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Nd(vers)3/Al(
i Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)3/Al(
i -Bu)2H/AlEt3/EASC Catalyst- 高分子学报 2021年52卷第5期 页码：541-548
- 作者机构：
1.沈阳理工大学材料科学与工程学院 沈阳 110159
2.中国科学院长春应用化学研究所 长春 130022
3.中国石油天然气股份有限公司石油化工研究院兰州化工研究中心 兰州 730060
- 作者简介：
E-mail: xqzhang@qust.edu.cn
- 基金信息：国家自然科学基金(基金号 51803206, U1862206)、吉林省自然科学基金(基金号 20200201089JC)、吉林省教育厅项目(项目号 JJKH20200665KJ)和中国石油天然气股份有限公司(项目号 2018B-2707)资助()
DOI：10.11777/j.issn1000-3304.2020.20287
中图分类号：纸质出版日期：2021-5-3，
网络出版日期：2021-3-15，
收稿日期：2020-12-28，
修回日期：2021-1-20，
扫 描 看 全 文
郑文洁, 毕吉福, 丛日新, 王凤, 刘恒, 胡雁鸣, 张学全. Nd(vers)3/Al(
i Wen-jie Zheng, Ji-fu Bi, Ri-xin Cong, Feng Wang, Heng Liu, Yan-ming Hu, Xue-quan Zhang. Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)3/Al(
i -Bu)2H/AlEt3/EASC Catalyst[J]. Acta Polymerica Sinica, 2021,52(5):541-548.郑文洁, 毕吉福, 丛日新, 王凤, 刘恒, 胡雁鸣, 张学全. Nd(vers)3/Al(
i Wen-jie Zheng, Ji-fu Bi, Ri-xin Cong, Feng Wang, Heng Liu, Yan-ming Hu, Xue-quan Zhang. Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)3/Al(
i -Bu)2H/AlEt3/EASC Catalyst[J]. Acta Polymerica Sinica, 2021,52(5):541-548. DOI： 10.11777/j.issn1000-3304.2020.20287.
摘要
采用新癸酸钕(Nd(vers)
3
)/氢化二异丁基铝(Al(
i
-Bu)
2
H)/三乙基铝(AlEt
3
)/乙基倍半氯化铝(EASC)体系催化丁二烯(Bd)/异戊二烯(Ip)及Bd/Ip/月桂烯(My)共聚合. 所得丁戊共聚物组成与催化剂用量无关，单体的投料量与共聚物中此单体的含量几乎呈线性关系；用示差扫描量热仪(DSC)测得共聚物只有一个玻璃化转变，共聚物中Ip含量与其玻璃化转变温度(
T
g
)呈良好的线性关系. 采用Fineman-Ross方法计算竞聚率得到
r
1
=1.04，
r
2
=1.18，Kelen-Tüdos法计算竞聚率得到
r
1
=1.33，
r
2
=1.59；
r
1
，
r
2
均接近于1，说明在此催化体系下反应可以得到无规的丁戊共聚物. 利用核磁碳谱对共聚物的序列结构进行了分析和归属，采用Bernoulli模型和一级Markov模型验证共聚物的序列结构，通过比较数均序列长度，一级Markov模型计算得到的序列长度与核磁计算的实际值更接近. Bd/Ip/My三元共聚合时，所得共聚物中My单元含量随着投料比的增加而增加，其DSC曲线上只有一个玻璃化转变，
T
g
值随着My含量的增加而稍增加.
Abstract
Copolymerization of butadiene (Bd)/isoprene (Ip) and Bd/Ip/myrcene (My) was carried out with Nd(vers)
3
/Al(
i
-Bu)
2
H/AlEt
3
/EASC catalyst system. For the BD and Ip copolymerization
the catalyst content has rare effect on the copolymer composition and the unit content in copolymer was almost proportional to the monomer feed; only one glass transition temperature (
T
g
) was detected by DSC and it increased linearly with the increasing Ip unit content in copolymers
which indicated the random structure of copolymers. The reactivity ratios of butadiene (
r
1
) to isoprene (
r
2
) were calculated with both Fineman-Ross and Kelen-Tüdos method.
r
1
and
r
2
were close to 1
suggesting random copolymerization of Bd and Ip with the present catalyst system. The structure and distribution of copolymer sequences were analyzed and assigned with
13
C-NMR. The number average sequence lengths calculated by
13
C-NMR and Bernoullian/Markov model
respectively
were compared
and the result showed that Markov model was more suitable for simulating the copolymer sequence distribution. Ternary copolymerization of Bd
Ip and My catalyzed by the catalyst system showed that the My unit content in the copolymer increased with the monomer feed
only one glass transition was detected and the value slowly increased with the increasing My unit content in copolymers. The reactivity ratios calculated by Kelen-Tüdos method were
r
12
=1.03
r
21
=1.69
r
23
=1.11
r
32
=3.62
r
13
=0.80
r
31
=4.67.
关键词
丁戊共聚物钕系催化剂月桂烯竞聚率序列分布
Keywords
Butadiene-isoprene copolymerNeodymium-based catalystMyrceneReactivity rateSequence distribution
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