Structures and Properties of in situ Polymethacrylates/Low-temperature Hydrogenated Butadiene-acrylonitrile Rubber†

doi:10.7503/cjcu20140788

Abstract

Abstract:

Salts of poly(methacrylic acid)(SPMAA) modified low-temperature hydrogenated butadiene-acrylonitrile rubber(HNBR) composites were prepared by in situ polymerization of alkali and methacrylic acid(MAA). The effects of SPMAA cations(Na⁺, Mg²⁺ and Al³⁺) on the properties of rubber composites were carefully analyzed by scanning electron microscope, transmission electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry and oil-swelling experiments. With the increase of cation’s charge numbers, ion clusters were developed in the rubber bulk which leads to the weak compatibility between SPMAA and rubber, even big aggregations generated. Various properties of aluminum polymethacrylate(AlSPMAA) modified rubber composites, including the tensile strength and oil-swelling resistance, were far less than those of sodium and magnesium polymethacrylates(NaSPMAA and MgSPMAA) due to these structures of phase separation. Importantly, the glassy temperatures of all rubber composites barely changed neglect of the SPMAA’s species, maintaining the elasticity at the temperature of -30 ℃. Therefore, we believe that the properties of low-temperature HNBR composites can be well tuned by varying the cations of in situ polymethacrylates.

Key words: Salt of poly(methacrylic acid), Hydrogenated butadiene-acrylonitrile rubber, Low-tempcrature elasticity, In situ polymerization

CLC Number:

O631.1⁺1

TrendMD:

ZHANG Jihua, FENG Huadong, ZAO Weitao, LING Mingbo, LIU Xiaoyan, ZHAO Yunfeng. Structures and Properties of in situ Polymethacrylates/Low-temperature Hydrogenated Butadiene-acrylonitrile Rubber^†[J]. Chem. J. Chinese Universities, 2015, 36(7): 1447.

Figures/Tables 11

Fig.1 SEM images of pHNBR(A), NaSPMAA-HNBR(B), MgSPMAA-HNBR(C) and AlSPMAA-HNBR(D)The insets of Fig.1(C) and (D) represent the magnified observations relative to different parts of rubber composites.

Fig.2 EDS spectra of MgSPMAA-HNBR(A) and AlSPMAA-HNBR(B)

Fig.3 Representative TEM images of NaSPMAA-HNBR(A), MgSPMAA-HNBR(B) and AlSPMAA-HNBR(C)

Fig.4 XRD patterns of pHNBR(a), NaSPMAA-HNBR(b), MgSPMAA-HNBR(c) and AlSPMAA-HNBR(d)

Fig.5 FTIR spectra of pHNBR(a), MAA(b), NaSPMAA-HNBR(c), MgSPMAA-HNBR(d) and AlSPMAA-HNBR(e)

Fig.6 Plots of tanδ vs. temperature of pHNBR(a), AlSPMAA-HNBR(b), MgSPMAA-HNBR(c) and NaSPMAA-HNBR(d)

Fig.7 Schematic illustration for the microscopic interactions in the rubber bulk

Table 1 Effects of cations on conversion ratio of SMAA, content of SPMAA particles and g-SPMAA

Type of SPMAA-HNBR	Conversion ratio(α) of SMAA(%)	Content(w) of SPMAA particles(%)	Content(1-w) of g-SPMAA (%)
NaSPMAA-HNBR	86.2	98.1	1.9
MgSPMAA-HNBR	98.2	31.8	68.2
AlSPMAA-HNBR	4.4

Fig.8 DSC curves of pHNBR(a), AlSPMAA-HNBR(b), MgSPMAA-HNBR(c) and NaSPMAA-HNBR(d)

Table 2 Mechanical properties of pHNBR, SPMAA-HNBR and the compared case of that from N330

Sample	Hardness (Shore A)	Tensile strength/ MPa	Elongation at break(%)	Permanent set(%)	Tearing strength/ (kN·m^-1)	Compression coefficient (-30, -40 ℃)
pHNBR	43	3.1	325.8	3.5	7.7	0.52, 0.07
NaSPMAA	81	26.6	370.1	33.4	44.5	0.47, 0.05
MgSPMAA	71	29.5	385.9	19.24	44.4	0.41, 0.05
AlSPMAA	67	13.5	428.4	12.4	28.7	0.35,
Carbon black N330	60	18.3	309.8	5.6	21.8	0.52, 0.06

Fig.9 Relationships of volume change ratios versus soaked time for pHNBR(a), AlSPMAA-HNBR(b), MgSPMAA-HNBR(c) and NaSPMAA-HNBR(d) at 100 ℃ under 10# oil

References 20

[1]	Choudhury A., Bhowmick A. K., Soddemann M., Polym. Degrad. Stabil., 2010, 95, 2555—2562
[2]	Hayashi S., Sakakida H., Oyama M., Nakagawa T., Rubber. Chem. Tech., 1991, 64, 534—544
[3]	Yuan X. F., Wu G. Z., Wu C. F., Chem. J. Chinese Universities, 2006, 27(10), 1978—1981
	(袁晓芳, 吴国章, 吴驰飞. 高等学校化学学报,2006, 27(10), 1978—1981)
[4]	Guan Y., Zhang L. X., Zhang L. Q., Lu Y. L., Polym. Degrad. Stabil., 2011, 96(5), 808—817
[5]	Li Q., Zhao S., Pan Y., J. Appl. Polym. Sci., 2010, 117, 421—427
[6]	Chen Y., Xu C., J. Appl. Polym. Sci., 2012, 123, 833—841
[7]	Yin D., Zhang Y., Zhang Y., Peng Z., Fan Y., Sun K., J. Appl. Polym. Sci., 2002, 85, 2667—2676
[8]	Guo B., Lei Y., Chen F., Liu X., Du M., Jia D., Appl. Surf. Sci., 2008, 255, 2715—2722
[9]	Wen S., Zhou Y., Yao L., Zhang L., Chan T., Liang Y., Liu L., Thermochim. Acta, 2013, 571, 15—20
[10]	Samui A., Dalvi V., Chandrasekhar L., Patri M., Chakraborty B., J. Appl. Polym. Sci., 2006, 99, 2542—2548
[11]	Wang L., Lang F., Du F., Wang Z., J. Macromol. Sci., Part B: Physics, 2013, 52, 178—189
[12]	Yu H., Zhang Y., Chen S., Ren W., Hoch M., Guo S., J. Appl. Polym. Sci., 2011, 119, 1813—1819
[13]	Lu Y., Liu L., Tian M., Geng H., Zhang L., Euro. Polym. J., 2005, 41, 589—598
[14]	Xu C., Chen Y., Zeng X., J. Appl. Polym. Sci., 2012, 125, 2449—2459
[15]	Nie Y., Huang G., Qu L., Zhang P., Weng G., Wu J., J. Appl. Polym. Sci., 2010, 115, 99—106
[16]	Wei Z., Lu Y., Meng Y., Zhang L., Polymer, 2012, 53, 1409—1417
[17]	Ren W., Jiang Y., Peng Z., Zhang Y., Zhang Y., China Syn. Rubber Ind., 2005, 28(2), 85—89
	(任文坛, 蒋逸, 彭宗林, 张勇, 张隐西. 合成橡胶工业,2005, 28(2), 85—89)
[18]	Lu Y., Metallic Salts of Unsaturated Carboxylate In-situ Polymerization-reinforcing POE Nano-composite, Beijing University of Chemical Technology,Beijing, 2001
	(卢咏来. 不饱和羧酸金属盐原位聚合增强POE纳米复合材料, 北京: 北京化工大学, 2001)
[19]	Lu Y., Liu L., Shen D., Yang C., Zhang L., Polym. Int., 2004, 53, 802—808
[20]	Ikeda T., Yamada B., Tsuji M., Sakurai S., Polym. Int., 1999, 48, 446—454