Terpolymerization of Ethylene， Cyclic Olefin and 1-Octene Catalyzed by Rare Earth Complexes

doi:10.19894/j.issn.1000-0518.230100

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (10): 1396-1404.DOI: 10.19894/j.issn.1000-0518.230100

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Terpolymerization of Ethylene， Cyclic Olefin and 1-Octene Catalyzed by Rare Earth Complexes

Lin-Feng WANG¹^,², Hui TIAN¹^,², Guang-Bi GONG³, Chun-Ji WU¹, Bao-Li WANG¹^,²(), Dong-Mei CUI¹^,²

^1.State Key Laboratory of Polymer Physics and Chemistry，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.School of Applied Chemistry and Engineering，University of Science and Technology of China，Hefei 230026，China
^3.Lanzhou Chemical Research Center，Petro China Company Limited，Lanzhou 730060，China

Received:2023-04-10 Accepted:2023-08-11 Published:2023-10-01 Online:2023-10-13
Contact: Bao-Li WANG
About author:wang@ciac.ac.cn
Supported by:
the National Natural Science Foundation of China(52273017);the Strategic Priority Program of the Chinese Academy of Sciences(ZDRW-CN-2023-1)

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Abstract

Abstract:

Cyclic olefin copolymer （COC） is produced through the copolymerization of ethylene and cyclic olefins， and has been used for the manufacturing of optical devices and diagnostic containers due to its high transparency and excellent water vapor barrier. However， COC with high glass-transition temperature usually needs high cycloolefin insertion in copolymer and has increased brittleness， which has significantly hampered its many end uses. The introduction of α-olefin into ethylene/cycloolefin binary copolymers that have been extensively studied is expected to expand the application of cyclic olefin copolymers. In this paper， we report the terpolymerization of ethylene/norbornene/1-octene and ethylene/dicyclopentadiene/1-octene catalyzed by modified cyclopentadienyl scandium complexes 1-3 activated with ［Ph₃C］［B（C₆F₅）₄］ and Al ⁱ Bu₃ because rare earth catalysts have shown excellent catalytic performance towards olefin polymerization. These rare earth catalysts exhibit high catalytic activities （4.4×10⁵~21.4×10⁵ g/（mol（Sc）·h·bar））. The resultant terpolymers show moderate number average molecular weight （M_n=3.8×10⁴~20.3×10⁴） and relatively narrow polydispersity index （PDI=1.2~2.4）. The introduction of 1-octene significantly improves the toughness of ethylene/norbornene/1-octene terpolymers， and the P3 sample （M_n 13.7×10⁴， norbornene 37.1%， 1-octene 11.0%） exhibits 2.0 times higher elongation at break （29.9% vs. 9.9%） than the P1 sample （M_n 14.0×10⁴， NB 42.6%， OCT 6.4%）

Key words: Cyclic olefin copolymer, Norbornene, Dicyclopentadiene, Toughness, Rare earth catalysts

CLC Number:

O631

Lin-Feng WANG, Hui TIAN, Guang-Bi GONG, Chun-Ji WU, Bao-Li WANG, Dong-Mei CUI. Terpolymerization of Ethylene， Cyclic Olefin and 1-Octene Catalyzed by Rare Earth Complexes[J]. Chinese Journal of Applied Chemistry, 2023, 40(10): 1396-1404.

Figures/Tables 6

Fig.1 Chemical structures of scandium catalysts 1-3

Table 1 Terpolymerization of ethylene， norbornene and 1-octene catalyzed by complexes 1-3 under various temperatures a

Entry	Cat.	Temperature/℃	10^-5 Activity/（ $g · m o l - 1 (S c)$ ·h^-1·bar^-1）	f_NB^b /%	f_1-octene^b /%	10^-4·M_n^c	PDI ^c	T_m^d /℃
1	1	25	7.1	30.1	6.5	10.1	1.7	107.9
2	2	25	6.7	30.0	3.4	14.6	2.2	111.3
3	3	25	4.4	27.7	2.6	10.0	2.4	121.6
4	1	40	8.1	22.5	10.9	7.2	1.6	105.7
5	1	60	8.2	26.5	7.8	4.7	2.0	97.9
6	2	40	6.6	23.7	3.9	8.8	2.1	110.7
7	2	60	7.5	22.8	7.1	5.1	2.6	103.6
8	3	40	5.7	24.6	0.8	20.3	1.7	119.4
9	3	60	4.8	27.2	1.6	11.3	2.2	122.1

Table 1 Terpolymerization of ethylene， norbornene and 1-octene catalyzed by complexes 1-3 under various temperatures a

Entry	Cat.	Temperature/℃	10^-5 Activity/（ $g · m o l - 1 (S c)$ ·h^-1·bar^-1）	f_NB^b /%	f_1-octene^b /%	10^-4·M_n^c	PDI ^c	T_m^d /℃
1	1	25	7.1	30.1	6.5	10.1	1.7	107.9
2	2	25	6.7	30.0	3.4	14.6	2.2	111.3
3	3	25	4.4	27.7	2.6	10.0	2.4	121.6
4	1	40	8.1	22.5	10.9	7.2	1.6	105.7
5	1	60	8.2	26.5	7.8	4.7	2.0	97.9
6	2	40	6.6	23.7	3.9	8.8	2.1	110.7
7	2	60	7.5	22.8	7.1	5.1	2.6	103.6
8	3	40	5.7	24.6	0.8	20.3	1.7	119.4
9	3	60	4.8	27.2	1.6	11.3	2.2	122.1

Table 2 Terpolymerization of ethylene/norbornene （or dicyclopentadiene）/1-octene catalyzed by complex 1 under various monomer account in-feed a

Entry	n（Cyclic monomer）/mmol	n（1-octene）mmol	Time/min	10^-5 Activity/ （g^-1·mol $- 1$ （Sc）·h^-1·bar^-1）	f_{cyclic monomer}^b /%	f_1-octene^b /%	10^-4·M_n^c	PDI ^c	T_g^d /℃
1	10 （NB）	5	5	17.0	34.8	4.2	6.5	1.8	101.9
2	15 （NB）	5	5	21.4	37.4	5.1	8.8	1.5	106.6
3	5 （NB）	10	5	14.6	31.9	16.5	4.5	1.9	86.4
4	5 （NB）	15	5	12.2	23.7	22.9	6.0	1.7	75.2
5	20 （NB）	5	20	8.0	44.2	5.5	8.1	1.2	118.4
6	20 （NB）	10	20	8.2	42.6	6.4	14.0 （P1）	1.7	116.1
7	20 （NB）	15	20	9.7	40.1	7.5	15.6 （P2）	1.6	112.4
8	20 （NB）	20	20	8.8	37.1	11.0	13.7 （P3）	1.4	106.1
9	20 （DCPD）	5	20	8.2	45.5	2.7	5.9	1.7	137.1
10	20 （DCPD）	10	20	8.6	43.9	4.1	3.8 （P4）	1.8	133.9
11	20 （DCPD）	15	20	8.9	40.6	7.8	5.6 （P5）	1.8	112.7
12	20 （DCPD）	20	20	8.1	39.8	10.2	4.7 （P6）	1.9	112.1

Table 2 Terpolymerization of ethylene/norbornene （or dicyclopentadiene）/1-octene catalyzed by complex 1 under various monomer account in-feed a

Entry	n（Cyclic monomer）/mmol	n（1-octene）mmol	Time/min	10^-5 Activity/ （g^-1·mol $- 1$ （Sc）·h^-1·bar^-1）	f_{cyclic monomer}^b /%	f_1-octene^b /%	10^-4·M_n^c	PDI ^c	T_g^d /℃
1	10 （NB）	5	5	17.0	34.8	4.2	6.5	1.8	101.9
2	15 （NB）	5	5	21.4	37.4	5.1	8.8	1.5	106.6
3	5 （NB）	10	5	14.6	31.9	16.5	4.5	1.9	86.4
4	5 （NB）	15	5	12.2	23.7	22.9	6.0	1.7	75.2
5	20 （NB）	5	20	8.0	44.2	5.5	8.1	1.2	118.4
6	20 （NB）	10	20	8.2	42.6	6.4	14.0 （P1）	1.7	116.1
7	20 （NB）	15	20	9.7	40.1	7.5	15.6 （P2）	1.6	112.4
8	20 （NB）	20	20	8.8	37.1	11.0	13.7 （P3）	1.4	106.1
9	20 （DCPD）	5	20	8.2	45.5	2.7	5.9	1.7	137.1
10	20 （DCPD）	10	20	8.6	43.9	4.1	3.8 （P4）	1.8	133.9
11	20 （DCPD）	15	20	8.9	40.6	7.8	5.6 （P5）	1.8	112.7
12	20 （DCPD）	20	20	8.1	39.8	10.2	4.7 （P6）	1.9	112.1

Table 3 Tensile Properties of terpolymers

Entry	Sample	10^-4M_n	f/%（cyclic monomer）	f_1-octene/%	Tensile strength/MPa	Strain at break/%
1	P1	14.0	42.6 （NB）	6.4	20.1	9.9
2	P2	15.6	40.1 （NB）	7.5	28.2	12.0
3	P3	13.7	37.1 （NB）	11.0	35.2	29.9
4	P4	3.8	43.9 （DCPD）	4.1	15.5	7.9
5	P5	5.6	40.6 （DCPD）	7.8	20.2	9.3
6	P6	4.7	39.8 （DCPD）	10.2	17.6	10.0

Fig.2 Stress-strain curves of ethylene/cycloolefin/1-octene terpolymers P1-P6

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Terpolymerization of Ethylene， Cyclic Olefin and 1-Octene Catalyzed by Rare Earth Complexes

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