丙烯与1，3-丁二烯配位共聚合制备兼具高刚性与高韧性的嵌段共聚物

吕仪; 高欢; 潘莉

doi:10.11777/j.issn1000-3304.2022.22141

您当前的位置：

首页 >

文章列表页 >

丙烯与1，3-丁二烯配位共聚合制备兼具高刚性与高韧性的嵌段共聚物

研究论文 | 更新时间：2024-10-08

- 丙烯与1，3-丁二烯配位共聚合制备兼具高刚性与高韧性的嵌段共聚物
- Block Copolymers with High Rigidity and Toughness Prepared via Coordination Copolymerization of Propylene with 1,3-Butadiene
- 高分子学报 2022年53卷第11期页码：1409-1420
- 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)
- DOI：10.11777/j.issn1000-3304.2022.22141
  中图分类号：
- 纸质出版日期：2022-11-20，
  
  网络出版日期：2022-08-19，
  
  收稿日期：2022-04-25，
  
  录用日期：2022-05-07
- 稿件说明：
移动端阅览
吕仪,高欢,潘莉.丙烯与1，3-丁二烯配位共聚合制备兼具高刚性与高韧性的嵌段共聚物[J].高分子学报,2022,53(11):1409-1420.

Lv Yi,Gao Huan,Pan Li.Block Copolymers with High Rigidity and Toughness Prepared via Coordination Copolymerization of Propylene with 1,3-Butadiene[J].ACTA POLYMERICA SINICA,2022,53(11):1409-1420.
吕仪,高欢,潘莉.丙烯与1，3-丁二烯配位共聚合制备兼具高刚性与高韧性的嵌段共聚物[J].高分子学报,2022,53(11):1409-1420. DOI： 10.11777/j.issn1000-3304.2022.22141.

Lv Yi,Gao Huan,Pan Li.Block Copolymers with High Rigidity and Toughness Prepared via Coordination Copolymerization of Propylene with 1,3-Butadiene[J].ACTA POLYMERICA SINICA,2022,53(11):1409-1420. DOI： 10.11777/j.issn1000-3304.2022.22141.

摘要

以二甲基吡啶胺铪/[Ph

]

[B(C

)

]

/Al

为催化体系，通过一锅两步法在温和条件下制备了一系列高分子量、窄分子量分布且具有高等规度的等规聚丙烯(

PP，硬段)与丙烯-1

3-丁二烯(1

3-BD)无

规共聚物(软段)的嵌段共聚物. 通过高温核磁(

H-NMR、

C-NMR)、高温凝胶渗透色谱(GPC)、示差扫描量热法(DSC)、动态力学分析(DMA)和拉伸力学性能测试，对所制备嵌段聚合物的结构和性能进行了分析表征. 结果表明，1

3-BD以1

2-和

trans

-1

4-2种方式无规插入共聚物分子链中，且以

trans

-1

4-插入方式为主；共聚物具有较高的熔融温度(

约为158 ℃)和极低的玻璃化转变温度(

可达-70 ℃). 独特的软-硬结构赋予材料优异的力学性能：共聚物同时具有较高的拉伸强度(≥33 MPa)和断裂伸长率(最高为800%). 以上研究结果表明，通过调节软硬段的结构，可以高效制备兼具高刚性与高韧性的

PP嵌段共聚物，结合的丙烯与1

3-BD无规共聚物软段是对全同PP进行增韧改性非常有效的手段.

Abstract

A series of propylene/1

‍3-butadiene (BD) block copolymers with high molecular weight (

1.3×10

) and narrow molecular weight distribution (1.8~2.0) were prepared

via

“one-pot

two-step” method by using dimethylpyridine amine hafnium/[Ph

]

[B(C

)

]

/Al

as catalyst system under mild conditions. By Varying the reaction time for each step and BD dosage in the second step

the block length of each block and composition of the soft block could be easily tuned. Molecular weight and molecular weight distribution

thermal properties

microstructure

and mechanical properties of the obtained block copolymers were clearly characterized by high temperature gel chromatography (GPC)

differential scanning calorimetry (DSC)

high temperature nuclear magnetic (NMR)

tensile test

etc

. The block copolymers contain both a hard

PP block and soft propylene/BD random copolymer block. It was revealed that 1

3-BD was randomly inserted into the molecular chain

via

both 1

2- and

trans

-1

4-insertion manners

and the amount of the latter was about six times that of the former. The copolymers showed high melting temperature (

≈ 158 ℃) and very low glass transition temperature (

around -70 ℃). The obtained block copolymers with both hard

PP segments and propylene/1

3-BD random copolymer block helped to achieve both high rigidity and toughness simultaneously. As proved

the block copolymers showed high tensile strength (≥33 MPa) and elongation at break (up to 800%). The above results indicated that

via

tuning the hard and soft block composition during the two-step copolymerization of propylene and BD

block copolymers with much improved tensile properties could be easily obtained. Incorporation of a very soft propylene-BD random copolymer block plays a vital role in

PP toughening. The research results will provide new idea for the development of the

PPs with excellent mechanical properties.

关键词

丙烯13-丁二烯配位共聚合嵌段共聚物增韧改性

Keywords

Propylene13-ButadieneCoordination copolymerizationBlock copolymerToughening modification

references

Chung T C M. Macromol React Eng, 2014, 8(2): 69-80. doi:10.1002/mren.201300176http://dx.doi.org/10.1002/mren.201300176

Franssen N M, Reek J N, Bruin B S. Chem Soc Rev, 2013, 42(13): 5809-5832

Galli P, Vecellio G. Prog Polym Sci, 2001, 26(8):1287-1336. doi:10.1016/s0079-6700(01)00029-6http://dx.doi.org/10.1016/s0079-6700(01)00029-6

Shang R N, Gao H, Luo F L, Li Y L, Wang B, Ma Z, Pan L, Li Y S. Macromolecules, 2019, 52(23): 9280-9290. doi:10.1021/acs.macromol.9b00757http://dx.doi.org/10.1021/acs.macromol.9b00757

Du Huizhen(杜惠真), 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://dx.doi.org/10.11777/j.issn1000-3304.2018.18090

Dasari A, Zhang Q X, Yu Z Z, Mai Y W. Macromolecules, 2010, 43(13): 5734-5739. doi:10.1021/ma100633yhttp://dx.doi.org/10.1021/ma100633y

Hernandez Y, Lozano T, Morales A B, Pardo F N, Lafleur P G, Valdes S S. J Compos Mater, 2017, 51(3): 373-380. doi:10.1177/0021998316644852http://dx.doi.org/10.1177/0021998316644852

Zhou F Q, Qi L C, He X L. Polym Adv Technol, 2020, 31(11): 2492-2503. doi:10.1002/pat.4964http://dx.doi.org/10.1002/pat.4964

Peng Wenli(彭文理), Chen Zhenbin(陈振斌), Zhang Wenxue(张文学), Zhang Yunfei(张云飞), Xu Renwei(徐人威), Zhu Bochao(朱博超). Petrochemical Technology(石油化工), 2019, 48(10): 1076-1083. doi:10.3969/j.issn.1000-8144.2019.10.015http://dx.doi.org/10.3969/j.issn.1000-8144.2019.10.015

Banerjee J, Soliya P, Pallavi M B, Mukhopadhyay S, Bandyopadhyay D, Chakrabarty K. Inter Polym Pros, 2016, 31(2): 188-197. doi:10.3139/217.3143http://dx.doi.org/10.3139/217.3143

Lin J H, Pan Y J, Liu C F, Huang C L, Hsieh C T, Chen C K. Materials, 2015, 8(12): 8850-8859. doi:10.3390/ma8125496http://dx.doi.org/10.3390/ma8125496

Lin Y, Chen H B, Chan C M, Wu J S. Macromolecules, 2008, 41(23): 9204-9213. doi:10.1021/ma801095dhttp://dx.doi.org/10.1021/ma801095d

Patel A C, Brahmbhatt R B, Devi S. J Appl Polym Sci, 2003, 88(1): 72-78. doi:10.1002/app.11554http://dx.doi.org/10.1002/app.11554

Poon B, Rogunova M, Chum S P, Hiltner A, Baer E. Polym Phys, 2004, 42(23): 4357-4370. doi:10.1002/polb.20290http://dx.doi.org/10.1002/polb.20290

Gao Huan(高欢), Shao Pingjun(邵平均), Li Bang(李邦), Pan Li(潘莉). Acta Polymerica Sinica(高分子学报), 2021, (11): 1498-1505. doi:10.11777/j.issn1000-3304.2021.21125http://dx.doi.org/10.11777/j.issn1000-3304.2021.21125

An Y J, Xing H P, Wang Y H, Tang T. J Appl Polym Sci, 2012, 125(4): 2724-2731. doi:10.1002/app.36591http://dx.doi.org/10.1002/app.36591

Tian J, Hustad P D, Coates G W. J Am Chem Soc, 2001, 123(21): 5134-5135. doi:10.1021/ja0157189http://dx.doi.org/10.1021/ja0157189

Naga N, Shiono T, Ikeda T. Macromolecules, 1999, 32(5): 1348-1355. doi:10.1021/ma9814144http://dx.doi.org/10.1021/ma9814144

Shi X C, Tang X Y, Li Y S. Polymer, 2011, 52(14): 3053-3058. doi:10.1016/j.polymer.2011.04.058http://dx.doi.org/10.1016/j.polymer.2011.04.058

Shao Y T, Wu C G, Cheng S Y, Zhou F, Yan H B. Polym Test, 2015, 41: 252-263. doi:10.1016/j.polymertesting.2014.12.008http://dx.doi.org/10.1016/j.polymertesting.2014.12.008

Guo Y T, Fu Z S, Xu J T, Fan Z Q. Polymer, 2017, 122: 77-86. doi:10.1016/j.polymer.2017.06.042http://dx.doi.org/10.1016/j.polymer.2017.06.042

Rose C D, Iacono S D, Auriemma F, Ciaccia E, Resconi L. Macromolecules, 2006, 39(18): 6098-6109

Edson J B, Wang Z G, Kramer E J, Coates G W. J Am Chem Soc, 2008, 130(14): 4968-4977. doi:10.1021/ja077772ghttp://dx.doi.org/10.1021/ja077772g

Hustad P D, Coates G W. Macromolecules, 2005, 38(3): 851-860

Hotta A E, Cochran J, Ruokolainen V, Khanna G H, Fredrickson E J, Kramer Y W, Shin F, Shimizu A E, Cherian P D, Hustad J M, Rose G, Coates W. Pans, 2006, 103(42): 15327-15332. doi:10.1073/pnas.0602894103http://dx.doi.org/10.1073/pnas.0602894103

Anatoliy K, Gaurav K M, Alexander A, Michael T, Zhang Q, Paul J D. ACS Sustainable Chem Eng, 2020, 8(8): 3273-3282. doi:10.1021/acssuschemeng.9b06881http://dx.doi.org/10.1021/acssuschemeng.9b06881

Zhong Y H, Wang B L, Cui D M. Polym Chem, 2021, 12(31): 4576-4582. doi:10.1039/d1py00840dhttp://dx.doi.org/10.1039/d1py00840d

Wu C J, Liu B, Lin F, Wang M Y, Cui D M. Angew Chem Int Ed, 2017, 56(24): 6975-6979. doi:10.1002/anie.201702128http://dx.doi.org/10.1002/anie.201702128

Zhang K, Dou Y L, Jiang Y, Zhang Z, Li S H, Cui D M. Macromolecules, 2021, 54(20): 9445-9451. doi:10.1021/acs.macromol.1c01384http://dx.doi.org/10.1021/acs.macromol.1c01384

Du G X, Xue J P, Peng D Q, Yu C, Wang H H, Zhou Y N, Bi J J, Zhang S W, Dong Y P, Li X F. Polym Chem, 2015, 53(24): 2898-290. doi:10.1002/pola.27769http://dx.doi.org/10.1002/pola.27769

Guo F, Meng R, Li Y, Hou Z M. Polymer, 2015, 76: 159-167. doi:10.1016/j.polymer.2015.08.060http://dx.doi.org/10.1016/j.polymer.2015.08.060

Ishihara T, Shiono T. Macromolecules, 2003, 36(26): 9675-9677. doi:10.1021/ma0349480http://dx.doi.org/10.1021/ma0349480

Ishihara T, Shiono T. J Am Chem Soc, 2005, 127(16): 5774-5775. doi:10.1021/ja050987ahttp://dx.doi.org/10.1021/ja050987a

Niu H, Dong J Y. Polymer, 2007, 48(6): 1533-1540. doi:10.1016/j.polymer.2007.01.067http://dx.doi.org/10.1016/j.polymer.2007.01.067

Annunziata L, Pragliola S, Pappalardo D, Tedesco D, Pellecchia C. Macromolecules, 2011, 44(7): 1934-1941. doi:10.1021/ma1028455http://dx.doi.org/10.1021/ma1028455

Shang Ruining(商睿凝), Pan Li(潘莉), Li Yuesheng(李悦生). Acta Polymerica Sinica(高分子学报), 2019, (11): 1187-1195. doi:10.11777/j.issn1000-3304.2019.19081http://dx.doi.org/10.11777/j.issn1000-3304.2019.19081

Wang X Y, Long Y Y, Wang Y X, Li Y S. J Polym Sci, Part B: Polym Chem, 2014, 52(23): 3421-3428. doi:10.1002/pola.27409http://dx.doi.org/10.1002/pola.27409

Li Z X, Shi S W, Yang F, Cao D F, Zhang K Y, Wang B, Ma Z, Pan L, Li Y S. ACS Omega, 2020, 5(22): 13148-13157. doi:10.1021/acsomega.0c01165http://dx.doi.org/10.1021/acsomega.0c01165

Li Y L, Song D P, Pan L, Ma Z, Li Y S. Polym Chem, 2019, 10(46): 6368-6378. doi:10.1039/c9py01225ghttp://dx.doi.org/10.1039/c9py01225g

Wang B, Shang R N, Ma Z, Pan L, Li Y S. Polymer, 2017, 116: 105-112. doi:10.1016/j.polymer.2017.03.067http://dx.doi.org/10.1016/j.polymer.2017.03.067

Pan L, Zhang K Y, Nishiura M, Hou Z M. Angew Chem Int Ed, 2011, 50(50): 12012-12015. doi:10.1002/anie.201104011http://dx.doi.org/10.1002/anie.201104011

Cueny E S, Johnson H C, Anding B J, Landis C R. J Am Chem Soc, 2017, 139(34): 11903-11912. doi:10.1021/jacs.7b05729http://dx.doi.org/10.1021/jacs.7b05729

Resconi L, Cavallo L, Fait A, Piemontesi F. Chem Rev, 2000, 100(4): 1253-1345. doi:10.1021/cr9804691http://dx.doi.org/10.1021/cr9804691

Fang Zhanqing(方展清), Zhang Yulan(张玉兰). Polymer Communications(高分子通讯), 1982, (3): 172-177

Ester L M, Rafael V G, Alicia C. Eur Polym J, 2017, 90: 183-194

浏览量

128

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

铁、钴金属配合物催化1,3-二烯烃聚合研究进展

极少量1,4-戊二烯对典型Ziegler-Natta催化剂催化的丙烯聚合反应及聚丙烯性质的影响

接枝位置异构的笼型两亲性分子的自组装模拟