Polymerization of Blending Cholesteryl Acrylate and Methyl Phenyl Benzoyl Acrylate

Liquid crystal is a material which is between solid and liquid phase and commonly called mesophase. Blends of liquid crystal are of great interest because of their unique optical properties. Blending in this study using two monomers of liquid crystal were cholesteryl acrylate and methyl phenyl benzoyl acrylate. The polymerization process using uv curing techniques by irradiation UV ray and without irradiation UV ray. Polymerization of blending liquid crystal acrylate using initiator 2-hydroxy-2-methyl-1-phenylpropane. Based on peak at GPC curve of polymerization by irradiation UV ray, type of that polymer is copolymer. Therefore the polymerization without UV ray, type of that polymer is homopolymer. SEM images of liquid crystal acrylate polymer showed lamella chain models that are characteristic of a polymer chains. Type of polymer liquid crystal acrylate was the type of Side Chain Liquid Crystalline Polymers (SCLCPs). Therefore acrylate polymer liquid crystal in this research has semi-crystalline phase, which contained crystalline phase and amorphous phase on the XRD pattern. The results of FT-IR spectroscopic characterization of the two monomers showed a peak at the wave number of 1600.43 cm ^-1 and 1622.86 cm^-1 which indicates a double bond (C=C) were obtained from acrylation. While the spectroscopy on the product blending the wave number of the peak regions is reduced that shows that carbon double bonds (C=C) in the acrylate group has polymerized. It also strengthened with a very sharp peak for CC functional groups on the wave number of 2855.15 cm^-1. The results of this study indicate that the liquid crystal polymer acrylic polymerization results with radiation UV ray and without UV ray, respectively absorb light in the UV wavelength region 363 nm and 351 nm.     

Photocrosslinking of functionalized rubber. II. Photoinitiated cationic polymerization of epoxidized liquid natural rubber

Low molecular weight epoxidized natural rubber has been crosslinked within seconds by UV irradiation in the presence of a triarylsulfonium salt. The photoinitiated cationic ring-opening polymerization was studied quantitatively by infrared spectroscopy and shown to proceed with surprisingly long kinetic chains in such solid medium. The high conversion (60%) needed for complete insolubilization, together with the presence of tetrahydrofuran structures, argue in favor of an intramolecular polymerization process involving neighboring epoxy groups. The photoinitiator concentration has a strong influence on the rate and extent of the reaction, as well as on the depth of cure profile. Because of an efficient dark process, close to 100% conversion was reached upon storage of the irradiated elastomer at ambient, with a concomitant increase of the gel fraction and the polymer hardness. The grafting of pendent acrylate groups onto the polymer chain leads to a three-fold decrease of the initial rate of polymerization of the epoxide. The photocuring of natural rubber bearing both epoxy and acrylate groups generates a dual polymer network which combines the properties of the two moieties. © 1995 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.     

Methacrylate-based polymer blends containing oligomeric 1,2-polybutadienes

Partly miscible polymer blends with semi-IPNs structure built from polydimethacrylate networks and hydroxyl-terminated liquid polybutadienes with predominant 1,2-structure (LBH) were prepared by photopolymerization method. Photopolymerization kinetics of dimethacrylate–LBH mixtures were monitored by DSC technique under isothermal conditions. Kinetic curves and related parameters, like polymerization rate and degree of double bond conversion were determined as functions of dimethacrylate structure, LBH molecular mass, and its content in the mixture as well as polymerization temperature. The photopolymerization kinetics and activation energy for the polymerization rate were discussed taking into account the phase separation occurring during the curing reaction. The extent of phase separation (based on T _g’s measurements) depended on LBH content and dimethacrylate chemical structure. The effect of LBH content on hardness of polymer blends was also examined.     

Sesamin as a co-initiator for UV photopolymerization

Sesamin, a nature compound from sesame seed, which contains two cyclic acetal structures, was used as a co-initiator for UV polymerization initiator system, and 1,6-Hexanedioldiacrylate was used as the photopolymerization monomer. Photopolymerization kinetics was recorded by real-time infrared spectroscopy. For BP/Sesamin initiator system, the double bond conversion increased with the increase of Sesamin concentration and light intensity. Combination of p-chlorobenzophenone and Sesamin had the highest initiating reactivity. The polymerization rate and final double bond conversion of acrylate monomer were higher than that of methacrylate monomer.     

Renewable epoxidized cardanol‐based acrylate as a reactive diluent for UV‐curable resins

A novel kind of biobased monomer, epoxidized cardanol‐based acrylate (ECA), was successfully synthesized from cardanol via acrylation and epoxidization. The chemical structure was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. Then, the ECA was employed to produce UV‐curable films and coatings copolymerized with castor oil‐based polyurethane acrylate. Compared to coatings from petroleum‐based diluent hydroxyethyl acrylate‐based castor oil‐based polyurethane acrylate resins, ECA‐based biomaterials exhibited a little inferior dilution ability but overcome the drawback of high volumetric shrinkage with a special lower value. Moreover, ultimate properties of the UV‐cured biomaterials such as thermal, mechanical, coating, swelling, and hydrophobic properties were investigated. The UV‐curing behavior was investigated using real‐time IR, and the overall double bond conversion was more than 90%. This biobased UV‐curable cardanol‐based diluent shows a promise in “green + green” materials technologies.     

Differential scanning calorimetric study on free-radical polymerization of <Emphasis Type="Italic">gem</Emphasis>-dinitroalkyl acrylates and methacrylate

2,2-dinitropropyl acrylate (DNPA), 2,2-dinitrobutyl acrylate (DNBA) and 2,2-dinitrobutyl methacrylate (DNBMA) were synthesized and the kinetics of their free-radical polymerization in the presence of 2,2′-azobisisobutyronitrile (AIBN) were investigated by DSC in the non-isothermal mode. The kinetics of the free-radical polymerization as estimated by the Kissinger and Ozawa methods showed that the reaction is disfavoured by increasing steric hindrance around the acrylyl double bond. The rate constants calculated from the activation parameters showed the structural dependency. The polymerization kinetics revealed that the polymerizability of three monomers decreased due to the presence of substituent methyl groups on the acrylyl double bond and 2,2-dinitrobutyl on ester group. Thus, the polymerization tendency increased in the order DNPA>DNBA>DNBMA.     

Light-stabilization of polymeric materials by grafted UV-cured coatings

The weathering resistance of organic materials has been substantially increased by protecting their surface with a photocured coating containing both a UV absorber (UVA) and a radical scavenger (HALS). A kinetic study by real-time IR spectroscopy has shown that HALS have no effect on the cure rate, whereas UV absorbers slow down the cure process, due to their radiation inner filter effect. 3D analysis of the depth of cure profile revealed an incomplete cure at the coating/substrate interface, leading to adhesion failure. To prevent this detrimental effect, the UV-cured coating was photochemically grafted onto the substrate. The polymer material was first coated with a thin layer of a benzophenone solution in a diacrylate monomer. Polymer radicals, generated by hydrogen abstraction from the substrate by the excited benzophenone molecules, effectively initiate the polymerization of the acrylate functions, thus ensuring a chemical bonding between the coating and the substrate. The grafting reaction was characterized by ATR spectroscopy analysis and by surface energy measurements. Excellent adhesion was achieved by applying to the treated substrate a photocurable acrylate coating, containing the light stabilizers, because of the copolymerization reaction taking place with the unreacted acrylate double bonds of the base coat, upon UV exposure. The efficiency of this on-line stabilization process has been demonstrated on poly(vinyl chloride) that was made eight times more resistant to accelerated weathering. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2571–2580, 1998     

环氧-丙烯酸酯混杂光固化体系的研究

研究环氧－丙烯酸酯混杂光固化体系中引发剂的协同作用，证实混杂光固化过程中自由基引发剂对阳离子引发剂二苯基碘Weng盐的增感作用，混杂光固化膜具有优良的机械性能，其抗冲击性能，抗弯曲性能及硬度优于单纯的阳离子体系固化膜，与自由基体系固化膜性能接近。混杂光固化膜的玻璃化转变温度高于自由基体系固化膜；它的耐溶剂性能优异，耐丙酮擦拭次数比自由基固化膜高25倍以上，比阳离子固化膜高3．5倍。这可能是由于混杂光固化过程中形成的IPN结构造成的，动态粘弹谱和扫描电镜的实验结果证实了这一结论。     

Synthesis and characterization of a self-crosslinkable polymer from cardanol: Autooxidation of poly(cardanyl acrylate) to crosslinked film

Cardanyl acrylate (CA), a monomer that yields crosslinkable copolymers, was synthesized by the reaction of cardanol with acryloyl chloride. A linear polymer was obtained by solution polymerization of the monomer in toluene using 0.8% azobisisobutyronitrile as initiator. Upon removal of solvent, the polymer undergoes crosslinking on exposure to air (or UV light) to give an insoluble transparent film. However, in bulk and suspension polymerization the polymer undergoes in situ crosslinking in the absence of any crosslinking agent. The polymer was characterized by IR, NMR, DSC, and GPC. The crosslinking reaction of soluble polymer on exposure to air at ambient conditions was explained by the hydroperoxide theory. © 1993 John Wiley & Sons, Inc.     

The Formation of Terminal Double Bonds in Vinyl Chloride Polymerization

The determination of double bonds in PVC is achieved with an increased accuracy in comparison with earlier methods by the addition of iodine monochloride (Wijs reaction) to PVC coupled with x-ray fluorescence analysis to determine the iodine content of the polymer. The number of double bonds per unit weight of polymer increases on increasing the polymerization temperature and is proportional to the number of polymer molecules. It is not affected, however, by the presence of the chain transfer agent tetrahydrofuran (THF). At the technically important polymerization temperatures of 30 to 80°C and in the absence of the chain transfer agent, 0.9 double bonds per polymer molecule are found. The number of double bonds per polymer molecule is lowered using the chain transfer agent THF. These results support the theory that the chain transfer to monomer and possibly the termination reaction are coupled with the formation of terminal double bonds. Contributions by internal double bonds formed by dehydrochlorination of the polymer during polymerization are excluded by investigating the Cl^θ content of the water phase in the oxygen-free VC suspension polymerization. No hydrogen chloride is formed. In IR spectra of PVC, the stretching vibration of the double bonds is detected at 1667 cm^?1 by the correlation of the double bond contents and the intensities of the absorption bands. The stretching vibration at 1667 cm^?1is in accordance with those of model compounds with a 1-chloro-2-alkene structure.     

NONCONJUGATED CONDUCTIVE POLYMERS

Conjugation is not a prerequisite for a polymer to be conductive. A polymer must have at least one double bond in the repeat to become conductive. Interaction with a dopant (e.g., electron acceptor) causes transfer of an electron from the double bond to the dopant creating a hole at the double bond site. Electrical conduction occurs via intersite hopping of holes. Various spectroscopic methods (FTIR, optical absorption, solid-state ¹³C NMR, etc.) along with electrical measurements have been used to elucidate the mechanism of conduction in specific nonconjugated conductive polymers. Examples of these polymers include 1,4-polyisoprene which has one double bond and three single bonds in the repeat. The conductivity of polyisoprene increases 100 billion times upon doping with iodine to a maximum value of 10 S/m. Polyisoprene (natural rubber) is used nonconjugated conductive polymers have a wide range of applications in antistatics, various sensors and optoelectronics.     

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.     

2,2′-二邻甲氧基苯基-4,4′,5,5′-四苯基-1,2′-二咪唑复合光引发体系的光聚合动力学研究

本文研究了对2,2′-二邻甲氧基苯基-4,4′,5,5′-四苯基-1,2′-二咪唑(BMOIM)复合光引发体系引发聚合动力学过程.采用紫外光谱仪对引发剂、供氢体、增感剂在紫外区的吸收谱图进行了表征.利用实时红外光谱仪对复合光引发体系引发聚合动力学过程进行实时监测,考察了不同光强、引发剂浓度以及不同官能度单体对反应速率及最终双键转化率的影响.结果表明,在引发剂浓度为0.6%(质量分数)时,20s内双键转换率达到96%,随着引发剂浓度的提高,聚合速率增大.聚合速率以及最终双键转化率随着光强增大而增大;双官能团单体的最终双键转化率比三官能团单体的最终双键转化率要高.     

UV‐curable acrylate‐based nanocomposites: effect of polyaniline additives on the curing performance

Composites of nanostructured polyaniline (PANI) conducting polymer in a polyester acrylate (PEA) formulation were made to provide conductive organic coatings. The effect of the presence and amount of PANI on the photocuring performance of the ultraviolet (UV)‐curable acrylate system has been investigated employing real‐time Fourier transform infrared spectroscopy as the main technique. Longer initial retardation of the radical polymerization and lower rates of cross‐linking reactions were observed for dispersions containing PANI of higher than 3wt.%. The PEA/PANI samples were more affected than the neat PEA resin by the changes in UV light intensity and oxygen accessibility during UV curing. Samples with higher PANI content, of up to 10wt.%, were tested and could be partially cured even at UV light intensities as low as 2 mW cm^?2 when the oxygen replenishment into the system was inhibited. Thermal analysis revealed that the presence of PANI did not induce any significant change in Tg of the cured system, meaning that early decrease in mobility and vitrification is not the reason for lower ultimate conversion of the dispersions with higher PANI content compared with the neat PEA resin. Curing under strong UV lamps, of 1.5 W cm^?2 intensity, made it possible to reach high degrees of conversion on films with similar mechanical properties independent of the PANI content. Copyright © 2013 John Wiley & Sons, Ltd.     

Studies of the polymerization of diallyl compounds. XXII. Polymerization of diallyl oxalate in the evolution of carbon dioxide at elevated temperatures

The polymerization of diallyl oxalate was conducted in the presence of radical initiators at a high temperature range of 80–180°C; a large decrease in degree of polymerization, an increase in residual unsaturation of the resulting polymer, and the evolution of carbon dioxide were observed with the elevation of temperature. These findings were reasonably interpreted by considering the dismutation of the uncyclized growing radical to yield the allyl radical, carbon dioxide, and polymer carrying a terminal double bond. The kinetics of the polymerization of diallyl oxalate in the evolution of carbon dioxide at elevated temperatures were also discussed in detail.     

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.     

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.     

Hydrogen bonding and rate enhancement in the photoinduced polymerization of telechelic urethane methacrylates based on a cycloaliphatic system: Tricyclodecane dimethanol

A new class of telechelic urethane methacrylic crosslinkers, based on a cycloaliphatic system (tricyclodecane dimethanol and tricyclodecane monomethanol), was synthesized. The synthesis was achieved by a two‐step condensation of 1,6‐hexamethylene diisocyanate or isophorone diisocyanate with tricyclodecane dimethanol and capping with hydroxyethyl methacrylate. Samples of hexanediol diacrylate, tricyclodecane monomethacrylate, and tricyclodecane dimethacrylate were used as non‐hydrogen‐bonding monomers for comparative studies of the curing kinetics. The photopolymerization of these telechelic systems was investigated with UV irradiation in the presence of 2,2‐diethoxy acetophenone as the photoinitiator, and the kinetics were followed by the monitoring of the double‐bond conversion at 815 cm^?1 with Fourier transform infrared spectroscopy. The hydrogen‐bonded crosslinkers had higher double‐bond conversions than their non‐hydrogen‐bonded counterparts under identical conditions. The higher cure rate could be explained by hydrogen‐bonding preassociation in these systems, which brought the methacrylate double bonds within close proximity. The temperature effects on the hydrogen bonding were also investigated. A decrease in the extent of the double‐bond conversion with increasing temperature was observed for the hydrogen‐bonded crosslinker, in contrast to an increased conversion with temperature for hexanediol diacrylate and tricyclodecane dimethacrylate. This was directly indicative of a reduction of hydrogen bonding at elevated temperatures leading to lower conversions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4384–4395, 2006     

紫外光快速固化的树枝状丙烯酸酯齐聚物的制备和性能

通过乙二胺(EDA)和三羟甲基丙烷三丙烯酸酯(TMPTA),以甲醇为催化剂,在30℃进行6小时Michael加成反应,可制得含多个双键的树枝状丙烯酸酯齐聚物(DAO).与相似分子量的线性丙烯酸酯齐聚物相比,DAO粘度低,用作紫外光固化树脂,其固化速度快,且固化产物硬度好,耐溶剂性好.