原位聚合甲基丙烯酸盐/低温氢化丁腈橡胶的结构与性能

doi:10.7503/cjcu20140788

摘要/Abstract

摘要：

采用不同阳离子的碱和甲基丙烯酸(MAA), 通过混炼和硫化过程的原位聚合, 制备了聚甲基丙烯酸盐(SPMAA)改性氢化丁腈橡胶(SPMAA-HNBR). 用扫描电子显微镜、透射电子显微镜、傅里叶变换红外光谱仪、示差扫描量热仪及浸泡溶胀实验研究了SPMAA阳离子种类(Na⁺, Mg²⁺和Al³⁺)对SPMAA-HNBR性能的影响. 结果表明, 随着阳离子电荷数的增加, SPMAA逐渐在SPMAA-HNBR内部形成强的离子簇结构, 导致其与HNBR间的相容性变差, 甚至出现大尺寸的聚集体. 这种明显的相分离结构造成聚甲基丙烯酸铝(AlSPMAA)改性氢化丁腈橡胶的拉伸强度和耐油溶胀性能都低于含电荷数较少的聚甲基丙烯酸钠(NaSPMAA)和聚甲基丙烯酸镁(MgSPMAA)改性氢化丁腈橡胶的性能. 各种SPMAA-HNBR的玻璃化转变温度均未发生变化, 保持了-30 ℃的低温弹性. 因此, 选择生成不同阳离子的SPMAA, 可在保持HNBR低温性能的基础上, 有效控制SPMAA-HNBR的性能.

关键词: 聚甲基丙烯酸盐, 氢化丁腈橡胶, 低温弹性, 原位聚合

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

中图分类号:

O631.1⁺1

TrendMD:

张继华, 冯华东, 皂伟涛, 凌铭博, 刘小艳, 赵云峰. 原位聚合甲基丙烯酸盐/低温氢化丁腈橡胶的结构与性能. 高等学校化学学报, 2015, 36(7): 1447.

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^†. Chem. J. Chinese Universities, 2015, 36(7): 1447.

图/表 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

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