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1.
In the study, we allowed PEG and dimethyl 5‐sulfoisophthalate sodium salt (SIP) to undergo transesterification to obtain PEG containing sulfonic groups (SE), then used SE and isophorone diisocyanate as soft and hard chains, respectively, and methyl ethyl ketoxime, hydroxyethyl methacrylate or 2,3‐Epoxy‐1‐propanol as blocking reagents to synthesize three kinds of reactive urethane oligomers (MSE, HSE, and OSE). PET textiles treated by oligomers were investigated for their effects to the durable hydrophilic properties of PET fibers under different processing temperatures, time lengths, and oligomer concentrations. The results are concluded and described later: The add‐on and durability of processed fabrics both were improved following the rise of processing temperature and a longer processing time. When oligomer concentration was increased, the add‐on on processed textiles also increased, but their durability decreased. When PEG segment was larger, the add‐on and durability both decreased. The hydrophilicity of processed textiles was proportional to the increase of oligomer concentration. The processing time was more crucial to the hydrophilic property of HSE processed textiles, but for that of MSE, the processing temperature was more important. The hydrophilic property of OSE processed textiles absolutely depended on the add‐on of processed textiles. Textiles processed in oligomers of PEG molecular weight 1000 showed the highest vertical wicking height. Within these three kinds of oligomers, MSE led to the highest add‐on on processed textiles and HSE textiles possessed the best of durability. OSE processed textiles possessed the best hydrophilic efficiency and electrostatic dissipating property. Textiles processed in HSE containing PEG molecular weight 1000 could have the best hydrophilic and durability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

2.
Four urethane acrylate oligomers were synthesized by a reaction of an excess of isophorone diisocyanate (D) with polypropylene glycol Acclaim 4200N (P) with a subsequent reaction of nonreacted D with a hydroxy acrylate Tone M100 (A). The latter has a common name caprolactone acrylate. Oligomers were prepared by different ways of addition of P to D or D to P and at different ratio of [D]/[P]. The fifth oligomer ADA was prepared as an individual compound. Viscosities, GPC traces, Tg's of oligomers were taken alongside with other physical properties of cured oligomers. It was demonstrated that oligomers with P consist of ADPDA, ADA, and of a chain‐extended product A… Pn… A, which has two or more Ps in a molecule. Additive contributions of these three components essentially determine properties of the liquid and cured oligomers. Structure‐property relations of urethane acrylate oligomers are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99:489–494, 2006  相似文献   

3.
The effects of ordered structure on isothermal crystallization kinetics and subsequent melting behavior of β‐nucleated isotactic polypropylene/graphene oxide (iPP/GO) composites were studied using differential scanning calorimetry. The ordered structure status was controlled by tuning the fusion temperature (Tf). The results showed that depending on the variation of crystallization rate, the whole Tf range could be divided into three regions: Region I (Tf > 179 °C), Region II (170 °C ≤ Tf ≤ 179 °C) and Region III (Tf < 170 °C). As Tf decreased from Region I to Region III, the crystallization rate would increase substantially at two transition points, due to the variation of the ordered structure status. Calculation of Avrami exponent n indicated that the ordered structure induced the formation of two‐dimensional growing crystallites rather than three‐dimensional growing crystallites. Moreover, in the case of isothermal crystallization, the ordered structure effect (OSE) can also greatly increase the relative content of β‐phase (βc). In Region II, OSE took place, resulting in evident increase of βc, achieving 92.4% at maximum. The variation of the isothermal crystallization temperature (Tiso) had little influence on the Tf range (Region II) of the OSE. The higher Tf in Region II was more favorable for the formation of higher βc. The ordered structure was favorable for the improvement of the nucleating efficiency of β‐nucleating agent (β‐NE), and was more effective for the improvement of lower β‐NE. © 2018 Society of Chemical Industry  相似文献   

4.
Thin polymer films were prepared under ultraviolet radiation with a triacrylated aliphatic urethane oligomer that was diluted with reactive monomers such as N‐vinyl pyrrolidone and tripropylene glycol diacrylate. These films were characterized. The effect of incorporation of a minute amount (>0.15%) of a titanium–pyridine complex and its ligands on the characterization of these polymers was investigated. Cotton and jute yarns were treated with the solutions containing these materials under the UV radiation. The change in tensile properties of the treated natural polymers (cotton and jute) was evaluated, and it was found that the titanium–pyridine‐based complex substantially enhanced the tensile strengths (tenacity) for both cotton and jute. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1131–1138, 1999  相似文献   

5.
Poly(benzoxazine‐co‐urethane) was prepared by melt‐blending bisphenol‐S/aniline‐type benzoxazine (BS‐a) with isocyanate‐terminated polyurethane (PU) prepolymer based on 2,4‐toluene diisocyanate and poly(ethylene glycol), followed by thermally activated polymerization of the blend. The copolymerization reaction between BS‐a and PU prepolymer was monitored using Fourier transform infrared spectroscopy. The morphology, dynamic mechanical properties, and thermal stability of the poly(benzoxazine‐co‐urethane) were studied using scanning electron microscopy, dynamic mechanical analysis, and thermogravimetry. Homogeneous morphology is shown in scanning electron micrographs of the fracture surfaces of poly(benzoxazine‐co‐urethane)s with different urethane weight fractions, and the roughness of the surface increases with urethane content increasing. Correspondingly, a single glass transition temperature (Tg) is shown on the dynamic mechanical analysis curves of the poly(benzoxazine‐co‐urethane)s, and the Tg is higher than that of the polybenzoxazine. With increase in the urethane content, the Tg and water absorption of poly(benzoxazine‐co‐urethane) increase, whereas the storage modulus and thermal stability decrease. POLYM. ENG. SCI., 53:2633–2639, 2013. © 2013 Society of Plastics Engineers  相似文献   

6.
The free volume of a bisphenol‐A‐type epoxide oligomer (DGEBA) was studied using Williams–Landel–Ferry parameters and thermal expansion coefficients above and below the glass transition temperature (Tg). The values of the free‐volume fraction at the Tg are around 0.02 for the DGEBA oligomers having weight‐average molecular weights (M w's) from 1396 to 2640. The dipole mobility, which was obtained from the analysis of the temperature dependence of the dielectric relaxation time, was compared with the segment mobility in terms of the critical volume for the transport of each moving unit. The critical volume for the segment transport increases with increase of the M w of the oligomer. The critical volume for the dipole movement, on the other hand, is not different between the oligomers studied (1396 ≤ M w ≤ 2640), which leads to that the dipole mobility in the epoxide oligomer is smaller than is the segment mobility. The low mobility of the dipole is considered to result from the molecular interaction restricting the dipole movement, especially in a smaller M w oligomer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 207–214, 1999  相似文献   

7.
Allyl ether (AE)‐modified unsaturated polyester oligomers were synthesized from polyethylene glycol (PEG), maleic anhydride (MAH), and trimethylolpropane mono allyl ether (TMPAE), and characterized by Fourier transform infrared (FTIR) spectra. The UV/air dual‐curable coatings were prepared from the oligomers using vinyl ether (VE) as a reactive diluent. FTIR spectra showed that C?C bonds in the coating composition had polymerized partially after cured by UV or air. The investigation of rheological behavior of the dual curable composition suggested that all the systems belonged to pseudoplastic fluid, and the increasing allyloxy content in oligomer resulted in a higher viscosity. Differential scanning calorimetry (DSC) analysis showed that the increasing TMPAE‐PEG molar ratio resulted in lower Tg, and all samples had the same glass transition temperature irrespective of the type of curing. The results of TGA for cured films indicated that UV‐cured film had better thermal stability than the air‐cured one. The air‐cured film showed superior pencil hardness, impact strength, and flexibility to the UV‐cured counterpart. However, the air‐cured film had poor adhesion and electric resistance properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2765–2770, 2004  相似文献   

8.
Novel asymmetric bismaleimide (BMI) oligomers with different molecular weights and dianhydrides were designed and synthesized by 3,4′‐oxydianiline (3,4′‐ODA), 2,3,3′,4′‐oxydiphthalic dianhydride (a‐ODPA), and 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA). The chemical structures of BMI oligomers were confirmed by Fourier transform infrared spectrometry (FTIR) and gel permeation chromatography (GPC). X‐ray diffraction (XRD) exhibited broad peaks, suggesting amorphous structures. Heat flow curves of oligomers measured by differential scanning calorimeter (DSC) displayed wide processing window due to low glass transition temperatures (Tg). BMI oligomers exhibited high solubility in common organic solvents. Particularly, the OD‐BMI‐1 oligomer exhibited excellent solubility of more than 50 wt% in DMAc solvent. Tg value and minimum complex viscosity of OD‐BMI‐1 oligomer were only 121 °C and 8.1 Pa · s, respectively. The cured BMI resins possess high thermal and thermal‐oxidative stability. The Tg and the temperature of 5% weight loss in nitrogen were above 256 and 449 °C, respectively, and the residual weight percentages at 800 °C were all >49%. Moreover, films made of BMI resins exhibited excellent mechanical properties flexibility, as confirmed by photograph and DMA results of films. The elongation at break of the prepared films was found to be high (almost >9.6%). POLYM. ENG. SCI., 59:2265–2272, 2019. © 2019 Society of Plastics Engineers  相似文献   

9.
Fluoroalkyl end‐capped 2‐methacryloxyethanesulfonic acid homo‐oligomer [RF–(MES)n–RF] and 2‐methacryloxyethanesulfonic acid–N,N‐dimethylacrylamide co‐oligomers [RF–(MES)x–(DMAA)y–RF] reacted with tetraethoxysilane (TEOS) under acidic conditions to afford RF–(MES)n–RF homo‐oligomer–SiO2 polymer hybrid and RF–(MES)x–(DMAA)y–RF co‐oligomer–SiO2 polymer hybrid, respectively. Thermogravimetric–mass spectra showed that the thermal stability of RF–(MES)n–RF homo‐oligomer–SiO2 polymer hybrid was superior to that of traditionally well‐known perfluorinated ion exchange polymers such as Nafion 112 (TR). The sol solutions of the fluorinated co‐oligomer–SiO2 polymer hybrid were applied to the surface modification of glass to exhibit not only a strong oleophobicity imparted by fluorine but also a good hydrophilicity on the glass surface. On the other hand, RF–(MES)x–(DMAA)y–RF co‐oligomer reacted with TEOS in the presence of a variety of silica nanoparticles (mean diameters: 11–95 nm) under alkaline conditions to afford fluoroalkyl end‐capped oligomers–silica nanoparticles (mean diameters: 32–173 nm) with a good dispersibility and stability in methanol. Similarly, a variety of fluorinated oligomers containing sulfo groups–silica nanoparticles were prepared by the homo‐ and co‐oligomerizations of fluoroalkanoyl peroxides with 2‐methacryloxyethane sulfonic acid (MES) and comonomers such as N,N‐dimethylacrylamide (DMAA) and acryloylmorpholine (ACMO) in the presence of silica nanoparticles. Interestingly, these isolated fluorinated particle powders were found to afford nanometer size‐controlled colloidal particles with a good redispersibility and stability in aqueous and organic media such as methanol. These fluorinated nanoparticles containing sulfo groups were also applied to an excellent heterogeneous catalyst for Bronsted acid‐catalyzed transformations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 110–117, 2007  相似文献   

10.
The vinyl ether functionalized oligomer is one of the most basic components of vinyl ether functionalized materials for cationic UV‐curable coatings. In this study, three types of vinyl ether functionalized polyurethane oligomers (i.e., polyether, polyester, and polydimethylsiloxane) were synthesized with diisocyanate, diol, and hydroxyethyl vinyl ether. These oligomers were characterized by IR, 1H‐NMR, and 13C‐NMR spectroscopy. The effect of the raw material ratio on the oligomer, UV‐curing behaviors, and thermal properties of these oligomers were investigated. The UV‐curing behavior was analyzed by real‐time Fourier transform infrared spectroscopy. The vinyl ether terminated polyester urethane oligomer exhibited better UV curing, with a higher final conversion and maximum UV‐curing rates. In addition, the light intensity was enhanced for oligomers with better UV‐curing properties. Research on these vinyl ether functionalized oligomers is essential to the development and applications of cationic vinyl ethers systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40501.  相似文献   

11.
This study develops a simple copolymerization/crosslinking technique to control the swelling and mechanical properties of hyaluronic acid‐based hydrogels. Because of the widespread acceptance of poly(ethylene glycol) in biomedical applications, functionalized oligomers of ethylene glycol (EG) were used as comonomers to crosslink methacrylated hyaluronic acid (MHA). The swelling degree, shear and elastic moduli, and fracture properties (stress and strain) of the gels were investigated as a function of the crosslinking oligomer length and reactive group(s). It was hypothesized that acrylated oligomers would increase the crosslink density of the gels through formation of kinetic chains by reducing the steric hindrances that otherwise may limit efficient crosslinking of hyaluronic acid into gels. Specifically, after crosslinking 13 wt % MHA (47% degree of methacrylation) with 0.06 mol % of (EG)n‐diacrylate, the swelling ratio of the MHA gel decreased from 27 to 15 g/g and the shear modulus increased from 140 to 270 kPa as n increased from 1 to 13 units. The length and functionality (i.e., acrylate vs. methacrylate) of the oligomer controlled the crosslink density of the gels. The significant changes in the gel properties obtained with the addition of low levels of the PEG comonomer show that this method allows precise tuning of the physical properties of hyaluronic acid (HA) gels to achieve desired target values for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42009.  相似文献   

12.
Novel fluoroalky end‐capped oligomers/titanium dioxide nanocomposites were prepared by the hydrolysis of titanium isopropoxide in the presence of fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer [RF‐(DOBAA)n‐RF], fluoroalkyl end‐capped N,N‐dimethylacrylamide oligomer [RF‐(DMAA)n‐RF], and fluoroalkyl end‐capped acrylic acid oligomer [RF‐(ACA)n‐RF] in tetrahydrofuran under mild conditions. In these fluorinated oligomers, RF‐(ACA)n‐RF oligomer is more effective for the preparation of the corresponding oligomers/titanium dioxide nanocomposites, and this oligomer can afford the expected fluorinated titanium dioxide nanocomposites in higher isolated yields. In addition, RF‐(ACA)n‐RF/titanium dioxide composites are nanometer size‐controlled very fine nanoparticles (14–48 nm), and exhibited a good dispersibility not only in water but also in traditional organic solvents. Fluoroalkyl end‐capped oligomers/titanium dioxide nanocomposites were also applied to the surface modification of the common organic polymers such as poly(methyl methacrylate) to exhibit a good oleophobic and hydrophilic characteristics on the surface. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.  相似文献   

13.
Dielectric properties have been investigated for a bisphenol-A type epoxide oligomer, whose weight average molecular weight (M?w) was 9454. The dielectric α-relaxation of the oligomer was found to be governed by the Havriliak–Negami equation as well as the same series of oligomers with smaller M?ws (388≦M?w ≦ 3903). The dielectric relaxation times (τ)s for the oligomers with different M?ws (1396 ≦ M?w ≦ 9454) can be expressed by the Williams–Landel–Ferry (WLF) equation as a function of the glass transition temperature (Tg) at fixed temperatures from 70 to 100°C. The finding indicates that the Tg of the epoxide oligomer is calculated from the τ through the WLF equation, providing the relation between Tg and τ. The same type of WLF equation was also successfully applied to describe the Tg, dependence of the practical dielectric relaxation time (τp), which was obtained from the peak of the dielectric loss vs. frequency curve. The τp can be calculated more easily than the τ, based on the Havriliak–Negami equation, not only in the measurement of epoxide oligomer, but also in that of the reactive epoxy resin systems during curing. The Tg of an epoxy–aromatic amine system, which was determined from the τp nondestructively detected in the dielectric cure monitoring, was consistent with the Tg experimentally measured by differential scanning calorimetry (DSC).  相似文献   

14.
A new main‐chain benzoxazine oligomer with o‐norbornene functionality as end groups has been designed and synthesized. As compared to traditional main‐chain type benzoxazine polymers, this benzoxazine oligomer with o‐norbornene terminal functionality can undergo further crosslinking polymerization after general ring‐opening polymerization of oxazine rings. Another main‐chain benzoxazine oligomer has also been designed based on the reaction of bisphenol‐A, 4,4′‐diaminodiphenylmethane, paraformaldehyde, and phenol for comparison. The structure of the synthesized oligomers is confirmed by 1H nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FTIR). The molecular weight has been determined by using gel permeation chromatography (GPC). The benzoxazine oligomer containing o‐norbornene functionality can polymerize with multiple polymerization mechanisms rather than the single mechanism common to traditional 1,3‐benzoxazine resins. The polymerization mechanisms are monitored by in situ FTIR and differential scanning calorimetry (DSC). Moreover, the thermoset derived from the benzoxazine oligomer containing o‐norbornene functionality exhibits high thermal stability with the transition temperature of 360 °C and a high Td5 of 404 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45408.  相似文献   

15.
Our previous studies showed that herringbone graphitic GNFs surface‐derivatized with reactive linker molecules bearing pendant primary amino functional groups capable of binding covalently to epoxy resins. Of special importance, herringbone GNFs derivatized with 3,4′‐oxydianiline (GNF‐ODA) were found to react with neat butyl glycidyl ether to form mono‐, di‐, tri‐, and tetra‐glycidyl oligomers covalently coupled to the ODA pendant amino group. The resulting reactive GNF‐ODA (butyl glycidyl)n nanofibers, r‐GNF‐ODA, are especially well suited for reactive, covalent incorporation into epoxy resins during thermal curing. Based on these studies, nanocomposites reinforced by the r‐GNF‐ODA nanofibers at nanofiber loadings of 0.15–1.3 wt% were prepared. Flexural property of cured r‐GNF‐ODA/epoxy nanocomposites were measured through three‐point‐bending tests. Thermal properties, including glass transition temperature (Tg) and coefficient of thermal expansion (CTE) for the nanocomposites, were investigated using thermal mechanical analysis. The nanocomposites containing 0.3 wt% of the nanofibers gives the highest mechanical properties. At this 0.3‐wt% fiber loading, the flexural strength, modulus and breaking strain of the particular nanocomposite are increased by about 26, 20, and 30%, respectively, compared to that of pure epoxy matrix. Moreover, the Tg value is the highest for this nanocomposite, 14°C higher than that of pure epoxy. The almost constant change in CTEs before and after Tg, and very close to the change of pure epoxy, is in agreement with our previous study results on a chemical bond existing between the r‐GNF‐ODA nanofibers and epoxy resin in the resulting nanocomposites. POLYM. COMPOS., 28:605–611, 2007. © 2007 Society of Plastics Engineers  相似文献   

16.
A number of formulations were developed using urethane diacrylate oligomer in combination with a series of monofunctional and multifunctional reactive diluents possessing diverse glass transition temperatures from ?50°C to 250°C. Films prepared with these formulations were cured under ultraviolet (UV) radiation; their properties, such as hardness, gel content, tensile characteristics, etc., were determined and compared with those of the films cured by electron beam (EB) radiation. Effect of comonomer diluents was investigated in these cases. A good correlation was observed between these properties and the glass transition temperature (T g) of the copolymer (cured film), prepared under radiation with urethane acrylate, monomer, and comonomer.  相似文献   

17.
Syntheses of several UV-autocurable methacrylourethanes and the effects of polyol type on their properties are investigated. Autocurable benzophenone tetracarboxylic dianhydride (BTDA)-based polyurethane methacrylates are prepared by addition reaction from benzophenone tetracarboxylic dianhydride (BTDA), 2,4-toluene diisocyanate (TDI), 2-hydroxyethyl methacrylate (HEMA), and polyol (polyethylene glycol, polydiethylene succinate, polydiethylene maleate, or polydiethylene hexamethylene-dicarbamate). Autocurable oligomers possess good pot life and are cured rapidly when exposed to ultraviolet (UV) radiation without the addition of photoinitiator. The different polyols are used to obtain wide range properties of cured films with a glass transition temperature (Tg) range of -10.5-5.5°C. Increasing the Tg of polyol shifts the dynamic mechanical storage modulus and loss factor of the cured film to high temperature. For practical application, oligomer is mixed with reactive monomers to bring the systems to a workable viscosity at room temperature. Among the monomers, the higher the composition of hydroxyethyl acrylate in the oligomer-monomer system, the higher the curing rate of the system as compared with neat oligomer. Moreover, increasing the chain length of dimethacrylate monomers results in a decrease in breaking strength from 160 to 140 kg/cm2, in Young's modulus from 771 to 400 kg/cm2, and in glass transition temperature from 18 to 6.5°C, while the elongation at breaking increases from 70 to 130%.  相似文献   

18.
We have developed photocurable bio-derived isosorbide (meth)acrylates for use in photoinitiated additive manufacturing (AM). We have shown that the viscosity of isosorbide-based resins obeyed logarithmic rule of mixtures, and the viscosity values were significantly lower than that of commercial stereolithography (SLA) resins as well as various other urethane (meth)acrylates and bisphenol A (meth)acrylates-containing blends. Using isobornyl acrylate or 4-acryloylmorpholine as reactive diluents, we were able to reduce the brittleness of the isosorbide-based polymers and retain high glass transition temperatures (Tg) of up to 231°C. The isosorbide-based resins were still somewhat brittle but had both greater Tg and strength relative to analogous bisphenol A dimethacrylate resins. Addition of oligomeric urethane (meth)acrylate crosslinkers further improved the mechanical properties of the polymers, whereby the strength approximately doubled to 55 MPa at 25°C, while maintaining high thermal properties, Tg > 190°C, and low viscosities, <140 cP, that are desirable for photoinduced AM applications. Furthermore, we were able to print this resin using SLA which produced specimens with similar moduls, but reduced strength relative to photocured resins and a commercial high temperature SLA resin.  相似文献   

19.
As part of an ongoing effort to develop processable, high-performance resins for aerospace applications, a phenylethynyl-terminated imide (PETI) oligomer designated LaRCMTPETI-1 was developed. This reactive oligomer has a number-average molecular weight of 6300 g/mol and a Tg of 218°C. Upon curing the reactive oligomer at 350°C for 1 h, a tough material with a Tg of 249°C was obtained. The properties of cured PETI-1 in the form of composites, adhesive specimens, thin films, and neat resin moldings are excellent. The synthesis, characterization, and mechanical properties of this polyimide are discussed. © 1996 John Wiley & Sons, Inc.  相似文献   

20.
Three calix [4]crown‐4 derivatives and their oligomers, p‐tert‐butylcalix [4]crown‐4 oligomer 5 , p‐tert‐butylcalix [4]dioxacrown‐4 oligomer 6 , p‐tert‐butylcalix [4]diazacrown‐4 oligomer 7 that contain hard and soft ion binding sites, are synthesized to estimate selective extraction of cesium ions from the aqueous to the organic phase. The binding sites may complex alkali metal ions or transition metal ions selectively. Oligomers are fairly good extractants for transition metal ions in comparison with their monomers, which suggests that polyoxyethylene bridges are efficient for complexing metal ions, especially for transition metal ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

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