Plasma polymerization and deposition of glycidyl methacrylate on Si(100) surface for adhesion improvement with polyimide

Thin polymer films were deposited on Si(100) surfaces by plasma polymerization of glycidyl methacrylate (GMA) under different glow discharge conditions. The FT‐IR, X‐ray photoelectron spectroscopy (XPS), and amine treatment results suggested that the epoxide functional groups of the deposited films had been preserved to various extents, depending on the plasma deposition conditions. The use of a low radio frequency power (～ 5 W) and a relatively high system pressure (100–400 Pa) readily resulted in the deposition of thin films having nearly the same composition of the epoxide functional groups as that of the GMA homopolymer. The plasma‐polymerized GMA (PP‐GMA) thin films deposited on the Ar plasma‐pretreated Si(100) surfaces were retained to a large extent after acetone extraction, suggesting the presence of covalent bonding between the PP‐GMA layer and the Si surface. Thermal imidization of the poly(amic acid) precursor of polyimide on the GMA plasma‐polymerized Si(100) surface resulted in a strongly adhered polyimide film. The adhesion results further suggested that the GMA polymer had been grafted on the Si(100) surface and the epoxide functional groups had undergone reactive interaction (curing) with the carboxylic and amine groups of the poly(amic acid) during thermal imidization. Copyright © 2001 John Wiley & Sons, Ltd.     

Plasma-Induced Graft Polymerization of Poly(ethylene glycol) Methyl Ether Methacrylate on Si(100) Surfaces for Reduction in Protein Adsorption and Platelet Adhesion

Argon plasma-induced graft polymerization of a solution-coated macromonomer, poly(ethylene glycol) methyl ether methacrylate (PEGMA), on the Si(100) surface was carried out to impart anti-fouling properties to the Si(100) surface. The surface composition and microstructure of the PEGMA graft-polymerized Si(100) surfaces were characterized by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and atomic force microscopy (AFM) measurements. The extent of crosslinking in the plasma-graft polymerized PEGMA (pp-PEGMA) was estimated by gel fraction determination. In general, an appropriate RF power of about 15 W and a PEGMA macromonomer concentration of about 1 wt% in the coating solution for plasma polymerization produced a high graft yield of pp-PEGMA on the Si(100) surface (the pp-PEGMA-g-Si surface). The Si(100) surface with a high concentration of the grafted pp-PEGMA was effective in preventing bovine serum albumin (BSA) adsorption and platelet adhesion.     

氩等离子体后辉光区对聚四氟乙烯膜表面的优化改性

在理想管式反应器中, 采用Langmuir双电子探针和电子自旋共振(ESR)诊断技术分别定量测定了氩等离子体场中各活性物种的轴向分布, 并利用氩等离子体放电区及后辉光区对聚四氟乙烯(PTFE)进行了表面改性. 通过接触角测量、扫描电子显微镜和X 射线光电子能谱分析比较了改性前后常规及后辉光氩等离子体对PTFE表面结构及性能的影响. 结果表明, 氩等离子体中电子及离子浓度随轴向距离的增大迅速降低, 30 cm后接近于0, 而自由基浓度则降低缓慢, 40 cm处仍为初始浓度的96%. 氩等离子体放电功率、处理时间和气体流量强烈影响着PTFE表面润湿性的改善效果. 后辉光区因抑制电子和离子的刻蚀作用, 强化自由基反应, 使改性效果远优于常规氩等离子体. 经氩等离子体后辉光区短时间(30 s)处理后, PTFE表面化学成分发生了变化, F/C原子比从3.27降至2.30, O/C原子比从0.02增至0.09. 脱氟作用和含氧基团(如CO)的引入是有效改善PTFE表面润湿性的关键因素.     

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization of glycidyl methacrylate and its relevance to the electroless deposition of copper

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and deposition of glycidyl methacrylate (GMA) was carried out. The effects of glow‐discharge conditions on the chemical structure and composition of the deposited GMA polymer were analyzed by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. XPS and FTIR results revealed that the epoxide groups in the plasma‐polymerized GMA (pp‐GMA) layer had been preserved to various extents, depending on the plasma deposition conditions. The morphology of the modified PTFE surface was investigated by atomic force microscopy (AFM). The pp‐GMA film with well‐preserved epoxide groups was used as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper on the PTFE film. The T‐peel adhesion test results showed that the adhesion strength between the electrolessly deposited copper and the pp‐GMA‐modified PTFE (pp‐GMA‐PTFE) film was much higher than that between the electrolessly deposited copper and the pristine or the Ar plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3498–3509, 2000     

Electroless Deposition of Copper on Poly(tetrafluoroethylene) Films Modified by Plasma-Induced Surface Grafting of Poly(4-vinylpyridine)

Argon plasma-pretreated poly(tetrafluoroethylene) (PTFE) films were solution coated with a thin layer of poly(4-vinyl pyridine) (P4VP). Subsequent exposure of the films to argon plasma resulted in the grafting of P4VP on the PTFE films. Electroless plating of copper could be carried out effectively on the P4VP-grafted PTFE (P4VP-g-PTFE) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn-free process). The catalytic processes of the electroless plating of copper in the presence and absence of sensitization by SnCl₂ were also compared. The effect of glow discharge conditions on the P4VP concentration and the adhesion strength of the electrolessly deposited copper was investigated. The T-peel adhesion strength of the electrolessly deposited copper with the graft-modified PTFE film was improved in the absence of SnCl₂ sensitization and could reach about 3 N/cm. PdCl₂ activation and electroless deposition of copper could not be carried out on the pristine or the Ar plasma-treated PTFE surface in the absence of prior sensitization by SnCl₂. X-ray photoelectron spectroscopic (XPS) analysis revealed that the electrolessly deposited copper delaminated from the P4VP-g-PTFE film by cohesive failure inside the PTFE film.     

PEG‐Modified Macroporous Poly(Glycidyl Methacrylate) and Poly(2‐Hydroxyethyl Methacrylate) Microspheres to Reduce Non‐Specific Protein Adsorption

To minimize non‐specific protein adsorption on macroporous poly(glycidyl methacrylate) and poly(2‐hydroxyethyl methacrylate) microspheres containing amino and/or carboxyl groups, the microspheres are coated with α,ω‐bis‐carboxy poly(ethylene glycol) and amino‐terminated poly(ethylene glycol‐co‐propylene glycol) or α‐methoxy‐ω‐amino poly(ethylene glycol). Adsorption of bovine serum albumin (BSA), γ‐globulin, ¹²⁵I‐BSA, pepsin, and chymotrypsin on neat and PEGylated microspheres is determined by UV–VIS spectroscopy of supernatants and eluates or by measurement of radioactivity in an ionization chamber. Neat and PEGylated microspheres adsorb 0.8–70% and 0.02–44% of protein, respectively.

     

Surface Modification of Textile Fibers and Cords by Plasma Polymerization

In this paper we report on the treatment of industrial fibers and cords by means of plasma polymerization techniques. Coatings of plasma-polymerized pyrrole or acetylene were deposited on aramid fibers, aramid cords and polyester cords. The equipment was a custom-built semi-continuous reactor operated on a pulsed DC glow discharge. The fibers and cords were tested for adhesion to various polymers such as tire cord skim stock rubber compounds and epoxy adhesives. Standard industrial pull-out force adhesion measurement techniques were used. The deposition conditions of the plasma polymer films were varied within wide limits. It was found that, in general, films deposited under low-power and high-pressure conditions performed better than films prepared under high-power and low-pressure conditions. For some systems pulsing of the discharge power improved the performance further. For all systems studied, the optimized plasma polymer surface modification outperformed current industrial standards. The plasma-polymerized coatings were characterized by various techniques and the excellent performance results are explained in a tentative model based on the molecular structure of the films. This structure was found to be strongly dependent on the discharge conditions.     

利用反向原子转移自由基聚合反应合成聚甲基丙烯酸缩水甘油酯

以偶氮二异丁腈为引发剂,CuBr2/bpy为催化体系,甲基丙烯酸缩水甘油酯(GMA)通过反向原子转移自由基聚合反应合成了聚甲基丙烯酸缩水甘油酯(PGMA),其结构经1H NMR,IR和GPC确证。聚合反应符合活性自由基聚合特征,在聚合过程中GMA转化率和PGMA分子量随反应时间的延长而增大,分子量分布较窄。     

甲基丙烯酸丁酯在纳米TiO2表面的原位接枝

利用分子自组装技术,对纳米TiO2粒子表面组装上有机单分子层,使其带上不饱和基团C=C,在自组装单分子层表面原位引发甲基丙烯酸丁酯（BMA）单体聚合反应,使纳米TiO2表面形成化学键合的聚合物层,达到对纳米TiO2粒子改性的目的。讨论了不同反应条件对接枝聚合率的影响,通过FTIR、TG-DTA等分析手段,研究聚合改性物质的结构和改性后纳米TiO2粒子的分散稳定性。实验发现聚合改性后的纳米TiO2在有机相中有良好的分散性。     

甲基丙烯酸甲酯原子转移自由基聚合等规度研究

在0～100℃温度范围内,由原子转移自由基聚合方法,采用助催化和非助催化体系,引发甲基丙烯酸甲酯聚合,利用¹³CNMR测定聚甲基丙烯酸甲酯的等规度.发现原子转移自由基聚合仍以间同立构为主,随着聚合温度的升高间同立构等规度降低,与通常自由基聚合对有规立构控制特征相似.助催化剂异丙醇铝和活性端羰基配位,对聚合物的立构规整性有一定的影响.     

调节pH控制载银纳米TiO2表面包覆的PMMA

测定了十二烷基磺酸钠(SDS)在载银离子纳米TiO2颗粒表面的等温吸附曲线,在SDS达到临界胶束浓度(CMC)时,研究了pH=2.0(等电点以下)和pH=7.0(等电点以上)时甲基丙烯酸甲酯(MMA)在TiO2粒子表面的乳液聚合.采用改性前后TiO2的Zeta 电位的变化、红外光谱(FT-IR)及差热分析(DTA)等表征方法评价了改性效果.结果表明:PMMA成功包覆到TiO2表面,包覆率达17.8%,载银TiO2的表面由亲水变为亲油;在pH=2.0,cSDS=5.0 mmol/L时,Ag+的脱附量只有8%.     

Benzyl Bromide Functionalized Poly(Phenyleneethynylene)s as Macroinitiators in the Atom Transfer Radical Polymerization of Methyl Methacrylate

Abstract

The behavior of benzyl bromide functionalized poly(phenyleneethynylene)s as macroinitiators in the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was investigated. The ¹H NMR observation of the ATRP using the exclusively para‐linked poly(phenyleneethynylene) macroinitiator PPE1A, and the low molecular weight initiator R‐BzBr, respectively, revealed lower reactivity for the macroinitiator. Comparison of graft copolymers, which were obtained from ATRP of MMA with PPE1A and the partially meta‐linked poly(phenyleneethynylene) PPE1B, showed higher reactivity in the case of PPE1B, expressed by a larger degree of polymerization in the PMMA side chains, as well as higher initiatior efficiency. This might be caused by better solubility of the less symmetric PPE1B. Investigation of the graft copolymers PPE2A and PPE2B was carried out by means of ¹H NMR spectroscopy, gel permeation chromatography (GPC) as well as UV/vis spectroscopy. Impairment of the delocalized π‐electron system of the conjugated polymers during the ATRP was not detectable.     

聚甲基丙烯酸甲酯与苯乙烯-丙烯腈共聚物混合体系相分离初期的固体NMR研究

本文用氢谱宽线固体NMR技术研究了聚甲基丙烯酸甲酯(PMMA)和苯乙烯-丙烯腈共聚物(SAN)混合体系不稳相分离初期阶段, 得到了在分相过程中弛豫谱的变化规律, 测定了相分离增长速率。结果指出: 随着退火时间的增加, 两相体系形成; 大分子扩散方式是由浓度低的区域向浓度高的区域扩散, 扩散系数为负值; 相分离增长速率的数量级与用光散射研究的结果相同; 分子相互作用的相关距离为46.5 nm。     

环氧基团功能化弹性体增韧聚乳酸的性能

以2种不同结构的弹性体乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)和乙烯-丙烯酯甲酯-甲基丙烯酯缩水甘油酯三元共聚物(E-MA-GMA)增韧聚乳酸(PLA), 研究了接枝型与嵌段型弹性体的结构对聚乳酸增韧效果的影响. 结果表明, 接枝型聚合物POE-g-GMA与基体PLA之间具有良好的界面相互作用, 当POE-g-GMA的质量分数为15%时, 共混体系的缺口冲击强度为72.4 kJ/m², 而E-MA-GMA的质量分数为15%时, 共混体系的缺口冲击强度为32.4 kJ/m², 结果表明, 接枝型聚合物POE-g-GMA增韧效果明显优于嵌段型E-MA-GMA.     

Synthesis of Poly(2‐Hydroxyethyl Methacrylate)‐based Hybrid Nanoparticles via Visible‐Light‐Initiated Radical Polymerization

We report a new, unique process for the design of poly(2‐hydroxyethyl methacrylate) (PHEMA )‐based hybrid materials, which involves the coating of PHEMA on TiO₂ and TiO₂ /Ag nanoparticle surface under visible light. New hybrid materials initiated under different conditions were prepared under visible light, which could be used for the theoretical design of nanohybrid materials. The hybrid materials thus prepared were characterized by Fourier transform infrared spectroscopy (FTIR ), transmission electron microscopy (TEM ), and thermogravimetric analysis (TGA ). The experimental results confirmed the successful synthesis of TiO₂–PHEMA hybrid materials. Compared to other methods, the method reported here involving the direct combination of PHEMA on the TiO₂ surface was simply catalyzed by visible light without the addition of initiators.     

Functionalization of Styrene-Olefin Block Copolymers by Melt Radical Grafting of Glycidyl Methacrylate and Reactive Blending with PET

Blocks copolymers styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and styrene-b-(ethylene-co-propylene) (SEP, SEPSEP), with different styrene content and number of blocks in the chain, were functionalized with glycidyl methacrylate (GMA) by melt radical grafting. The influence of monomer concentration, radical initiator and copolymer structure on the grafting degree was examined. The grafted copolymers were characterised by DSC and capillary rheometry. Blends of PET with functionalized SEBS and SEPSEP showed a marked improvement of phase morphology and elongation at break when compared to blends with unfunctionalized copolymers.     

Synthesis and Characterization of Water Soluble Carboxymethyl Chitosan Grafted with Glycidyl Methacrylate

Carboxymethyl chitosan grafted with glycidyl methacrylate was synthesized by the reaction of carboxymethyl chitosan (CSCM) which was prepared from chitosan first and glycidyl methacrylate. The product has been characterized by Fourier transform infrared spectrum (FT-IR), X-ray diffraction (XRD), proton nuclear magnetic resonance (¹H-NMR), solid ¹³carbon nuclear magnetic resonance (Solid ¹³C-NMR), ¹³carbon nuclear magnetic resonance (¹³C-NMR), and chemical analysis, which had different thermal properties from chitosan.     

阴离子聚合法合成PMMA-b-PMTFPS嵌段共聚物

以含缩醛官能团的有机锂为引发剂, 将甲基丙烯酸甲酯(MMA)与含氟硅氧烷单体1,3,5-三甲基-1,3,5-三(3',3',3'-三氟丙基)环三硅氧烷(F3)阴离子嵌段共聚, 获得了窄分子量分布的聚甲基丙烯酸甲酯-b-聚[甲基(3,3,3-三氟丙基)硅氧烷](PMMA-b-PMTFPS)嵌段共聚物, 并用GPC, 1H NMR, FTIR和DSC对嵌段共聚物进行了表征. 研究结果表明, 在THF中利用PMMA-OLi对F3进行阴离子开环聚合时, 单体F3浓度的选择对提高嵌段共聚物产率至关重要.     

PREPARATION OF LOW MOLECULAR WEIGHT POLY（GLYCIDYL METHACRYLATE） BY PHOTOPOLYMERIZATION

Low molecular weight poly（glycidyl methacrylate）s （PGMAs） were prepared by photopolymerization in ethyl acetate, with benzophenone （BP） as photoinitiator, and triethylamine （TEA） as hydrogen donor. The existence of semipinacol dormant end groups in PGMA was confirmed by FT-IR and ^1H-NMR, and the content of the semipinacol dormant groups was determined quantitatively by ^1H-NMR measurement. The effects of various thctors, such as reaction time, BP concentration and monomer concentration on the synthesis of the polymers were investigated systematically. The molecular weights of the polymers were also investigated with GPC. It is shown that increasing BP concentration and decreasing irradiation time and monomer concentration led to a significant decrease of the molecular weights.