Grafting of styrene onto poly(butyl acrylate) in emulsion

The effect of time, temperature, the concentration of initiator and emulsifier, and the ratio of starting polymer to monomer on the degree of conversion (MC) of styrene and the grafting efficiency (GE) of polystyrene has been investigated. The reaction was initiated with potassium persulphate. It has been found that the degree of conversion of styrene and the grafting efficiency change in opposite directions when plotted as functions of the reaction parameters studied. The graft copolymerization is assisted by short reaction times and weight ratios of poly(butyl acrylate) to styrene greater than unity. The results obtained suggest that higher grafting efficiencies are obtained when the concentration of emulsifier is below its c.m.c. (critical micellar concentration) value. When using two different anionic emulsifiers it has been observed that the effect of initiator concentration on the degree of conversion of styrene and the grafting efficiency is complicated. Both the quantities studied (MC and GE) exhibit extrema in the range of initiator concentration studied (3.7?33.3 × 10^?5 mol dm^?3 of H₂O). No meaningful effect of temperature in the range 60°–90°C or that of dodecyl mercaptan (molecular weight regulator) used in an amount 0–0.4% in relation to poly(butyl acrylate) and styrene has been observed on the MC and GE values.     

Grafting of ethyl acrylate onto monofilament polyester fibers using benzoyl peroxide

Ethyl acrylate was grafted onto monofilament poly(ethylene terephthalate) fibers using benzoyl peroxide as a chemical initiator. Breaking tenacity and densities of grafted fibers decreased while breaking elongation increased with the graft yield. Scanning electron micrographs showed that the fiber geometry and its diameter were not affected by grafting. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1701–1705, 1998     

Elastomeric films from structured latexes

A model structured latex that is capable of forming a self-curable elastomeric film under mild temperature conditions was developed. In this model latex system, a small amount of dimethyl meta-isopropenyl benzyl isocyanate (TMI®) was copolymerized with n-butyl acrylate (BA) onto poly(butadiene-co-styrene) [(P(Bd-S)] seed latex particles. In the final stage of the film formation process, the latex particles coalesce with each other, and interdiffusion of PBA-based polymer chains in the shell layers of adjacent structured particles occurs. At this stage, the isocyanate groups in the P(BA-TMI) shell layer would begin to crosslink by either a moisture-cure reaction via trace amounts of water remaining in the latex film or by a post-added crosslinker that contains amine groups. Improved elastomeric properties of the latex film are expected from this kind of “interphase” crosslinking structure. However, latex films prepared from the model P(Bd-S)/P(BA-TMI) core/shell latexes were cracked and brittle, which was explained by the formation of a highly crosslinked/grafted core/shell interphase zone. Saturation of the residual double bonds in the P(Bd-S) seed latex particles by hydrogenation was found to be an effective way to reduce the development of the interphase zone and the degree of crosslinking during the second-stage polymerization. An elastomeric film with good mechanical and anti-aging properties was formed from this hydrogenated-P(Bd-S)/P(BA-TMI) structured latex. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1143–1152, 1997     

Grafting of end-functionalized poly(tert-butyl acrylate) to poly(ethylene-co-acrylic acid) film

Poly(tert-butyl acrylate) (PtBA) was grafted to the surface of poly(ethylene-co-acrylic acid) (EAA) film and the pendant groups of the tethered PtBA were modified to create chemically tailored surface modifying layers. The carboxylic acid groups in the copolymer film served as the grafting sites for the covalent tethering of end-functionalized PtBA. The progression of these reactions was monitored using attenuated total reflectance (ATR)-FTIR and X-ray photoelectron (XPS) spectroscopies along with static contact angle measurements. By controlling the reaction conditions, the chemical functionality of the grafted layer ranged from tert-butyl ester (EAA-g-PtBA) to carboxylic acid (EAA-g-PAA) and was demonstrated by corresponding changes in wettability. The choice of PtBA as the tethered polymer allows for the subsequent substitution of the tert-butyl ester groups. To demonstrate, a novel procedure was used to replace the tert-butyl ester with N,N-dimethylethylenediamine (DMEDA) to form EAA-g-PDMEDA. These reaction schemes can be used to create tunable surface-grafted layers with various pendant group chemistries.     

In-situ polymerization of n-butyl acrylate in poly(vinyl chloride)

The in situ polymerization of n-butyl acrylate with poly(vinyl chloride) has been studied. Butyl acrylate was polymerized using a peroxydicarbonate initiator and a thiol chain transfer agent in the presence of poly (vinyl chloride) beads suspended in water. The products were examined, after pressing into sheets, for optical clarity and by dynamic mechanical analysis. It was found that if 10% butyl acrylate was peesent in the mixture homogeneous blends were formed but if 15% or more butyl acrylate was present two phase mixtures were formed. If homogeneous blends prepared as above were reswollen in butyl acrylate, and the latter then polymerized, homogeneous blends containing more poly(butyl acrylate) could be prepared. The interaction parameters between both poly(vinyl chloride' and poly(butyl acrylate) and butyl acrylate were estimated by inverse gas chromatography. Using these and an estimate of the polymer/polymer interaction parameter the three component phase diagram could be qualitatively explained.     

Preparation of high solids content poly(n-butyl acrylate) latexes through miniemulsion polymerization

An approach to prepare high solids content latexes (> 50 wt %) is presented. The approach is based on a two-stage polymerization where in the first stage low-to-medium solids content seed latexes with a broad particle-size distribution (PSD) were prepared by semicontinuous miniemulsion polymerization. In the second polymerization stage, the solids contents of the latexes prepared in the previous step were increased to 60–70 wt % using relatively low emulsifier concentrations. The approach was used successfully to prepare fluid- and coagulum-free poly(n-butyl acrylate) latexes up to solids contents of 61 wt % using an emulsifier (sodium lauryl sulfate) concentration of 0.5 wt % based on a monomer. Nonfluid (pastelike) latexes having solids contents higher than 61 wt % were also prepared using this method. As a result, some guidelines related to the required particle-size distribution to produce fluid latexes of higher solids contents are also presented. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1797–1809, 1997     

Effects of compatibilizing agents in poly(n-butyl acrylate)/poly(methyl methacrylate) composite latexes

Graft copolymers with poly(n-butyl acrylate) (PBA) backbones and poly(methyl methacrylate) (PMMA) macromonomer side chains are used as compatibilizing agents for PBA/PMMA composite latexes. The composite latexes are prepared by seeded emulsion polymerization of methyl methacrylate (MMA) in the presence of PBA particles. Graft copolymers were already incorporated into the PBA particles prior to using these particles as seed via miniemulsion (co)polymerization of n-butyl acrylate (BA) in the presence of the macromonomers. Comparison between size averages of composite and seed particles indicates no secondary nucleation of MMA during seeded emulsion polymerization. Transmission electron microscopy (TEM) observations of composite particles show the dependence of particle morphologies with the amount of macromonomer (i.e., mole ratio of macromonomer to BA and molecular weight of macromonomer) in seed latex. The more uniform coverage with the higher amount of macromonomer suggests that graft copolymers decrease the interfacial tension between core and shell layers in the composite particles. Dynamic mechanical analysis of composite latex films indicates the existence of an interphase region between PBA and PMMA. The dynamic mechanical properties of these films are related to the morphology of the composite particles, the arrangement of phases in the films, and the volume of the interphase polymer. © 1997 John Wiley & Sons, Inc.     

Hydrogenation of styrene-butadiene rubber (SBR) latexes

The mechanism and the optimum conditions for the reduction of residual double bonds in styrene-butadiene rubber (SBR) latex by hydrogenating the polybutadiene in the latex form were studied. The hydrogenation involves a copper ion (II)-catalyzed procedure in which diimide hydrogenation agent is generated in situ at the surfaces of latex particles by a hydrazine/hydrogen peroxide redox system. The surface density of the copper ion in particle surfaces was found to be a crucially important parameter in controlling the degree of hydrogenation. The distribution of the double bonds in the latex particles after the hydrogenation was found to be dependent on the particle size and the extent of crosslinking in the particles. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2047–2056, 1997     

Fabrication and apparent kinetic study of poly(methyl methacrylate)/poly(octyl acrylate) and poly(octyl acrylate)/poly(methyl methacrylate) latex interpenetrating polymer networks

Two latex interpenetrating polymer networks (LIPNs) were synthesized with methyl methacrylate (MMA) and octyl acrylate (OA) as monomers, respectively. The apparent kinetics of polymerization for the LIPNs was studied. This demonstrates that network II does not have a nucleus formation stage. The monomers of network II were diffused into the latex particles of network I and then formed network II by in situ polymerization. It indicates that the polymerization of network I obeys the classical kinetic rules of emulsion polymerization. But the polymerization of network II only appears a constant‐rate stage and a decreasing‐rate stage. The apparent activation energies (E_a) of network I and network II of PMMA/POA were calculated according to the Arrhenius equation. The E_a values of POA as network I (62 kJ/mol) is similar to that of POA as network II PMMA/POA (60 kJ/mol). However, the E_a value of PMMA as network II POA/PMMA (105kJ/mol) is higher than that of PMMA as network I (61 kJ/mol). Results show that the E_a value of the network II polymerization is related to the properties of its seed latex. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Grafting of low density poly(ethylene) with butyl acrylate: Synthesis and characterisation

Low density poly(ethylene) was grafted with butyl acrylate using benzoyl peroxide as free radical initiator in an inert atmosphere and toluene as solvent. Various parameters such as reaction time, temperature, initiator concentration and ratio of monomer to polymer were varied to study their effects on percentage of grafting and grafting efficiency of butyl acrylate on to low density poly(ethylene). The graft copolymers were characterised by IR spectroscopy. The change in the solubility behaviour of low density poly(ethylene) due to grafting was studied by turbidometric titration. Thermal stability of graft copolymers was found to be higher than that of LDPE. Intrinsic viscosity data showed an increase in viscosity with increasing grafting percentage.     

Grafting reactions onto poly(organophosphazenes). VI. Thermooxidative stabilization of poly[bis (4-benzylphenoxy)phosphazene] by grafting acrylate polymers containing HALS groups

Poly[bist 4-benzylphenoxy phosphazene] is heated at 200 C in air and the oxidation of the 4-diphenylmethane side substituent to phosphazene-supported benzophenone, benzhydrol, and hydroperoxides is observed. The thermo-oxidative stabilization of the polymer is obtained by light-induced grafting copolymerization of the acrylic acid 2.2.6.6-tetramethyl-piperidin-4-yl ester onto the polyphosphazene substrate. The HALS moieties grafted onto the polyphosphazene films prevent the oxidative modification of the substituents and preserve the polymer against thermal damage. This process, investigated by IR. UV, and EPR spectroscopy, is basically dependent on the amount of HALS groups grafted onto the polyphosphazene matrix and on the composition of the reaction medium used to carry out the grafting process. The comparison between the thermooxidative stabilization process and the corresponding photooxidative stabilization reaction is also discussed.Presented at the 1st Italian Workshop on Cyclo- and Poly(phosphazene) Materials. Lebruary 15–16, 1996, at the CNR Research Area in Padova, Italy.     

Grafting of butyl acrylate onto gelatin in a water-isopropanol medium

Graft copolymerization of butyl acrylate onto gelatin using potassium persulphate initiator was studied in a water-isopropanol medium. The crude graft copolymers were soxhlet extracted with acetone to remove the loosely bound ungrafted homopolymer. The influence of a number of experimental factors such as effect of time, monomer concentration, initiator concentration, backbone concentration and temperature on the graft copolymerization of gelatin were investigated.     

Grafting of partially hydrolysed poly(methyl methacrylate) onto mesylated cellulose acetate

A new synthetic route to cellulose graft polymers by nucleophilic displacement of mesylate groups from mesyl cellulose acetate (MCA) by the polystyrylcarboxylate anion has been recently reported by us. This approach to cellulosic graft polymers overcomes the drawbacks of the radical polymerization methods and allows for precise control of parameters such as the molecular weight and molecular weight distribution of the grafted side chains, higher degree of substitution on the cellulose backbone, the number and nature of grafted side chains and overall better control and reproducibility of the grafting process. In this report, partially hydrolysed poly(methyl methacrylate) was successfully grafted on to mesylated cellulose acetate in excellent yields by nucleophilic displacement of mesylate groups in less than 60 min at 75°C.     

Optimized conditions for the grafting reaction of poly(methyl acrylate) onto rubberwood fiber

Graft copolymerization of poly(methyl acrylate) (PMA) onto rubberwood fiber (RWF) was carried out by free radical initiation. Hydrogen peroxide and ferrous ions were used as an initiator system. Effects of various parameters (reaction temperature and reaction time, as well as hydrogen peroxide, ferrous ammonium sulfate and monomer concentrations) on the grafting percentage were investigated. A high percentage of grafting was achieved when optimum reaction conditions were used. The optimum temperature of the reaction was determined to be about 55 °C and the reaction time was 120 min. The optimum concentration of H₂O₂ was 0.03 M and the amounts of Fe²⁺ and MA were 0.4 mmol and 0.05 mol, respectively. The PMA homopolymer was removed from the graft copolymer by Soxhlet extraction using acetone. The presence of PMA on the fiber was confirmed by FT-IR spectroscopy and gravimetry. The surface morphology of the poly(methyl acrylate)-graft-(rubberwood fiber) was studied by means of scanning electron microscopy. Copyright © 2004 Society of Chemical Industry     

聚丙烯酸正丁酯增韧酚醛泡沫塑料的研究

考察了催化剂、反应时间等因素对合成聚丙烯酸正丁酯改性酚醛树脂的影响，并用动态力学的方法研究了改性酚醛树脂的固化行为，表明聚丙烯酸正丁酯的引入可加快酚醛树脂的固化。采用正交实验的方法，得到室温下制备改性酚醛泡沫的配方。对所得酚醛泡沫的压缩强度、导热系数等测定及泡孔形貌的观察表明，在保证酚醛泡沫绝热性能不变的前提下，聚丙烯酸正丁酯可有效地改善酚醛泡沫的脆性。     

Synthesis of composite latexes of polyhedral oligomeric silsesquioxane and fluorine containing poly(styrene‐acrylate) by emulsion copolymerization

A novel octavinyl polyhedral oligomeric silsesquioxane/fluorine containing poly (styrene‐acrylate) (OvPOSS/FPSA) composite latexes with star‐type structure was synthesized by emulsion copolymerization. The structures of OvPOSS/FPSA composite materials were characterized by Fourier Transform Infrared, which indicated that OvPOSS could be grafted onto FPSA latexes by emulsion copolymerization. Transmission electron microscopy images disclosed that FPSA latexes possessed obvious core–shell structure and OvPOSS/FPSA composite latexes probably present star‐shape structure. Dynamic light scattering data indicated that the average diameter of OvPOSS/FPSA was slightly larger than that of FPSA, which was probably attributed to the encapsulation of POSS cages. Atomic force microscopy photos illustrated that the grafting reaction had increased the roughness of the composite surface. The water contact angle of composite films was found increasing as the percentage of OvPOSS increasing. Thermogravimetric analysis curves demonstrated that the OvPOSS/FPSA composite films displayed much better thermal stability than that of FPSA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43455.     

Synthesis and characterization of butyl acrylate/methyl methacrylate/glycidyl methacrylate latexes

The butyl acrylate (BA)/methyl methacrylate (MMA), and glycidyl methacrylate (GMA) composite copolymer latex was synthesized by seeded emulsion polymerization technique taking poly(methyl methacrylate) (PMMA) latex as the seed. Four series of experiments were carried out by varying the ratio of BA : MMA (w/w) (i.e. 3.1 : 1, 2.3 : 1, 1.8 : 1, and 1.5 : 1) and in each series GMA content was varied from 1 to 5% (w/w). The structural properties of the copolymer were analyzed by FTIR, ¹H‐, and ¹³C‐NMR. Morphological characterization was carried out using transmission electron microscopy (TEM). In all the experiments, monomer conversion was ～99% and final copolymer composition was similar to that of feed composition. The incorporation of GMA into the copolymer chain was confirmed by ¹³C‐NMR. The glass transition temperature (T_g) of the copolymer latex obtained from the differential scanning calorimetry (DSC) curve was comparable to the values calculated theoretically. With increase in GMA content, particles having core‐shell morphology were obtained, and there was a decrease in the particle size as we go from 2–5% (w/w) of GMA. The adhesive strength of the latexes was found to be dependent on the monomer composition. With increase in BA : MMA ratio, the tackiness of the film increased while with its decrease the hardness of the film increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fluorinated poly(meth)acrylate: Synthesis and properties

Due to good reactivity of fluorinated (meth)acrylates with other monomers or polymer segments, fluorinated poly(meth)acrylates possess more economical and convenient synthesis routes than other fluoropolymers. This feature article initially summarizes different types of fluorinated (meth)acrylates, which can be divided into fluorinated alkyl (meth)acrylates and fluorinated aryl (meth)acrylates. Subsequently, various approaches for synthesizing fluorinated poly(meth)acrylates including random, block, graft or star copolymers are described. Conventional free radical polymerization can be used in synthesizing random copolymers, while controlled/“living” radical polymerization can provide well-defined copolymers with accurate control over molecular weight and special structures as expected. In particular, introduction of fluorinated components into as-prepared copolymers offers an alternative route to synthesize fluorinated poly(meth)acrylates which are difficult to be obtained directly via polymerization. The incorporation of fluorine can confer unique and highly desirable properties to poly(meth)acrylates such as low surface energy, thermal stability, chemical and weather resistance, low refractive index, and self-organization characteristics. Such properties are described in great details based on many recent articles.     

GMA/St多组分单体熔融接枝高全同聚1-丁烯

采用Haake转矩流变仪研究了甲基丙烯酸缩水甘油酯(GMA)-苯乙烯(St)多组分单体熔融接枝高全同聚1-丁烯(iPB).考察了温度,过氧化二异丙苯(DCP),GMA,St用量对接枝的影响.结果表明:在180℃下,DCP用量为0.8 phr时,接枝率最高;DCP用量一定时,随着GMA用量增加,接枝率增加,熔体流动速率减...     

ARGET ATRP法合成聚氯乙烯接枝丙烯酸丁酯共聚物

以不稳定氯含量高的聚氯乙烯（U-PVC）和氯乙烯-溴代异丁酸烯丙酯共聚物（PVC-co-ABrMP）为大分子引发剂,使用电子转移催化再生原子转移自由基聚合（ARGET ATRP）进行丙烯酸丁酯（BA）的溶液接枝共聚。在固定CuCl₂：三（2-吡啶甲基）胺：辛酸亚锡（摩尔比）时,当CuCl₂用量（相对于氯乙烯链节数）小于0.1%时,BA转化率随CuCl₂用量增加而明显增加;辛酸亚锡与CuCl₂摩尔比大于50时,辛酸亚锡用量对聚合速率的影响较小;相同催化体系用量下,采用PVC-co-ABrMP为引发剂,可获得更高的BA转化率。通过PVC-co-ABrMP酯基水解得到PBA支链,其分子量分布指数为1.29,符合“活性”自由基聚合的特征。接枝PBA对PVC有明显的内增塑效果,PBA摩尔分数为32.75%的PVC-g-BA的玻璃化温度为8.34℃。