Photoinitiated cationic polymerization of urethane vinyl ether crystalline monomers

Photoinitiated cationic polymerization of crystalline monomers based on urethane vinyl ether has been investigated by means of differential photocalorimetry (DPC). The crystalline monomers in the melt state polymerized rapidly by exposure to UV light in the presence of a cationic photoinitiator such as an iodonium salt, sulfonium salt or iron arene salt. The kinetics of the cationic photopolymerization process were studied by following k_p[M⁺] as a function of conversion. High conversions, of around 90 %, were obtained for most of the systems investigated. The efficiency of the cationic photoinitiators in initiating the polymerization of the vinyl ether monomers was in the order: iodonium salt > iron arene salt > sulfonium salt. Monomers modified with different saturated alcohols had different activities in photopolymerization, although they all carry the same functional group, i.e. vinyl ether. Copyright © 2005 Society of Chemical Industry     

Synthesis and photo‐curing behaviors of silicon‐containing (vinyl ether)–(allyl ether) hybrid monomers

A series of silicon‐containing (vinyl ether)–(allyl ether) hybrid monomers used in nano‐imprint lithography resists were synthesized and subjected to photo‐initiated polymerization. The surface energies of the monomers and the resulting polymer films were then investigated. The surface energies of the monomers were very low at less than 15 mJ m^–2. The photo‐curing behaviors of the five hybrid monomers were investigated using real‐time Fourier transform infrared spectroscopy. The monomers were sequentially initiated with cationic (PAG201) and mixed (cationic initiator PAG201, radical initiator ITX or TPO) initiators. The vinyl ether double bond polymerized both rapidly and completely, whereas the allyl ether double bond remained when PAG201 was used as the photo‐initiator and polymerized completely with mixed initiators. The different double bonds of the silicon‐containing (vinyl ether)–(allyl ether) hybrid monomer increased the efficiency of the polymerization and overcame the intrinsic limitations of the free radical and cationic polymerization processes, including strong oxygen inhibition, large volume shrinkage and high humidity sensitivity. The five monomers with low viscosity, low surface energy, good thermal stability and good photo‐polymerization properties were suitable for nano‐imprint photoresists. © 2013 Society of Chemical Industry     

Synthesis of end-group functionalized poly(octadecyl vinyl ether)

The cationic polymerization of octadecyl vinyl ether (ODVE) initiated by trimethylsilyl iodide and 1,1-diethoxyethane in the presence of ZnI₂ in toluene at 0°C and 10°C has been investigated. For molecular weights lower than 6000, a linearity of M̄_n with conversion was observed, but for higher molecular weights a strong deviation from calculated values, assuming a living mechanism, was found. Kinetic analysis of the polymerization and the variation of molecular weight as a function of conversion was in agreement with a transfer to monomer with k_tr/k_p ≌ 0.006 at 10°C. Analysis of the polymers obtained by termination with methanol provided evidence that the alkenyl ether end-groups formed by the transfer reaction lead to the same acetal end-groups as the active species. As a consequence, it is possible to prepare functionalized polyODVE polymers by end-capping with alcohols. This was confirmed by the synthesis of polyODVE macromonomers by end-capping with 2-hydroxyethyl methacrylate.     

Living copolymerization of octadecyl vinyl ether with isobutyl vinyl ether: copolymerization parameters and crystallization behaviour of the copolymers

Cationic copolymerization of octadecyl vinyl ether (ODVE) with isobutyl vinyl ether (IBVE) under reaction conditions leading to living vinyl ether polymerization has been studied. The experimental results show that, under such conditions, the living nature of the copolymerization can be retained. The copolymerization parameters were found to be r_IBVE = 2.2 and r_ODVE = 0.30. Incorporation of up to 50% of IBVE units has only a small effect on the crystallinity of ODVE units. This is ascribed to the fact that the crystallinity is due to the octadecyl side‐chains and not to the main chain, and that the copolymers have a gradient‐like (tapered) structure. © 2000 Society of Chemical Industry     

Synthesis and characterization of thermotropic liquid crystalline poly(azomethine ether)s

Two series of monomers, namely 4,4′-diformyl-α,ω-diphenoxydecane and 4,4′-diformyl-3,3-methoxy-α,ω-diphenoxydecane, were prepared from 1,10-dibromodecane with p-hydroxybenzaldehyde and 4-hydroxy-3-methoxybenzaldehyde (vanillin), respectively. The poly(azomethine ether)s were prepared by solution polycondensation using 4,4′-diformyl-α,ω-diphenoxydecane, 4,4′-diformyl-3,3-methoxy-α,ω-diphenoxydecane with various diamines. The monomers and polymers were characterized by intrinsic viscosity, FT-IR, ¹H, and ¹³C NMR spectroscopy. The thermogravimetric analysis reveals that the polymers are stable up to 320-500 °C and decomposed with good char yield. The thermotropic liquid crystalline properties of the polymers were examined by differential scanning calorimetry (DSC) and their textures observed under hot stage optical polarized microscopy (HOPM). All the polymers were exhibited thermotropic liquid crystalline properties except tetramethylene diamines-based polymers.     

Photoinitiated radical copolymerization of vinyl ether and maleate system

The photoinitiated radical copolymerization of difunctional vinyl ether/unsaturated polyester containing maleate has been studied by differential photocalorimetry. The copolymerization kinetics were found to be affected by various factors, such as the composition, the photoinitiator concentration, the light intensity and the presence of oxygen. No temperature effect on the copolymerization was found. The mixture of vinyl ether and unsaturated polyester containing maleate was studied by fluorospectrophotmetry and the existence of a complex of electron donor‐acceptor was detected. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3541–3547, 1999     

氯化橡胶与氯醚树脂的合成与应用

介绍了氯化橡胶的应用及其合成方法,以及作为取代氯化橡胶应用于防腐材料中的氯醚树脂的主要合成方法。通过使用2种材料制成的漆的性能比较发现,氯醚树脂这种环保性更好的材料完全可以取代氯化橡胶,并且有更好的发展前景。     

乳液法合成氯乙烯/乙烯基异丁醚共聚树脂

介绍了10L聚合釜乳液法氯乙烯/乙烯基异丁醚共聚树脂研制开发状况。讨论了pH值缓冲剂、聚合温度、引发体系、乳化剂等对合成氯醚树脂的影响规律。     

Compatibilization and property characterization of polycarbonate/polyurethane polymeric alloys

Semi‐crystalline dendritic poly(ether‐amide)s were synthesized by modifying hydroxyl end‐groups of dendritic poly(ether‐amide) with aromatic urethane acrylate and octadetyl isocyanate. The ratio of these modifiers can adjust the final properties of products to fulfill the requirements of UV‐curable powder coatings. These UV‐curable semi‐crystalline dendritic poly(ether‐amide)s have a T_g in the range of 41–45°C and a T_m of around 120°C. Their thermal behavior and semi‐crystalline properties were studied by DSC and XRD. The photopolymerization kinetics was investigated by Photo‐DSC. The residual unsaturation, thermal stability, and hardness of the UV‐cured films were also studied. The obtained results show that these semi‐crystalline dentritic poly(ether‐amide)s may be used as prepolymers in UV‐curable powder coating systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 287–291, 2003     

可聚合松香基紫外光固化涂层的合成和性能分析

以两种松香基单体———歧化松香(β-丙烯酰氧基乙基)酯(DREA)和丙烯酸松香(β-甲基丙烯酰氧基乙基)酯(AREA)为原料,通过紫外光固化的方式,合成基于松香的涂层,研究松香基单体配比和交联度对涂层硬度和附着力的影响。结果表明,松香基单体固化效率高,有助于提高聚合物涂层的硬度和储存模量(E’),但附着力差。在配方中加入丙烯酸-2-羟基乙基酯(HEA),可以改善涂层的附着力。涂层组成的最佳配比为:DREA 50%,AREA30%,其它辅助成分20%。     

Radiation-induced cationic polymerization of vinyl ethers in solution: 3. The influence of monomer and solvent concentrations on the rate of polymerization of ethyl vinyl ether in ether solvent

The influence of the monomer concentration on the rate of propagation of the radiation-induced polymerization of super-dry ethyl vinyl ether has been examined in detail in two ether solvents, diethyl ether and diglyme, chosen for their different dielectric constants and their different abilities to solvate ions. Estimations of the rate of initiation and of the rate of termination have made possible the evaluation of the rate constants of polymerization. Very similar values were obtained in both ethers. Experiments were also performed in benzene-diglyme and diglyme-methylene chloride mixtures. The results are in good agreement with the previous studies, made in benzene and methylene dichloride, and confirm the important role of the solvation of the free propagating species concerning the reactivities observed in the radiation-induced polymerization of EVE in solution.     

Hydrolytic resistance of model poly(ether urethane ureas) and poly(ester urethane ureas)

Poly(ester urethane ureas) (PesURUs) and poly(ether urethane ureas) (PetURUs) synthesized from diphenylmethane-4,4′-diisocyanate and poly(butylene adipate) diol, and poly(tetramethylene oxide) diol or poly(propylene oxide) diol, respectively, were hydrolyzed at 70°C for various periods up to 16 weeks. Differences in thermal and mechanical properties of as-received dry samples are correlated with the number and strength of hydrogen bonds formed between urea/urethane groups of hard segments and polyester or polyether groups of soft segments. Gel permeation chromatography measurements show that the molar mass of linear PesURUs markedly decreases with the hydrolysis time, whereas that of linear PetURUs remains almost unaffected. PesURU crosslinked by polymeric isocyanate has lower crystallinity, but shows somewhat better resistance to hydrolysis than its linear counterpart because of its more stable three-dimensional molecular structure. Water uptake at 37°C, dynamic mechanical thermal analysis, and differential scanning calorimetry thermograms determined for redried hydrolyzed specimens concurrently show that advancing hydrolysis accounts for decrease in the crystallinity (if any) of soft polyester segments, in the efficacy of hydrogen bonding and in crosslinking density. Experimental data indicate that hydrolytic resistance of PetURUs is primarily determined by (1) the hydrolytic stability of individual types of present groups, (2) steric hindrances affecting the access of water molecules to these groups, and (3) the hydrophilicity of backbones. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 577–586, 1998     

氯乙烯-异丁基乙烯基醚共聚物组成及性能

用核磁共振法表征了间歇乳液共聚合制备的氯乙烯一异丁基乙烯基醚(VC—IBVE)共聚物的结构．讨论了共聚物组成与性能的关系。结果发现,共聚物中VC摩尔分数随聚合转化率的增大而减小：共聚物组成对其在甲苯中的溶解性和溶液粘度有很大影响,当IBVE质量分数[ω(IBVE)]大于或等于13．9％时,共聚物可溶于甲苯;溶液粘度随ω(IBVE)的增大而减小;共聚物的玻璃化转变温度随ω(IBVE)的增大而降低．并符合Gordon—Taylor方程。     

Poly(methyl vinyl ether-b-octadecyl vinyl ether): a new non-ionic surfactant

Block copolymers consisting of methyl vinyl ether (MeVE) units and octadecyl vinyl ether (ODVE) units were synthesized using the cationic living polymerization technique. The polymerization of MeVE was initiated with the trimethyl silyl iodide/1,1-diethoxyethane/ZnI₂ system at −40°C in toluene and the living polymer thus obtained was used as initiator for the polymerization of ODVE at 07deg;C. The combination of hydrophilic (PMeVE) and hydrophobic (PODVE) segments provides the block copolymers with non-ionic surfactant properties, which have been evaluated by measurement of the stabilities of water–decane emulsions.     

Synthesis and characterization of fluorinated poly(azomethine ether)s from new core-fluorinated azomethine-containing monomers

In this work, we describe the design and synthesis of novel core-fluorinated Schiff base monomers and conjugated polymers based on them. The new fully aromatic highly fluorinated poly(azomethine ether)s (PAMEs) were prepared by polycondensation of core-fluorinated azomethine-containing compounds. The structure of the monomers and polymers were confirmed by FTIR, ¹H, ¹³C, and ¹⁹F NMR spectroscopic analysis. The influence of synthesis condition on the properties of PAME compounds was investigated. Application of polarization microscopy with a temperature control thermal stage revealed thermotropic liquid crystalline (LC) behavior in the synthesized materials. Transition temperatures and a range of the existence of the LC phase were studied by a combination of the optical microscopy and DSC analysis. According to the TGA analysis, all the synthesized PAMEs show high thermal stability and thus offer a wide range of thermal processibility (up to 410–477 °C), which makes them prospective materials for many modern applications.     

Synthesis of acrylate modified vinyl chloride and vinyl isobutyl ether copolymers and their properties

With acrylic acid, butyl acrylate and methyl methacrylate as the monomers, acrylate modified vinyl chloride and vinyl isobutyl ether copolymers were prepared by solution polymerization. Firstly, vinyl chloride and vinyl isobutyl ether copolymers were grafted with acrylic monomers to obtain a product containing acrylate grafted vinyl chloride and vinyl isobutyl ether copolymers and polyacrylate, which was then neutralized by triethylamine and dispersed into water to get a self-emulsified emulsion. The acrylate modified vinyl chloride and vinyl isobutyl ether copolymers were characterized by Fourier transform infrared spectroscopy. The mean molecular weight of grafted polymer was determined by gel permeation chromatography, and the particle sizes and their distributions of the dispersions were measured by laser light scattering. The influences of initiator concentration, acrylate content, acrylic acid content and neutralization degree upon the properties of the modified copolymers were discussed. The results show that the emulsion will be with good storage stability, and the modified polymer will be with high water resistance, impact resistance and excellent adhesion when initiator concentration is 1.5%, acrylate content is 50%, acrylic acid content ranges from 9% to 11%, and neutralization degree is between 80% and 100%.     

Radiation-induced cationic polymerization of vinyl ethers in solution: 4. Polymerization of isopropyl vinyl ether in bulk and in various solvents

The influences of the polymerization media, the monomer and solvent concentrations and the temperature on the radiation-induced polymerization of isopropyl vinyl ether (IPVE) have been studied in detail under super-dry conditions. Rates of polymerization were measured and estimates of the rate constants of polymerization were calculated according to the simplified Hayashi-Williams equation. A comparison of the results with those previously reported for ethyl vinyl ether (EVE) is made. The much higher reactivity of IPVC in low polar solvents is interpreted by a drastic reduction of the polymer intramolecular solvation of the growing chain ends. This is ascribed to the bulkiness of the isopropyl side-chain groups. The radiation-induced polymerization of IPVE in bulk and in various solvents with different physical and solvating properties was studied. This was to obtain further information on the kinetics and the mechanisms involved with this monomer and also the role of the polymerization media. The influence of the monomer and solvent concentrations and of the polymerization temperature on the rate of polymerization have also been investigated.     

Grafting of vinyl monomers onto silk using redox systems. Yellowing of silk

The aim of this study is to investigate the influence of temperature, initiator concentration, and vinyl monomer on silk yellowing during grafting. A series of silk fabrics was treated at four different temperatures (70, 75, 80, and 88°C), with different concentrations of initiator in the range 1–4% owf, with and without methacrylamide (MAA) or 2-hydroxyethyl methacrylate (HEMA). By treating silk with ammonium persulphate (APS), in the absence of a monomer, the degree of silk yellowing increased linearly with increasing both initiator concentration and treatment temperature, indicating that the initiator plays a specific role in enhancing silk yellowing through macroradical formation. The graft copolymerization of MAA (with APS as the initiator) caused only slight changes in the intensity of silk yellowing compared to blank-treated fabrics. On the other hand, the use of HEMA resulted in a deeper yellowing of silk fabrics, especially in the 70–80°C temperature range, due to its higher reactivity and to the tendency to form a homopolymer, leaving unreacted macroradicals on silk fibroin backbone. Compared to APS, other initiators, such as 2,2′-azobis(isobutyronitrile) (AIBN) and 2–2′-azobis-(2-amidino propane) dihydrochloride (ADC), caused a significantly lower degree of silk yellowing when tested in the absebce of a monomer. The yellowness of silk fabrics tended to increase by grafting with HEMA, while decreased by grafting with MAA. The use of variable amounts of monomer (25–150% owf) did not influence the degree of yellowing with ADC as the initiator. The results reported in this study show that the extent of yellowing induced on silk fabrics by grafting MAA and HEMA with APS as the initiator can be limited by a suitable selection of the processing parameters (initiator concentration, temperature). Moreover, the use of both AIBN and ADC appears promising, owing to their negligible effect on silk yellowing. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 239–246, 1998     

Synthesis and characterization of thermotropic liquid crystalline poly(aryl ether ketone) copolymers with pendant 3‐(trifluoromethyl) phenyl groups

Novel poly(aryl ether ketone) copolymers with pendant 3‐(trifluoromethyl)phenyl groups were synthesized by the reaction of a crystal‐disrupting monomer, 3‐(trifluoromethyl)phenylhydroquinone (FH) and a mesogenic monomer, 4,4′‐biphenol (BP) with 1,4‐bis(p‐fluorobenzoyl)benzene (BF). Thermotropic liquid crystalline behavior of the copolymers was investigated by means of differential scanning calorimetry, polarized optical microscope and wide‐angle X‐ray diffraction. As a result, the copolymers with the respective molar ratios of FH/BP/BF of 0/100/100–10/90/100 and 80/20/100–100/0/100 were semi‐crystalline without liquid crystalline properties, and amorphous polymers, respectively. In contrast, copolymers with the molar ratio of FH/BP/BF of 20/80/100–70/30/100 had liquid crystalline characteristics. Interestingly, the formation of a highly ordered smectic phase was confirmed for copolymers with the molar ratio of FH/BP/BF of 20/80/100–50/50/100, respectively. All the liquid crystalline copolymers had a wide liquid crystalline temperature range (57–75 °C). Copyright © 2006 Society of Chemical Industry