首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
Novel dibenzylpiperidinium salts with nonnucleophilic anions (DBPi‐SbF6, DBPi‐PF6) have been prepared as latent cationic initiators. Utility of these salts in the photo and thermal‐induced cationic polymerizations of epoxide and vinyl ether monomer systems has been studied. The new initiator, DBPi‐SbF6 showed good solubility, high reactivity, and high thermal latency for polymerizations of epoxide and vinyl ether monomers with only 1 wt % of concentration. Cationic polymerization of vinyl ether monomer was significantly faster than epoxide monomer by the synthesized initiators. This article describes the synthesis, characterization, and activity of novel initiators. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

2.
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.  相似文献   

3.
Various properties of UV‐initiated acrylate/epoxide and acrylate/vinyl ether hybrid photopolymerizations with and without photosensitizer in the presence of free radical and cationic‐type photoinitiators have been determined by dynamic mechanical thermal analysis (DMTA), calorimetric analysis (photodifferential scanning calorimetry, photo‐DSC; and differential scanning calorimetry), and scanning electron microscopy. DMTA experiments revealed that the UV curing of hybrid systems may produce interpenetrating polymer networks. Photo‐DSC analyses indicated that the acrylates polymerized faster than the epoxide and vinyl ether in the hybrid systems; the addition of a photosensitizer, isopropylthioxanthone (ITX), increased the polymerization rate of the epoxide and vinyl ether in the hybrid systems. SEM analysis confirmed that the free radical system seemed to be significantly affected by oxygen inhibition, while the cationic and hybrid systems were not nearly inhibited by oxygen; the presence of photosensitization produced by the addition of ITX enhanced the surface curing of the hybrid systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1473–1483, 2004  相似文献   

4.
Poly(2-acetoxyethyl vinyl ether (AcOVE)) and poly(2-acetoxyethyl vinyl ether-co-2-vinyloxyethyl phthalimide) were synthesized by traditional cationic polymerization, typically at −20°C in toluene with BF3O(C2H5)2 as initiator, to give polymers with degrees of polymerization (Dp) in the range of 600–1100. In addition, poly(AcOVE) was polymerized by controlled cationic polymerization at 0°C with molecular weights in a predetermined fashion. The Dp's were calculated from Dp = [M]0/[I]0 and typical values were 5, 10, 100 and 200. The molecular weight values obtained for a theoretical Dp = 200, were for poly(2-acetoxyethyl vinyl ether), Mn = 19,200, Mw = 22,700 and POLYDISPERSITY = 1.2, as determined by GPC. The deprotected hydrophilic polymers, poly(2-hydroxyethyl vinyl ether) and poly(2-hydroxyethyl vinyl ether-co-2-aminoethyl vinyl ether), were used for the preparation of novel gel filtration media as well as new anion exchangers. In the case of gel filtration, poly(2-hydroxyethyl vinyl ether) was attached to a beaded agarose matrix (34 μm), i.e. Sepharose® HP. It was shown that the attachment of the poly(vinyl ether) affected the selectivity. In gel filtration of selected biomolecules, the poly(vinyl ether) modified agarose matrix showed performance characteristics comparable to the reference used, i.e. Superdex® 30 prep grade. In addition the poly(vinyl ether)s were shown to be stable in a wide pH-range. The stability was confirmed by the conclusion that no changes in molecular weight were observed after treatment with 0.1 M HCl (pH = 1) or 0.01 M NaOH (pH = 12) for six weeks at 40°C. For the preparation of anion-exchanger media, the beads containing poly(2-hydroxyethyl vinyl ether) was further modified with a quaternary ammonium group, to produce a separation media having a high dynamic binding capacity for bovine serum albumin (BSA).  相似文献   

5.
Toshihiro Sagane  Robert W. Lenz   《Polymer》1989,30(12):2269-2278
Two vinyl ether monomers with alkoxybiphenyl groups, 2-(4′-ethoxy-4-biphenyloxy)ethyl vinyl ether (EtOVE) and 2-(4′-hexyloxy-4-biphenyloxy)ethyl vinyl ether (HexOVE), were polymerized by living cationic polymerization reactions using either the hydrogen iodide/iodine (HI/I2) or the hydrogen iodide/zinc iodide (HI/ZnI2) initiator systems, or both. These initiators yield polymers with narrow molecular weight distributions (MWDs) and for comparison broad MWD polymers were also prepared by using the BF3OEt2 initiator. The thermal properties and phase transitions of these polymers were determined by differential scanning calorimetry, by visual observations of samples on a hot stage on a polarizing microscope, by polarized light transmission intensity measurements and by wide angle X-ray diffraction analysis. The polymer from EtOVE, P(EtOVE), with a weight average molecular weight, , of less than about 8000 formed both smectic and nematic liquid crystalline, LC, phases after one heating cycle. In contrast, the polymer from this monomer which had an of more than about 8000 exhibited only a nematic LC phase. For the polymer from HexOVE, P(HexOVE), both the narrow and broad MWD samples showed only a nematic LC phase over the range from 2600 to 7300. The phase transitions of both types of polymers are discussed in relation to the molecular weight and MWD of the samples. The effect of the terminal group attached to the biphenyl group in the polymer is considered in relation to its possible steric effects.  相似文献   

6.
Novel Sulfonium salts with non‐nucleophilic anions were synthesized and applicability of these salts as initiators was demonstrated by carried out polymerization (photo and thermal) of epoxides as well as vinyl ether monomers. Newly synthesized initiators showed good activity for the photo and thermal polymerization. Synthesis, characterization, and activity of initiators have been described. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.  相似文献   

7.
Synthesis of high molecular weight poly(vinyl acetate) having less branched structure via photo‐induced emulsion polymerization of vinyl acetate in the presence of poly(oxyethylene)20 nonyl phenyl ether, a nonionic emulsifier, was attempted at 0°C or even below 0°C in the presence of methanol. It was found that 100% conversion is always achieved in all runs and poly(vinyl acetate) having the number‐average degree of polymerization of 9000 with less branched structure (degree of branch < 0.5) can be obtained from this photo‐induced emulsion polymerization system. Mechanisms of the polymerization were also discussed on the basis of the kinetic results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2153–2158, 2002  相似文献   

8.
Novel diblock copolymers designed for the preparation of micellar drug delivery systems, consisting of hydrophobic poly(allyl glycidyl ether) (PAGE) and hydrophilic poly(ethylene oxide) (PEO), were prepared, and their self‐assembly into micellar structures was studied. Copolymers differing in the length of the polymer blocks were purified and characterized. These amphiphilic copolymers with narrow molecular weight distributions were prepared through the anionic polymerization of allyl glycidyl ether with PEO monomethyl ether sodium salt as the macroinitiator. The PAGE–PEO copolymer readily formed small micelles with narrow size distributions via simple dissolution in water. The addition of pendant double bonds to the hydrophobic part of the chain was intended for further covalent modifications. Catalytic hydrogenation, the radical crosslinking of the micelle core, and the addition of thiol to double bonds of the copolymer were examples of such modifications that were proved to proceed with a quantitative yield for this copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 201–211, 2005  相似文献   

9.
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 kp[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  相似文献   

10.
A new vinyl ether monomer bearing a glycerol pendant moiety protected with an isopropylidene group (2‐(2,2‐dimethyl‐[1,3]dioxolan‐4‐ylmethoxy)‐ethyl vinyl ether, IpGEVE) was designed as the precursor of a novel type of hydrophilic poly(vinyl ether) containing glycerol pendants. It was found that the polymerization of IpGEVE proceeded in a controlled manner, and the protecting groups of isopropylidene moieties could be cleaved with trifluoroacetic acid. Living cationic polymerization of IpGEVE with an initiator bearing a methacryloyl group (VEM‐HCl) and subsequent deprotection of the pendant isopropylidene groups of the resultant precursor afforded a glycerol‐substituted hydrophilic macromonomer MA‐PGEVE. Nearly monodispersed polymer particles in the submicron size range were successfully obtained via dispersion copolymerization of MA‐PGEVE with styrene.© 2013 Society of Chemical Industry  相似文献   

11.
2,4‐Di‐(2′,2′‐dicyanovinyl)‐1‐(2′‐vinyloxyethoxy)benzene and 2,4‐di‐(2′‐carbomethoxy‐2′‐cyanovinyl)‐1‐(2′‐vinyloxyethoxy)benzene were prepared by condensation of 4‐(2′‐vinyloxyethoxy)isophthaldehyde with malononitrile and methyl cyanoacetate, respectively. The two vinyl monomers were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ether)s containing two oxybenzylidenemalononitrile and oxybenzylidenecyanoacetate groups, which are effective chromophores for second‐order nonlinear optical applications. These polymers were soluble in common organic solvents such as acetone and dimethyl sulforide. They showed thermal stabilities up to 300 °C from thermogravimetric analysis (TGA), with differential scanning calorimeter (DSC) thermograms giving Tg values in the range 73–87 °C. The second harmonic generation (SHG) coefficients (d33) of poled polymer films were around 1.8 × 10?9 esu, and these polymers showed good long‐term thermal stability for 60 days at room temperature, which is acceptable for nonlinear optical (NLO) device applications. Copyright © 2004 Society of Chemical Industry  相似文献   

12.
A new method of preparation of living cationic polymer of isobutyl vinyl ether via photoinduced polymerization in the presence of diphenyliodonium iodide (DPII, initiator) and zinc iodide in a mixed solvent of toluene/diethyl ether, which was irradiated at ?78°C for short period, was completed within 15 min. The reaction was allowed for further reaction in the dark until monomer was fully consumed. It was found that increase in the conversion of monomer to polymer during the irradiation is very limited. Confirmation of the linear dependence of number‐average molar mass of resulting polymer on % conversion together with the fact that polymerization proceeds until monomer consumption, and controllability of number‐average molar mass of resulting polymer, depending on the molar ratio of monomer and initiator, strongly suggests the living nature of this polymerization, unless reaction temperature becomes higher than 0°C, i.e., the absence of chain breaking process. The narrow molar mass distribution, whose polydispersity index values are less than 1.2, reveals that the rate of initiation where irradiation is usually completed within 15 min is much faster than that of propagation in cationic nature in this system. Effect of some major factors, such as solvent polarity and temperature, on the living nature of the polymerization was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3581–3586, 2006  相似文献   

13.
以1,3,5-三羟乙基异氰脲酸酯(THEIC)为引发剂、三氟化硼乙醚络合物为催化剂,环氧化合物为环单体,进行了阳离子开环聚合反应的研究.发现THEIC与环氧单体可在非均相体系中平稳地进行阳离子开环聚合反应.在THEIC体系,就链引发而言,环氧氯丙烷的大于环氧丙烷、丁基醚环氧乙烷.调整环单体加料次序就可以获得嵌段共聚醚多元醇.  相似文献   

14.
Poly(vinyl alcohol) (PVA) having a number‐average degree of polymerization of 7000 was obtained from the poly(vinyl acetate) (PVAc) having a number‐average degree of polymerization 9000, a product of photo‐induced emulsion polymerization of vinyl acetate (VAc), carried out at 0°C, using poly(oxyethylene)10 nonyl phenyl ether ammonium sulfate as an anionic emulsifier. It was found that 100% conversion is always attained in the whole range of the investigation and the emulsifier plays an important role in the initiation process. The applicability of the photo‐induced emulsion polymerization system to a relatively large‐scale production was tested by using an apparatus equipped with an internal high‐pressure Hg lamp with a capacity of several hundred grams per batch under nitrogen atmosphere. It was found that both the rate of polymerization and the degree of polymerization of resulting polymers are slightly lower than those obtained from corresponding small‐scale polymerizations prepared on a high vacuum system because of the presence of oxygen. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2425–2431, 2002  相似文献   

15.
In this study, novel thermolatent cationic initiators based on dibenzocycloheptenyl phosphonium salts ( 1a , 1b , 1c , 1d , 2a , and 3a ) were synthesized and their efficiency was examined in bulk polymerization of glycidyl phenyl ether (GPE). The polymerization of GPE was performed with 1 mol % of dibenzocycloheptenyl triphenylphosphonium salts ( 1a – 1d ) with different counter anions (SbF6?, PF6?, AsF6?, and BF4?) at 25–200°C for 1 h. The order of initiator activity was found as 1a > 1d > 1b > 1c . To examine the effect of phosphine moiety, the activity of 1a was compared with dibenzocycloheptenyl‐tri‐n‐butylphosphonium hexafluoroantimonate ( 2a ). The order of initiator activity was observed as 1a > 2a. The initiator activity of 1a was compared with that of 10,11‐dihydro‐dibenzocycloheptenyltriphenylphosphonium hexafluoroantimonate ( 3a ) to understand the effect of extended conjugation in dibenzocycloheptenyl ring. In general, with the increase in the polymerization temperature, conversion (%) also increases. The solubility of initiators in various solvents and epoxy monomers was also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

16.
Novel 1‐methoxycarbonylethylmethylphenylsulfonium salts with nonnucleophilic anions, namely, hexafluorophosphate, hexafluoroantimonate, and tetrafluoroborate, were synthesized by the reaction of 1‐methoxycarbonylethylphenylsulfide and dimethyl sulfate followed by anion exchange with potassium hexafluorophosphate, sodium hexafluoroantimonate, and sodium tetrafluoroborate, respectively. The cationic polymerization (photopolymerization and thermal polymerization) of epoxy and vinyl ether monomers was carried out to demonstrate the applicability of the newly synthesized sulfonium salts. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3157–3163, 2007  相似文献   

17.
Allyl methacrylate was polymerized by γ‐radiation under vacuum in solution and atom transfer radical polymerization (ATRP) methods and also in the presence of atmospheric oxygen in bulk. The kinetic curve is S‐type with a longer induction period, because of the presence of oxygen, in bulk polymerization. The curve for the solution polymerization is almost linear with a short induction period. The rate started to decrease after about 60% conversion and reached to a limiting conversion of 100%. The polymerization by ARTP method using γ‐radiation as initiator instead of conventional heating method gave a kinetic curve of linear character up to about limiting conversion of 100%. The polymers obtained were mostly gel type with linear chain fractions at lower conversions. The polymer characterizations were carried out by FTIR, differential scanning calorimetry, NMR, TGA, and XRD methods. The polymers were shown to proceed by the opening of vinyl groups. The allyl groups caused a limiting crosslinking, but 98–99% of the allyl groups are shown by FTIR and NMR, unchanged during the polymerization. The cyclic type polymer formation was not likely taking place. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1076–1083, 2007  相似文献   

18.
N‐Methyleneamines, formed by treating 1,3,5‐trimethylhexahydro‐1,3,5‐triazines with Lewis acids, have been shown to be capable initiators in the cationic polymerization of tert‐butyl vinyl ether, yielding polymers with amine functionality at the chain ends. Previous work was limited to titanium(IV) chloride (TiCl4) as the Lewis acid in dichloromethane solvent at 0 °C (with resulting polymers possessing relatively broad polydispersity index (PDI) values near 2), while this contribution details the effect of reaction parameters on the polymeric products; specifically, the role of temperature, solvent, Lewis acid and additives. Ultimately, performing the polymerization at ?78 °C in dichloromethane with TiCl4 as the Lewis acid and tetra‐n‐butylammonium chloride (nBu4NCl) as the additive afforded the best control over the system, with polymers formed possessing low PDI values (<1.2). Dramatic changes in number‐average molecular weight and PDI were observed in polymers formed by initiating systems of Lewis acid‐induced N‐methyleneamines, with temperature, solvent, Lewis acid and additives all playing a role. By varying single parameters, optimization of the system was achieved. Copyright © 2009 Society of Chemical Industry  相似文献   

19.
Narrow‐disperse or monodisperse poly{[poly(ethylene glycol) methyl ether acrylate]‐co‐(acrylic acid)} (poly(PEGMA‐co‐AA)) microspheres were prepared by distillation precipitation polymerization with ethyleneglycol dimethacrylate (EGDMA) as crosslinker with 2,2′‐azobisisobutyronitrile as initiator in neat acetonitrile in the absence of any stabilizer, without stirring. The diameters of the resultant poly(PEGMA‐co‐AA‐co‐EGDMA) microspheres were in the range 200–700 nm with a polydispersity index of 1.01–1.14, which depended on the comonomer feed of the polymerization. The addition of the hydrogen bonding monomer acrylic acid played an essential role in the formation of narrow‐disperse or monodisperse polymer microspheres during the polymerization. Copyright © 2006 Society of Chemical Industry  相似文献   

20.
Acrolein was polymerized in a polar solvent in the presence of terc‐ and sec‐butyl lithium as initiators. Using a low monomer to initiator molar ratio and 1‐h reaction time, cyclic structures were shown to be formed in the main chain of the resulting oligomers. The influence of different monomer to initiator molar ratios on molecular weight and on molecular weight distribution was investigated. Chain‐transfer reactions toward the monomer resulted in lower molecular weights and narrower polydispersions as [M]/[I] increased. The influence of initiator type on the polymer molecular weight was also evaluated. FTIR analysis of the degradation products at different heating temperatures indicated that the oligomers structure is composed of aldehyde, ether, and vinyl functional groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号