Crosslinking poly[1-(trimethylsilyl)-1-propyne] and its effect on physical stability

Poly[1-(trimethylsilyl)-1-propyne] (PTMSP) has been crosslinked using 3,3′-diazidodiphenylsulfone to improve its solvent resistance and physical stability. This study reports the influence of crosslinking on N₂, O₂ and CH₄ gas permeabilities and fractional free volume (FFV) as a function of time. Crosslinking PTMSP renders it insoluble even in excellent solvents for the uncrosslinked polymer. The gas permeability and FFV of uncrosslinked and crosslinked PTMSP decreased over time, so crosslinking PTMSP does not arrest physical aging. The addition of 10 wt.% polysiloxysilsesquioxanes (POSS) nanoparticles decreased the permeability of PTMSP by 55%, and the permeability and FFV values were stable over time for PTMSP films containing 10 wt.% POSS nanoparticles. The permeability of PTMSP at a given FFV was greater than that of other substituted polyacetylenes, polysulfones or polycarbonates, which is consistent with differences in the arrangement of free volume in these polymers, as probed by positron annihilation lifetime spectroscopy (PALS). Ellipsometry was used to characterize physical aging of thin (400 nm) uncrosslinked and crosslinked PTMSP films supported on silicon wafers. The ellipsometry results showed that crosslinking does not markedly slow physical aging of thin PTMSP films.     

Chemical modification of polyolefin blends

The effect of crosslinking on the properties of low density polyethylene / polypropylene blends was investigated. It was found that crosslinking results in much higher deformability of the blends compared to uncrosslinked materials. A decrease in crystalline portion determined by DSC leads to lower modulus in crosslinked samples. High drawability of crosslinked samples is mainly attributed to peculiar behaviour of PE part of the crosslinked blend where thicker lamellae are formed during drawing.     

Mesomorphic properties of liquid crystalline polysiloxanes and elastomers based on a tri-vinyl crosslinker

A series of crosslinked liquid crystalline polymers and the corresponding uncrosslinked liquid crystalline polymers were prepared by graft copolymerization; their liquid crystalline properties were characterized by DSC, POM and X-ray measurements. The results show that the crosslinking obtained in the isotropic state leads to a reduction of the clearing point (T_c) of the crosslinked polymers, as compared with the corresponding uncrosslinked polymers. The crosslinked polymers with low crosslinking density (P₁-P₇) exhibit nematic mesogenic phases, as do the uncrosslinked polymers. In contrast, a high crosslinking density leads to the crosslinked polymers P₈ and P₉ losing their thermotropic liquid crystalline phases; they instead exhibit stress-induced orientation.     

The effect of crosslinking of polyolefins on the crack growth rate during three-point bending

The effect of crosslinking on the stress - strain curves and on the crack growth rate was investigated in three point experiments for notched samples of polyethylene, polypropylene, blends of PE and polypropylene, and PE filled with silica. The crosslinking was found to affect positively the tear resistance of multiphase materials. The stress - strain curves as recorded during experiments for uncrosslinked samples show maxima which are entirely a result of the notch growth. The dependence is almost linear if the curves are recalculated with respect to the change of the sample cross-section during the experiment. The same curve for crosslinked materials indicates a significant portion of plastic deformation. The rate of the crack growth of crosslinked samples is approx. by one order of magnitude lower than that of uncrosslinked materials.     

Dynamics of cyclodimerization and viscoelasticity of photo‐crosslinkable PVA

We investigated the interfacial properties of poly(vinyl alcohol) carrying UV‐crosslinkable pendant quaternized stilbazole (styrylpyridinium), PVA‐SbQ. The extent and dynamics of PVA‐SbQ cyclodimerization reactions and crosslinking induced by UV irradiation were monitored in situ and in real time by quartz crystal microgravimetry (QCM). Sensograms reflecting time‐dependent changes in density and viscoelasticity of crosslinking films followed a Boltzmann sigmoidal model, depending on precursor film composition and irradiation power. The shifts in QCM frequency and energy dissipation upon PVA‐SbQ cyclodimerization correlated with three photo‐crosslinking phases involving soft‐to‐rigid transitions, namely, induction (initiation), main crosslinking (interaction), and termination. PVA‐SbQ films crosslinked to different degree were used as protein carriers and a slower release profile was determined for the films that underwent more extensive crosslinking. Overall, this study demonstrates for the first time the dynamics of PVA‐SbQ crosslinking and its impact in system viscoelasticity and protein release. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 345–355     

同轴静电纺丝法制备具有核-壳纤维结构的多功能敷料

利用同轴静电纺丝制备了具有核壳结构纳米纤维的未交联敷料,其中纤维内核为载有抗菌药物莫匹罗星的聚己内酯(PCL),外壳则由载有麻醉剂利多卡因的胶原构成;通过京尼平将胶原外壳交联后得到交联敷料.用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察了未交联敷料的表面形貌和纤维的核壳结构.体外药物释放实验结果表明,在2种敷料中,2种药物在1 h内均出现了突释现象,而在随后的60 h中,2种药物均能从敷料中缓慢释放出来,说明2种敷料均具有较好的持续止痛与抗菌性能.二辛可宁酸(Bicinchonininc acid,BCA)蛋白测试结果表明,未交联敷料外壳上的胶原蛋白能够持续地释放出来.体外细胞培养结果表明,与交联敷料相比,未交联敷料能够更好地促进成纤维细胞L929的黏附和生长,具有更好的促进伤口愈合作用.体外抗菌实验结果显示,负载了莫匹罗星的2种敷料的抗菌性能均明显高于对照组,具有良好的抗菌性能.     

Study on the toughening mechanism of PP/EVA dynamically crosslinked blend

The toughening mechanism of polypropylene (PP)/ethylene-co-vinyl acetate (EVA) dynamically crosslinked blend was investigated. The results indicated that dynamical crosslinking technology not only improved the interfacial adhesion between PP and EVA, but also increased the mechanical properties of PP/EVA blend. The quantitative and qualitative analysis of scanning electron microscopy (SEM) micrographs demonstrated that dynamical crosslinking technology could refine EVA particles in PP/EVA blend and promote the size distribution of EVA particles. The critical matrix ligament thickness of dynamically crosslinked and uncrosslinked blend was about 0.55 μm and 0.6 μm, respectively, indicating that the brittle-ductile transition occurred. Dynamic mechanical analysis (DMA) results illustrated that the tan δ peak of PP component in the dynamically crosslinked blend moved toward lower temperature compared with that of pure PP and the PP component in uncrosslinked blend; and the tan δ value of the dynamically crosslinked blend was higher than that of the uncrosslinked blend, which interpreted the toughening mechanism of dynamical crosslinking technology from the dynamic mechanical property of the blend.     

Living cationic polymerization of a coumarin‐substituted vinyl ether and reversible photoinduced crosslinking of the resulting homopolymers and amphiphilic block copolymers

Living cationic polymerization of 4‐methyl‐7‐(2‐vinyloxyethoxy)coumarin (CMVE) was achieved using SnCl₄ in the presence of nBu₄NBr as an added salt at 0 °C. The number‐average molecular weight of the resulting polymers increased in direct proportion to the monomer conversion while retaining relatively low polydispersity. Structural analysis revealed that the resulting polymers carried pendant coumarinyl moieties. These coumarinyl moieties were crosslinked by irradiation with UV light at λ_max = 366 nm, and the crosslinked sites were then cleaved by irradiation with UV light at λ_max = 254 nm. The crosslinking behaviors of the polymers were studied by UV and FTIR spectroscopic measurement. PolyCMVE was soluble in dichloromethane but was found to be insoluble upon UV light irradiation. We also synthesized amphiphilic block polymers bearing coumarinyl moieties by living cationic copolymerization with an amphiphilic vinyl ether. The resulting block polymers were soluble in an aqueous medium and also formed micelle‐like aggregates. Upon UV irradiation of aqueous solutions above the critical micelle concentration, an efficient crosslinking reaction occurred. Photoinduced structural changes of these polymer aggregates in the solution state were further investigated. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Photoresponsive water‐dispersible polyaniline nanoparticles through template synthesis with copolymer micelle containing coumarin groups

A novel kind of photosensitive water‐dispersible polyaniline (PANI) nanoparticles was designed and prepared by template synthesis using a photo‐responsive vinyl‐coumarin (VM)/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) copolymer micelle containing coumarin moieties. The resulting PANI nanoparticles exhibited reversible photo‐crosslinking and photo‐decrosslinking behavior similar to coumarin moiety upon irradiation with different UV light as verified by UV–vis absorption. In addition, photoinduced size change of the PANI nanoparticles after 365 nm UV light irradiation was successfully monitored by dynamic light scattering and transmission electron microscopy measurements, further confirming the photosensitivity of the obtained PANI nanoparticles by the incorporation of VM/AMPS copolymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

丙烯酸交联壳聚糖渗透汽化膜研究（Ⅰ）——膜结构及交联机理

报道了一种新型渗透汽化膜－－丙烯酸交联壳聚糖膜，通过溶胀、拉伸、渗透汽化分离以及红外光谱等手段研究了膜的结构和交联机理。实验结果表明，交联反应由两部分组成：丙烯酸的双键和壳聚糖的氨基的加成反应和丙烯酸另一端的羧基和壳聚糖的氨基的酸碱中和反应。     

Crosslinkable poly(propylene carbonate): High‐yield synthesis and performance improvement

A crosslinking strategy was used to improve the thermal and mechanical performance of poly(propylene carbonate) (PPC): PPC bearing a small moiety of pendant C?C groups was synthesized by the terpolymerization of allyl glycidyl ether (AGE), propylene oxide (PO), and carbon dioxide (CO₂). Almost no yield loss was found in comparison with that of the PO and CO₂ copolymer when the concentration of AGE units in the terpolymer was less than 5 mol %. Once subjected to UV‐radiation crosslinking, the crosslinked PPC film showed an elastic modulus 1 order of magnitude higher than that of the uncrosslinked one. Moreover, crosslinked PPC showed hot‐set elongation at 65 °C of 17.2% and permanent deformation approaching 0, whereas they were 35.3 and 17.2% for uncrosslinked PPC, respectively. Therefore, the PPC application window was enlarged to a higher temperature zone by the crosslinking strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5329–5336, 2006     

Preparation and characterization of poly(l-lactic acid)/TiO2 nanoparticle nanocomposite films with high transparency and efficient photodegradability

Poly(l-lactic acid)-TiO₂ nanoparticle nanocomposite films were prepared by incorporating surface modified TiO₂ nanoparticles into polymer matrices. In the process of preparing the nanocomposite films, severe aggregation of TiO₂ nanoparticles could be reduced by surface modification by using carboxylic acid and long-chain alkyl amine. As a result, the nanocomposite films with high transparency, similar to pure PLA films, were obtained without depending on the amount of added TiO₂ nanoparticles. A TEM micrograph of the nanocomposite films suggests that the TiO₂ nanoparticles of 3-6 nm in diameter were uniformly dispersed in polymer matrices. Photodegradation of PLA-TiO₂ nanoparticle nanocomposite films was also investigated. The results showed that nanocomposite films could be efficiently photodegraded by UV irradiation in comparison with pure PLA.     

1,4-双(二苯基膦)丁烷交联的季膦化聚芳醚酮阴离子交换膜

以1,4-双(二苯基膦)丁烷为交联剂,以具有四甲基联苯结构的聚芳醚酮为基体材料,分别制备了刚性三苯基膦和柔性三丁基膦修饰的阴离子交联膜材料.交联剂在交联结构形成的过程中转变成季膦盐,在提高膜材料机械稳定性的同时保持离子交换功能基团的含量.研究了2种阴离子交换膜的尺寸稳定性、电导率、机械性能及耐碱稳定性等.研究结果表明,当交联度为20%时,三苯基膦与三丁基膦修饰的阴离子交换膜的拉伸强度分别由未交联时的27和18 MPa提高到45和30 MPa;交联的膜材料在60℃的3 mol/L KOH溶液中浸泡120 h后,三苯基膦修饰的阴离子交换膜的电导率保留率为81%,三丁基膦修饰的阴离子交换膜的电导率保留率为69%,膜的耐碱稳定性均较未交联时有明显提高.交联度相同时,三苯基膦修饰的阴离子交换膜表现出更高的拉伸强度和更好的耐碱稳定性.     

Effect of UV irradiation on the physico-chemical properties of iron crosslinked collagen

Collagen is the main component of connective tissue and finds immense applications as a biomaterial. In this study, effect of UV irradiation on collagen crosslinked with iron has been carried out. The physical and optical properties of crosslinked collagen affected by UV irradiation were analyzed using electrospectral and fluorescence studies. The electronic spectral studies showed that the photoproducts formed on UV radiation decrease in the presence of iron. Circular dichroic studies revealed that the conformational changes brought about in the protein due to UV irradiation have been reduced owing to the crosslinking with iron. However, prolonged irradiation does bring about conformational changes to the protein.     

UV-INDUCED PROTEIN ALTERATIONS AND LIPID OXIDATION IN ERYTHROCYTE MEMBRANES

Certain ultraviolet radiation-induced effects in skin may result from primary photochemical alterations in cell membranes. We have studied isolated erythrocyte membranes in order to determine the UV-fluence and wavelength dependence for protein alterations and lipid oxidation. Protein crosslinking was detected as high molecular weight protein (greater than 200,000 DA) on polyacrylamide/agarose gel electrophoresis. Spectrin decreased more rapidly than the other membrane proteins upon exposure to lambda = 250-380 nm radiation. Nitrogen-purging inhibited the UV-induced decrease in spectrin by 60% and decreased crosslinking to an even greater degree. The decrease in spectrin was not inhibited by superoxide dismutase, catalase, or sodium azide. Radiation at 280 nm was most effective for spectrin loss, 265 and 297 nm were less effective and 254 and 313 nm were not effective. Prior irradiation at 280 nm did not sensitize the membranes to subsequent irradiation at 313 nm indicating that photodecomposition products of tryptophan are not involved. Lipid photooxidation was measured with the thiobarbituric acid assay and was induced at higher fluences of UV radiations than those required for loss of spectrin. These results indicate that the major effects of UV radiation on cell membranes are alterations of proteins and suggest that tryptophan is the major chromophore for these alterations.     

UV‐induced crosslinking of ring opening metathesis block copolymer micelles

Statistical and amphiphilic block copolymers bearing cinnamoyl groups were prepared by ring opening metathesis polymerization (ROMP). The UV‐induced [2 + 2] cycloaddition reaction of polymer bound cinnamic acid groups was studied in polymer thin films as well as in block copolymer micelles. In both cases, exposure to UV‐light for 10 min led to a crosslinking conversion of about 60%, as determined by FT‐IR spectroscopy and UV–vis absorption measurements. Time based IR‐spectroscopy revealed a maximum conversion of 78% reached after an irradiation time of about 16 min. For micelles obtained from polymers bearing 5 mol % or more cinnamoyl groups, the crosslinking reaction proceeded smoothly, yielding in crosslinked particles which were stable in a non‐selective solvent (CHCl₃). Diameters determined by dynamic light scattering in the selective solvent (MeOH) were similar for both, non‐crosslinked and crosslinked micelles, whereas diameters of crosslinked micelles in the non‐selective solvent (CHCl₃) were significantly larger compared to MeOH samples. This strategy of direct self assembly of block‐copolymers in a selective solvent followed by “clean” crosslinking, without the need for additional crosslinking reagents or crosslinking initiators, provides a straight forward approach toward ROMP‐based polymeric nano‐particles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2402–2413, 2008     

脉冲电沉积Pd-Ni合金纳米颗粒及其甲酸电催化氧化

采用方波脉冲方法,在钯镍合金电解液中成功地电化学沉积出镍原子含量分别为12.0%、16.4%和22.6%的钯镍合金纳米颗粒. 钯镍合金纳米颗粒为球状,粒径50 ~ 80 nm. 随钯镍合金生长电位负移,合金的镍含量提高,其纳米颗粒大小基本相似但纳米颗粒数目增多,交联度提高和真实活性面积增大. 钯镍合金纳米颗粒镍含量提高,在硫酸溶液中其氢弱吸附峰电流增大. 钯镍合金纳米颗粒电极的甲酸电催化氧化活性较好,随合金纳米颗粒的镍含量提高和交联度增加,合金纳米颗粒电极的甲酸电催化氧化稳定性更高.     

Photochemical precipitation of copper particles on the quartz surface modified with polybutoxytitanium

Results of photochemical precipitation of copper nanoparticles on the surface of polybutoxytitanium film applied to the surface of quartz sublayer and modified by the UV irradiation with the excitation wavelength 254 nm are presented. Photocatalytic activity of polybutoxytitanium film modified by the UV light was confirmed. It was established that photoprecipitated copper nanoparticles form a uniform stable coating consisting of tightly packed particles of 50 nm diameter and 8 nm height.     

Effect of crosslinking on the properties of partially fluorinated anion exchange membranes

A series of crosslinked, ammonium‐functionalized, and partially fluorinated copolymers have been prepared and evaluated as anion exchange membranes. In order to investigate the effect of crosslinking on the membrane properties, precursor copolymers containing chloromethyl groups were crosslinked with various aliphatic diamines followed by quaternization with monoamines. Crosslinking was effective in lowering water absorbability at no expense of high hydroxide ion conductivity of the membranes. By tuning the degree of crosslinking (20 mol %) and crosslinker chain length (C6 and C8), the highest ion conductivity of 73 mS/cm (at 80°C in water) was achieved. Furthermore, alkaline stability of the membranes was also improved by the crosslinking; the remaining ion conductivity after the stability test (in 1 M potassium hydroxide at 80°C) was 8.2 mS/cm (after 1000 h) for the C6 crosslinked membrane and 1 mS/cm (after 500 h) for the uncrosslinked membrane, respectively. The ammonium groups attached with the crosslinkers seemed more alkaline stable than the uncrosslinked benzyltrimethylammonium groups, while the polymer main chain was intact under the harsh alkaline conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1059–1069     

EFFECTS OF ORGANIC COLORANTS ON PHOTO-INITIATED CROSSLINKING AND PHOTO-OXIDATION DEGRADATION OF POLYETHYLENE AND RELATED MECHANISM

The effects of three organic colorants on photo-initiated crosslinking and photo-oxidation degradation of polyethylene (PE) samples irradiated by microwave excited (MWE) UV lamp in the melt and the related mechanism have been studied by gel content and thermal extension rate determinations,X-ray photoelectron spectroscopy (XPS),mechanical property tests,UV spectroscopy,and light microscope.The data from the gel content and thermal extension rate determinations of photo-crosslinked polyethylene (XLPE) sam...