Well‐defined polystyrene homopolymers with surface‐adhesive triethoxysilyl end group were synthesized via living carbanionic polymerization, epoxide end‐functionalization and subsequent hydrosilylation with triethoxysilane. Grafting‐to performance of polymers with various molecular weight (M_n = 3000–14,000 g mol⁻¹) to a silicon surface was examined in dependence of reaction time, polymer concentration, solvent and number of alkoxysilyl end groups. Crosslinkable polymers for surface modification were synthesized by statistical carbanionic copolymerization of 4‐vinylbenzocyclobutene (4‐VBCB) and styrene, followed by epoxide end‐functionalization and triethoxysilane modification (M_n = 4000–14,000 g mol⁻¹). The copolymers were characterized by ¹H‐NMR, THF‐SEC, and matrix‐assisted laser desorption and ionization time‐of‐flight mass spectrometry. In situ ¹H‐NMR kinetic studies in cyclohexane‐d₁₂ provided information regarding the monomer gradient in the polymer chains, with styrene being the more reactive monomer (r_s = 2.75, r_4‐VBCB = 0.23). Thin polymer films on silicon wafers were prepared by grafting‐to surface modification under conditions derived for the polystyrene homopolymer. The traceless, thermally induced crosslinking reaction of the benzocyclobutene units was studied by DSC in bulk as well as in 3–6 nm thick polymer films. Crosslinked films were analyzed by atomic force microscopy, ellipsometry, and nanoindentation, showing smooth polymer films with an increased modulus. © 2019 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019

中文翻译：

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苯乙烯和4-乙烯基苯并环丁烯通过碳离子聚合反应制成的可交联聚合物薄膜的锥形共聚物

通过活性碳离子聚合，环氧基末端官能化以及随后与三乙氧基硅烷的氢化硅烷化反应，合成了具有表面粘合性的三乙氧基甲硅烷基端基的定义明确的聚苯乙烯均聚物。根据反应时间，聚合物浓度，溶剂和烷氧基甲硅烷基端基数量的不同，研究了各种分子量（M _n = 3000–14,000 g mol ^-1）的聚合物在硅表面的接枝性能。表面改性的可交联聚合物是通过4-乙烯基苯并环丁烯（4-VBCB）和苯乙烯的统计碳负离子共聚，然后进行环氧端基官能化和三乙氧基硅烷改性而合成的（M _n = 4000-14,000 g mol^-1）。该共聚物的特征在于¹ H-NMR，THF-SEC和基质辅助激光解吸和电离飞行时间质谱。在 环己烷d _{12中进行的}原位¹ H-NMR动力学研究提供了有关聚合物链中单体梯度的信息，其中苯乙烯是反应性更高的单体（r _s = 2.75，r _{4 -VBCB} = 0.23）。硅片上的聚合物薄膜通过接枝制备在衍生于聚苯乙烯均聚物的条件下进行表面改性。DSC研究了本体和3–6 nm厚的聚合物膜中苯并环丁烯单元的无痕，热诱导的交联反应。通过原子力显微镜，椭圆偏振法和纳米压痕分析交联的膜，显示出具有增加的模量的光滑聚合物膜。©2019作者。高分子科学杂志A部分：高分子化学，由Wiley Periodicals，Inc. J. Polym出版。科学，A部分：Polym。化学 2019年