Surface modification of poly(vinyl chloride) for antithrombogenicity study

A process was established to conduct heparinization on the surface of poly(vinyl chloride) for antithrombogenicity utilization. A bifunctional monomer, glycidyl methacrylate (GMA), was grafted onto the surface of PVC by gas‐phase photografting polymerization without degassing first; then heparin was immobilized onto the poly(glycidyl methacrylate) segments. The branch structure of GMA and heparin were characterized by Fourier transfer infrared (FTIR) spectroscopy and electron spectroscopy (ESCA). It was confirmed that the bifunctional monomer GMA and heparin were grafted successfully onto the surface of PVC. The antithrombogenicity of the samples was tested both in vitro and in vivo, respectively. Results indicated that the blood compatibility of those products was improved greatly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1013–1018, 2002     

Surface modification of polyethylene by plasma pretreatment and UV‐induced graft polymerization for improvement of antithrombogenicity

The purpose of this study was to enhance blood compatibility of polyethylene (PE) films. Glycidyl methacrylate (GMA) was grafted onto the surface of PE by Ar plasma pretreatment and UV‐induced graft polymerization without photo‐initiator, then heparin was immobilized onto the poly (glycidyl methacrylate) segments. The surface compositions and microstructure of GMA graft polymerized PE films were studied by X‐ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR‐FTIR) spectroscopy. It was confirmed that heparin was successfully immobilized onto the surface of PE films by XPS analysis. The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT), and plasma recalcification time (PRT) tests and platelet adhesion experiment. Results indicated that the antithrombogenicity of modified PE was improved remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2014–2018, 2004     

Photoinitiated surface grafting of synthetic fibers,III. Photoinitiated surface grafting of poly(ethylene terephthalate) fibers

Photoinitiated surface grafting of acrylic acid (AA), acrylamide (AM) and 4-vinyl pyridine (VP) onto poly(ethylene terephthalate) (PET) fibers (a commercial textile yarn) has been studied using benzophenone (BP) as photoinitiator. A continuous process as previously described has been applied, which involves presoaking of the PET yarn in a solution of initiator and monomer in acetone and UV irradiation in nitrogen atmosphere. The resulting grafted polymer on the fiber surface has been analyzed by ESCA, titration of carboxy groups (grafted AA), and dye absorption. The relative ESCA intensities (RI) of O1s/C1s and N1s/C1s are used as measure for grafted AA, AM and VP, respectively, after recording the RI-values for ungrafted fibers. For grafting with AA, the RI-values increased from 32.8% (background) to 48.6% after 20 s irradiation time. The amount of carboxy groups measured by titration increased from 0.045 to 0.106 mmol/m². Assuming an even coverage of grafted AA polymer, this means a grafted layer of 4.8 nm thickness. After grafting, the adsorption of the dye Crystal Violet (CV) from aqueous solution increased by about 3 times. With AM as monomer, the RI-values increased from 2.6 (background) to 14.8% and the adsorption of a direct dye Sirius Lichtbordo B-LL increased by about 6 times. With VP as grafted monomer, the RI-values increased from about 2.6 (background) to 5.1% and the adsorption of the direct dye increased by about 4 times.     

Photoinitiated surface grafting of synthetic fibers,I. Photoinitiated surface grafting of ultra high strength polyethylene fibers

Photoinitiated surface grafting of acrylic monomers has been carried out onto high strength polyethylene (HSPE) yarn by means of a continuous process. The grafting reaction is initiated by UV irradiation of the yarn after presoaking in an acetone solution of initiator and monomer. Four initiators, benzophenone (BP), 4-chlorobenzophenone (4-CBP), 2-hydroxy-2-cyclohexylacetophenone (HHA), and 2,2-dimethoxy-2-phenylacetophenone (DMPA), and two monomers, acrylic acid (AA) and acrylamide (AM), have been used. After short irradiation time (10 to 20 s) successful grafting is obtained, as shown by ESCA and IR-ATR spectra, dye adsorpotion from aqueous solution, and measurements of adhesion of single filaments to epoxy resin. Grafting efficiency of 74% has been reached for AA as monomer (26% is homopolymer). The tensile strength and modulus of the HSPE yarn are retained in the grafting process. The degree of surface grafting is mainly a function of structure and concentration of monomer and photoinitiator in the presoaking solution and of the irradiation conditions used. Increasing irradiation time gives increasing amounts of grafted polymer up to a certain limiting value. The reactivities of the four initiators have been compared showing the highest grafting yields of AA with BP and of AM with 4-CBP as photoinitiator. AA grafted HSPE yarn can be dyed to rather deep color by dipping in an aqueous solution of Crystal Violet. Increased dye absorption by a factor of up to seven has been measured for yarn grafted with AA to the maximum level obtained. The filaments of the grafted yarn show increased adhesion to epoxy resin by a factor of up to five compared with the ungrafted filaments.     

Characteristics of acrylic acid and N-isopropylacrylamide binary monomers–grafted polyethylene film synthesized by photografting

Method for introducing grafted chains consisting of two types of monomer components, acrylic acid (AA) and N-isopropylacrylamide (NIPAAm), into low-density polyethylene (PE) film (thickness = 25 μm) was investigated by two photografting technique using xanthone photoinitiator at 60°C. In the first method (one-step method), AA and NIPAAm binary monomers were graftcopolymerized onto PE film. In the second method (two-step method), AA was first photografted onto PE film and then NIPAAm was further introduced into the AA-grafted PE film by a second-step photografting. Water absorbencies of the grafted films (one- and two-step samples) prepared by the one- and two-step methods, respectively, decreased in the order of AA-grafted film > one-step sample > two-step sample > NIPAAm-grafted film. The water absorbency steeply decreased at 20 to 40°C with increasing temperature when immersed in water at the temperatures (5–60°C) for 24 h. Thermosensitivity, which was defined as the ratio of water absorbencies of the grafted samples at 5 and 60°C, was higher for the one-step sample than the two-step one. The different extent of the water absorbency and the thermosensitivity between both samples is discussed in terms of location of grafted chains in the film substrate, which was determined by electron probe microanalysis and attenuated total reflection–infrared measurements, and monomer sequence distribution of the grafted chains. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2057–2064, 1998     

Surface modification of UHMWPE fibers by ozone treatment and UV grafting for adhesion improvement

In this study, the surface of ultra-high-molecular-weight-polyethylene (UHMWPE) fibers was modified by ozone pretreatment, followed by ultraviolet (UV) grafting, to enhance the interfacial properties of UHMWPE fibers/rubber composites. The fibers were first pretreated by ozone to introduce oxygen-functional groups. The graft polymerization of glycidyl methacrylate (GMA) onto the ozone-treated fibers was implemented by UV irradiation. The effects of time and GMA concentration on the grafting efficiency were investigated. The modified fibers were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS). The XPS and FTIR results revealed that GMA was successfully grafted onto the fibers with epoxy groups. SEM images confirmed that a continuous layer of poly-(GMA) (PGMA) was grafted onto the fibers. The interfacial adhesion force of UHMWPE fibers with rubber matrix was characterized by H pullout testing, which showed that the maximum force the fibers/rubber composites increased by 79% over that of the untreated fibers.     

HDPE-AA-SSS预辐照接枝膜的表征及其湿敏性能的研究

采用预辐照法将亲水性单体丙烯酸(AA)和对苯乙烯磺酸钠(SSS)接枝到疏水性高密度聚乙烯(HDPE)薄膜上,制备出新型的接枝膜湿敏元件.通过扫描电镜观测了辐照接枝前和接枝后HDPE膜的表面形貌,并通过红外光谱表征了膜的结构,同时测定了接枝膜湿敏元件的湿敏性能.实验结果表明,制备的接枝膜湿敏元件具有良好的湿敏特性,响应和恢复时间短.它具有较好的稳定性,能在高湿、高温环境下使用.实验结果也表明了接枝HDPE膜具有良好的湿敏性能.     

Effect of reactive group types on the properties of core-shell modifiers toughened PA6

Summary  Reactive monomers such as acrylic acid (AA), maleic anhydride (MA) and glycidyl methacrylate (GMA) were grafted onto acrylonitrile-butadiene-styrene core-shell copolymer (ABS) by emulsion polymerization method. These functionalized ABS were used to toughen PA6. FTIR and Molau tests showed that these monomers were introduced onto ABS copolymers and compatibilization reactions took place between PA6 and the AA, MA and GMA grafted ABS. TEM result showed that the modified ABS copolymer dispersed in PA6 matrix uniformly and no obvious difference could be found between the different PA6 blends. However, mechanical test showed that GMA and MA modified ABS achieved much better toughening effect than the AA grafted ABS copolymer due to the stronger interfacial reactions. Fracture characterization indicated that PA6 toughened with GMA and MA modified ABS showed higher G_ivalues according to the Vu-Khanh approach and much obvious shear yielding in the deformed zone could be found.     

Electrochemical properties of polyethylene membrane modified with sulfonic and phosphonic acid groups

Ion-exchange membranes modified with sulfonic (-SO₃H) and phosphonic acid (-PO₃H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polyethylene (PE) films and sub-sequent sulfonation and phosphonation of poly(GMA) graft chains. The surface area, thickness and volume of grafted PE film increased with increasing grafting yield. The specific electrical resistance of PE membrane modified with the -PO₃H and -SO₃H groups decreased with increasing the ion-exchange capacity. The PE membrane modified with -PO₃H group had a lower specific electrical resistance than that of PE membrane modified with -SO₃H group.     

Surface structure and adhesive properties of biaxially oriented polypropylene film grafted with poly(acrylic amide) using corona discharge

Corona discharge was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene (BOPP) film. The active species formed in air was used to induce graft copolymerization of acrylic amide (AAM) in aqueous solution. The surface structure, hydrophilicity and adhesion of the grafted BOPP film were characterized by the extent of grafting, electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), peel strength and contact angle measurements. Surface graft‐copolymerization of AAM onto BOPP film by corona discharge in air can be carried out with high efficiency. With increasing copolymerization time, the degree of grafting of AAM onto BOPP increases. The degree of grafting achieved a relatively high value of 2.13 wt% for the conditions of 1 min corona discharge and a copolymerization reaction time of 2.5 hr in 20% AAM aqueous solution at 70°C. After corona discharge grafting, the contact angle of water on the BOPP film decreased and the peel strength increased compared with those for ungrafted BOPP film. The hydrophilicity and adhesion of BOPP were improved by surface graft copolymerization with AAM induced by corona discharge.     

SEM study of the morphologic change of high‐density polyethylene surface grafted with glycidyl methacrylate

Scanning electron microscopy (SEM) study of the morphologic change of high‐density polyethylene (HDPE) surface grafted with glycidyl methacrylate (GMA) was reported. Radiation‐induced grafting of GMA onto HDPE was carried out in acetone and dichloromethane solution, respectively. The effects of irradiation dose, atmosphere, and swelling time on grafting were investigated. Generally, the extent of grafting increased with irradiation dose, but for the grafting carried out in acetone solution, the extent of grafting initially increased with irradiation dose and then remained almost constant. The extent of grafting was higher in acetone solution than in dichloromethane solution at the same irradiation dose. The extent of grafting in nitrogen was higher than that in air. The successful grafting of GMA onto HDPE was confirmed by weighing and FTIR analysis. SEM investigations showed that the morphologies of the PE samples grafted in acetone solution were quite different to those grafted in dichloromethane. The grafting of GMA carried out in acetone was mainly on HDPE surface and that carried out in dichloromethane was mainly in the bulk of HDPE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface grafting of poly(vinylamine) onto poly(ethylene) film by corona discharge‐induced grafting

Poly(vinylamine) (PVAm) was grafted on a poly(ethylene) (PE) film surface via the surface graft polymerization of N‐vinylformamide (NVF) and N‐vinylacetamide (NVA) and the subsequent hydrolysis of those grafted polymers. The surface was characterized by X‐ray photoelectron spectroscopy (XPS), contact angle, moisture absorption, and the leakage of electrostatic charge from the films. PNVF and PNVA were introduced onto the surface of the PE film successfully, in spite of the fact that the initiator for polymerization was a peroxide group. The grafted amounts of PNVF and PNVA were dependent on the grafting time. A PVAm‐grafted surface was obtained via the hydrolysis of the grafted PNVF. The grafted‐PNVA was not hydrolyzed under mild hydrolysis. The obtained PVAm‐grafted surface appeared to be useful for various applications, such as protein immobilization or chemical modification. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1583–1587, 1999     

Microstructure and sulfonation of dual monomer-grafted polypropylene nonwoven fabrics

The sulfonation of styrenic polymers often needs harsh reaction conditions, such as concentrated sulfuric acid and elevated temperature. The awkward situation is handled by grafting copolymerization of polar and nonpolar monomers, and essentially the surface wettability between sulfonating agent and matrix polymer is circumvented in the study. Two pairs of dual monomers, glycidyl methacrylate (GMA)-acrylic acid (AA), styrene (St)-acrylic acid (AA), were grafted onto polypropylene nonwoven fabrics (PP) using thermal polymerization, and the resulted fabrics were further sulfonated using sodium sulfite and sulfuric acid, respectively. The microstructure of the modified fabrics was characterized by infrared spectroscopy and scanning electron microscopy. The ion exchange property was verified by copper (II) removal from aqueous solution, and its reutilization was carried out in electrochemical desorption process. The results show that hydrophilic and active monomer AA speeds grafting and sulfonation, but overload of AA will deteriorate copolymerization of GMA, and switch copolymerization chain component due to acylation with benzene ring. Although interfacial compatilizer promotes dual grafting, its overdosing may intensify microphase segregation of the grafting polymers owing to emulsification. The resultant granular polymers will be drained off during functionalization and reutilization processes. The ion exchange fabrics can be applied for treatment of metal ion wastewaters with unique electrochemical desorption feature. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48300.     

Glucose oxidase immobilization onto a plasma-induced graft copolymerized polymeric membrane modified by poly(ethylene oxide) as a spacer

Plasma-induced graft copolymerization of acrylic acid, which was incorporated onto polyethylene (PE) film, was prepared. A bisamino poly(ethylene oxide) (PEO) was immobilized onto the poly(acrylic acid) (PAAc)-grafted PE membrane to modify the surface properties. The samples were characterized by ESCA. A respective chemical shift of Ar plasma-treated and control polymeric film was revealed by ESCA. The presence of the grafted PAAc and PEO was also verified. Glucose oxidase (GOD) was immobilized onto this novel grafted polymeric film with and without PEO being used as a spacer. The Michaelis constant, K_m, and the maximum reaction velocity, V_max, were estimated for the free and the immobilized GOD. GOD immobilized onto the polymeric films with and without a spacer obeyed Michaelis kinetics. The Michaelis constant, K_m, was larger for the immobilized GOD than for the free one whereas V_max was smaller for the immobilized GOD. The bioactivity of PEO-modified PAAc-grafted PE membrane (PAAc–PEO–GOD) was higher than that of PAAc-grafted PE membrane (PAAc–GOD). The pH and thermal stabilities of the immobilized GOD without a spacer (PAAc–GOD) were higher than those of the immobilized GOD with a spacer (PAAc–PEO–GOD) and the free form. © 1993 John Wiley & Sons, Inc.     

Thermosensitive surface properties of polyethylene film with poly(N-isopropylacrylamide) chains prepared by corona discharge induced grafting

Polyethylene (PE) film was treated by corona discharge and then grafted with N-isopropylacrylamide (NIPAAm) for modification of the surface. The grafted amount was determined by gravimetry and the surface morphology was observed by using a scanning electron microscope. The surface analysis was carried out with a x-ray photoelectron spectroscopy and electron probe microanalysis. It was clarified that grafting was limited surface and there was no change of the surface morphology after grafting. The water absorption at various temperature under the absolute humidity (11.4 g/cm³) and the leakage of electrostatic charge from PE film were measured. PolyNIPAAm that was introduced onto PE surface has hydrophilic-hydrophobic transition properties at the 32°C in the atmospheric condition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1773–1779, 1998     

Surface modification by continuous graft copolymerization. II. Photoinitiated graft copolymerization onto polypropylene film surface

A method for photochemically induced graft copolymerization of acrylamide (AM) onto polypropylene (PP) film surface by a continuous presoaking process under nitrogen atmosphere has been developed. After removal of homopolymer formed, ESCA, UV spectroscopy, contact angle, and adhesion measurements confirmed a photografted layer on the surface of the PP film. The results from spectral analysis and surface properties measurements were consistent. The best grafting yield was obtained for 7–10 s irradiation time. Stabilizing additives in the PP film had no evident effect on the photografting. Benzophenone was an efficient photoinitiator for photografting of PP film with AM. An AM concentration of 0.5–1.3M in the presoaking solution was appropriate in the present case. Acetone was the best solvent among the three alifatic ketones tested (acetone, methylethylketone, and methylpropylketone).     

Surface structure of low density polyethylene films grafted with acrylic acid using corona discharge

Chemical composition, morphology, and crystalline structure of low density polyethylene (LDPE) films surface grafted with acrylic acid (AA) using corona discharge were studied by attenuated total reflection infrared (ATR-IR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) techniques. The grafted film surface is covered with grafted chains. After grafting for 3.0 h in 20% aqueous solution of AA, the depth of the grafted layer is more than 10 nm. A grain structure was observed on the grafted surfaces which was probably caused by the isolated dispersion of active sites generated by corona discharge, and these active sites initiated the graft copolymerization. However, surfaces of grafted films were smoother than that of ungrafted ones. DSC curves of grafted films show a small peak at about 100°C due to vaporization of adsorbed water. The longer the graft copolymerization time, i.e. the higher the graft degree of AA on LDPE, the higher the amount of adsorbed water. The position of each peak in WAXD patterns, crystal axial length, crystal plane distance and crystal grain size remain almost unchanged during the graft copolymerization time of 2.0 h. However, when the graft copolymerization time reaches 3.0 h, twin peaks at about 21.4° and 22.0° are observed, indicating that a different crystal form is formed at longer copolymerization time, i.e. at a higher graft degree.     

Structure and adhesion properties of linear low‐density polyethylene powders grafted with acrylic acid via ultraviolet light

The structure and adhesion properties of linear low‐density polyethylene (LLDPE) powder grafted with acrylic acid (AA) via ultraviolet light (UV) were studied by Fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), and water contact angle, peel strength, and graft degree measurements. The results show that the chemically inert LLDPE powder can be graft‐copolymerized with AA via this photografting method. The graft degree increases with the ultraviolet irradiation time. The hydrophilicity of the grafted LLDPE powder and the peel strength of high‐density polyethylene (HDPE)/steel joint with the grafted LLDPE powder used as hot‐melt adhesive are improved considerably, as compared to that with the ungrafted LLDPE powder. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2549–2553, 2006     

接枝支链结构对聚乙烯多单体接枝共聚物结晶性能的影响

采用固相接枝法合成聚乙烯(PE)与甲基丙烯酸缩水甘油酯、苯乙烯、丙烯酸丁酯的固相接枝共聚物(PETM),利用差示扫描量热法、X射线衍射和偏光显微镜等测试手段研究了接枝支链对接枝共聚物的结晶过程的影响,并对接枝共聚物的X射线衍射峰进行分峰,计算接枝共聚物的晶胞参数。结果表明:接枝支链并没有改变PE的晶型,只是充当异相成核剂的作用并阻碍PE的晶体生长;受接枝支链影响,PE中存在不完善的结晶,PETM的结晶度比PE低。     

一种新型辐射接枝材料的制备及性能

采用直接辐射法将丙烯酸(AA)和丙烯酰胺(Am)的混合单体接枝于聚乙烯(PE)膜制备了一种新型的功能性材料。研究了单体浓度、辐照环境和剂量率对接枝反应的影响。结果表明,AA/Am(1:1)混合单体体系的接技率大大高于AA和Am单独体系的接枝率。利用光学显微镜观察到接枝链充满整个基材。接枝材料具有优良的亲水性、染色性、离子交换能力、导电性能、机械性能、耐热和耐化学性能。