Manipulating Latex Polymer Microstructure Using Chain Transfer Agent and Cross‐Linker to Modify PSA Performance and Viscoelasticity

Two series of butyl acrylate (BA)/acrylic acid (AA)/2‐hydroxy ethyl methacrylate latexes were produced via starved seeded semi‐batch emulsion polymerization. The first series, five latexes with gel contents ranging from 0 to 75 wt.‐%, were generated by varying the amount of chain transfer agent (CTA, n‐dodecyl mercaptan) in the absence of cross‐linker. The second series, two latexes with gel contents of 49 and 74 wt.‐%, were obtained by manipulating the amount of CTA in the presence of a constant cross‐linker (allyl methacrylate) concentration. Latexes with similar gel contents, one from each series, were compared with respect to their microstructure, viscoelastic properties and pressure‐sensitive adhesive performance. At similar gel contents, latexes obtained in the absence of cross‐linker had larger sol polymer molecular weight ($\overline {M} _{{\rm w}} $ ) and molecular weight between cross‐linking points (M_c), compared to the latexes generated using both CTA and cross‐linker. The different microstructures of latexes with similar gel contents resulted in significantly different viscoelastic properties and shear strength of the pressure‐sensitive adhesive films cast from the latexes.

     

Surface waves in an exponentially graded, general anisotropic elastic material under the influence of gravity

In a recent paper Destrade [1] studied surface waves in an exponentially graded orthotropic elastic material. He showed that the quartic equation for the Stroh eigenvalue p is, after properly modified, a quadratic equation in p² with real coefficients. He also showed that the displacement and the stress decay at different rates with the depth x₂ of the half-space. Vinh and Seriani [2] considered the same problem and added the influence of gravity on surface waves. In this paper we generalize the problem to exponentially graded general anisotropic elastic materials. We prove that the coefficients of the sextic equation for p remain real and that the different decay rates for the displacement and the stress hold also for general anisotropic materials. A surface wave exists in the graded material under the influence of gravity if a surface wave can propagate in the homogeneous material without the influence of gravity in which the material parameters are taken at the surface of the graded half-space. As the wave number k → ∞, the surface wave speed approaches the surface wave speed for the homogeneous material. A new matrix differential equation for surface waves in an arbitrarily graded anisotropic elastic material under the influence of gravity is presented. Finally we discuss the existence of one-component surface waves in the exponentially graded anisotropic elastic material with or without the influence of gravity.     

Experimental investigation of interface curing stresses between PMMA and composite using digital speckle correlation method

This paper studies the interface curing stresses between polymethyl methacrylate (PMMA) and composite by means of digital speckle correlation method (DSCM). A new method by combining DSCM with the marker points is developed to measure the interface curing stresses, and the measurement principle is introduced. The interface curing stresses between PMMA and composite with different curing bonding conditions are measured and analyzed, this indicates that the residual stress for furnace heating and furnace cooling is the smallest. Finally, the measurement error is discussed by means of finite element method, the influences of glass microsphere between adhesive and PMMA can be ignored.     

Manipulation of chain transfer agent and cross-linker concentration to modify latex micro-structure for pressure-sensitive adhesives

N-Dodecyl mercaptan (NDM) chain transfer agent and allyl methacrylate (AMA) cross-linker were used to manipulate latex properties in a starved seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA) or with a third monomer, acrylic acid (AA). Latexes with higher gel content and lower sol polymer molecular weight (M_w) were produced by adding only AMA. On the other hand, latexes with lower gel content and M_w were produced by adding only NDM. In addition, at a constant AMA concentration (0.2 phm), the addition of NDM (0.2 phm) decreased gel content, increased molecular weight between cross-linking points (M_c), and decreased M_w. Adding more NDM (to a total of 0.4 phm) further decreased the gel content, while decreasing the tested M_c and increasing M_w. It was also found that using higher concentrations of both AMA and NDM could produce latex with similar gel content, but smaller M_c and M_w, compared to the latex produced at lower concentrations of both NDM and AMA. Regarding the influence of AA, gel content was increased and M_w was significantly decreased with an increase in AA concentration and a decrease in MMA concentration. The performance of the latexes was evaluated for application as a pressure-sensitive adhesive (PSA).     

化学接枝改进ZnO-有机硅纳米复合材料的光学性能

采用N-(三甲氧基硅丙基)-4-叠氮-2,3,5,6-四氟苯甲酰胺(PFPA-silane)改性纳米氧化锌,并将PFPA-silane接枝在有机硅聚合物链上.接枝反应改变了纳米复合物的折光指数,并使ZnO纳米粒子与有机硅基体的折光指数更加匹配.这减少了纳米氧化锌粒子对光的散射作用,增加了纳米ZnO-有机硅纳米复合物的透明性.所制备的复合物通过接枝改性后透光率最多可提高50%.研究结果表明无机物和聚合物的折光指数的匹配程度可以通过偶联剂与聚合物基体的反应来进行调控.     

Multi‐functional poly(vinylidene fluoride) graft copolymers

Poly(vinylidene fluoride) (PVDF) is known for its biocompatibility, piezo and pyro‐electricity, and membrane forming capability. In order to tune its properties, modification through grafting from approach by atom transfer radical polymerization (ATRP) is preferred. Hydrophilic polymers like poly(ethylene glycol) methacrylate, poly(methacrylic acid), poly(dimethylaminoethyl methacrylate) (PDMAEMA), and so forth have been anchored from PVDF backbone in order to make permeation of water molecules through the PVDF based membranes. The successful solution grafting of PDMAEMA chains from PVDF backbone by ATRP resulted appreciable graft conversion and hence its bulk properties showed a significant change. This water soluble graft copolymer shows incredible mechanical and adhesive properties. PVDF‐g‐poly(n‐butyl methacrylate) generates honey‐comb porous film using “breath figure” technique. Recently, they have used further improvement of grafting where model ATRP initiators are anchored using atom transfer radical coupling and used them as macroinitiators for grafting. This approach simplified the grafting reactions even more and enabled successful grafting of a large number of monomers under relatively less drastic conditions with appreciable conversion compared with the previous conditions. This technique has resulted interesting solution properties, ion and electron conducting PVDF, antifouling membrane, super glue and super tough materials, capable of generating metal nanoparticles tunable with pH and temperature. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2569–2584     

Novel L‐DOPA‐Derived Poly(ester amide)s: Monomers,Polymers, and the First L‐DOPA‐Functionalized Biobased Adhesive Tape

The synthesis, characterization, and testing of a range of novel bio‐inspired L‐DOPA‐derived poly(ester amide)s is presented, using a widely applicable, straightforward chemistry. A model system is used to study and establish the monomer and polymer synthetic protocols, and to provide a set of optimum reaction conditions. It is further shown that fully biobased L‐DOPA‐containing adhesive tapes can be fabricated, which are positively evaluated in terms of their adhesive properties. The newly developed synthetic protocol constitutes a versatile platform for accessing and tailoring a plethora of relevant structures, including a variety of potentially biocompatible poly(ethylene glycol)‐based materials.

     

纳米沟槽表面黏着接触过程的分子动力学模拟研究

采用大规模分子动力学方法研究了刚性球型探头与具有不同纳米沟槽基体表面的黏着接触过程,探讨了表面沟槽结构对载荷-位移曲线、接触引力和拉离力以及材料转移的影响规律.研究结果表明:在相同的压入深度下,与原子级光滑表面的黏着接触过程相比,刚性探头与具有纳米沟槽结构基体表面的接触压力较小,接触加载过程中的引力作用范围较大,并伴随载荷的多次跳跃,且接触引力和拉离力均有减小;当沟槽深度相同时,随着沟槽宽度的增大,接触引力和拉离力逐渐减小,当沟槽宽度逐渐接近探头与光滑表面的接触直径时,接触引力和拉离力又逐渐增大,趋于接近探头与光滑表面的接触过程;当沟槽宽度相同时,随着沟槽深度的增大,接触引力相对减小,拉离力变化不大.     

结构胶固化收缩对反射镜面形影响的分析与试验

在空间遥感领域,使用胶粘接技术安装光学元件越来越受到光机工程师们的青睐。与机械方法相比,胶粘接方法具有更轻的质量、更低的成本、更容易装配。大部分结构胶在固化期间存在收缩现象,结构胶的收缩会导致内应力出现,内应力又会导致光学表面发生变形,从而影响成像质量。为了在有限元分析中模拟这一过程,提出了等效线胀法的概念。该方法是将结构胶的线收缩率等效成胶的线胀系数,从而将结构胶固化过程的收缩等效成均匀温降导致的冷缩,以便进行热弹性分析。分析结果表明:在采用环带粘接方式时,粘接面积越小,镜面相应位置的面形误差越小,反之越大;粘接位置离镜面越远,镜面相应位置的面形误差越小,反之越大。对分析结果进行了试验验证,结果表明:当胶层质心到镜面距离为20.5mm、胶层宽度分别为15mm、20mm、25mm时,镜面PV值变化量分别为0.64λ、0.92λ、1.10λ;当胶层宽度为15mm、胶层质心到镜面距离分别为15.5mm、20.5mm、25.5mm时,镜面PV值变化量分别为1.08λ、0.64λ、0.40λ;当胶层质心到镜面距离为25.5mm、胶层宽度为25mm、胶层环形分布角分别为40°、60°、80°时,镜面PV值变化量分别为0.38λ、0.52λ、0.88λ。分析和试验结果为实际的工程应用提供了理论指导。