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1.
Polyurethane cationomers with increased contents of ions were synthesised in the reaction of 4,4′-methylenebis(phenyl isocyanate) (MDI) with polyoxypropylene glycol (M = 450) and N-methyl diethanolamine (N-MDA). Amine segments were built-in to the urethane–isocyanate prepolymer in the reaction with formic acid and then they were converted to alkyl-ammonium cations. The obtained isocyanate prepolymers were then extended in the aqueous medium with the use of 1,6-hexamethylenediamine. That yielded stable aqueous dispersions, which were applied on the surfaces of test poly(tetrafluoroethylene) samples. After evaporation of water, the dispersions formed thin polymer coatings. 1H and 13C NMR spectral methods were employed to confirm chemical structures of synthesised cationomers and to modify their quantitative composition in relation to that assumed on the basis of the stoichiometry of the reactions, which were conducted on successive stages of the polyaddition process. Furthermore, the GPC method was used to learn the sizes and distributions of mean molecular weights of those cationomers. Based on 1H NMR spectra, the factor κ was calculated which represented the polarity level of the obtained cationomers. Good correlation was found between that factor and the free surface energy γ S (increasing in the range 38–42 mJ/m2) as well as its polar and acid-base components, as determined from the van Oss–Good model on the basis of measured wetting angles between the coatings and model liquids with various polarities. The values of κ and γ S parameters resulted principally from the increasing amounts of cations NH+, which were evaluated on the basis of the concentrations of tertiary nitrogen atoms increasing within 1.37–2.66 wt%. Those concentrations and amounts resulted, in turn, from the amounts of amine N-MDA which could be built into cationomers. The effects were discussed of chemical structures and polarity specifications of polyurethane cationomers on the viscosities of produced aqueous dispersions and on the sizes of their colloidal particles, on the values of free surface energy and on its polar and acid-base components, and on the glass transition temperatures T g2 of the rigid segments as found by the differential scanning calorimetry (DSC) method.  相似文献   

2.
α‐Butyl ω‐N, N‐dihydroxyethyl aminopropylpolymethylhydrosiloxane (PDMS), a monotelechelic polydimethylsiloxane with a diol‐end group, which is used to prepare siloxane–urethane dispersion, was successfully synthesized. Then, novel silicone‐based polyurethane (PU)‐dispersion was prepared by the addition polymerization of hexamethylene diisocyanate, to PDMS, polyethylene glycol (PEG) and dimethylol propionic acid. The goal of this study was to explore the potential use of polysiloxane–urethane in marine coatings in order to boost the flexibility, adhesion, erosion and foul‐release property with respect to PDMS/PEG ratio (PDMS wt%). The PDMS was characterized by Fourier‐transform infrared (FT‐IR), proton nuclear magnetic resonance and carbon‐13 nuclear magnetic resonance spectroscopic techniques. The results showed that each step was successfully carried out and the targeted products were synthesized in all cases. The structural elucidation of the synthesized waterborne PU and waterborne polysiloxane–urethane (WBPSU) was carried out by FT‐IR spectroscopic technique. Thermal properties of the resins were studied by using thermogravimetric analysis and differential scanning calorimetry. The antifouling property of the coatings was investigated by the immersion test under a marine environment for 90 days. The fouled area was calculated for all the samples, and the fouled area (%) decreased with increasing PDMS content. After 90 days, the lowest fouled area (6%) was observed in the sample using WBPSU2 (PDMS 4.48 wt%) among all of the samples. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

3.
It is of great significance to synthesize polyolefin/polysiloxane hybrid materials due to their unique combination of crystalline polyolefin segments and semiorganic polysiloxane segments. Herein, we report the syntheses of a novel polypropylene/polydimethylsiloxane (PP‐g‐PDMS) graft copolymer via the coupling reactions between maleic anhydride‐grafted PP and monoaminopropyl‐terminated PDMS. The chemical structures of PP‐g‐PDMS have been characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The correlation between reaction conditions and the structural parameters of PP‐g‐PDMS has been established. Consequently, the potential applications of resultant PP‐g‐PDMS were investigated, and the results showed that PP‐g‐PDMS can serve as an efficient compatibilizer in heterogeneous PP/PDMS blend system and also as an ideal processing aid for high‐viscosity PP.  相似文献   

4.

A new cross‐linkable waterborne siloxane‐polyurethane dispersion (PEDA‐SiPU) was synthesized by incorporating the acrylate groups into the side chain of the polyurethane using the pentaerythritol diacrylate(PEDA) and introducing polysiloxane groups into the soft segment of the polyurethane using dihydroxybutyl‐terminated polydimethylsiloxane (PDMS). They can form the cross‐linking structure by UV radiation in the presence of a photo‐initiator. Fourier transform infrared spectroscopy (FTIR) was used to identify the chain structure of PEDA‐SiPU. The effect of the PDMS content and the PEDA content on the C?C conversion behaviors under UV irradiation was investigated. Water resistance and the mechanical properties of the UV cured films were also studied. Through the controlling of suitable content of PDMS and PEDA introduced in the chain, the obtained PEDA‐SiPU films were proved to possess both good water resistance and mechanical properties.  相似文献   

5.
The reaction in bulk at high temperature of α,ω-aminopropyl oligodimethylsiloxane and thermoplastic polyurethane (TPU) allowed observing interesting behavior. Mixing at 200 °C first involved dissociation of urethanes and splitting of polyurethane chains followed by reaction of the released isocyanates with amino end-groups of the oligosiloxane. At this stage, a copolymer was formed which morphology consisted of a very fine dispersion of the polysiloxane domains at the nanoscale (20 nm) with a narrow size dispersity. The polymer blend was perfectly transparent. Increasing the reaction time resulted in a significant coarsening of the morphology and a consequent loss of transparency. The reason for such a morphology evolution has been elucidated. The progressive formation of alkyl–alkyl urea linkages at the expense of aryl–alkyl bonds obtained earlier in the process caused an increase in the average number of successive polydimethylsiloxane (PDMS) blocks that organized in larger domains. The average number of consecutive polysiloxane segments was found to evolve from ~1.5 in the first 10–15 min to a value of 3–5 at the end of the reactive process.  相似文献   

6.
Our main objective was the design, synthesis, characterization, and testing of a novel class of materials, thermoplastic amphiphilic conetworks (TP‐APCNs). A further objective was the evaluation of TP‐APCNs as biomaterials, for example, as immunoisolatory membranes in a bioartificial pancreas, or as extended‐wear soft contact lenses. The synthesis of the first TP‐APCNs was accomplished by blending an amphiphilic graft polymer, poly(dimethyl acryl amide)‐g‐polydimethylsiloxane (PDMAAm‐g‐PDMS), with a commercial PDMS‐containing polyurethane (PU). The common PDMS segments coalesce and form a single phase, whereas the hard/crystalline segments of the PU physically crosslink the blend. The properties of TP‐APCNs can be controlled by the graft/PU ratio and segment molecular weights. TP‐APCNs with cocontinuous hydrophilic and hydrophobic phases were prepared as demonstrated by swelling in water and n‐heptane. Depending on the blend ratio and molecular weights, optically clear water‐swollen TP‐APCNs with 0.5–4 MPa tensile strength, 70–280% elongation, together with 2–11 × 10?7 cm2/s glucose permeability, and 1.2–8 × 10?8 cm2/s insulin permeability were prepared. TP‐APCNs are processible by casting and molding. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 682–691, 2009  相似文献   

7.
An ionic diol bearing a one‐sided urethane‐stilbene group located on the ammonium quaternary structure was prepared and proposed as an intermediate for polyurethane ionomer synthesis. Polyurethane cationomers with stilbene ionic groups based on poly(tetramethylene oxide) diols, 4,4′‐diphenylmethane diisocyanate and the aforementioned ionic diol, were synthesized and characterized. Some aspects of the trans–cis photoisomerism and fluorescent emission of the stilbene chromophore in polyurethane cationomers were studied comparatively with the urethane‐stilbene diol. The stilbene polycations absorbed at λA = 316 nm and emitted violet‐blue light with an emission maxima at λF = 444 nm (dimethylformamide solution) and λF = 465 nm (film). These polymers are known for their elastomeric properties and are assumed to be of great interest for some future applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1918–1928, 2002  相似文献   

8.
Hyperbranched polysiloxane polymers with multivinyl functionality were designed and synthesized through a “one‐step and one‐pot” deactivation enhanced atom transfer polymerization (DE‐ATRP) approach from the copolymerization of polydimethylsiloxane (PDMS) macromonomers and divinylbenzene (DVB). Various feed ratios of siloxane‐based monomer and divinyl monomers were investigated. We showed that even at DVB concentrations as high as 80 mol % in the feed, 65% yield of hyperbranched polymer could be obtained without gelation because the DE‐ATRP suppressed the rapid formation of macronetwork structures. The molecular weight, polydispersity, macromolecular structure of hyperbranched poly(DVB‐co‐PDMS) as well as its viscosity in silicone oil were characterized by GPC‐MALLS, 1H NMR and rheometer. By tracking the relationship between the radius of gyration, elution volume and molecular weight from MALLS analysis, solid evidences of the highly branched and condensed structure of the polymers were obtained. Furthermore, the oil thickening experiments demonstrate that this hyperbranched polymer can act as a well‐controlled viscosity‐modifier for Silicone oils, which potentially will have important application in coating, cosmetic and pharmaceutical products. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

9.
Well‐defined amphiphilic pentablock copolymers Siy‐(EGx‐FAz)2 composed of polysiloxane (Si), polyethylene glycol (EG), and perfluorohexylethyl polyacrylate (FA) blocks are synthesized by ATRP of FA monomer starting from a difunctional bromo‐terminated macroinitiator. Diblock copolymers EGx‐FAz are also synthesized as model systems. The block copolymers are used, either alone or blended with a PDMS matrix in varied loadings, to prepare antibiofouling coatings. Angle‐resolved XPS and contact angle measurements show that the coating surface is highly enriched in fluorine content but undergoes reconstruction after contact with water. Protein adsorption experiments with human serum albumin and calf serum highlight that diblock copolymers resist protein adhesion better than do pentablock copolymers. Blending of the pentablock copolymer with PDMS results in increased protein adsorption. By contrast, the PDMS‐matrix coatings show high removal percentages of sporelings of the green fouling alga Ulva linza. © 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015 , 53, 1213–1225  相似文献   

10.
Polyurethane cationomers were synthesised in the reaction of various diisocyanates with polyoxypropylene glycol and two N-alkyldiethanolamines. The obtained isocyanate prepolymers were then extended in the aqueous medium by means of 1,6-hexamethylenediamine; stable aqueous dispersions were thus obtained, which were applied to and distributed over the poly(tetrafluoroethylene) surface. After evaporation of water from those dispersions, thin polymer coatings were produced. The analyses with the use of 1H, carbon-13 nuclear magnetic resonance and infrared spectroscopy methods confirmed chemical structures of synthesised cationomers. Also, attempts were made to quantitatively characterise polarities of those structures by means of factors that were defined especially for that purpose. Moreover, the physical model of van Oss–Good and wetting angles for coatings obtained from the polyurethane cationomers in question, measured with the use of standard liquids with various polarity specifications, were utilised to determine the surface free energy values for the obtained ionomers.  相似文献   

11.
Polyurethane cationomers were synthesised in the reaction of 4,4’-methylenebis(phenyl isocyanate) with polyoxyethylene glycol (M?= 2,000) or poly(tetrafluoroethyleneoxide-co-difluoromethylene oxide) α,ω-diisocyanate and N-methyl diethanolamine. Amine segments were built-in to the urethane-isocyanate prepolymer in the reaction with 1-bromobutane or formic acid, and then they were converted to alkylammonium cations. The obtained isocyanate prepolymers were then extended in the aqueous medium that yielded stable aqueous dispersions which were applied on the surfaces of test poly(tetrafluoroethylene) plates. After evaporation of water, the dispersions formed thin polymer coatings. 1H, 13C NMR and IR spectral methods were employed to confirm chemical structures of synthesised cationomers. Based on 1H NMR and IR spectra, the factors κ and α were calculated, which represented the polarity level of the obtained cationomers. The DSC, wide angle X-ray scattering and atom force microscopy methods were employed for the microstructural assessment of the obtained materials. Changes were discussed in the surface free energy and its components, as calculated independently according to the method suggested by van Oss–Good, in relation to chemical and physical structures of cationomers as well as morphology of coating surfaces obtained from those cationomers. Fluorine incorporated into cationomers (about 30%) contributed to lower surface free energy values, down to about 15 mJ/m2. That was caused by gradual weakening of long-range interactions within which the highest share is taken by dispersion interactions.  相似文献   

12.
Polyurethane cationomers were synthesised in the reaction of 4,4′-methylenebis(phenyl isocyanate) with polyoxypropylene glycol (M = 450) and N-methyl diethanolamine. Amine segments were built-in to the urethane–isocyanate prepolymer in the reaction with 1-bromoalkanes (C2–C10), and then they were converted to alkyl-ammonium cations. The obtained isocyanate prepolymers were then extended in the aqueous medium. That yielded stable aqueous dispersions which were applied on the surfaces of test poly(tetrafluoroethylene) plates. After evaporation of water, the dispersions formed thin polymer coatings. 1H and 13C NMR spectral methods were employed to confirm chemical structures of synthesised cationomers. Based on 1H NMR and IR spectra, the factors κ and α1 or α1 were calculated, which represented the polarity level of the obtained cationomers. The differential scanning calorimetry method revealed decline of T g for the hard urethane and urea segments from 60 °C to 46 °C when the number of carbon atoms increased in the alkyl radical attached to the ammonium cation. Changes were discussed in the surface free energy (SFE) and its components, as calculated independently according to the methods suggested by van Oss-Good and by Owens–Wendt, in relation to chemical structures of cationomers. The growing length (from C2 to C10) of the alkyl radical attached to the N atom in the cationomer chain was found to reduce the value of SFE of the polymer coating from 46 to 28 mJ/m2. That is caused by gradual weakening of long-range interactions, within which the highest share is taken by dispersion interactions.  相似文献   

13.
Polyurethane (PU) cationomers have been synthesized by quaternizing tertiary amine-containing linear polyurethanes using different quaternizers containing acid groups. The effect of chemical structure of PU cationomers on the physical properties was studied. The mechanical properties of PU cationomers were improved with decreasing molecular weight of poly(caprolactone) glycol, and increasing concentration of quaternary ammonium. Decreasing the carbon number in the alkyl group of the N-alkyl diethanol-amine chain-extenders, and using rigid symmetrical diisocyanates, the mechanical properties of the PU cationomers were increased. The effects of these factors on the glass transition temperature of PU cationomers were also examined. The mechanical properties of the PU cationomers decreased by immersion in water and recovered after removal of the water.  相似文献   

14.
Various novel block cationomers consisting of polyisobutylene (PIB) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) segments were synthesized and characterized. The specific targets were various molecular weight diblocks (PIB‐b‐PDMAEMA+) and triblocks (PDMAEMA+b‐PIB‐b‐PDMAEMA+), with the PIB blocks in the DPn = 50–200 range (number‐average molecular weight = 3,000–9000 g/mol) connected to blocks of PDMAEMA+ cations in the DPn = 5–20 range (where DP is the number‐average degree of polymerization). The overall synthetic strategy for the preparation of these block cationomers had four steps: (1) synthesis by living cationic polymerization of mono‐ and diallyltelechelic polyisobutylenes, (2) end‐group transformation to obtain PIBs fitted with termini capable of mediating the atom transfer radical polymerization (ATRP) of DMAEMA, (3) ATRP of DMAEMA, and (4) quaternization of PDMAEMA to PDMAEMA +I? by CH3I. Scheme 1 shows the microarchitecture and outlines the synthesis route. Kinetic and model experiments provided guidance for developing convenient synthesis methods. The microarchitecture of PIB–PDMAEMA di‐ and triblocks and the corresponding block cationomers were confirmed by 1H NMR and FTIR spectroscopy and solubility studies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3679–3691, 2002  相似文献   

15.
A series of phenyl polysiloxane‐modified polyurea/polyurethanes ( SPUs ) with different silicone loadings (10, 20, 30, and 40 wt %) have been designed and synthesized. The structures of SPUs were confirmed by 1H NMR, 13C NMR, and FT‐IR. The impact of phenyl polysiloxane content on the properties of SPUs was fully studied. The residual methoxy groups on silicon could help SPUs form interpenetrating networks accompanying with the residual isocyanate under moisture, which was different with the conventional moisture‐crosslinking polyurethane system. The properties of SPUs films have been fully researched by attenuated total reflection flourier transformed infrared spectroscopy, thermal analysis, tensile tests, water contact angle, X‐ray photoelectron spectroscopy, SEM, and AFM. Results indicated that the introduction of phenyl polysiloxane improved the thermal stability and remarkably increased the water contact angles accompanying with a comparable mechanical strength to the pure polyurethane. Meanwhile, it also brought out the decreased microphase separation and water absorption. The obvious surface migration has been observed in the SPUs , which changed their surface properties. Some voids were observed in all moisture curing SPUs system, but the phenyl silicone content impacted on the numbers and sizes of the voids. The phenyl groups introduced and carbon dioxide produced in the crosslinking procedure helped to form and stabilize the voids in the SPUs . © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1794–1805  相似文献   

16.
Polyurethane and polyurethane cationomers were synthesized using 2,3-dihydroxypyridine and 2,3-dihydroxypyridine hydrochloride as chain extenders. Poly(butyl methacrylate-co-methacrylic acid) was synthesized by free radical solution polymerization and was converted into its sodium salt. The polyurethane cationomer and the acrylic anionomer were blended in different proportions in N,N-dimethylformamide. Simple blends without ionic groups were also prepared. Miscibility enhancement in these systems was studied by means of differential scanning calorimetry and scanning electron microscopy.  相似文献   

17.
Composite latex particles of acrylate and polydimethylsiloxane (PDMS) with high PDMS content was prepared by emulsion copolymerization and characterized by particle size analyzer, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). With gemini surfactant as the co-emulsifier in the system, the PDMS content in the system reached 50%, which was far higher than the other reported values. Through the characterization of the particle size analyzer, the particle size augmented with the increase of the amount of PDMS, which could be said that the polysiloxane had participated into the reaction and had been introduced into the colloid particle. The results of FTIR indicated that almost all the monomer had been exhausted in the reaction because there was no C=C and D4 characteristic peaks in the spectrum. Besides the surface properties also were measured by surface tension analysis, water absorption, and the static contact angle, it could be found that with the increase of polysiloxane content, the excellent properties acquired by PDMS were clearly revealed by the findings, such as the decrease of surface tension and water absorption, and the increase of static contact angle. All the measurements were consistent with the conclusion that the composite latex particles of polysiloxane and acrylate with high siloxane content had been prepared successfully.  相似文献   

18.
The synthesis of copolymers constituted of a central polydimethylsiloxane (PDMS) block flanked by two polyamide (PA) sequences is described. α, ω-diacyllactam PDMS, when used as macroinitiator of lactam polymerization, gives rise to the expected triblock copolymer. Likewise, PDMS-g-PA graft copolymers are obtained from acyllactam containing polysiloxanes. NaAlH2(OCH2CH2OMe)2 turns out to be the best suited activating agent for the polymerization of ?-caprolactam, in the experimental conditions required for the synthesis of polysiloxane–polyamide copolymers. The nucleophilic species formed by reaction of NaAlH2(OCH2CH2OMe)2 with ?-caprolactam—2-[bis(methoxyethoxy) aluminumoxy]-1-azacycloheptane sodium—is indeed nucleophilic enough to bring about the growth of PA chains and mild enough to stay inert towards PDMS. © 1993 John Wiley & Sons, Inc.  相似文献   

19.
A series of α, ω–bishydroxyl terminated PDMS, hydroxypoly(ethylene oxide) propyl–b–polydimethylsiloxane–b–propyl hydroxypoly(ethylene oxide) (HPEO–PDMS–HPEO) was prepared by a hydrosilation reaction of monoallyloxy substituted poly(ethylene oxide) with α,ω–bishydrogen terminated PDMS (HPDMS) that obtained via acid–catalyzed ring–opening polymerization of octamethylcyclotetrasiloxane with 1,1,3,3–tetramethyldisiloxane. Chloroplatinic acid was employed as the catalyst of hydrosilation. The molecular weight of HPEO–PDMS–HPEO could be controlled easily by varying the chain length of HPDMS. FTIR and 1H–NMR spectroscopy were used to identify the structure of HPEO–PDMS–HPEO and HPDMS. The conversion of Si–H bond to Si–C bond was affected by the catalyst amount, reaction time and temperature. It was found that the optimum condition of hydrosilation reaction was the catalyst amount of 22 μg/g and 5 h time at 100°C. Synthesized HPEO–PDMS–HPEO showed good storage stability at ambient temperature. Urethane reaction of OH and NCO group revealed that HPEO–PDMS–HPEO was more reactive toward to diisocyanate than α, ω –bishydroxylbutyl terminated PDMS.  相似文献   

20.
Novel copolymers of polyurethane (PU) were prepared by direct transurethanetion reaction of a commercial PU with polydimethylsiloxanes (PDMS, MW 1000, 5000, and 10,000) containing hydroxyl end-groups. Transurethanetions with different mass ratios of hydrophobic PDMS to hydrophilic PU chains (PDMS1000–PU: 43:57, 67:33, 71:29, and 80:20; PDMS5000–PU: 37:63, and 51:49; PDMS10000–PU: 51:49) were carried out in solution at 65 and 100 °C. In catalyzed reactions, dibutyltin dilaurate (SnC32H64O4) was used to promote bond breaking in the PU chain and accelerate the reaction between hydroxyl end-groups of PDMS and regenerated isocyanates of PU. The chemical structures of the prepared copolymers were comprehensively characterized by 1H, 13C, and 29Si NMR spectroscopies. According to elemental analysis, the content of PDMS varied between 3 wt.% and 16 wt.%, and results obtained from the 1H NMR spectroscopy were in good agreement with the results of elemental analysis. Increased length of the hydrophobic chain increased the content of PDMS in the copolymer. The GPC results showed that molar masses of the PUPDMS copolymers were lower than the molar mass of the starting PU. The glass transitions (Tg) of the copolymers were shifted to lower temperature as compared with Tg of the starting polyurethane. ATR FTIR spectroscopy showed the surface of the copolymer films to be enriched with siloxane groups and, according to electron microscopy, it was textured with microspheres. The static contact angles for copolymer films measured with deionized water ranged from 94° to 117°. The different structural, thermal and surface properties of the PUPDMS copolymers as compared with PU indicated that transurethanetion had taken place.  相似文献   

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