腈纶接枝蛋白质水解条件对吸水率和接枝率的影响

研究了腈纶表面接枝蛋白质水解工艺条件对吸水率和接枝率的影响关系。通过红外光谱分析结果证实了腈纶纤维已接枝上大豆蛋白。实验结果还表明,水解时间、水解温度及NaOH浓度都对腈纶纤维的吸水率和接枝率有很大的影响。在一定的水解强度范围内,腈纶的吸水率及接枝率均随水解强度的增加而不断提高;当水解强度过高时,接枝率反而会下降。腈纶表面接枝蛋白质的最佳水解工艺条件为:水解时间15 min、水解温度为90℃、NaOH浓度为10%。X-射线衍射分析表明,腈纶经过水解、接枝后,纤维的聚集态结构没有明显变化。     

腈纶表面接枝蛋白质改性的基本工艺过程与效果

论述了腈纶表面接枝大豆蛋白质的基本工艺过程与效果,结果表明:腈纶经过表面水解、酰氯化、接枝反应等几个简单步骤就可以接枝上大豆蛋白质表面覆盖层,从而达到对腈纶进行蛋白质化学改性的目的。SEM观察表明:接枝之后,蛋白质将会填充腈纶的表面裂纹与微孔,赋予纤维以新的结构形态。     

Adhesion of cornstarch-g-poly (2-hydroxyethyl acrylate) to cotton fibers in sizing

Abstract

A range of starch-g-poly (2-hydroxyethyl acrylate) (S-g-PHEA) with different grafting ratio was prepared by graft copolymerization of 2-hydroxyethyl acrylate (HEA) onto granular cornstarch using ammonium cerium nitrate as initiator. The adhesive ability of the sizes to cotton fibers, film properties, and desizing ability of HEA branch grafted onto starch were investigated. The effects of grafting conditions (such as reaction time, temperature, HEA and initiator concentration, etc.) on grafting ratio and efficiency were investigated. Fourier transformed infrared spectroscopy (FTIR) and Thermogravimetric analysis (TGA) was employed to characterize the complexes of S-g-PHEA. The effect of grafting ratio on the sizing properties of grafted starch was studied by testing the ability of the grafted starch to adhere to cotton fiber and film properties. It was confirmed that the HEA branch can effectively improve the adhesion ability of starch to cotton fibers, improves the flexibility of the starch film while reduces the brittleness, and enhances the abrasion resistance of the yarns (the highest enhancement ratio up to 225.71%). An increase in the grafting ratio facilitates the adhesion to the cotton fibers while making the desizing difficult. The desizing efficiency was high when the grafting ratio was less than 10%, which lead to easy access to desizing and then fewer residues have remained, and at the same time, good sizing performance is maintained, which indicates that the S-g-PHEA possesses the application potential of cotton warp sizing.     

Graft copolymers of starch–polyacrylonitrile prepared by ferrous ion–hydrogen peroxide initiation

The effect of concentration, reactant ratios, temperature, and starch pretreatment on grafting of acrylonitrile onto starch were studied. Grafting was efficient at high concentrations (8–12% starch) when granular starch was used. The molecular weights for grafted polyacrylonitrile (PAN) were higher when gelatinized starch was used, but grafting efficiencies (grafted PAN/total PAN) were much lower. The molecular weight of the grafted side chain increased with increased concentration of reactants. The grafting frequency was highest when the reaction mixture was kept at 5°C and decreased with increased swelling of the starch. The starch–polyacrylonitrile graft copolymers were saponified and dried to give products which absorbed 75–440 ml H₂O per gram and 20–70 ml synthetic urine per gram.     

Surface Modification of Acrylonitrile Copolymer Membranes by Grafting Acrylamide. II. Initiation by Fe2+/H2O2

Surface modification of membranes of an acrylonitrile copolymer (PAN) containing 5.5% methyl methacrylate and 4.0% sodium methylpropylenesulfonate by grafting acrylamide (AAm) with ferrous ammonium sulfate/H₂O₂ as an initiator in aqueous medium was studied. The grafted copolymer was verified by infrared spectra, X-ray photoelectron spectroscopy, and a scanning electron microscope (SEM). From the SEM photos, we know that the AAm homopolymer branches were grafted onto the surface of the membrane and the morphology of the PAN membrane did not change. The results showed that the extent of grafting was varied with some parameters, such as the pH value of the medium, reaction time and temperature, and concentration of AAm and H₂O₂. The results of the water-absorption percent of the membrane showed that the wettability of the modified PAN membrane was improved. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1907–1915, 1998     

Grafting of methyl methacrylate (MMA) onto Antheraea assama silk fiber

Graft copolymerization of methyl methacrylate (MMA) onto nonmulberry silk fiber Antheraea assama was investigated in aqueous medium using the KMnO₄–oxalic acid redox system. Grafting (%) was determined as a function of the reaction time, temperature, and monomer and initiator concentrations. The rate of grafting increased progressively with increase of the reaction time up to 4 h and then decreased. The extent of grafting was maximum at 55°C. The extent was also dependent upon monomer and initiator concentrations up to 75.5 × 10^?2 and 6 × 10^?3 M, respectively. The grafted products were evaluated by infrared spectroscopy and their thermal decompositions were studied by TG and DTG techniques in static air at 20°C min^?1 and 30°C min^?1 in the range 30–800°C. The kinetic parameters for ungrafted and grafted fibers were evaluated using the Coats and Redfern method. The grafted products were found to be thermally more stable than were those of the ungrafted fibers. The surface characteristics of the ungrafted and grafted fibers were evaluated by scanning electron microscopy. The water‐retention values (WRVs) of the grafted fibers were in decreasing order with increase in the grafting (%). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2633–2641, 2001     

The preparation of poly[N(n-butoxymethyl) methacrylamide] grafted silk fibers by polymerization using a low pH system

The graft polymerizations of the N(n-butoxymethyl) methacrylamide (BMA) monomer onto silk fibers were effected after reducing the pH of the grafting system to 2.5 by the addition of a formic acid solution. We compared the grafting efficiencies, surface characteristics, and thermal behaviors, as well as the whiteness levels and the extent of reduction of the rate of yellowing following UV irradiation, with the equivalent features of poly(BMA)-grafted silk fibers, prepared under normal (pH 6) conditions. The grafting efficiency [as poly(BMA) weight gain] onto silk fiber that was attained was almost 100% through optimization of the pH environment in the polymerization system by the addition of formic acid. The stiffness of the silk fabrics observed, following the conventional grafting, was markedly higher than that of equivalent silks after the polymerization at pH 2.5. The rates of yellowness index increase, for these latter silk fabrics following UV irradiation were also reduced, specifically in the initial irradiation period (up to 60 h). The SEM of the grafted silk fabrics reveal the absence of granules on the surface of the grafted silk fiber, when the silk was grafted with poly(BMA), after reducing the pH of the grafting system to 2.5. These findings suggest that the BMA monomer was polymerized specifically within the silk fiber and not on the surface. It is suggested that the increase in the polymer weight gain, and the reduced adverse effect on the fabric handle, arise because of the modified polymer location. © 1993 John Wiley & Sons, Inc.     

Study on the Graft Reaction of Poly(propylene) Fiber with Acrylic Acid

Summary: In this paper, the graft of poly(propylene) fiber with acrylic acid is investigated. The effects of grafting temperature, monomer concentration, and grafting time on the grafting degree of acrylic acid onto poly(propylene) fiber are discussed. In contrast to the conventional method of determining the grafting degree gravimetrically, the acid‐base titration method used in this paper was more efficient, even at low grafting degree. High‐performance liquid chromatography (HPLC) was used to estimate the averaged length of the grafted poly(acrylic acid) chains on each grafted site of poly(propylene) backbone. And also a mechanism for the grafting polymerization is proposed.

Possible microstructures of two PP‐g‐AA samples at the same grafting degree.     

ESCA spectroscopy of poly(methyl methacrylate) grafted onto wood fibers

The incompatibility of hydrophilic wood fiber and hydrophobic polymers is the main difficulty with wood thermoplastic polymer composites. To overcome this issue, many researchers suggest grafting polymer onto wood fiber for improving the interfacial adhesion during mixing. A systematic ESCA study of chemi-thermo-mechanical pulp (CTMP) grafted fiber has been performed to provide chemical information about surface composition modification. The material analyzed included initial CTMP fiber, the pure polymer i.e., poly(methyl methacrylate) (PMMA) as reference material, and grafted fiber at different polymer loadings. Interest is focused on the carbon and oxygen spectra. Samples at high polymer loading or high grafting level have an O/C, C₁, C₂, C₄, O₁, and O₂ intensities much similar to those of the PMMA but a little different since some wood fiber sites have still not fixed the polymer. ESCA spectra provide information on about 1–5 nm depth. The ESCA technique allows the monitoring of grafting polymer onto wood fiber as a surface phenomenon.     

Reinforcement of polypropylene using sisal fibers grafted with poly(methyl methacrylate)

Sisal fiber (SF) surface modification was carried out by grafting with methyl methacrylate (MMA) using cerium and ammonium nitrate as initiator. The effects of reaction time, monomer, and initiator concentration on the grafting parameters were systematically investigated. The results showed that MMA was successfully grafted onto the sisal fiber surface. The PMMA‐grafted sisal fibers were melt blended with polypropylene (PP) and then injection molded. The PP/SF composites were characterized by means of thermal analysis, mechanical testing, wide‐angle X‐ray diffraction, and SEM examination. PMMA grafted onto the surface of SF enhanced the intermolecular interaction between the reinforcing SF and PP matrix, improved the dispersion of SF in the PP matrix, and promoted the formation of β‐crystalline PP. These enhanced the thermal stability and mechanical properties of PP/SF composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1055–1064, 2003     

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     

Ultrafiltration membranes obtained by poly(acrylonitrile) grafted onto poly(vinylchloride)

Acrylonitrile (AN) has been grafted onto Polyvinylchloride (PVC) dissolved in Dimethylformamide (DMF) by means of gamma rays from a Co⁶⁰ source. The grafting yield has been studied as a function of irradiation dose and initial AN/PVC ratio in the solution.

The ratio PAN/PVC has been evaluated both in the grafted copolymer and its fractions by infrared spectroscopy. Ultrafiltration membranes have been prepared from the grafted PVC and its fractions, using the phase inversion technique.

The UF performances have been studied as a function of PAN grafted %.

The results show that both water flux and rejection increase with the grafting. Electron microscopy has also been employed to investigate the membrane structure.     

Graft Copolymerization of Methyl Acrylate onto Oil Palm Empty Fruit Bunch (OPEFB) Fiber

Graft copolymerization of methyl acrylate (MA) onto OPEFB fiber has been successfully carried out using hydrogen peroxide and ferrous ammonium sulfate as initiators in an aqueous medium. The effects of reaction temperature, reaction period, and amount of monomer and initiators on the percentage of grafting were investigated. The results show that the percentage of grafting depends on reaction period and temperature as well as concentration of monomers and initiators. With 33.36 mmol of MA, the optimum percentage of grafting was obtained when the reaction was carried out using 6.00 mmol of H₂O₂ and 0.191 mmol of Fe²⁺ for 210 min at 75°C. The presence of the functional group in the grafted polymers was characterized by FTIR spectroscopy. Scanning electron microscopy was used to study the surface morphology. Thermogravimetric analysis indicated that the grafted OPEFB is thermally stable than the OPEFB     

Styrene‐assisted melt‐free radical grafting of glycidyl methacrylate onto isotactic poly(1‐butene)

The melt‐free radical grafting of glycidyl methacrylate (GMA) onto powered isotactic poly(1‐butene) (iPB‐1) using styrene (St) as a comonomer in a Haake mixer was studied. The effects of temperature, initial GMA, and peroxide concentration, as well as the addition of St comonomer, on the final grafting degree, grafting efficiency, and the melt flow rate of grafted polymer were studied. It was shown that the addition of St as a comonomer could significantly enhance the grafting degree of GMA on iPB‐1 and reduce the extent of degradation of iPB‐1 to some degree. It has been found that the grafting degree of dual‐monomer melt‐grafted iPB‐1 was about twice that of single‐monomer‐grafted iPB‐1 for the same monomer and peroxide concentrations. The grafting of GMA onto iPB‐1 remarkably accelerated the crystal form II → I transformation of iPB‐1. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis of functional polypropylene via solid‐phase grafting soft vinyl monomer and its mechanism

Solid‐phase grafting of a soft vinyl monomer, butyl methylacrylate (BMA), onto polypropylene (PP) matrixes with 2,2′‐azobisisobutyronitrile (AIBN) as initiator was carried out to enhance the polarity of polymer. Soft vinyl monomer was a novel notion in grafting modification of PP. Effects of swell time, BMA concentration, AIBN concentration, grafting reaction time, and temperature on grafting percentage (G_p) and grafting efficiency (G_e) were examined. The optimal conditions of grafting reaction were obtained: swell time of 60 min, BMA concentration of 6 wt %, AIBN concentration of 0.05 wt %, reaction temperature of 85°C, and reaction time of 2 h. The grafting samples were investigated by such characterization techniques as Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and scanning electron microscope (SEM) analysis. FTIR results indicated that BMA was actually grafted onto PP backbone. TGA results showed that the decomposition temperature increases with addition of BMA into PP backbone. SEM results indicated that the surfaces of PP‐g‐BMA had a markedly bumpy texture, whereas the pure PP surface was very smooth. Water contact angle results showed that the polarity and hydrophilicity of PP were improved effectively. Compared with the traditional monomer MAH, G_p, and G_e, melt flow rate and mechanical property results all indicated that the soft vinyl monomer had a many advantages in the modification of PP. In the end, the mechanism of solid grafting was discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

苯乙烯存在下马来酸酐熔融接枝聚丙烯的研究

分别在哈克流变仪（Haake）和双螺杆挤出机（TSE）中,研究了苯乙烯（St）存在下马来酸酐（MAH）熔融接枝聚丙烯（PP）的过程。讨论了过氧化二异丙苯（DCP）用量、St用量、MAH用量、反应时间、反应温度、螺杆转速以及反应器型式对接枝反应的影响．实验发现：随DCP用量的增加,MAH的接枝率先增加后减小,熔体流动速率（MFR）一直增加;保持MAH用量不变增加St用量时,MAH的接枝率在MAH与St的摩尔比为1：1时达到最大,MFR却一直减小;保持St用量不变增加MAH用量,MAH的接枝率先增加后略有减小,MFR却存在极大值;随反应时间的增加,MAH的接枝率与MFR都先增加后减小;温度过高,MAH的接枝率降低,PP热降解较严重;螺杆转速较低时,MAH的接枝率较低,螺杆转速较高时,PP降解增加;在TSE中的MAH接枝率比Haake中的低,但降解比Haake中的小得多。     

Chemical grafting of aniline and o‐toluidine onto poly(ethylene terephthalate) fiber

Graft copolymerization of poly(aniline) and poly(o‐toluidine) onto poly(ethylene terephthalate) fiber was conducted by using peroxydisulfate as a lone initiator under nitrogen atmosphere at various experimental conditions in aqueous hydrochloric acid medium. The grafting of poly(aniline) and poly(o‐toluidine) onto poly(ethylene terephthalate) fiber was verified by recording cyclic voltammetry of the grafted fiber, conductivity measurements, and thermal analysis. Graft parameters—such as % grafting, % efficiency, and the rate of grafting—were followed. Grafting was always accompanied by homopolymerization. The rate of homopolymerization was also followed in all experimental conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 121–128, 1999     

Preparation of a carbon nanotube/carbon fiber multi-scale reinforcement by grafting multi-walled carbon nanotubes onto the fibers

To prepare a carbon nanotube (CNT)/carbon fiber multi-scale reinforcement (MSR), multi-walled carbon nanotubes (MWCNTs) functionalized at the end caps with hexamethylene diamine (HMD) are grafted onto the surfaces of carbon fibers treated with acyl chloride. The surface element concentrations, surface functional groups and morphology of the MSR were examined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS spectra indicate that sp² and sp³ carbon atoms are major components in the MSR surface, and the carbon fiber surface structure is not destroyed. There is 17.41% of C-NH_x in the surface of the MSR, which suggests that MWCNTs are covalently grafted onto carbon fiber surfaces. SEM shows that the grafted MWCNTs stick to the carbon fiber surface at different angles, and are uniformly distributed along the outer edges of the grooves in the fiber surface. The grafted MWCNTs are 50-200 nm in length and around 14 nm in diameter. It was found that the grafting increases the weight of carbon fiber by 1.2%, which implied that a considerable amount of MWCNTs were grafted onto carbon fiber surfaces.     

Optimized condition for grafting reaction of poly(butyl acrylate) onto oil palm empty fruit bunch fibre

Preparation of poly(butyl acrylate)‐grafted oil palm empty fruit bunch fibre (OPEFB) has been successfully carried out using H₂O₂/Fe²⁺ as a redox initiator in aqueous solution. The effects of reaction temperature and period, as well as the amount of monomer, initiator and nitric acid, on the percentage of grafting were investigated. The percentage of grafting increases with amount of monomer and can be controlled by setting the appropriate reaction conditions. The maximum percentage of grafting (about 265%) was obtained when the reaction was carried out without acid under optimum conditions (reaction period: 2 h, reaction temperature: 55 °C, amount of H₂O₂: 5.88 mmol) with 42.2 mmol of monomer. Mechanisms of grafting of butyl acrylate onto OPEFB were proposed. Characterization of the grafted OPEFB was done by Fourier‐transform infrared spectroscopy and scanning electron microscopy. The thermal properties were studied by thermogravimetric analysis. Copyright © 2003 Society of Chemical Industry     

Investigation on selective adsorption of Hg(II) ions using 4‐vinyl pyridine grafted poly(ethylene terephthalate) fiber

In the work, poly(ethylene terephthalate) (PET) fibers were grafted with 4‐vinyl pyridine (4‐VP) monomer using benzoyl peroxide (Bz₂O₂) as initiator in aqueous media. The removal of Hg(II) ions from aqueous solution by the reactive fiber was examined by batch equilibration technique. Effects of various parameters such as pH, graft yield, adsorption time, initial ion concentration, and adsorption temperature on the adsorption amount of metal ions onto reactive fibers were investigated. The optimum pH of Hg(II) was found 3. The maximum adsorption capacity was found as 137.18 mg g^?1. Moreover such parameters as the adsorption kinetics, the adsorption isotherm, desorption time and the selectivity of the reactive fiber were studied. The adsorption kinetics is in better agreement with pseudo‐first order kinetics, and the adsorption data are good fit with Freundlich isotherms. The grafted fiber is more selective for Hg(II) ions in the mixed solution of Hg(II)‐Ni(II), Hg(II)‐Zn(II), and Hg(II)‐Ni(II)‐Zn(II) at pH 3. Adsorbed Hg(II) ions were easily desorbed by treating with 1M HNO₃ at room temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012