拉曼Mapping成像研究聚苯乙烯/聚甲基丙烯酸甲酯共混体系的相态结构

doi:10.16085/j.issn.1000-6613.2020-1705

摘要/Abstract

摘要：

利用拉曼光谱成像技术研究了聚苯乙烯/聚甲基丙烯酸甲酯（PS/PMMA）共混薄膜体系及其增容体系（增容剂为PS-b-PMMA嵌段共聚物）的相态结构及化学成分分布。实验结果表明，拉曼Mapping成像技术不仅可以得到PS/PMMA共混体系化学成分的精确分布图，同时也可以获取共混体系中分散相、界面相和连续相的分子指纹光谱。研究发现，共混体系中分散相和连续相组分分布与体系的组成紧密相关，当PS/PMMA质量比30/70时，分散相为PS，连续相为PMMA；当PS/PMMA质量比为50/50时，分散相为PS，但PS分子链仍存在于PMMA连续相中；当PS/PMMA质量比为70/30时，分散相为PMMA，连续相为PS。当增容剂PS-b-PMMA加入到PS/PMMA共混体系中后，分散相粒径减小、分布更加均匀、共混体系相容性指数（N_c）增大，说明PS/PMMA共混体系由完全不相容体系趋向变成半相容性体系，这是因为增容剂能增加PS和PMMA之间的相互作用，降低了体系的相分离程度，改善了共混体系的相容性。

关键词: 拉曼光谱, 光谱成像, 聚苯乙烯, 聚甲基丙烯酸甲酯, 聚合物共混

Abstract:

In this paper, the phase structure and phase distribution of polystyrene/poly(methyl methacrylate)(PS/PMMA) blend with PS-b-PMMA block copolymer as the compatibilizer were studied by Raman spectroscopy imaging. The experimental results showed that Raman Mapping technology can not only provide accurate distribution of chemical components, but also give the molecular fingerprint spectra of dispersed phase, interface phase and continuous phase in the blend system. It is found that the phase structure of the blend system distributed in a “sea-island” form. When PS/PMMA=30/70, the dispersed phase was PS, and the continuous phase was PMMA; when PS/PMMA=50/50, the dispersed phase was PS, and PS also presented in the PMMA continuous phase; when PS/PMMA=70/30, the dispersed phase was PMMA, and the continuous phase was PS. The particle size of the dispersed phase decreased and distributed more uniformly when the block copolymer PS-b-PMMA was added into the PS/PMMA blend. Moreover, the semicompatible blends showed much smaller subphase distributions with less distinct interphase and increased compatibility number (N_c). It revealed that the compatibilizers could enhance the interaction between PS and PMMA, reduce the phase separation degree and improve the compatibility of the blend system.

Key words: Raman spectroscopy, spectral imaging, polystyrene, poly(methyl methacrylate), polymer blending

中图分类号:

O631

陈韶云, 田杜, 李奇, 钟敏, 胡成龙, 纪红兵. 拉曼Mapping成像研究聚苯乙烯/聚甲基丙烯酸甲酯共混体系的相态结构[J]. 化工进展, 2021, 40(7): 3900-3908.

CHEN Shaoyun, TIAN Du, LI Qi, ZHONG Min, HU Chenglong, JI Hongbing. Study on the phase structure of polystyrene/poly(methyl methacrylate) blend film by Raman Mapping imaging[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3900-3908.

图/表 7

图1 PS/PMMA共混薄膜的制备过程及其拉曼光谱成像示意图

图2 聚合物共混体系的光学图、拉曼光谱成像图和粒径分布图

图3 聚合物共混体系的光学图、拉曼光谱成像图和粒径分布图

图4 图2(a2)、(b2)、(c2)中点1、2、3处的拉曼光谱

图5 共混体系PS/PMMA=30/70和PS/PMMA/PS-PMMA=30/70/5的光谱图及其谱带1001cm-1（PS的特征峰）和814cm-1（PMMA的特征峰）的拉曼散射强度在光学图彩色区域的强度分布图

图6 共混体系中PS和PMMA随横向扫描步径的成分比例图

（PS/PMMA=70/30）

图7 共混体系PS/PMMA=30/70中加入不同质量分数增容剂PS-b-PMMA的拉曼光谱成像图及平均粒径和Nc与增容剂质量分数的关系

参考文献 34

1	IDE F, HASEGAWA A. Studies on polymer blend of nylon 6 and polypropylene or nylon 6 and polystyrene using the reaction of polymer[J]. Journal of Applied Polymer Science, 1974, 18(4): 963-974.
2	ROLAND C M, NGAI K L. Dynamical heterogeneity in a miscible polymer blend[J]. Macromolecules, 1991, 24(9): 2261-2265.
3	KARIM A, DOUGLAS J F, LEE B P, et al. Phase separation of ultrathin polymer-blend films on patterned substrates[J]. Physical Review E, 1998, 57(6): r6273.
4	EAGAN J M, XU J, DI GIROLAMO R, et al. Combining polyethylene and polypropylene: enhanced performance with PE/iPP multiblock polymers[J]. Science, 2017, 355(6327): 814-816.
5	ULCNIK-KRUMP M. Study of morphology influence on rheological properties of compatibilized TPU/SAN blends[J]. Journal of Applied Polymer Science, 2006, 100(3): 2303-2316.
6	PARAMESWARANPILLAI J, JOSEPH G, CHELLAPPAN R V, et al. The effect of polypropylene-graft-maleic anhydride on the morphology and dynamic mechanical properties of polypropylene/polystyrene blends[J]. Journal Polymer Research, 2015, 22(2): 1-11.
7	ZHANG Y, LI Y, ZHAO S, et al. Compatibility effect of radiation-grafting-functionalized styrene-butadiene-styrene on polyamide 6/styrene-butadiene-styrene blends[J]. Journal of Applied Polymer Science, 2008, 108(2): 1029-1036.
8	FAHMY A, MOHAMED T A, FRIEDRICH J F. XPS and IR studies of plasma polymers layer deposited from allylamine with addition of ammonia[J]. Applied Surface Science, 2018, 458: 1006-1017.
9	BAJPAI A K, BHATT R. Time of flight secondary ion mass spectrometry (ToF-SIMS) enabled analysis of inter-polymer phases formation in poly(diaminonaphthalene) doped conducting poly(vinyl alcohol) films[J]. Polymer, 2017, 110: 211-217.
10	GAMBINO T, ALEGRÍA A, ARBE A, et al. Applying polymer blend dynamics concepts to a simplified industrial system. A combined effort by dielectric spectroscopy and neutron scattering[J]. Macromolecules, 2018, 51(17): 6692-6706.
11	WANG D, RUSSELL T P. Advances in atomic force microscopy for probing polymer structure and properties[J]. Macromolecules, 2018,51: 3-24.
12	MARKWORT L, KIP B. Micro-Raman imaging of heterogeneous polymer systems: general applications and limitations[J]. Journal of Applied Polymer Science, 1996, 61(2): 231-254.
13	TANG F, BAO P, SU Z. Analysis of nanodomain composition in high-impact polypropylene by atomic force microscopy-infrared[J]. Analytical Chemistry, 2016, 88 (9): 4926-4930.
14	YE J, MIDORIKAWA H, AWATANI T, et al. Nanoscale infrared spectroscopy and AFM imaging of a polycarbonate/acrylonitrile-styrene/butadiene blend[J]. Microscopy Analysis, 2012, 26: 24-27.
15	SU W, KUMAR N, DAI N, et al. Nanoscale mapping of intrinsic defects in single-layer graphene using tip-enhanced Raman spectroscopy[J]. Chemical Communications, 2016, 52(53): 8227-8230.
16	KO J, PARK S G, LEE S, et al.Culture-free detection of bacterial pathogens on plasmonic nanopillar arrays using rapid Raman mapping[J]. ACS Applied Materials & Interfaces, 2018, 10(8): 6831-6840.
17	HOFFMANN G G, BÂRSAN O A, VAN DER VEN L G, et al.Tip-enhanced Raman mapping of single-walled carbon nanotube networks in conductive composite materials[J]. Journal of Raman Spectroscopy, 2017, 48(2): 191-196.
18	WANG M, VANTASIN S, WANG J, et al. Distribution of polymorphic crystals in the ring-banded spherulites of poly(butylene adipate) studied using high-resolution raman imaging[J]. Macromolecules, 2017, 50(8): 3377-3387.
19	MORGAN R L, HILL M J, BARHAM P J, et al. A study of the phase behaviour of polyethylene blends using micro-Raman imaging[J]. Polymer, 2001, 42(5): 2121-2135.
20	HUAN S, LIN W, SATO H, et al. Direct characterization of phase behavior and compatibility in PET/HDPE polymer blends by confocal Raman mapping[J]. Journal of Raman Spectroscopy, 2007, 38(3): 260-270.
21	XUE L, LI W, HOFFMANN G G, et al. High-resolution chemical identification of polymer blend thin films using tip-enhanced Raman mapping[J]. Macromolecules, 2011, 44(8): 2852-2858.
22	TANAKA K, TAKAHARA A, KAJIYAMA T. Film thickness dependence of the surface structure of immiscible polystyrene/poly(methyl methacrylate) blends[J]. Macromolecules, 1996, 29(9): 3232-3239.
23	THOMAS S, PRUD R E. Compatibilizing effect of block copolymers in heterogeneous polystyrene/poly(methyl methacrylate) blends[J]. Polymer, 1992, 33(20): 4260-4268.
24	LIU W, PANG Y, WANG K, et al. Structure evolution driven by phase separation and the corresponding foaming behavior of polystyrene/poly(methyl methacrylate) blends via a batch foaming process[J]. Journal of Applied Polymer Science, 2018, 135(39): 46704.
25	SEO Y, JANG S, AHN S, et al. phase behavior of 18-arm star-shaped polystyrene-block-poly(methyl methacrylate) copolymers with different second block initiations[J]. Macromolecules, 2018, 51(7): 2750-2755.
26	MATSUSHITA A, REN Y, MATSUKAWA K, et al. Two-dimensional Fourier-transform Raman and near-infrared correlation spectroscopy studies of poly(methyl methacrylate) blends: 1. Immiscible blends of poly(methyl methacrylate) and atactic polystyrene[J]. Vibrational spectroscopy, 2000, 24(2): 171-180.
27	KOULIC C, YIN Z, PAGNOULLE C, et al. Premade versus in situ formed compatibilizer at the PS/PMMA interface: contribution of the Raman confocal microscopy to the fracture analysis[J]. Polymer, 2001, 42(7): 2947-2957.
28	TOMBA J P, PASTOR J M. Confocal Raman microspectroscopy with dry objectives: a depth profiling study on polymer films[J]. Vibrational Spectroscopy, 2007, 44(1): 62-68.
29	MANSON J A. Polymer blends and composites[M]. Berlin: Springer Science & Business Media, 2012.
30	HU C L, CHEN X D, CHEN J, et al. Observation of mutual diffusion of macromolecules in PS/PMMA binary films by confocal Raman microscopy[J]. Soft Matter, 2012, 8(17): 4780-4787.
31	KAPLAN D S. Structure-property relationships in copolymers to composites: molecular interpretation of the glass transition phenomenon[J]. Journal of Applied Polymer Science, 1976, 20(10): 2615-2629.
32	DAI K H, KRAMER E J, SHULL, K R. Interfacial segregation in two-phase polymer blends with diblock copolymer additives: the effect of homopolymer molecular weight[J]. Macromolecules, 1992, 25(1): 220-225.
33	DAI K H, WASHIYAMA J, KRAMER E J. Segregation study of a BAB triblock copolymer at the A/B homopolymer interface[J]. Macromolecules, 1994, 27(16): 4544-4553.
34	VALERA T S, MORITA A T, DEMARQUETTE N R. Study of morphologies of PMMA/PP/PS ternary blends[J]. Macromolecules, 2006, 39(7): 2663-2675.

[1]	陈志华, 周键, 王三反. 聚苯乙烯磺酸钠对掺混聚偏氟乙烯阴离子交换膜的改性表征[J]. 化工进展, 2021, 40(S2): 290-294.
[2]	王逸伟, 刘智琪, 孙强, 刘爱贤, 杨兰英, 宫敬, 郭绪强. 聚苯乙烯磺酸钠作用下Ⅰ型水合物的生成热力学与动力学[J]. 化工进展, 2021, 40(S1): 168-181.
[3]	李酽, 宋双, 连晓雪. MoS₂/ZnO纳米复合材料的光学和光催化性能[J]. 化工进展, 2021, 40(7): 3870-3877.
[4]	罗菊香, 程德书, 李明春, 辛梅华. 室温可见光引发聚合诱导自组装制备P2VP-b-PSt纳米材料[J]. 化工进展, 2021, 40(5): 2676-2684.
[5]	宋万仓,熊光,臧甲忠,于海斌,王祥生. 碱性添加剂在钛硅分子筛/H₂O₂催化丙烯环氧化反应中的作用[J]. 化工进展, 2020, 39(3): 1021-1028.
[6]	郝军正,祝琳华,王红,司甜,何艳萍,孙彦琳. 孔结构可调聚合物微球的制备及贯通性能[J]. 化工进展, 2020, 39(2): 658-666.
[7]	欧阳杰,朱文仙,张小会,唐华东,黄荣斌. 疏水性钯纳米团簇的合成及其作为表面增强拉曼散射基底的应用[J]. 化工进展, 2019, 38(11): 5048-5056.
[8]	牛方昊, 胡志德, 晏华, 杨健健, 张寒松. 油酸、聚甲基丙烯酸甲酯修饰可磁化颗粒的磁流变液的流变行为[J]. 化工进展, 2018, 37(05): 1888-1895.
[9]	黄凤磊, 刘淼, 李志鹏, 蔡子琦, 高正明. 共混用动态混合器的研究与应用进展[J]. 化工进展, 2017, 36(10): 3549-3557.
[10]	李素娟, 陈勐, 郑星, 郑经堂, 许倩, 胡平, 郭建波. 核壳型PS@ZnO纳米复合材料的制备及其光催化性能[J]. 化工进展, 2016, 35(08): 2513-2517.
[11]	尹艳山, 王泽忠, 田红, 张巍, 鄢晓忠, 陈冬林. 热解温度对无烟煤焦微观结构和脱硝特性的影响[J]. 化工进展, 2015, 34(06): 1636-1640.
[12]	薛向欣, 许东铎, 常立民. 表面增强拉曼散射基底的研究进展[J]. 化工进展, 2015, 34(05): 1317-1322.
[13]	刘杉杉，李举豹，陈玉清. 聚四氟乙烯超疏水薄膜的制备和表征[J]. 化工进展, 2012, 31(03): 604-606.
[14]	张艳辉1，2，邓建国2，黄奕刚1. 乙二醇双硬脂酸酯/PMMA核壳储能微胶囊制备[J]. 化工进展, 2012, 31(03): 580-585.
[15]	王结祥，王强，李云华，陈秉辉. 聚苯乙烯树脂催化羟醛缩合研究进展 [J]. 化工进展, 2011, 30(7): 1521-.