The polymerization of acrylamide initiated with CE(IV) and KMNO4 redox systems in the presence of glycine

Glycine-Ce(IV) salts and −KMnO₄ initiator systems were used for the polymerization of acrylamide, resulting in water-soluble polyacrylamide, which contains amino acid end groups. The dependence of polymerization yields and molecular weights of polymers on the mole ratio of acrylamide monomer to glycine, the polymerization time, the temperature, and the concentration of sulfuric acid were investigated. The decrease in the mole ratio of acrylamide to glycine resulted in a decrese in the molecular weight, and an increase in the yield of acrylamide polymer, which contains a glycine end group. With increasing acid concentration of the polymeric solution, the polymerization yield and the molecular weight of polymer decrease. Ce(IV) and Mn(IV) reduced to Ce(III) and Mn(II) in the polymerization reaction. The amounts of Ce(III) and Mn(II) bound to polymer were determined. The composition of the polymerization product was investigated and a bimodal character of the molecular weight distribution was observed. The mechanism of this phenomena is discussed. © 1996 John Wiley & Sons, Inc.     

高分子表面活性剂存在下超声辐照引发苯乙烯乳液聚合的研究

采用高分子表面活性剂(CMC-A9)和十二烷基硫酸钠(SDS)做乳化剂,用超声辐照乳液聚合方法制备了相对分子质量高(>106)的寡链聚苯乙烯纳米粒子。研究结果表明,在适当的反应条件下,CMC-A9的加入使反应速率大大提高,反应60min单体转化率能达到85%,制得直径30～60nm的聚苯乙烯胶乳粒子,乳胶粒子中含平均分子链数为3～20。CMC-A9或SDS质量浓度提高,能降低乳胶粒径和乳胶中所含的平均分子链数,增加聚合物相对分子质量。超声波输出功率对乳胶粒径影响不大。     

Distribution of end groups and comonomer of the acrylonitrile-vinyl acetate copolymer

The number average molecular weight and strong acid end groups (SAG) of fractionated polymers were measured for the acrylonitrile-vinyl acetate copolymers (93:7 in weight), which were prepared by continuous polymerization in aqueous medium with the persulfate-bisulfiteion redox system. Average number of SAG per polymer molecule was nearly 1 for fractionated portions of the polymers prepared under the polymerization conditions of water/monomer ratio in the range 4.0–2.5 in weight. No marked difference existed in comonomer content in fractions of these polymers. For unfractionated polymers prepared under the conditions of water/monomer ratio varied from 4.0 to 1.75, average number of SAG was roughly 0.8–1. The proportion of sulfoxy end groups to SAG was estimated to be roughly from 0.5 to 0.6 and increased slightly with increased bisulfite/persulfate ratio. Based on the above results, disproportionation and transfer to bisulfite-ion are considered to be the main processes of termination of polymer radicals in the studied range of polymerization conditions.     

Preparation of acrylic/acrylate copolymeric surfactants by emulsion polymerization used in pesticide oil‐in‐water emulsions

In this work, acrylic/acrylate copolymeric surfactants, which can be used in the preparation of pesticide oil‐in‐water emulsions (EW), were synthesized by emulsion polymerization, using potassium persulfate (K₂S₂O₈) as an initiator, dodecyl mercaptan (DDM) as a chain transfer agent at the temperature range of 82–85°C. When the weight ratio of monomers was m(butyl acrylate) : m(methyl methacrylate) : m(acrylic acid) = 4 : 4 : 1.6 and the dosage of DDM was 2% (percentage of monomer mass), the prepared acrylic/acrylate copolymeric surfactants had a number‐average molecular weight of 2.5 × 10⁴ and exhibited good stability for pesticide EW. The carboxylic group distribution studies show that only the surface carboxylic groups make dispersed pesticide oil droplets more stable. The acrylic/acrylate copolymeric surfactants prepared by shot‐monomer had the most surface carboxylic group distribution (46.6%). To obtain greater surface carboxylic group distribution, maleic anhydride (MA) was used to modify the polymer system. Adding 2% MA (percentage of monomer mass) to the polymerization system, the surface carboxylic groups were increased 12% over unmodified acrylic/acrylate copolymeric surfactants. Compared with traditional pesticide EW, the avermectin EW prepared with acrylic/acrylate polymeric surfactant had much better stability. Meanwhile, its pesticide effect was similar to that of a control (1.8% abamectin emulsifiable solution). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Superparamagnetic latex synthesized by a new route of emulsifier‐free emulsion polymerization

The aim of this study was to design polymeric nanospheres containing magnetic nanoparticle which could display superparamagnetic behavior and thus find application in allied fields. First magnetite nanoparticles were synthesized with coprecipitation method and then their stable acidic dispersion was prepared without surfactant and dropped into the polymerization system during a certain time interval after the polymerization started. The effects of time at which the magnetic sol was added into polymerization system on latex size and stability, average molecular weight of polymer were examined in the case of two different monomer concentrations. Extensive characterization by transmission electron microscopy, dynamic light scattering, thermal gravimetric analysis and magnetic measurements shows that when the magnetic sol was dropped during earlier time of polymerization at stage 1, the latex size, average molecular weight of polymer, thermal stability of polymeric composite, and saturation magnetization reduced, whereas polydispersity of size and molecular weight increased because of the reaction between persulfate and naked surface of magnetite at the aqueous phase. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photopolymerization of N,N-Didodecyl- N-methyl-N-ethylmethacrylate ammonium chloride,a reverse micelle forming surfactant

A detailed study of the photopolymerization of N,N-didodecylmethylethylmethacrylate ammonium chloride, a reverse micelle forming surfactant, is presented. The polymerization was photochemically initiated at 350 nm using AIBN and p-AIBN as initiators. However, the polymerization could also be initiated through direct excitation of the methacrylate group. High rates of polymerization resulted because of the organization of the monomer in reverse micellar assemblies. The molecular weights of the polymer decrease with increasing initiator concentration and are always larger than the molecular weight of the reverse micelle. The properties of the monomeric reverse micellar system are compared with those of the polymeric system and show that the dynamic character of the reverse micellar system can be lowered upon polymerization. The properties of the polymeric aggregates, however, differ if a given amount of water is solubilized before or after polymerization. The mean aggregation number of the monomeric and polymeric aggregates as well as the aggregation behaviour of both systems are compared. This comparison suggests that a polymeric aggregate consists of more than one polymer chain.     

Synthesis of well‐defined comblike hydroxy‐functionalized atactic polystyrene promoted by metallocene/tin/poly(phenyl glycidyl ether)‐co‐formaldehyde

Well‐defined comblike atactic polystyrene functionalized with hydroxyl groups was synthesized via living/controlling radical polymerization promoted by metallocene complexes in the presence of poly(phenyl glycidyl ether)‐co‐formaldehyde as the initiator and Sn as a reducing agent. The effect of the polymerization conditions, such as the ratio of initiator to monomer, temperature, and polymerization time, and the structure of the metallocene complex on the polymerization process were investigated. The resulting polymers were characterized by gel permeation chromatography, multiangle laser light scattering, ¹H‐NMR, and ¹³C‐NMR. The results show that the polymer had a narrow molecular weight distribution in the range 1.1–1.4 and the number‐average molecular weight of the polymer linearly depended on the monomer conversion within the polymerization timescale, which confirmed that living radical polymerization characteristics prevailed in the polymerization process. Both the number of arms and the number of hydroxyl groups in each polymer molecule were about four, which suggested that they arose from the epoxy functional groups of the initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dual stimuli-responsive polymers derived from α-amino acids: Effects of molecular structure,molecular weight and end-group

Four kinds of well defined poly(N-methacryloyl-L-amino acid)s were prepared via reversible addition fragmentation chain transfer polymerization. The effects of molecular structure, molecular weight, and end-group on their responsive properties in water were investigated. We found that the monomer structure is critical for the polymer to exhibit stimuli-responsive properties in water; only polymers derived from aspartic acid showed defined dual thermo- and pH-responsive properties. To study the effects of molecular weight and end group on the lower critical solution temperature behavior of poly(N-methacryloyl-L-β-isopropyl aspartic acid) (PMAIPAC), a series of PMAIPAC homopolymers with controlled molecular weights and narrow polydispersities were prepared and treated with excess radical initiators to give defined end groups. The cloud point of PMAIPAC was found to increase with the increase of solution pH, due to the ionization of carboxylic acid groups, and decrease with the increase of molecular weight. The structure of end groups also affects the cloud point of PMAIPAC particularly for low molecular weight samples at low pH.     

Synthesis and characterization of clay dispersed polystyrene nanocomposite via atom transfer radical polymerization

Finely well‐defined polystyrene nanocomposites were prepared by ATRP method in bulk at 110°C using organically modified montemorillonite, cloisite 30B. The living nature of ATRP reaction was employed to in situ synthesize tailor‐made polystyrene nanocomposite with narrow molecular weight distribution and controlled molecular weight polystyrene chains. The amount of clay loading and time of swelling of clay in the monomer before polymerization were proved to have a positive effect on polymerization rate and also broadened the molecular weight destribution. The gas chromatography (GC) results showed the linear increase of Ln(M₀/M) versus time, which indicates the controlled/living polymerization in the presence of nanoclay. Another confirmation of the living nature of the polymerization was linear elevation of molecular weight against monomer conversion concluded from gel permeation chromatography (GPC) data. X‐ray diffraction analysis showed the interlayer spacing of nanoclay platelets as well as the exfoliated clay morphology in the nanocomposite samples. Transfer electron microscopy (TEM) revealed the exfoliated morphology of the in situ prepared nanocomposite as opposed to conventional solution‐blending technique which resulted in an intercalated structure. The effect of nanoclay on acceleration of polymerization was proved by GC and GPC; similarly, Fourier transform infrared spectroscopy (FTIR) was used to discuss the reasons of such a rate acceleration. A shifting in the wave number of characteristic bonds of nanoclay after polymerization mostly in the case of O H and Si O bonds, revealed the interaction between polymer chains and clay layers which resulted in an accelerated polymerization process. The living nature of polymeric chains was more elucidated by FTIR data. Atomic force microscopy (AFM) images also confirmed the proper dispersion of nanoparticles in the polymer medium. POLYM. COMPOS., 31:1829–1837, 2010. © 2010 Society of Plastics Engineers     

单环戊二烯基钛类茂金属催化剂的应用

综述了限制几何构型茂金属(单环戊二烯基钛类茂金属)催化剂在烯烃聚合方面的应用,包括乙烯/链烯烃共聚合,长链α-烯烃和降冰片烯的共聚,含乙烯端基大分子单体的共聚,乙烯和苯乙烯的聚合以及高分子量的无规聚丙烯的合成。研究表明,单环戊二烯基允许各种单体的插入,环戊二烯上的取代基团及配体基团的引入,影响催化烯烃聚合活性,控制聚合物的分子量和聚合分散度。     

Preparation of hyperbranched polymers through ATRP of in situ formed AB* monomer

The self‐condensing vinyl polymerization of an AB* monomer formed in situ by atom transfer radical addition from divinylbenzene (DVB) and (1‐bromoethyl)benzene (BEB) using atom transfer radical polymerization technique was studied. The catalyst concentration has a dramatic effect on polymerization. To study the polymerization mechanism and to achieve high molecular weight polymer, the polymerization was carried out in bulk with a catalyst to monomer ratio, 2,2′‐bipyridine to DVB, of 0.2 at 90°C. Proton nuclear magnetic resonance (¹H NMR) spectroscopy and size‐exclusion chromatography coupled with multiangle laser light scattering were used to analyze the polymerization aliquots and the obtained polymer. The intrinsic viscosities of the prepared polymers were also measured. Experimental results, from the comparison of the apparent molecular weights measured by size‐exclusion chromatography with the absolute values measured by multiangle laser light scattering as well as viscosity measurements, indicate the existence of hyperbranched structures in the prepared polymers. In sharp contrast to hyperbranched polymers from AB* monomer preprepared, hyperbranched ploy(divinylbenzene) prepared at equimolar amount of DVB and BEB has numerous residual pendant vinyl groups rather than only one double bond at its focal point. The hyperbranched polymers show relatively narrow molecular weight distribution (2.13–3.77) and exhibit excellent solubility in common organic solvents such as acetone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 850–856, 2006     

Effects of SBA-15 and its content on MMA solution polymerization and PMMA composites

An ordered mesoporous material, such as SBA-15 was considered as a promising reinforcement agent for polymeric materials due to its large surface area and uniform pore structure. In this paper, poly(methyl methacrylate) (PMMA)/SBA-15 composites were prepared by in situ free-radical solution polymerization of MMA in the presence of SBA-15. The effects of SBA-15 content on solution polymerization and the properties of the final polymer composite were investigated. The PMMA molecular weight and its distribution in PMMA/SBA-15 composites were determined by gel permeation chromatography. Fourier-transform infrared spectra, X-ray diffraction, thermal gravimetric analysis (TGA), differential scanning calorimeter and dynamic mechanical analysis were used to characterize the structure and properties of the composites. The morphology of the composites was observed by scanning electric microscopy (SEM) and transmission electron microscopy (TEM). The results showed that the monomer conversion dropped off, but the polymer average molecular weight increased upon the introduction of SBA-15 into solution polymerization process. When compared with pure PMMA, the storage modulus of the composites was improved and the highest improvement was acquired at 1 wt% of SBA-15, based on the monomer feed content. The glass transition temperatures of the composites were increased slightly. TGA results confirmed that the thermal stability of the composite was not influenced much and a higher degree of terminal vinyl groups was formed in the product of polymerization. SEM and TEM images indicated that SBA-15 particles were incorporated into the polymer matrix.     

Coumarin end-capped polystyrene by ATRP and photodimerization reaction

Summary New coumarin-end-capped polystyrenes have been prepared using functional initiators by atom-transfer radical polymerization (ATRP). In the first case, the photosensitive initiator, 7-chloroacetoxy-4-methyl-coumarin, was prepared. Then the styrene was initiated by 7-chloroacetoxy-4-methyl-coumarin in the presence of a CuBr/bipyridine. The functionalization of the polymers was nearly quantitative, the molecular weight and structure were well controlled by adjusting the monomer/initiator molar ratio, polymerization temperature and time. At high monomer conversion, the polydispersity index of polymer was about 1.40. These coumarin-end-capped polystyrenes underwent [2+2] cycloaddition reaction under UV irradiation in film state. After irradiation the molecular weight and polydispersity index of polystyrene both increased, but the maximum molecular weight was less than the double of original one. It means that the photodimerization reaction was not complete throughly in film state for the diffusion of coumarin groups was blocked by polymeric chain entanglement.     

非极性混合介质中分散聚合法制备聚乙烯基吡咯烷酮

以乙烯基吡咯烷酮(NVP)为单体,环己烷的混合溶剂为分散介质,AIBN为引发剂,SEBS为分散剂,采用分散聚合的方法制备了分散性能好、粒径为1μm左右、热稳定性较好的聚乙烯基吡咯烷酮。考察了单体含量、引发剂用量、分散剂用量对分散聚合反应的影响。结果表明,转化率和分子量均随单体含量增加而增大,随引发剂的量的增大而减小;且在单体含量为30%、AIBN的用量为0.5%,分散剂用量为10%时,所合成的聚合物分子量最大。     

The research of preparation of polyvinyl acetate with lower polydispersity index

In this study, the way of preparing polyvinyl acetate (PVAc) with lower polydispersity index (PDI) was studied. By adding small amount of monomer with polar group, such as acrylic acid (AA), α-methacrylic acid (MAA), or acrylamide (AM), as modulation monomer, the polymerization was carried out at 65°C with a mechanical agitator using AIBN as initiator under N₂ atmosphere. Effects of the mol ratio of modulation monomer/VAc and structure of the modulation monomer on the polymerization conversion, the molecular weight and molecular weight distribution of the obtained polymers were investigated through ¹H NMR, gravity method, and gel permeation chromatography. The results show that by adding modulation monomer into the reactive system the PVAc with lower PDI could be got. With the increase of the modulation monomer amount, the conversion and the molecular weight decrease, and the PDI of the obtained polymer is lower. When the mol ratio of AA/VAc is 3 : 100, the PDI of the obtained polymer is 1.84. When the mol ratio of AM/VAc is 1 : 100, the PDI of the obtained polymer is 1.68, which is narrower than that without AM. All researches we have done laid a foundation for further study. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

间歇式乳液聚合法制备超支化聚丙烯酸丁酯

以丙烯酸丁酯为单体,二乙烯基苯为支化剂,十二硫醇为链转移剂,通过间歇式乳液聚合法成功制备了一系列高转化率的聚丙烯酸丁酯超支化聚合物。通过核磁共振对其结构进行了表征,同时还对聚合物乳液粒径及其分布,超支化聚合物的溶解性、支化度、相对分子质量及相对分子质量分布进行了研究。结果表明:超支化聚合物分子结构中含有丙烯酸丁酯、二乙烯基苯和十二硫醇;聚合物乳液粒径较小,粒径分布较窄;超支化聚合物在有机溶剂中具有良好的溶解性;随着支化剂用量的增加,聚合物支化度增加,相对分子质量降低,相对分子质量分布变窄;随着链转移剂用量的增加,聚合物支化度增加,相对分子质量分布变窄。     

Highly efficient interpenetrating polymerization of styrene and 4‐vinylpyridine with poly(ethylene terephthalate) using benzoyl peroxide

A polymerization method for the preparation of an interpenetrating network polymer with poly(ethylene terephthalate) is reported. Two types of monomer, styrene and 4‐vinylpyridine, were chosen as hydrophobic and hydrophilic representatives, respectively, in order to show the versatility of this polymerization method. The polymer‐immobilized poly(ethylene terephthalate) samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy and X‐ray photoelectron spectroscopy. The immobilization efficiency of styrene as a function of reaction temperature, monomer‐to‐initiator molar ratio, reaction time, addition of solvent, surface hydrophilicity and immersion in initiator was studied. The maximum immobilization percentage of styrene reaches 111%. The immobilization efficiency is proportional to polymer molecular weight and sample thickness. Based on these results, this strategy is shown to be an efficient, versatile method for preparing interpenetrating network polymers and can be used as a means to modify the structures and properties of polymeric substrates. © 2013 Society of Chemical Industry     

Synthesis of chemically amplified photoresist polymer containing four (Meth)acrylate monomers via RAFT polymerization and its application for KrF lithography

KrF photoresist polymers (PASTMs) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Four (meth)acrylates with lithographic functionalities including styrene (St), 4-acetoxystyrene (AST), 2-methyl-2-adamantyl methacrylate (MAMA), and tert-butyl acrylate(TBA) were used as monomer components and 2-methyl-2-[(dodecylsulfanylthiocarbonyl) sulfanyl]propanoic acid (MDFC) was used as RAFT agent, varying the RAFT content could modulate molecular weight. Fourier-transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H NMR) indicated that the synthesis was successful. Gel permeation chromatography (GPC) showed that the molecular weight decreased with the increased content of MDFC, and all the polymers possessed weight-average molecular weight below ten thousand and polydispersity less than 1.32. Thermogravimetric analysis (TGA) characterized the thermal properties, the results implied that initial thermal decomposition temperature reached 200 °C, which could satisfy the lithography process. Differential scanning calorimetry (DSC) showed that the Tg decreases with molecular weight. The RAFT polymerization kinetics plots demonstrated that the polymerization was first-order, the number-average molecular weights of the polymers with relatively low polydispersity index values increased with total monomer conversions indicating that the concentration of growing radicals was constant throughout the polymerization process. The narrow molecular weight distribution and composition uniformity of the polymers prepared by RAFT polymerization could be beneficial for lithography, after alcoholysis, lithography evaluation under KrF lithography showed that this homogeneous polymer photoresist exhibited better space and line (S/L) pattern with resolution of 0.18 μm according to the SEM image.     

高吸水树脂对崩解型聚苯乙烯性能的影响

实验采用乳液聚合法合成了一系列单体组成和吸水倍率不同的高吸水树脂。选取部分吸水树脂与苯乙烯、表面活性剂组成聚合体系，用过氧化苯甲酰引发进行原位共混聚合，制备了遇水崩解型聚苯乙烯。同时，考察了吸水树脂的种类、添加量、吸水倍率和聚苯乙烯的摩尔质量对材料崩解性的影响。研究发现：吸水树脂添加量越大，吸水倍率越高，聚苯乙烯摩尔质量越小，越有利于材料的崩解。当吸水树脂中含有强亲水性基团时，虽然其吸水倍率没有显著提高，但却能明显改善共混物的崩解性。     

Kinetics study of an acrylic tetrapolymer: Poly(IBMA–MMA–MAA–TBMA)

In this study, the polymerization kinetics and the molecular structure of the tetrapolymer poly[isobornyl methacrylate (IBMA)–methyl methacrylate (MMA)–methacrylic acid (MAA)–tert‐butyl methacrylate (TBMA)] were investigated. The relationships among the tetrapolymer composition, monomer conversion, and reaction time were studied. Kinetic equations of the four‐component copolymerization related to the mean sequence length, the run number, the reactivity ratio, and the monomer concentration were derived. The mean sequence length of the monomer IBMA increases with the reaction time and monomer conversion. However, those of the other three monomers remain an insignificant variation. Furthermore, the run number decreases rapidly at the end of polymerization. These results suggest that the slow polymerization rate of IBMA is due to its bulky side group. The mean sequence lengths of IBMA, MMA, MAA, and TBMA at the end of polymerization are 1.772, 1.304, 1.169, and 1.229, respectively. On the other hand, the run number of the prepared tetrapolymer is 70.25. The results of the mean sequence length, run number, and the single glass transition temperature suggest that the prepared tetrapolymer is a random copolymer. The molecular weight distribution of the prepared tetrapolymer is significantly affected by polymerization conditions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 853–863, 2001