Photocrosslinking of acrylated natural rubber

Photocrosslinkable elastomers with pendent acrylate groups have been synthesized by ringopening reaction of epoxidized natural rubber with acrylic acid. The kinetics of the acrylation reaction has been studied by infrared spectroscopy and shown to obey a simple first-order law. The acrylated natural rubber undergoes a fast crosslinking-polymerization when it is exposed to UV radiation in the presence of an aryl ketone photoinitiator, with formation of a tridimensional polymer network within a few seconds. The cure kinetics has been studied in real time by monitoring the disappearance of the IR absorption of the grafted acrylate double bond. The rate of polymerization was found to increase linearly with the degree of acrylation of the rubber, reaching values up to 3 mol kg^?1 s^?1. The isoprene double bond, which is inactive in virgin natural rubber, also undergoes polymerization upon UV exposure when epoxy or acrylate groups are present. The UV-cured polymer becomes totally insoluble in the organic solvents and exhibits remarkable mechanical properties, such as hardness, flexibility, and impact resistance. The gel fraction and the hardness were both shown to increase with the degree of acrylation and with the cure extent. © 1993 John Wiley & Sons, Inc.     

Photocrosslinking of functionalized rubber. III. Polymerization of multifunctional monomers in epoxidized liquid natural rubber

Different types of tridimensional polymer networks have been synthesized by photoinitiated polymerization of difunctional monomers blended to an epoxidized natural rubber. The crosslinking reaction was followed by infrared spectroscopy and shown to proceed extensively within less than 1 s for the cycloepoxy, vinyl ether, and acrylate monomers used. By acting as a plasticizer, the monomer was found to markedly accelerate the ring-opening polymerization of the epoxy groups of the rubber chain. Cationic polymerization continues to proceed effectively after the UV-exposure, until total consumption of the epoxy groups. The nature of the comonomer has a strong influence on the properties of the crosslinked rubber. Low-modulus polymers were obtained with divinyl ether monomers, while hard but still flexible films were obtained with dicycloepoxy and diacrylate monomers. © 1996 John Wiley & Sons, Inc.     

镶嵌型乳胶粒子的合成

以苯乙烯、甲基丙烯酸甲酯、丙烯腈等单体或它们的混合物为硬单体,天然胶乳为弹性组分,经多步种子乳液聚合法制得了在天然胶乳的粒子上镶嵌硬聚合物相的互穿网络型乳胶粒子.考察了十二烷基硫酸钠、十二烷基苯磺酸钠、壬基酚聚氧乙烯醚、油酸等乳化体系,过硫酸钾、过氧化苯甲酰热引发体系及异丙苯过氧化氢-四乙烯五胺、叔丁基过氧化氢-四乙烯五胺等氧化还原引发体系对聚合反应的影响.研究了交联剂用量对互穿结合率、溶胶含量的影响及溶胀时间、硬单体组成、乳化剂种类对乳胶粒子形态的影响,确定了适宜的聚合配方和工艺条件.透射电镜观察乳粒形态结果表明,单一使用极性或非极性单体,仅得到核-壳结构乳液,而采用不同极性单体复合、溶胀、互穿,得到的是镶嵌硬聚合物型乳粒结构.     

Depolymerization and ionic conductivity of enzymatically deproteinized natural rubber having epoxy group

Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (T_g) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH₄)₂S₂O₈ in the presence of propanal. The resulting liquid epoxidized rubber (M_n≈10⁴) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li⁺ as an ionic conducting medium, that is, solid polymer electrolyte.     

Development of a rubber elongation factor, surface-imprinted polymer-quartz crystal microbalance sensor, for quantitative determination of Hev b1 rubber latex allergens present in natural rubber latex products

Molecularly imprinted polymers (MIPs) for screening to detect rubber latex allergens (Hev b1) in natural rubber based products were designed as artificial recognition polymeric materials coated onto a quartz crystal microbalance (QCM). The polymers were prepared using a stamp imprinting procedure after mixing optimum amounts of methacrylic acid–vinylpyrrolidone–dihydroxyethylene bisacrylamide and Hev b1 latex allergen proteins, obtained from rubber gloves. QCM measurements showed that the resulting polymer layers after removal of the proteins used in their preparation could incorporate structures and features down to nanometer scale of protein templates into the imprinted polymer much better than a non-specific control polymer under controlled sensor conditions and an optimized polymerization process. This selective polymer but not the non-selective polymer clearly distinguished between the latex allergen Hev b1 and proteins such as lysozyme, ovalbumin and bovine serum albumin, with a selectivity factor of from 2 to 4, and the response of the rubber elongation factors by an astonishing factor of 12. The imprinted cavities recognized specific binding sites and could distinguish among related hevein latex allergenic proteins isolated from fresh natural rubber latex; Hev b1, Hev b2, and Hev b3 with a selectivity factor of from 4 to 6. The different QCM measurements obtained presumably reflected slightly different conformations and affinities to the MIP binding sites. The sensor layers selectively adsorbed Hev b1 within minutes in amounts ranging from 10 to 1500 μg L⁻¹ and with a detection limit of 1 μg L⁻¹. This work has demonstrated that this new sensor provides a fast and reliable response to natural rubber latex protein, even after being extracted from the matrix of rubber gloves.     

Role of Functional Groups in the Monomer Molecule on the Radical Polymerization in the Presence of Graphene Oxide. Polymerization of Hydroxyethyl Acrylate under Isothermal and Non-Isothermal Conditions

Functional groups in a monomer molecule usually play an important role during polymerization by enhancing or decreasing the reaction rate due to the possible formation of side bonds. The situation becomes more complicated when polymerization takes place in the presence of graphene oxide since it also includes functional groups in its surface. Aiming to explore the role of functional groups on polymerization rate, the in situ bulk radical polymerization of hydroxyethyl acrylate (HEA) in the presence or not of graphene oxide was investigated. Differential scanning calorimetry was used to continuously record the reaction rate under both isothermal and non-isothermal conditions. Simple kinetic models and isoconversional analysis were used to estimate the variation of the overall activation energy with the monomer conversion. It was found that during isothermal experiments, the formation of both inter- and intra-chain hydrogen bonds between the monomer and polymer molecules results in slower polymerization of neat HEA with higher overall activation energy compared to that estimated in the presence of GO. The presence of GO results in a dissociation of hydrogen bonds between monomer and polymer molecules and, thus, to higher reaction rates. Isoconversional methods employed during non-isothermal experiments revealed that the presence of GO results in higher overall activation energy due to the reaction of more functional groups on the surface of GO with the hydroxyl and carbonyl groups of the monomer and polymer molecules, together with the reaction of primary initiator radicals with the surface hydroxyl groups in GO.     

Persulphate initiated graft copolymerization of methacrylamide in natural rubber latex—II. A kinetic study

A kinetic study of the persulphate initiated polymerization of methacrylamide in natural rubber latex has shown that the overall course of polymerization resembles the analogous aqueous polymerization. However, the rate of polymerization increases with increasing rubber concentration in a complex manner, together with a concomitant decrease in induction period. The overall activation energy of polymerization decreases from 18.4 to 11.8 kcal mole^?1 as the rubber concentration is increased from 0–306 gl^?1, at constant monomer and initiator concentrations. Activation of polymerization probably occurs by increase in the rate of initiation perhaps by interaction of the negatively charged latex particles with the persulphate dianion. The kinetic results indicate that, in contrast to earlier studies with oil soluble monomers, the site of polymerisation is the aqueous phase or surface of the rubber particles rather than the rubber interior.     

Role of epoxidized natural Eucommia ulmoides gum in modifying the interface of styrene‐butadiene rubber/silica composites

Eucommia ulmoides gum (EUG) is a renewable and sustainable polymer, which could be used as rubber or plastic by altering its crosslinking density while the complicated extracting process and nonpolar molecular chains limited its application. In this effort, a novel extraction method was introduced, which could simplify the extraction process of EUG. Then, the extracted EUG‐chloroform (CHCl₃) solution was directly used to prepare epoxidized EUG (EEUG) with an epoxy degree of 40.0% to improve its polarity. The epoxidized natural EUG exhibiting both polar and nonpolar motives had an advantage in working as an interfacial compatibilizer for polymer composites, especially bio‐based composites due to its inherent biocompatibility. Accordingly, the role of EEUG in modifying the interface of styrene‐butadiene rubber (SBR)/silica composites were explored. The results showed that EEUG in SBR/silica composites acted not only as a compatibilizer but also as a constructure generating better mechanical properties than other compatibilizers, such as silane couplings, Si‐69 and KH‐550, and epoxidized natural rubber (ENR). The simplified extracting process and the epoxy modification of EUG would extend its application in rubber materials, medical materials, and biopolymer materials.     

Laser-initiated polymerization of epoxies in the presence of maleic anhydride

Laser-initiated polymerization of cyclohexene oxide in the presence of maleic anhydride was investigated. The influences of solvents laser irradiation time and the monomer feed ratio on the polymer yield and composition were evaluated. The rate of polymerization increased with an increase in the molar concentration of maleic anhydride in the monomer feed. Short irradiation times of 1–3 min duration gave very high yield of epoxy polymer (>80% conversion). Infrared spectral studies of the polymer product indicated the formation of polyether linkage at lower levels of conversion and an adduct of polyether and maleic anhydride at higher polymer conversions. The quantitative chemical analyses results also showed similar results. The results indicated that the polymerization was initiated by the excited charge transfer complex between the electron donor, cyclohexane oxide, and the electron acceptor–maleic anhydride. In the initial stages of polymerization, cyclohexene oxide undergoes a cationic polymerization in the presence of the radical anion of maleic anhydride. Laser-initiated polymerization of cyclohexene oxide/maleic anhydride is several hundred times more efficient than UV-initiated polymerization, as measured by the energy absorbed by the polymer system.     

Kinetic Study and New Applications of UV Radiation Curing

Highly crosslinked polymers can be readily synthesized by photoinitiated polymerization of multifunctional monomers or functionalized polymers. The reaction can be followed in situ by real‐time infrared (RT‐IR) spectroscopy, a technique that records conversion versus time curves in photosensitive resins undergoing ultrafast polymerization upon UV exposure. For acrylate‐based resins, UV‐curing proceeds with long kinetic chains (7700 mol/radical) in spite of the high initiation rate. RT‐IR spectroscopy proved very valuable in assessing the influence of various parameters, such as initiation efficiency, chemical structure of the telechelic oligomer, light intensity, inhibitory effect of oxygen, on polymerization kinetics. Interpenetrating polymer networks can be rapidly synthesized by means of UV irradiation of a mixture of difunctional acrylate and epoxy monomers in the presence of both radical and cationic‐type photoinitiators. The same UV technology can be applied to crosslink solid polymers at ambient temperature, which bear different types of reactive groups (acrylate and vinyl double bonds, epoxy ring). UV radiation curing has been successfully used to produce within seconds weathering resistant protective coatings, high‐resolution relief images, glass laminates and nanocomposites materials.

Photoinitiated crosslinking polymerization.     

Cationic graft copolymerization of styrene onto chlorinated butyl rubber

The graft copolymerization of styrene onto chlorinated butyl rubber (Cl-IIR) with stannic chloride as cationic catalyst was studied in cyclohexane, and the rate of polymerization, per cent grafting and grafting efficiency were obtained. Polymerization was carried out in a sealed tube. The product was precipitated in methanol and dried. The increase in weight of Cl-IIR used was regarded as styrene conversion, and the increase in weight after extraction by boiling acetone as the weight of grafted styrene. Grafting was confirmed by fractional dissolution and infrared spectra. The rate of polymerization of styrene was proportional to concentrations of styrene, Cl-IIR and SnCl₄. The per cent grafting increased with styrene and SnCl₄ concentration, but was constant with Cl-IIR concentration. It also increased with time and with halogen content in the polymer. The addition of a polar solvent such as nitrobenzene greatly promoted the grafting reaction and the per cent grafting was 200%.     

Functionalization of polymers prepared by ATRP using radical addition reactions

Low molecular weight linear poly(methyl acrylate), star and hyperbranched polymers were synthesized using atom transfer radical polymerization (ATRP) and end‐functionalized using radical addition reactions. By adding allyltri‐n‐butylstannane at the end of the polymerization of poly(methyl acrylate), the polymer was terminated by allyl groups. When at high conversions of the acrylate monomer, allyl alcohol or 1,2‐epoxy‐5‐hexene, monomers which are not polymerizable by ATRP, were added, alcohol and epoxy functionalities respectively were incorporated at the polymer chain end. Functionalization by radical addition reactions was demonstrated to be applicable to multi‐functional polymers such as hyperbranched and star polymers.     

Persulphate initiated graft copolymerization of methacrylamide in natural rubber latex—III. Characterization of graft copolymer

An investigation of the grafting efficiency of methacrylamide during graft polymerization in natural rubber latex has shown that the efficiency is independent of the initiator and rubber concentrations but increases markedly with temperature. The overall activation energy of the graft polymerization was found to be 25 ± 2 kcal mole^?1 greater than that for the corresponding homopolymerization. The molecular weight of the free homopolymer isolated from the graft copolymerization was very close to that of polymer isolated from the analogous homopolymerization, thus demonstrating that chain transfer with rubber hydrocarbon was unimportant. Electron micrographs of grafted and control latex particles confirm earlier conclusions that grafting occurs on the surface rather than the interior of the rubber particles.     

Cationic graft copolymerization of styrene onto natural rubber

The polymerization of styrene was carried out in a cyclohexane solution of natural rubber with stannic chloride. It was found that the grafting copolymerizations of styrene took place as well as the cyclization of rubber. The rate of polymerization of styrene was proportional to the second power of the concentration of styrene and to the concentrations of stannic chloride and natural rubber, respectively. The overall activation energy was about 6 kcal./mole. The percentage grafting increased with increasing concentration of rubber. On the other hand, the grafting efficiency showed the reverse tendency. The percentage grafting could be increased to 150% by the addition of nitrobenzene, a polar solvent.     

Synthesis,characterization, and photopolymerization of (meth)acrylate-functional polyisobutylene macromers produced by cleavage/alkylation of butyl rubber

Linear, multi-functional polyisobutylene (PIB) macromers bearing pendent and terminal (meth)acrylate moieties were prepared via electrophilic cleavage/alkylation of butyl rubber in the presence of (3-bromopropoxy)benzene, followed by displacement of the resulting bromide moieties with potassium (meth)acrylate. Number average functionality (F_n) ranged from 2.8–7.9; functional equivalent weights ranged from 2.3–4.7 kg/mol. For comparison, a three-arm, end-functional PIB triacrylate with equivalent weight of 3.3 kg/mol was also synthesized via living polymerization and end quenching with 4-phenoxy-1-butyl acrylate. All polymers were photocured using Darocur 1173 photoinitiator, and curing kinetics were monitored by real time Fourier-transform infrared spectroscopy. All systems reached ~100% conversion by 1,800 s, but the linear macromers displayed slower curing rates compared to the PIB triacrylate. The curing rate of linear macromers increased as molecular weight decreased. Cured networks were characterized using dynamic mechanical analysis and tensile testing. Tensile strength varied from 0.15–0.80 MPa. Young's modulus varied from 0.13–1.8 MPa. Strain at break for most networks ranged from 34–54%, but the network derived from the lowest molecular weight PIB reached 113% at failure. Percent extractables, measured using solvent extraction, was about 2% for linear macromers and about 4% for PIB triacrylate.     

Regularities of optical property changes in epichlorohydrin rubber solutions in methylmethacrylate during photoinduced polymerization

Regularities of photoinduced polymerization of epichlorohydrin rubber solutions in methylmethacrylate are studied. It is established that the main stage of process is accompanied with a decrease of the value of the optical density, which testifies to the good compatibility of the forming polymer phases. The dependence characters of the monomer conversion rate, structure, and optical properties of composites on the type and amount of the rubber initially dissolved are shown.     

Tailor‐made poly(ethyl acrylate) by atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) of ethyl acrylate (EA) was carried out using different initiators, CuBr or CuCl as catalyst in combination with different ligands e.g., 2,2′‐bipyridine (bpy) and N,N,N′,N″N″‐pentamethyl diethylenetriamine (PMDETA). Use of PMDETA as ligand resulted in faster polymerization rate (95% conversion in 15 min) than those using bipyridine (～58% conversion in 10.5 h). This is due to the lower reduction potential of copper‐amine than that of copper‐bpy complex, resulting in higher rates of activation of dormant halides. Use of ethylene carbonate as solvent lead to faster polymerization rate and better control in polymerization when compared with p‐xylene as solvent. The reaction temperature had a positive effect on polymerization rate and the optimum reaction temperature was found to be 90 °C. An apparent enthalpy of activation of ～85 kJ/mol was determined for the ATRP of ethyl acrylate, corresponding to an enthalpy of equilibrium of ～64 kJ/mol. By judicious choice of the reaction parameters it was possible to tailor the end group of the final polymer. MALDI‐TOF‐MS analysis and the chain extension experiment of poly(ethyl acrylate) (PEA) prepared using bpy as ligand showed the presence of ? Br as the end group. On the contrary, when PMDETA was used as the ligand, the mass spectra analysis showed hydrogen terminated polymer as the major species towards the end of polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1661–1669, 2007     

单电子转移活性自由基聚合制备支化聚丙烯酸甲酯的研究

以丙烯酸2-(2-溴异丁酰氧基)乙酯(BIEA)为引发剂单体(inimer),丙烯酸甲酯(MA)为单体,Cu0/CuBr2和N,N,N',N″,N″-五甲基二亚乙基三胺(PMDETA)为催化体系,二甲亚砜(DMSO)为溶剂,在常温(25℃)下通过单电子转移活性自由基聚合(SET-LRP)合成支化聚丙烯酸甲酯.聚合反应过程中,采用气相色谱(GC)、核磁共振(1H-NMR)和三检测体积排除色谱(TD-SEC)等测试手段跟踪分析和表征支化聚合物的结构.研究结果表明,采用SET-LRP方法,铜粉作为催化剂,常温下聚合反应就能快速进行,130 min之内MA的转化率已达99%以上,制备出高分子量支化聚合物.随着反应的不断进行,聚合物支化程度不断提高,相比较同分子量下的线型聚合物其黏度不断下降,Mark-Houwink特征常数α最小可达0.290.此外,低分子量聚合物组分随着反应不断减少,在高单体转化率下,聚合体系中以高支化度的聚丙烯酸甲酯为主.     

(Meth)acrylate vinyl ester hybrid polymerizations

In this study, vinyl ester monomers were synthesized by an amine catalyzed Michael addition reaction between a multifunctional thiol and the acrylate double bond of vinyl acrylate. The copolymerization behavior of both methacrylate/vinyl ester and acrylate/vinyl ester systems was studied with near‐infrared spectroscopy. In acrylate/vinyl ester systems, the acrylate groups polymerize faster than the vinyl ester groups resulting in an overall conversion of 80% for acrylate double bonds in the acrylate/vinyl ester system relative to only 50% in the bulk acrylate system. In the methacrylate/vinyl ester systems, the difference in reactivity is even more pronounced resulting in two distinguishable polymerization regimes, one dominated by methacrylate polymerization and a second dominated by vinyl ester polymerization. A faster polymerization rate and higher overall conversion of the methacrylate double bonds is thus achieved relative to polymerization of the pure methacrylate system. The methacrylate conversion in the methacrylate/vinyl ester system is near 100% compared to only ～60% in the pure methacrylate system. Utilizing hydrophilic vinyl ester and hydrophobic methacrylate monomers, polymerization‐induced phase separation is observed. The phase separated domain size is in the order of ～1 μm under the polymerization conditions. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2509–2517, 2009     

Polymerization of styrene in presence of masticated rubber

The influence of the concentration of hydroperoxide (peroxide) groups in rubber (formed during mastication) and the influence of concentration of rubber on the polymerization of styrene were studied at 95, 105, 115 and 130°. The retardation effect of rubber (or non-rubber ingredients) is also due to the participation of less reactive (allylic) radicals from rubber on the termination. The derived kinetic relations allows calculation of a complex constant B* and the rate constant of decomposition of -OOH groups of rubber (k_d) at various temperatures; the latter are essentially smaller than those in masticated rubber. From kinetic analysis of experimental results, it follows that, during the polymerization of styrene in the presence of rubber, two types of rubber radicals can be formed, viz. a less reactive allylic radical and a more reactive alkyl radical.