Surface grafting polymerization of N‐vinyl‐2‐pyrrolidone onto a poly(ethylene terephthalate) nonwoven by plasma pretreatment and its antibacterial activities

The objective of this research was the surface grafting polymerization of biocompatible monomer N‐vinyl‐2‐pyrrolidone (NVP) onto a plasma‐treated nonwoven poly(ethylene terephthalate) (PET) substrate with ultraviolet (UV)‐induced methods. The effects of various parameters, such as the monomer concentration, reaction time, initiator (ammonium peroxodisulfate) concentration, and crosslinking agent (N,N′‐methylene bisacrylamide) concentration, on the grafting percentage were studied. The grafting efficiency of the modified nonwoven PET surfaces reached a maximum at 50 min of UV irradiation and with a 30 wt % aqueous NVP solution. After the plasma activation and/or grafting, the hydrophobic surface of the nonwoven was modified into a hydrophilic surface. NVP was successfully grafted onto nonwoven PET surfaces. The surface wettability showed that the water absorption of NVP‐grafted nonwoven PET (NVP‐g‐nonwoven PET) increased with increasing grafting time. NVP‐g‐nonwoven PET was verified by Fourier transform infrared spectra and scanning electron microscopy measurements. An antibacterial assessment using an anti‐Staphylococcus aureus test indicated that S. aureus was restrained from growing in NVP‐g‐nonwoven PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 803–809, 2006     

Ammonia adsorption behavior of polypropylene nonwoven fabric grafted with acrylic acid

An attempt was made to synthesize an adsorbent by the photoinduced grafting of acrylic acid (AA) onto polypropylene nonwoven fabrics using benzophenone (BP) as a photosensitizer in a CH₃OH/H₂O medium. As the BP concentration was increased, the graft yield was increased up to a specific value and then decreased, and the effect of AA concentration showed the same tendency. It was also found that the graft yield increased with the reaction time and temperature. The amounts of ammonia adsorbed onto polypropylene nonwoven fabrics grafted with AA (PP‐g‐AA) were dependent on the graft yield, adsorption time, and ammonia gas pressure. The adsorption capacity of PP‐g‐AA was 5.86 mmol/g at the graft yield of 116.6%, which was much higher than that of active carbon or silica gel. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 295–301, 2002; DOI 10.1002/app.10328     

Lipases improve the grafting of poly(ethylene terephthalate) fabrics with acrylic acid

In this study, poly(ethylene terephthalate) (PET) fabrics were modified with two types of commercial lipases, namely, Lipex and Lipolase, and grafted with acrylic acid (AA) to improve their absorption properties. The effects of the enzyme concentration, reaction temperature, time, and pH on the grafting of AA onto PET were investigated. The pretreatment of PET with lipases increased the amount of AA that was introduced to the PET fibers, whereas AA grafting onto the untreated PET fabrics led to lower graft yields. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the AA‐grafted pretreated polyester fabrics. A new band appearing at 1546 cm^?1 in the Fourier transform infrared spectrum implied that AA was introduced onto the PET fabrics. The surfaces of the fabric fibers presented in scanning electron microscopy micrographs clearly indicated the formation of a layer of grafted poly (acrylic acid). The results show that the density of surface grafting was improved by the lipase pretreatment. The increase in grafting was higher for Lipex than for Lipolase. The highest graft yield was obtained with 1% Lipex and Lipolase for 30 min at pH values of 7 and 5, respectively. There were no significant changes in the tenacity or weight reduction of the fabrics. The moisture content of the samples increased linearly with increasing graft yield. This was higher for the pretreated fabrics grafted with Lipex. A higher color strength was obtained for grafted PET samples that were pretreated with Lipex when they were dyed in alkaline aqueous solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PET非织造布等离子改性及抗菌性能研究

采用低温氧等离子体处理聚对苯二甲酸乙二酯(PET)非织造布接枝丙烯酸(AA)后,再接枝壳聚糖,探讨了氧等离子体参数对接枝AA后PET亲水性的影响,以及接枝壳聚糖后其PET非织造布抗菌性能的变化。结果表明:低温氧等离子体处理PET非织造布后,其纤维表面粗糙度增加,接枝AA后PET亲水性提高。低温氧等离子体处理PET非织造布接枝AA改性的最佳条件为:工作压强30 Pa,放电功率40 W,处理时间2 min。接枝壳聚糖后,PET非织造布具有抑菌性能,对大肠杆菌和金黄色葡萄球菌有明显的抑菌效果。     

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse dyes

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse red dye was studied in the temperature range 283–363 K. 1‐vinyl 2‐pyrrolidone (NVP), acrylic acid (AA) or their mixture was used to graft poly(ethylene terephthalate) (PET) fabric. The effects of pH of the dye solution, graft yield (GY), dyeing time (t), dye concentration (C), and dyeing temperature (T) on the colour difference (CD) of PET fabric were studied. The best dyeing condition was achieved at pH 5.5. CD increases linearly with the increase in GY, with slopes depending on the type of grafted copolymer. CD increased rapidly as the dyeing time increased; this was followed by a relatively slow dyeing rate within a few minutes. The initial dyeing rate (R) was found to increase with an increase in C and T. The dyeing rates for all grafted samples followed 0.35‐order kinetics and are temperature‐independent. Average activation energy 9.26 kJ mol^?1 is calculated for the dyeing process and is independent of the fabric treatment. Pre‐exponential rate constants 1976, 1839, and 1579 (CD/GY) s^?1 were calculated for dyeing PET samples grafted with AA/NVP mixture, NVP and AA, respectively, while 1074 CD s^?1 was evaluated for carrier dyeing of ungrafted fabric. Analysis of the kinetic parameters and the dyeing mechanism revealed that dyeing PET fabric was diffusion‐controlled. Grafting PET fabric improved significantly the dyeing affinity of the DR dye over ungrafted samples dyed in solutions containing a carrier. Copyright © 2005 Society of Chemical Industry     

Graft copolymerization of an itaconic acid/acrylamide monomer mixture onto poly(ethylene terephthalate) fibers with benzoyl peroxide

A mixture of acrylamide (AAm) and itaconic acid (IA) was grafted onto poly(ethylene terephthalate) (PET) fibers with benzoyl peroxide in aqueous media. The effects of polymerization conditions such as the temperature, polymerization time, initiator concentration, and monomer mixture ratio on grafting were investigated. The maximum graft yield was 76.1% with an AAm/IA mixture ratio of 90/10 (mol/mol). The graft yield was as low as 3% in the single grafting of IA, whereas the use of AAm as a comonomer increased the amount of IA that entered the fiber structure to 33.5%. An increase in the temperature from 65 to 85°C increased the grafting rate and saturation graft yield. However, an increase in the temperature above 85°C decreased the saturation graft yield. The graft yield increased up to an initiator concentration of 1.0 × 10^?2 M and decreased afterwards. The grafting rate was 0.65th‐ and 0.74th‐order with respect to the initiator and AAm concentrations, respectively. The densities, diameters, and moisture‐regain values of the AAm/IA‐grafted PET fibers increased with the graft yield. Similarly, there was an increase in the dyeability of the AAm/IA‐grafted fibers with acidic and basic dyes. The grafted fibers were characterized with Fourier transform infrared and thermogravimetric analysis, and their morphologies were examined with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1795–1803, 2005     

Preparation of chelating fabrics by radiation‐induced grafting of itaconic acid and acrylonitrile onto polypropylene nonwoven fabrics and subsequent amination of graft copolymer

A mixture of acrylonitrile (AN) and itaconic acid (IA) was cografted onto polypropylene (PP) nonwoven fabrics by preirradiation method. The effects of graft polymerization conditions such as temperature, reaction time, Mohr's salt concentration, solvent mixture ratio, and comonomer composition on the total grafting yield were investigated. The addition of AN as a comonomer increased the amount of IA that reacted with PP fabrics. An increase in the temperature from 40 to 60°C increased the grafting rate, but the final grafting yield decreased at high temperature. The addition of 0.01 wt % Mohr's salt to the reaction medium leaded to a sharp increase of grafting yield. The accelerative effect of solvent medium on the grating yield was higher in dimethylformamide (DMF) and methanol mixtures, when compared with DMF or methanol. Chelating fabrics was synthesized by subsequent amination of grafted fabric with ethylene diamine (EDA) and phenylhydrazine (PH). The conversion yield reached maximum value at about 90% for 80% PP‐g‐AN‐IA fabrics at 90°C. At same amination conditions, the conversion yield is higher when PP‐g‐AN‐IA fabrics react with EDA compared with PH. FT‐IR data indicate that amine groups were introduced onto PP‐g‐AN‐IA fabric through amide linkage between grafted AN or IA and EDA or PH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of acrylic acid grafted poly(ethylene terephthalate) fabric

The preirradiation grafting of acrylic acid (AA) onto poly(ethylene terephthalate) (PET) had been found to affect the thermal and physical characteristics of fabric. The grafted fabrics with various graft levels were characterized by thermal gravimetric analysis (TGA), ATR‐FTIR spectroscopy, contact angle, differential scanning calorimetry (DSC), X‐ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The initial decomposition temperature and T₅₀ were increased with the increase in degree of grafting. The percentage crystallinity was decreased as the degree of grafting increases. The detailed elemental analysis was done by X‐ray photoelectron spectroscopy (XPS). The atomic ratio (O_1s/C_1s) was found to increase significantly with increasing the degree of grafting and reached 0.64 at 14.5% grafting from 0.38 for virgin PET. The surface topography and morphology was strongly influenced as the degree of grafting was increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface graft copolymerization of acrylic acid onto corona-treated poly(ethylene terephthalate) fabric

Acrylic acid (AA) was grafted onto the surface of poly(ethylene terephthalate) (PET) fabric after having short-time corona-discharge treatment (CDT) in an atmosphere in the presence of the initiator. The effect of N,N-dimethylformamide (DMF) pretreatment time, CDT time, graft copolymerization time and temperature, concentration of AA, and the content of initiator on graft yield of PET fabric was discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1161–1164, 1999     

Graft polymerization of acrylic acid onto polyphenylene sulfide nonwoven initiated by low temperature plasma

Graft copolymerization of acrylic acid (AA) onto polyphenylene sulfide (PPS) nonwoven initiated by low temperature plasma was studied. The effects of various conditions on graft reaction and the grafting rate were investigated. SEM images showed that PPS nonwoven was grafted, and the graft copolymerization only occurred on the surface of PPS. It may be due to the chain transference going with the graft copolymerization. It was found that with the increasing of plasma power, treatment time, space between electrodes, monomer concentration, and temperature of graft polymerization, the grafting rate increased at first, went to the top, and then decreased. The PPS nonwoven surface graft reaction could be optimized by the following processing conditions: 120 s of plasma treatment time, 50 W of plasma power, 1.5 cm of space between electrodes, 30% (w/w) of monomer concentration, and 50°C of temperature of graft polymerization. Measurement of XPS showed that the peak of C1s of graft polyacrylic acid was existed, and the peak area increased with the increase of the grafting rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5884–5889, 2006     

等离子体诱导PET纤维接枝丙烯酸的研究

利用低温等离子体技术对PET织物在氧气下经等离子处理后生成过氧化物,然后接枝丙烯酸进行研究。通过改变低温等离子体各种处理条件来研究其接枝后织物的吸水性、润湿性等性能变化。随着放电功率的增加、放电时间的延长,PET织物的吸液高度呈现先增大后减小的趋势;随着放电功率的增加,PET织物与去离子水接触角呈现先减小后增大的趋势;随着等离子体放电时间的增加,PET织物与去离子水的接触角迅速减小,然后趋于稳定。经过处理后试样的吸湿率、吸液高度和回潮率均随接枝率的增加而增加,染色性能提高。     

Surface characterization of PET nonwoven fabric treated by He/O2 atmospheric pressure plasma

The surface of polyethyleneterephthalate (PET) nonwoven fabric was modified by He/O₂ atmospheric pressure plasma treatment, varying plasma exposure time. The plasma treated PET surfaces have been analyzed to investigate the chemical nature and morphology of surface by X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The change of wettability was measured depending on plasma exposure time. XPS results indicated the presence of oxygen‐based functional groups on the PET nonwoven fabric surface after plasma treatment and oxygen content increased as exposure time increased. The mean roughness increased after 30 s exposure and further increase in exposure to 60 s led to decrease of the roughness and then again increase. The root mean square roughness followed the similar trend to mean roughness. The average difference in height, Rz, increased after plasma exposure for 30 s, while it slightly decreased after 60 s exposure. Despite of redeposition, the Rz of 90 s exposed sample increased more than two times compared with those of 30 and 60 s exposed. Wettability increased progressively up to 10 times after 90 s exposure compared with the untreated. It is attributed to the increases of hydrophilicity and surface roughness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Radiation grafting of acrylic acid/N‐vinyl pyrrolidone binary mixture onto poly(ethylene terephthalate) fabric and growth of human mesenchymal stem cell

Radiation grafting of acrylic acid (AA)/N‐vinyl pyrrolidone (NVP) binary mixture onto poly(ethylene terephthalate) (PET) knittings was investigated by preirradiation technique. The influence of the grafting conditions, such as monomer composition, reaction temperature, and the effect of storage time with temperature after irradiation on the degree of grafting was determined. ATR‐FTIR spectroscopy analysis of the grafted knittings confirmed the existence of amide group of NVP in the knittings. The concentration of peroxides and effect of storage time on peroxide concentration were also determined by 2,2‐Diphenyl‐1‐picrylhydrazyl at different temperatures. There was an increase in surface roughness of grafted PET in comparison to virgin PET as determined by atomic force microscopy and scanning electron microscopy. The grafted knittings were subsequently immobilized with collagen Type I which was further apt for the study of growth and morphology of human mesenchymal stem cell (hMSC). The immobilization of collagen on PET knittings has provided an excellent surface for the growth of hMSCs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of acrylic acid grafted polypropylene nonwoven fabric by photoinduced graft polymerization with preabsorption of monomer solution

We improved photoinduced graft polymerization by absorbing the monomer solution onto the substrate (Ab‐type) instead of immersing the substrate in the monomer solution (Im‐type) before photoirradiation to yield a more practical and effective grafting system. With this system, acrylic acid (AA) was effectively grafted onto polypropylene (PP) nonwoven fabric. The maximum degree of grafting obtainable was restricted by the amount of monomer preabsorbed onto the PP fabric. However, we effectively enhanced the degree of grafting by increasing the monomer concentration, adding trimethylolpropane triacrylate (TMPTA) to the monomer solution, and repeating the photoirradiation with supplementation of the monomer solution. The net availability of the monomer for graft polymerization was 50% or greater; this increased to 90% or greater with the addition of TMPTA and was much higher than for conventional Im‐type photografting (≤13%). Fourier transform infrared spectra, scanning electron microscopy morphology observations, and the adsorption–regeneration properties confirmed that the PP‐g‐AA fabric prepared by the improved Ab‐type photografting method had comparable qualities to those of fabric prepared by conventional Im‐type photografting. Thus, the improved Ab‐type photografting system provides potential for the preparation of graft adsorbents on a large scale at a competitive cost with a continuous reactor, such as a conveyer belt system, instead of a batch reactor. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Anti‐bacterial and swelling properties of acrylic acid grafted and collagen/chitosan immobilized polypropylene non‐woven fabrics

The various weight ratios of collagen/chitosan were used to immobilize the various grafted amounts of acrylic acid (AA) grafted polypropylene nonwoven fabric. For a given value of grafting percentage of AA and the immobilizing time period, the values of the immobilizing percentage of collagen/chitosan are increased with the increasing of chitosan contained in the mixtures of collagen/chitosan. The antibacterial properties are also increased with the increasing of chitosan in the mixtures of collagen/chitosan and the immobilizing percentage of collagen/chitosan. The crosslinking reaction between the AA‐grafted PP nonwoven fabrics and collagen/chitosan with glutaraldehyde are clearly sustained by examination from the spectra of the surface reflection infrared spectroscopy (IR). The values of water uptake and water diffusion coefficients are decreased with the increasing of chitosan in the mixtures of collagen/chitosan and the immobilizing percentages of collagen/chitosan at the same pH value of buffering water. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 391–400, 2005     

聚丙烯无纺布预辐射接枝改性及胺化研究

采用丙烯酸(AA)、二乙烯三胺(DETA)依次对聚丙烯(PP)无纺布进行预辐射接枝改性及胺化处理,研究了接枝反应及胺化反应的影响因素,并用红外光谱对产物进行表征。结果表明:随着AA用量的增加,接枝率呈先增长后下降趋势;随着反应温度的升高,反应时间的延长,接枝率增加;随着接枝率的增大,胺化反应温度的升高及反应时间的增加,胺化率增加。接枝反应温度为95℃,25 mL AA与无纺布反应2 h,接枝率可达到276%;接枝率为250%的无纺布与50 mL DETA反应7 h,胺化温度205℃,胺化率可达到73%。红外光谱分析表明,经辐射接枝及胺化处理后的PP无纺布有胺基基团。     

Solvent effects in the polyethylene terephthalate surface modification by cold argon plasma‐induced grafting polymerization of methacrylic acid

We studied the surface modification of polyethylene terephthalate (PET) by grafting with methacrylic acid (MAA) through plasma‐induced polymerization method. The results show that the grafting yield increases with the increase of reaction temperature. The grafting yield is in proportion to the increase of monomer concentration. The grafting yield increases along with the prolonging of reaction time. The solvent has great influence to the grafting reaction. The grafting yield increases with the increase of volume ratio R, which is defined by the volume of water to the volume of alcohol, when using alcohol and water as mixed solvent. The grafting yield is not zero when only using methanol, ethanol or isopropanol as the solvent. The red shift in UV spectrum could be ascribed to different reactive activities of MAA in different solvents, which also can explain the change trend of the grafting yield. The UV‐vis absorbance difference and the FTIR integrated peak area of the C?O stretching increase steadily with the increase of grafting yield, which are almost linear relationship. It was confirmed that MAA was grafted onto the PET surface in terms of UV‐vis spectrophotometric, FTIR and atomic force microscopy analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Swelling-assisted graft copolymerization of 4-vinyl pyridine on poly(ethylene terephthalate) films using a benzoyl peroxide initiator

Graft copolymerization of 4-vinyl pyridine (4-VP) on poly(ethylene terephthalate) (PET) films using a benzoyl peroxide (Bz₂O₂) initiator was investigated under different conditions including polymerization time, temperature, monomer concentration, and initiator concentration. Dimethyl sulfoxide (DMSO) was used as swelling agent to promote the incorporation and the subsequent polymerization of 4-VP to PET films. Maximum percent grafting was obtained when the polymerization was carried for a period of two hours at 65°C. Increasing the monomer concentration from 0.2M to 0.8M and Bz₂O₂ concentration from 1.0×10⁻³M to 2.5×10⁻³M was accompanied by a significant enhancement in percent grafting. Monomer diffusion on PET films and its effect on the grafting yield were studied and intrinsic viscosities of grafted films were also measured. © 1996 John Wiley & Sons, Inc.     

The effect of N,N-dimethylformamide and polymer grafting on the morphology of polyester fibers in fabric substrate

Photo-induced graft polymerization of acrylic acid (AA) and methyl acrylate (MA) in the liquid and vapor phase, respectively, onto N,N-dimethyformamide (DMF)-pretreated poly(ethylene terephthalate) (PET) fibers in fabric substrate was studied. The effect of various synthesis conditions and DMF pretreatment on the graft yields on PET was investigated. The internal morphology and properties of DMF-pretreated and grafted PET fibers in the fabric were characterized using density and birefringence measurements, differential thermal analysis (DTA), Fourier transform infrared spectroscopy (FTIR), dyeing methods, and critical dissolution times. The grafting was promoted by increasing DMF pretreatment temperature and the amount of DMF retention in the PET. Increasing biacetyl and monomer flow time and irradiation time enhanced grafting. DMF pretreatment resulted in increases in total void content, degree of crystallinity, trans-isomer content, chain folding, segmental mobility, and molecular packing of the PET, but caused decreases in its amorphous orientation, intermolecular forces, and individual void size through longitudinal shrinkage, lateral swelling, and removal of oligomers. Subsequent graft copolymerization led to further changes in the internal morphology and properties of the PET. PET grafted with AA had a higher cohesive energy density, lower degree of molecular packing, and larger individual void size, but less total void content, lower segmental mobility, less chain orientation, and a lower degree of crystallinity. PET grafted with MA showed increases in total void content, individual void size, segmental mobility, and molecular packing, but showed decreases in chain orientation and degree of crystallinity. © 1996 John Wiley & Sons, Inc.     

Gamma preirradiation and grafting of 2N-morpholino ethyl methacrylate onto polypropylene fabric

The radiation-induced grafting of 2N-morpholino ethyl methacrylate (MEMA) in aqueous solution onto polypropylene fabric by a preirradiation technique has been investigated. Among the most important factors affecting the graft yield are monomer concentration, irradiation dose, reaction temperature, and time. It was found that the graft yield increased with increasing monomer concentration, grafting temperature, and preirradiation dose. The kinetic studies showed that the dependence of the grafting rate on monomer concentration is of 1.1 order. Moreover, the calculated overall activation energy was 14.2 kcal/mol. The grafted PP fabric shows an increase in moisture regain with increasing graft yield. Also, the dyeability with acid dye was significantly increased due to grafting with MEMA. © 1995 John Wiley & Sons, Inc.