含混杂活性端基新型多官能团齐聚物的结构与性能

doi:10.7503/cjcu20141118

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (5): 996.doi: 10.7503/cjcu20141118

含混杂活性端基新型多官能团齐聚物的结构与性能

钱建华^1,², 刘坐镇^1,², 黄锐², 付建辉², 陈建辉¹, 郭卫红^1,³()

1.华东理工大学材料科学与工程学院, 特种功能高分子材料及其相关技术教育部重点实验室,2. 华东理工大学华昌聚合物有限公司, 上海防腐蚀新材料工程技术研究中心, 上海 200237
2. 华东理工大学华昌聚合物有限公司, 上海防腐蚀新材料工程技术研究中心, 上海 200237
3. 安徽省石油化工新材料协同创新中心, 安庆 246011

收稿日期:2014-12-19 出版日期:2015-05-10 发布日期:2015-04-13
作者简介:联系人简介: 郭卫红, 女, 博士, 教授, 主要从事聚合物加工研究. E-mail: guoweihong@ecust.edu.cn
基金资助:
上海市重大科技攻关项目(批准号: 12dz1100401)和上海工程技术研究中心能力提升项目(批准号: 13DZ2280900)资助

Structures and Properties of Novel Multifunctional Hybrid Oligomers^†

QIAN Jianhua^1,², LIU Zuozhen^1,², HUANG Rui², FU Jianhui², CHEN Jianhui¹, GUO Weihong^1,^3,^*()

1. Key Laboratory for Specially Functional Polymers and Related Technology of Ministry of Education,School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
2. Shanghai Engineering Research Center of New Anticorrosion Material,Sino Polymer Co., Ltd., Shanghai 200237, China
3. Anhui Collaborative Innovation Center for Petrochemical New Materials, Anqing 246011, China

Received:2014-12-19 Online:2015-05-10 Published:2015-04-13
Contact: GUO Weihong E-mail:guoweihong@ecust.edu.cn

摘要/Abstract

摘要：

通过控制4,4'-二氨基二苯甲烷环氧树脂(TGDDM)和丙烯酸(AA)的摩尔比(1∶2)合成了化学共混的含混杂活性端基的多官能团齐聚物MVEO-2, 直接将多官能团环氧树脂TGDDM与多官能团环氧乙烯基树脂MVER通过物理共混得到聚合物共混物MVEO_mix. 研究了化学共混和物理共混对含混杂活性端基多官能团齐聚物的结构、性能和形态的影响. 红外光谱(FTIR)和核磁共振谱(¹H NMR)表明, MVEO-2和MVEO_mix具有相同的结构组成. 凝胶渗透色谱(GPC)分析表明MVEO_mix具有双峰结构且分子量分布较窄, 而MVEO-2具有多峰结构且分子量分布较宽. 热重分析(TGA)和动态热机械分析(DMA)表明, MVEO-2的热稳定性比MVEO_mix更高. MVEO-2的强度和韧性比MVEO_mix明显提高, 弯曲强度提高17%, 拉伸强度提高38%, 断裂伸长率提高35%, 冲击强度提高24%. 扫描电镜结果表明化学共混形成了更均匀紧密的互穿聚合物网络结构.

关键词: 化学共混, 物理共混, 多官能团齐聚物, 混杂, 热稳定性, 力学性能

Abstract:

Tetraglycidyl 4,4'-diaminodiphenylmethane(TGDDM) was toughened by reactive blending and physical blending respectively with multifunctional vinyl ester resin(MVER). Novel multifunctional hybrid oligomer(MVEO-2) containing two different reactive groups was synthesized through the esterfication of TGDDM with acrylic acid(AA)[n(TGDDM)/n(AA)=1∶2] while MVEO_mix was obtained by physical blending TGDDM with MVER. The structures and properties of MVEO-2 and MVEO_mix were studied. FTIR and ¹H NMR show that two oligomers have same structural components. It was found that MVEO_mix presented bimodal and narrow molecular weight distribution while MVEO-2 had multimodal and broad molecular weight distribution. MVEO-2 showed obvious improvement in thermal stability than MVEO_mixfrom thermogravimetric analysis(TGA) and dynamic mechanical analysis(DMA) analysis. The strength and toughness of MVEO-2 were improved than those of MVEO_mix: flexural strength improved 17%, tensile strength improved 38%, elongation improved 35% and impact strength improved 24%. The excellent performance of MVEO-2 was attributed to the formation of close and even interpenetrating polymer network(IPN), which was demonstrated by scanning electron microscope(SEM).

Key words: Reactive blending, Physical blending, Multifunctional oligomer, Hybrid, Thermal stability, Mechanical property

中图分类号:

O631

TrendMD:

钱建华, 刘坐镇, 黄锐, 付建辉, 陈建辉, 郭卫红. 含混杂活性端基新型多官能团齐聚物的结构与性能. 高等学校化学学报, 2015, 36(5): 996.

QIAN Jianhua, LIU Zuozhen, HUANG Rui, FU Jianhui, CHEN Jianhui, GUO Weihong. Structures and Properties of Novel Multifunctional Hybrid Oligomers^†. Chem. J. Chinese Universities, 2015, 36(5): 996.

图/表 15

Scheme 1 Structure of TGDDM

Scheme 2 Structures of MVEO-2 and MVER

Fig.1 FTIR spectra of MVEO-2(a), MVEOmix(b), casting of MVEO-2(c) and MVEOmix(d)

Fig.2 1H NMR spectra of MVEO-2(a) and MVEOmix(b)

Fig.3 Molecular weight distributiona. TGDDM; b. MVEO-2; c. MVEOmix; d. MVER.

Table 1 Molecular weight and molecular weight distribution of TGDDM, MVEO-2, MVEOmix and MVER

System	M_n	M_w	Polydispersity index
TGDDM	526	566	1.08
MVEO-2	718	1282	1.79
MVEO_mix	622	861	1.38
MVER	846	1128	1.33

Fig.4 DSC scanning curves of TGDDM/MeTHPA(a),MVEO-2/MEKP/Co/MeTHPA(b),MVEOmix/MEKP/Co/MeTHPA(c)and MVER/MEKP/Co(d)

Table 2 Heat of polymerization and peak temperature for MVEO-2/MEKP/Co/MeTHPA, MVEOmix/MEKP/Co/MeTHPA, MVER/MEKP and TGDDM/MeTHPA

System	Temperature of the peak exotherm/℃	Heat of polymerization/ (J·g^-1)	Calculated heat/ (J·g^-1)
TGDDM	179	431
MVEO-2	85(peak 1), 147(peak 2)	357	389
MVEO_mix	140(peak 1), 171(peak 1)	355	389
MVER	64	347

Table 3 Mechanical properties of TGDDM, MVEO-2 and MVEOmix

System	Flexural strength/ MPa	Flexural modulus/ MPa	Tensile strength/ MPa	Tensile modulus/ MPa	Elongation(%)	Impact strength/ (kJ·m^-2)
TGDDM	111.1	3755	43.2	3650	1.21	7.54
MVEO-2	159.0	3990	62.6	3760	1.71	17.32
MVEO_mix	136.5	4148	45.4	3634	1.27	14.00

Scheme 3 Schematic of cross-linked network for MVEO-2(A) and MVEOmix(B)

Fig.5 TGA curves of MVEO-2(a) and MVEOmix(b)

Fig.6 Variation of E' as a function of temperaturea. TGDDM; b. MVEO-2; c. MVEOmix.

Fig.7 Variation of tanδ as a function of temperaturea. TGDDM; b. MVEO-2; c. MVEOmix.

Table 4 DMTA thermographs for TGDDM, MVEO and MVEOmix

System	T_g(E')/℃	T_g(E″)/℃	T_g(tanδ)/℃
TGDDM	202	217	226
MVEO-2	196	216	224
MVEO_mix	185	205	219

Fig.8 SEM images of TGDDM(A), MVEO-2(B) and MVEOmix(C)

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含混杂活性端基新型多官能团齐聚物的结构与性能

Structures and Properties of Novel Multifunctional Hybrid Oligomers^†

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含混杂活性端基新型多官能团齐聚物的结构与性能

Structures and Properties of Novel Multifunctional Hybrid Oligomers†

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Structures and Properties of Novel Multifunctional Hybrid Oligomers^†