Preparation of High-performance Montmorillonite/hydrogenated Butadiene-acrylonitrile Rubber by Using Electrostatic Interfaces

doi:10.7503/cjcu20190595

Abstract

Abstract:

After amine-modified montmorillonite(MMT) and methacrylic acid(MA) were mixed to prepare a slurry, they were added to the hydrogenated butadiene-acrylonitrile rubber(HNBR). By thermal vulcanization, MMT/HNBR composites were successfully achieved. The MA-modified MMT/rubber interfaces and their dispersion were carefully investigated by scanning electron microscopy, transmission electron microscopy, small angle X-ray scattering pattern, Fourier transform infrared spectroscopy and vulcameter. Moreover, various properties of rubber composites were analyzed. The experimental results showed that chemical crosslinking networks were developed during vulcanization. In the meantime, MA was in-situ self-polymerized in the rubber matrix and ion pairs were formed between polymethacrylic acid and amine on MMT, which therefore constructed strong electrostatic interfaces between MMT and rubber matrix. The self-polymerization of MA extended interlayer spacing of MMT, leading to a good dispersion of MMT in rubber matrix. MMT with good dispersion and ion interfaces constrained the slippage of rubber chains during stretching, which was proved by the dynamic mechanical properties and stress relaxation at 200%. So the tensile strength and toughness of rubber composites were greatly improved. In addition, the N₂ permeability of rubber composites was reduced, showing a good gas barrier property. Therefore, the preparation of MA/MMT slurry is a simple and convenient method to modify the MMT. We believe that as-prepared MMT/HNBR composites can be used in the rubber products with the requirements of high mechanical and good gas barrier properties.

Key words: Hydrogenated butadiene-acrylonitrile rubber, Amine-modified montmorillonite, Methacrylic acid, Strengthening and toughening, Gas barrier property

CLC Number:

O631.1 ⁺1

TrendMD:

ZHANG Jihua,WANG Chao,ZAO Weitao,LI Li,LIU Xiaoyan,YANG Yuan,WANG Hao. Preparation of High-performance Montmorillonite/hydrogenated Butadiene-acrylonitrile Rubber by Using Electrostatic Interfaces[J]. Chem. J. Chinese Universities, 2020, 41(4): 803.

Figures/Tables 13

Fig.1 FTIR spectra of various samples(A) and Si—O absorption of MMT and HNBR-x samples(B) (A) a. MA; b. pure rubber; c. HNBR-0; d. HNBR-10; e. HNBR10. ^ (B) a. MMT; b. HNBR10; c. HNBR-8; d. HNBR-10; e. HNBR-15; f. HNBR-20.

Fig.2 TEM images of HNBR-0(A), HNBR-5(B), HNBR-10(C) and HNBR10(D)

Fig.3 Magnified TEM images of HNBR10(A) and HNBR-10(B)

Fig.4 SAXS spectra of HNBR-8(a), HNBR-10(b), HNBR-20(c) and HNBR10(d)

Sample	Scorch time/s	Cure time/s	M_L/(N·m)	M_H/(N·m)	ΔH/(N·m)
Pure rubber	148	704	0.19	1.60	1.41
HNBR10	147	935	0.35	1.73	1.38
HNBR-0	40	1305	0.17	0.74	0.57
HNBR-5	43	1226	0.16	0.72	0.56
HNBR-10	48	1007	0.17	0.69	0.52
HNBR-15	41	856	0.26	0.88	0.62
HNBR-20	30	803	0.27	1.05	0.78

Fig.5 Vulcanization curves of HNBR10(a), HNBR-0(b), HNBR-5(c), HNBR-10(d), HNBR-15(e) and HNBR-20(f)

Rubber	Pure rubber	HNBR-0	HNBR-8	HNBR-10	HNBR-15	HNBR-20	HNBR10
Hardness/Shore A	40	40	50	50	55	62	47
Tensile strength/MPa	1.02±0.41	6.31±0.53	14.42±1.35	13.83±1.28	11.52±0.93	12.63±1.07	5.90±0.22
Elongation at break(%)	121±8	614±21	594±13	697±9	699±11	638±7	129±5
Stress at 100% strain/MPa	0.88±0.07	0.78±0.14	1.28±0.14	1.53±0.09	1.70±0.08	1.80±0.12	1.32±0.16
Stress at 300% strain/MPa		1.58±0.21	2.80±0.13	3.18±0.16	3.53±0.14	3.91±0.21

Fig.6 Stretching-releasing curves(A) and calculated hysteresis energy(B) of HNBR-x

Scheme 1 Schematic of well-dispersed MMTs and their ionic interfaces in HNBR-x by using MA/MMT slurry

Fig.7 Relaxation curves of HNBR-x after a fast stretching at the strain of 200%

Fig.8 Storage modulus(E') versus temperature plots of HNBR-x

Fig.9 tanδ vs. temperature plots of HNBR-x (A) and their relations among constrained tanδ peak (tanδpeak), volume fraction(Vs) and MMT content(B)

Fig.10 N2 permeability of HNBR-x samples

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