen Changle(陈昶乐), Chen Min(陈敏). Acta Polymerica Sinica(高分子学报) , 2018 . ( 11 ): 1372 - 1384 . DOI:10.11777/j.issn1000-3304.2018.18155http://doi.org/10.11777/j.issn1000-3304.2018.18155 .

Jian Zhongbao(简忠保). Acta Polymerica Sinica(高分子学报) , 2018 . ( 11 ): 1359 - 1371 . DOI:10.11777/j.issn1000-3304.2018.18146http://doi.org/10.11777/j.issn1000-3304.2018.18146 .

Acik G, Sey E, Tasdelen M A. Express Polym Lett , 2018 . 12 418 - 428 . DOI:10.3144/expresspolymlett.2018.35http://doi.org/10.3144/expresspolymlett.2018.35 .

Banerjee S S, Bhowmick A K. Ind Eng Chem Res , 2015 . 54 8137 - 8146 . DOI:10.1021/acs.iecr.5b01176http://doi.org/10.1021/acs.iecr.5b01176 .

Dong J Y, Liu Y. J Organomet Chem , 2015 . 798 311 - 316 . DOI:10.1016/j.jorganchem.2015.04.034http://doi.org/10.1016/j.jorganchem.2015.04.034 .

Gawish S, Ramadan A, Mosleh S. Egypt J Chem , 2019 . 62 49 - 62.

Jahani Y, Ghetmiri M, Vaseghi M R. RSC Adv , 2015 . 5 21620 - 21628 . DOI:10.1039/C5RA00030Khttp://doi.org/10.1039/C5RA00030K .

Du Huizhen(杜慧真), Yang Fei(杨飞), Zhang Kunyu(张坤玉), Ma Zhe(马哲), Wang Bin(王彬), Pan Li(潘莉) , Li Yuesheng(李悦生). Acta Polymerica Sinica(高分子学报) , 2018 . ( 12 ): 1539 - 1547 . DOI:10.11777/j.issn1000-3304.2018.18090http://doi.org/10.11777/j.issn1000-3304.2018.18090 .

Chung T C, Rhubright D. Macromolecules , 1993 . 26 ( 12 ): 3019 - 3025 . DOI:10.1021/ma00064a004http://doi.org/10.1021/ma00064a004 .

Chung T C. Macromol React Eng , 2014 . 8 69 - 80 . DOI:10.1002/mren.201300176http://doi.org/10.1002/mren.201300176 .

Zhang M, Yuan X, Wang L, Chung T C M, Huang T, de Groot W. Macromolecules , 2014 . 47 571 - 581 . DOI:10.1021/ma402328khttp://doi.org/10.1021/ma402328k .

Galli P, Vecellio G. Prog Polym Sci , 2001 . 26 1287 - 1336 . DOI:10.1016/S0079-6700(01)00029-6http://doi.org/10.1016/S0079-6700(01)00029-6 .

Zhang D, Pan L, Li Y, Wang B, Li Y. Macromolecules , 2017 . 50 2276 - 2283 . DOI:10.1021/acs.macromol.6b02550http://doi.org/10.1021/acs.macromol.6b02550 .

Wang X, Long Y, Wang Y, Li Y. J Polym Sci Chem , 2014 . 52 3421 - 3428 . DOI:10.1002/pola.v52.23http://doi.org/10.1002/pola.v52.23 .

Meng Qingqing(孟晴晴), Wang Bin(王彬), Pan Li(潘莉), Li Yuesheng(李悦生), Ma Zhe(马哲). Acta Polymerica Sinica(高分子学报) , 2017 . ( 11 ): 1762 - 1772 . DOI:10.11777/j.issn1000-3304.2017.17028http://doi.org/10.11777/j.issn1000-3304.2017.17028 .

Chen M, Chen C. ACS Catal , 2017 . 7 1308 - 1312 . DOI:10.1021/acscatal.6b03394http://doi.org/10.1021/acscatal.6b03394 .

Chen M, Chen C. Angew Chem Int Ed , 2018 . 57 3094 - 3098 . DOI:10.1002/anie.201711753http://doi.org/10.1002/anie.201711753 .

Song D, Wu J, Ye W, Mu H, Li Y. Organometallics , 2010 . 29 2306 - 2314 . DOI:10.1021/om100075uhttp://doi.org/10.1021/om100075u .

Zhang Y, Mu H, Pan L, Wang X, Li Y. ACS Catal , 2018 . 8 5963 - 5976 . DOI:10.1021/acscatal.8b01088http://doi.org/10.1021/acscatal.8b01088 .

Zou C, Dai S, Chen C. Macromolecules , 2017 . 51 49 - 56.

Sui X, Dai S, Chen C. ACS Catal , 2015 . 5 5932 - 5937 . DOI:10.1021/acscatal.5b01490http://doi.org/10.1021/acscatal.5b01490 .

Mitsushige Y, Yasuda H, Carrow B P, Ito S, Kobayashi M, Tayano T, Watanabe Y. ACS Macro Lett , 2018 . 7 305 - 311 . DOI:10.1021/acsmacrolett.8b00034http://doi.org/10.1021/acsmacrolett.8b00034 .

Nakamura A, Anselment T M J, Claverie J, Goodall B, Jordan R F, Mecking S, Rieger B. Acc Chem Res , 2013 . 46 1438 - 1449 . DOI:10.1021/ar300256hhttp://doi.org/10.1021/ar300256h .

Chen J, Gao Y, Wang B, Lohr T L, Marks T J. Angew Chem Int Ed , 2017 . 56 15964 - 15968 . DOI:10.1002/anie.201708797http://doi.org/10.1002/anie.201708797 .

Chen J, Motta A, Wang B, Gao Y, Marks T J. Angew Chem Int Ed , 2019 . 58 1 - 6 . DOI:10.1002/anie.201813481http://doi.org/10.1002/anie.201813481 .

Radlauer M R, Buckley A K, Henling L M, Agapie T. J Am Chem Soc , 2013 . 135 3784 - 3787 . DOI:10.1021/ja4004816http://doi.org/10.1021/ja4004816 .

Pan L, Hong M, Liu J, Ye W, Li Y. Macromolecules , 2009 . 42 4391 - 4393 . DOI:10.1021/ma9008548http://doi.org/10.1021/ma9008548 .

Cherian A E, Rose J M, Lobkovsky E B, Coates G W. J Am Chem Soc , 2005 . 127 13770 - 13771 . DOI:10.1021/ja0540021http://doi.org/10.1021/ja0540021 .

Rose J M, Deplace F, Lynd N A, Wang Z, Hotta A, Lobkovsky E B, Kramer E J, Coates G W. Macromolecules , 2008 . 41 9548 - 9555 . DOI:10.1021/ma8019943http://doi.org/10.1021/ma8019943 .

Kesti M R, Coates G W, Waymouth R M. J Am Chem Soc , 1992 . 114 9679 - 9680 . DOI:10.1021/ja00050a069http://doi.org/10.1021/ja00050a069 .

Stehling U M, Stein K M, Kesti M R, Waymouth R M. Macromolecules , 1998 . 31 2019 - 2027 . DOI:10.1021/ma971053chttp://doi.org/10.1021/ma971053c .

Stehling U M, Stein K M, Fischer D, Waymouth R M. Macromolecules , 1999 . 32 14 - 20 . DOI:10.1021/ma980856chttp://doi.org/10.1021/ma980856c .

Wang M Q, Ren G Y, Zhao S, Lian G C, Chen T T, Ci Y, Li H Y. Spectrochim Acta A , 2018 . 199 441 - 447 . DOI:10.1016/j.saa.2018.03.083http://doi.org/10.1016/j.saa.2018.03.083 .

Park Y, Jung J, Jeon H, Lee S, Han W S. J Molr Struct , 2018 . 1164 23 - 27 . DOI:10.1016/j.molstruc.2018.03.039http://doi.org/10.1016/j.molstruc.2018.03.039 .

Yang T, Xu H, Wang K, Tao P, Wang F, Zhao B, Wang H. Dyes Pigments , 2018 . 153 67 - 73 . DOI:10.1016/j.dyepig.2018.02.005http://doi.org/10.1016/j.dyepig.2018.02.005 .

Gluszynska A, Juskowiak B, Kuta-Siejkowska M, Hoffmann M, Haider S. Int J Biol Macromol , 2018 . 114 479 - 490 . DOI:10.1016/j.ijbiomac.2018.03.135http://doi.org/10.1016/j.ijbiomac.2018.03.135 .

Salimi Beni A, Zarandi M, Hosseinzadeh B, Najafi Chermahini A. J Mol Struct , 2018 . 1164 155 - 163 . DOI:10.1016/j.molstruc.2018.02.094http://doi.org/10.1016/j.molstruc.2018.02.094 .

Wongsilarat C, Namuangruk S, Prachumrak N, Sudyoadsuk T, Promarak V, Sukwattanasinitt M, Rashatasakhon P. Org Electron , 2018 . 57 352 - 358 . DOI:10.1016/j.orgel.2018.03.035http://doi.org/10.1016/j.orgel.2018.03.035 .

Domski G J, Lobkovsky E B, Coates G W. Macromolecules , 2007 . 40 3510 - 3513 . DOI:10.1021/ma062824shttp://doi.org/10.1021/ma062824s .

Buslov I, Keller S C, Hu X. Org Lett , 2016 . 18 1928 - 1931 . DOI:10.1021/acs.orglett.6b00792http://doi.org/10.1021/acs.orglett.6b00792 .

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

高压处理对聚丁烯-1/聚丙烯共混物结晶结构及力学性能的影响

湿度对高分子氢键复合物纤维力学行为的影响

含引发单体交联聚合物的光调控可逆生长

硬段含量对聚氨酯弹性体的吸水动力学及力学性能的影响