Fixation of cationic P (st‐BA‐AA‐GMA) emulsion on pigment particles in dyeing of cotton fabrics

Cationic copolymer emulsions of St, BA, AA, and GMA were successfully synthesized via semi‐continuous emulsion polymerization. The properties of synthesized cationic emulsions were characterized by monomer conversion and solid content, differential scanning calorimeter, particle size and distribution, zeta potential, and centrifugal stability. The film performance of the cationic emulsions formed on cotton fiber surface was observed by scanning electricity microscopy. The influence of cationic emulsions on the color data, K/S values and rubbing fastness of dyed cotton fabrics was also investigated. The results show that P (St‐BA‐AA‐GMA) emulsion had larger particle size and higher zeta potential than P (St‐BA‐AA) emulsion. When the films were formed at room temperature, P (St‐BA‐AA‐GMA) emulsion film had better performance than P (St‐BA‐AA) emulsion film. The addition of GMA monomers improved the film performance. P (St‐BA‐AA‐GMA) emulsion films formed at 120 °C after acetic acid solution treatment had the best water resistance. Dyed cotton fabrics pretreated with P (St‐BA‐AA‐GMA) emulsion had better pigment dyeing performance than those pretreated with P (St‐BA‐AA) emulsion. It demonstrates that the addition of GMA monomers further improved the effect of pigment dyeing for cotton fabrics with cationic emulsions as binders. With the increase of P (St‐BA‐AA‐GMA) concentration, the color performance of dye fabrics improved while the rubbing fastness decreased a little. But, the handle and fastness still meets the use standards for consumers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44987.     

双单体AA/St熔融接枝OBC的研究

利用HAAKE转矩流变仪,采用熔融接枝法制备了双单体丙烯酸/苯乙烯接枝乙烯-辛烯嵌段共聚物(OBC-g-(AA-co-St)),探讨了丙烯酸(AA)、苯乙烯(St)和过氧化二异丙苯(DCP)的用量对接枝反应的影响,并通过红外光谱分析表征了该接枝产物的结构。结果表明:采用熔融接枝技术,成功地将AA接枝到OBC上,得到了OBC-g-AA接枝共聚物;当AA为4%、DCP为0.2%、反应温度为170℃、反应时间为12 min时,OBC-g-AA的相对接枝率达到峰值;另外,第二单体St的引入使接枝率有所提高,当St与AA质量比为1:2时,其相对接枝率达到1.68。     

官能化乙丙橡胶的制备和表征

用２,５－二甲基－２,５－二叔丁基过氧基己烷为引发剂,甲基丙烯酸环氧丙酯（ＧＭＡ）、马来酸酐（ＭＡＨ）和丙烯酸（ＡＡ）为接枝单体,对三元乙丙橡胶（ＥＰＤＭ）和二元乙丙橡胶（ＥＰＲ）进行熔融接枝,接枝产物用ＦＴＩＲ、１３Ｃ－ＮＭＲ等进行了表征,并用化学滴定方法对接枝率进行了测定。实验结果表明,影响接枝率和凝胶质量分数的主要因素为乙丙橡胶的化学结构、引发剂和单体的用量、反应时间及温度等。接枝单体反应活性大小依次为ＧＭＡ,ＡＡ,ＭＡＨ。     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. II. Characterization of sulfonated graft copolymer membranes

PFA‐g‐polystyrene sulfonic acid membranes were prepared by simultaneous radiation‐induced graft copolymerization of styrene onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA) film followed by sulfonation. The membrane physico‐chemical properties such as swelling behavior, ion exchange capacity, hydration number, and ionic conductivity were studied as a function of the degree of grafting. Thermal as well as chemical stability of the membranes was also investigated. The membrane properties were found to be mainly dependent upon the degree of grafting. The water uptake, ion exchange capacity, hydration number, and ionic conductivity of the membranes were increased, whereas the chemical stability decreased as the degree of grafting increased. The membranes showed reasonable physico‐chemical properties compared to Nafion 117 membranes. However, their chemical stability has to be further improved to make them acceptable for practical use in electrochemical applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1–11, 2000     

Self‐driven graft polymerization of vinyl monomers on poultry chicken feathers in the absence of initiator/catalyst

An efficient and simple method for graft copolymerization of powdered chicken feather (CF) with vinyl monomers without any free radical initiator is reported. Various vinyl monomers such as glycidyl methacrylate (GMA), styrene (S), and methyl methacrylate (MMA); (20–60 wt % with respect to CF) were successfully grafted to chicken feather (CF) by using sodium dodecyl sulfate (SDS, 0.086–0.5 mmol) in the absence of any catalyst or initiator. Most likely, the hydrophilicity, hydrophobicity, and complex forming properties of chicken feather keratin with surfactant molecules were responsible for efficient grafting of polymers on CF surface. The effect of polymerization conditions, such as monomer concentration, temperature, and time of reaction, on the grafting parameters such as monomer conversion, grafting efficiency, and molar grafting ratio were studied. The described method showed a good potential of using low cost, easily accessible poultry chicken feathers as grafting material and self catalyzing agent for graft copolymerization with vinyl monomers to produce low cost commodity plastic for various end uses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44645.     

Synthesis and properties of new sulfonated poly(p-phenylene) derivatives for proton exchange membranes. I

Several high molecular weight poly(2,5-benzophenone) derivatives were synthesized by high yield nickel-catalyzed coupling polymerization of 2,5-dichloro-4′-substituted benzophenones. The monomers were prepared by Friedel-Crafts catalyzed reaction of 2,5-dichlorobenzoyl chloride and several aromatic compounds. The resulting polymers are organosoluble and show no evidence of crystallinity by differential scanning calorimetry (DSC). The temperatures of 5% weight loss of the polymers via dynamic thermogravimetric analysis in air were above 480 °C. Sulfonation of selected polymers utilizing concentrated or fuming sulfuric acid at room temperature introduced sulfonic acid moieties to the aromatic side group. Activated fluoro aryl groups were also used to generate pendent sulfonated functionalities. The sulfonated polymers were examined for ion exchange capacities, water absorption capacities and proton conductivities. The sulfonated polymers were not good film formers, but could be demonstrated to show high values of proton conductivity in the range of 0.06-0.11 S/cm when supported on glass fabrics or via polymer blending strategies.     

Proton exchange membranes by grafting of styrene–acrylic acid onto FEP by preirradiation technique. II. Physicochemical properties of the membrane and its sulfonated derivatives

Poly(tetrafluoroethylene‐co‐haxafluoropropylene) (FEP)‐g‐styrene–acrylic acid and its sulfonated derivative membranes were prepared by graft copolymerization of styrene–acrylic acid onto FEP by using preirradiation of γ‐ray technique followed by sulfonation. The physiochemical properties such as ion exchange capacity, water uptake, ionic resistance of the grafted membranes, and their sulfonated derivatives were studied as a function of degree of grafting. These membranes on sulfonation gave acid base, indicating property. The membranes gave yellow color in acidic medium and purple color in alkali medium. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2318–2325, 2004     

Polymer electrolyte membranes having sulfoalkyl grafts into ETFE film prepared by radiation‐induced copolymerization of methyl acrylate and methyl methacrylate

Polymer electrolyte membranes (PEMs) containing alkylsulfonic acid grafts can be prepared by radiation‐induced graft copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) into a poly(ethylene‐co‐tetrafluoroethylene) film followed by sulfonation of the MA units in the copolymer grafts using an equimolar complex of chlorosulfonic acid and 1,4‐dioxane (ClSO₃H‐Complex). PEMs with MA/MMA copolymer grafts that are 33%–79% MA units were prepared by preirradiation with a dose of 20 kGy and grafting in bulk comonomers at 60°C. The grafted films are treated with ClSO3H‐Complex to obtain PEMs with ion exchange capacity of 0.36‐0.81 mmol/g (sulfonation degrees of 20%–40%) and proton conductivity of 0.04‐0.065 S/cm. These values can be controlled by changing the MA content the sulfonation occurring at an α‐carbonyl carbon. The PEMs with higher MMA content showed higher durability in water (80°C) and under oxidative conditions (3% H₂O₂) at 60°C. This is because the PMMA grafts in the PEMs have no proton at an α‐carbonyl carbon, which is considered to be a trigger of the degradation of grafting polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Atmospheric plasma‐aided biocidal finishes for nonwoven polypropylene fabrics. I. Synthesis and characterization

Novel biocidal fabrics were synthesized by the graft copolymerization of glycidyl methacrylate (GMA) onto plasma‐treated nonwoven polypropylene (PP) to produce PP/GMA grafts. Atmospheric oxygenated helium plasma was used to enhance the PP fabrics' initiation before GMA grafting. The grafted PP/GMA epoxide group was reacted with β‐cyclodextrin, monochlorotrizynyl‐β‐cyclodextrins, or a quaternary ammonium chitosan derivative [N‐(2 hydroxy propyl) 3‐trimethylammonium chitosan chloride]. Some interesting biocidal agents were complexed into the cyclodextrin (CD) cavity of PP/GMA/CD grafted fabrics. Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and optical and scanning electron microscopies were used to characterize the grafted complexed fabrics. These synthesized biocidal fabrics proved to be antistatic, antimicrobial, and insect‐repelling (see part II of this study). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1900–1910, 2007     

聚丙烯纤维接枝丙烯酸反应条件优化

The optimum conditions of grafting copolymerization reaction of acrylic acid (AA) onto polypropylene (PP) fiber was studied by using benzoyl peroxide (BPO) as initiator. The primary and secondary sequences of the grafting copolymerization reaction conditions was analysed. The results showed that grafting copolymerization reaction was greatly influenced by the temperature, reaction time, concentration of BPO and that of AA in the primary and secondary role as the above sequence. The optimum reaction conditions of gaining higher exchange capacity for the weak acidic cation-exchange fiber are as follows: the grafting temperature 80℃, the reaction time 7h, the concentration of BPO 2% and AA 80%.     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. III. Thermal stability of the membranes

Thermal stability of cation exchange, PFA‐g‐polystyrene sulfonic acid membranes prepared by radiation‐induced graft copolymerization of styrene onto PFA films followed by sulfonation was studied by thermal gravimetric analysis (TGA) and oven heat treatment. The tested samples included original and grafted PFA films as reference materials. All the membranes showed multistep decomposition patterns due to dehydration, desulfonation, dearomatization, and decomposition of the PFA matrix. Investigations of the individual decomposition behaviors showed that the weight loss strongly depends upon the degree of grafting. However, the decomposition temperatures were found to be independent of the degree of grafting. The loss in some selected membrane properties such as ion exchange capacity and water uptake was found to be function of the degree of grafting, temperature, and the time of heat treatment. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1877–1885, 2000     

Radiation‐induced GMA/DMAA graft copolymerization onto porous PE hollow‐fiber membrane

Radiation‐induced graft copolymerization is a powerful technique to prepare a grafted chain with the desired properties pending onto the trunk material. In this work, a polyethylene hollow‐fiber membrane was modified by this technique. The monomers glycidyl methacrylate (GMA) and N,N‐dimethylacrylamide (DMAA) were cografted onto macroporous polyethylene hollow fiber with a grafting degree in the order of 200%. DMAA/GMA cografted membranes were compared to GMA grafted ones for the introduction of an amino acid as a specific ligand. Grafted membranes with a copolymer composition between 0 and 2 DMAA/GMA were prepared by soaking them in solutions of different mixtures of monomers. Copolymers were characterized by FTIR and their composition was estimated by the analysis of the ratio of carbonyl signals. Copolymers with a higher proportion of DMAA showed improved hydrophilic properties and higher conversion rates of epoxy groups on phenyalanine ligands than those of the GMA grafted ones. However, copolymers with a DMAA/GMA ratio higher than 1 showed a detrimental effect on the pure water flux. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1646–1653, 2003     

Studies on the fabrication of strong‐acid/weak‐base amphoteric ion exchange fibers and their adsorption property for amino acids

The strong acid/weak base amphoteric ion exchange fibers with different ratios of acidic and basic groups and different grafting percentages were prepared by grafting styrene and 4‐vinylpyridine onto polypropylene fiber and then sulfonating with chlorosulphonic acid, under various reaction conditions, such as the feed ratio of styrene and 4‐vinylpyridine, monomers concentration, sulfonation temperature, and sulfonation time, swelling time, etc. The produced strong acidic and basic groups are the sulfonic group and the pyridyl group, respectively. Only one sulfonic group is induced into an aromatic ring in most of PP‐g‐St‐4VP and it is located in the para‐position of styrene. The contents of the strong‐acid group and the weak‐base group of the PP‐g‐SO₃H‐Py fibers produced in this work are in the range of 1.98 to 4.22 and 2.33 to 4.24 mmol/g, respectively. The strong acid/weak based amphoteric fibers obtained possess good static adsorption property for basic and acidic amino acids, and they also have a good dynamic adsorption and elution property for amino acids like related strong acid ion exchange fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 418–425, 2004     

Surface modification of mesoporous silica by radiation induced graft polymerization of styrene and subsequent sulfonation for ion-exchange applications

In this study, the fabrication of silica-grafted-sulfonated styrene (S-g-SSt) resin by grafting of styrene onto silanized silica via gamma radiation-induced polymerization and subsequent sulfonation of the grafted styrene is described. The grafting was strongly affected by the reaction conditions; absorbed dose, monomer concentration, and the type of solvent used. The structural analysis of the silica and all the relevant products were carried out by FTIR, SEM, TGA, XRD, and BET. FTIR analysis confirmed the presence of styrene onto silica and subsequent sulfonation. The BET nitrogen adsorption–desorption isotherms indicated that grafting occurs on the surface as well as inside the pores. Finally, the ion exchange capacity (IEC) of the fabricated S-g-SSt was evaluated by ion exchange titrations (back titration method). The IEC was found to be in the range of 0.43–2.97 meq/g depending on the degree of grafting. The facile fabrication method and high IEC value (2.97 meq/g) could lead to potential application of the fabricated S-g-SSt resin in ion exchange resin in waste water treatment and metal recovery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48835.     

Preparation of molecularly imprinted polymer films on monodisperse macromolecular beads

A new and facile technique for preparing homogeneous and highly selective molecularly imprinted polymers (MIPs) films on porous monodisperse poly‐(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) beads (P_GMA‐EDMA beads) has been described: before polymerization, initiator was immobilized on the P_GMA‐EDMA beads' surface by chemical reactivity; then functional monomers and crosslinkers were initiated by the surface‐bound initiator and copolymerized to form MIPs films on the P_GMA‐EDMA beads' surface in the presence of template molecules. The resulting beads were analyzed by FTIR spectroscopy and X‐ray photoelectron spectra. The effects of the initiator amount and copolymerization time on the content of MIPs, and MIPs contents on morphologies and pore properties of the resulting beads were investigated. The results show that the content of MIPs can be adjusted by changing initiator amount or by controlling copolymerization time. The binding experiments indicate that, at lower grafting level, with the increase of MIPs content, the adsorption and recognition capabilities of the resulting beads enhance. When MIPs content increase to 16.75%, the highest adsorption and recognition capabilities are obtained. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Grafting of Methacrylic Acid and Other Vinyl Monomers Onto Cotton Fabric Using Ce (IV) Ion–Cellulose Thiocarbonate Redox System

Graft copolymerization of methacrylic acid (MAA) onto cotton fabric using tetravalent ceric ion (Ce^IV)–cellulose thiocarbonate redox system was investigated under different conditions including pH of the polymerization medium (1–4), ceric sulphate (CS) concentration (4–20 m mole/l), MAA concentration (1%–6%), polymerization time (1/4–2 h) and polymerization temperature (0–70°C). Results obtained indicated that the optimal conditions for MAA grafting onto cotton fabric using the said redox system consisted of: [CS], 20 m mole/l; [MAA], 4%; pH of the medium, 2; time, 2 h; temperature, 60 °C keeping a material-to-liquor ratio at 1:0. Applying optimized conditions to different monomers, namely, acrylic acid (AA), methacrylic acid (MAA), acrylamide (Aam), acrylonitrile (AN), butyl acrylate (BuA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and glycidyl methacrylate (GMA) onto the same substrate, the rates of grafting followed the order:

Preparation of proton exchange membranes based on crosslinked polytetrafluoroethylene for fuel cell applications

We prepared proton exchange membranes by the γ-ray-induced post grafting of styrene into crosslinked polytetrafluoroethylene (PTFE) films and subsequent sulfonation. The degree of grafting was controlled in the range of 7-75% by the crosslinking density of the PTFE matrix as well as the grafting conditions. Under our preparation conditions, the films at the grafting yield of ≥30% were found to produce ion exchange membranes with a homogeneous distribution of sulfonic acid groups. The resulting membranes showed a large ion exchange capacity up to 2.9 meq g⁻¹, which exceeded the performance of commercially available perfluorosulfonic acid films such as Nafion; nevertheless, they appeared to be dimensionally stable in water. These should undoubtedly result from the use of the crosslinked PTFE films as graft substrates and make our ion exchange membranes promising for applications to polymer electrolyte fuel cells.     

Synthesis and characterization of cellulose ion exchangers. I. Polymerization of glycidyl methacrylate,dimethylaminoethyl methacrylate,and acrylic acid with cotton cellulose using thiocarbonate-H2O2 redox system

Polymerization of glycidyl methacrylate (GMA), dimethylaminoethyl methacrylate (DMAEMA) and acrylic acid (AA) with cotton fabric using a cellulose thiocarbonate-hydrogen peroxide redox system as an initiator was investigated under different conditions. This includes the nature and concentration of the initiator and monomer, polymerization time and temperature, and liquor ratio. The percent of polymer add-on is generally favored by increasing monomer and H₂O₂ concentration, as well as duration and temperature of the polymerization, but with the certainty that the percent of polymer add-on follows the following order: GMA > DMAEMA > AA. On the other hand, the percent of polymer add-on increases by decreasing the liquor ratio. Incorporation of Fe²⁺ or Cu²⁺ ion in the polymerization system enhances the percent of polymer add-on significantly. Replacing the H₂O₂ by other oxidants such as Cr⁶⁺ or Mn⁴⁺ is made, and the capability of such cations to expedite polymerization of the said monomers with cotton cellulose is studied. Also studied is the synthesis of cation exchanger via reaction of poly(GMA)-cellulose copolymer with hexamethylene tetramine. Furthermore, the ion exchange characteristics of the cellulosic copolymers obtained with this as well as with other monomers are reported. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1029–1037, 1997     

官能化线性低密度聚乙烯的流变行为及力学性能

利用毛细管流变仪研究了官能化ＬＬＤＰＥ（ＬＬＤＰＥ－ｇ－ＡＡ、ＬＬＤＰＥ－ｇ－ＧＭＡ）的流变行为。结果表明：在高的剪切应力下ＬＬＤＰＥ－ｇ－ＡＡ、ＬＬＤＰＥ－ｇ－ＧＭＡ的表观粘度比纯ＬＬＤＰＥ的小。表明官能化ＬＬＤＰＥ的流动性提高了,其加工性能变好。官能化ＬＬＤＰＥ的表观粘度随接枝单体含量的增加而降低,这说明接枝到ＬＬＤＰＥ分子链土的单体起到了内润滑剂的作用。利用Ｉｎｓｔｒｏｎ１１２１拉力机测试了     

自硫化型丙烯酸酯橡胶的合成

在负离子型乳化剂的存在下,实现了丙烯酸（或甲基丙烯酸）／内烯酸乙酯／烯丙基缩水甘油醚（或甲基丙烯酸缩水甘油酯）的三元乳液共聚合,制得了主链上既带有羧基又带有环氧基的自交联型丙烯酸酯橡胶。用ＩＲ、＾１Ｈ－ＮＭＲ表征了共聚物的结构,用盐酸－丙酮法测定了共聚物中环氧基保留率。考察了多种金属离子、络合剂ＥＤＴＡ用量、交联点单体配体对共聚物凝胶质量分数的影响。