Copolymerization of hydroxyalkyl methacrylates with acrylamide and methacrylamide. II. Properties of the copolymers

Copolymers of 2-hydroxyethyl–methacrylate, 2-hydroxypropyl–methacrylate, or 3-chloro-2-hydroxypropyl methacrylate with acrylamide or methacrylamide having different compositions were synthesized by free radical bulk polymerization. Some of their properties, for example, density, polymerization shrinkage, Vicat's softening point, glass transition temperature, hardness, and thermal and chemical stability were measured. The effect of the content of acrylamide or methacrylamide units on the properties of copolymers is discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1243–1248, 1998     

Segmented organosiloxane copolymers: 2 Thermal and mechanical properties of siloxane—urea copolymers

The structure-property behaviour of new siloxane-urea containing segmented copolymers has been investigated. Amino-propyl terminated poly(dimethylsiloxane) oligomers of from 900–3660 M_n were reacted with various diisocynates to form segmented copolymers with urea linkages. The length of the hard segments in these copolymers corresponds approximately to the length of the diisocynate unit employed. A number of mechanical and thermal properties were investigated for these phase separated materials. It was found that the performance of these copolymers was effected by varying the hard segment type and/or content and that high strength necessitates a microphase texture. The two phase nature of these copolymers was verified by dynamic mechanical, thermal and SAXS studies. The phase separation was found to occur in these copolymers even with 6% hard segment by weight. In conclusion, these materials displayed a behaviour similar to the segmented polyurethanes and were found to be superior to the unfilled silicone elastomers.     

Thermal and mechanical properties of copolymers of methyl methacrylate with N‐aryl itaconimides

The article describes the preparation of cast copolymer sheets of methyl methacrylate with varying mole fractions of N‐(p‐methoxyphenyl) itaconimide/N‐(2‐methoxy‐5‐chlorophenyl) itaconimide/N‐(3‐methoxy‐5‐chlorophenyl) itaconimide monomers by bulk copolymerization using azobisisobutyronitrile as an initiator. The effect of incorporation of varying mole fractions of N‐arylsubstituted itaconimides in poly(methyl methacrylate) (PMMA) backbone on the thermal, optical and physicomechanical properties of cast acrylic sheets were evaluated. The glass transition temperature and the thermal stability increased with increasing amounts of itaconimides in the polymer backbone. An increase in tensile strength, flexural strength, and storage modulus was also observed. The impact strength decreased marginally upon incorporation of imides into the polymer backbone. A slight decrease in the transparency and a significant increase (4–50%) in the haze was observed. The chemical resistance of PMMA remains unaffected by copolymerization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Network structure and compositional effects on tensile mechanical properties of hydrophobic association hydrogels with high mechanical strength

Hydrophobic association hydrogels (HA-gels) were successfully prepared through micellar copolymerization of acrylamide (AM) and a small amount of octylphenol polyoxyethylene acrylate (OP-4-AC) in an aqueous solution containing sodium dodecyl sulfate (SDS). HA-gels exhibited excellent mechanical properties and transparency. Especially, HA-gels possessed the capability of re-forming, such as self-healing and molding. From Fourier transform infrared, swelling behavior and re-forming capability of HA-gels, the network structure was established. On the basis of the micellar copolymerization theory, the statistical molecular theory of rubber elastic, and using uniaxial stretching data, the length of the hydrophobic microblocks, the effective network chain density and the molecular weight of the chain length between cross-linking points were evaluated for all HA-gels; furthermore, they were also evaluated for the region of medium deformation by the Mooney-Rivlin theory. For HA-gels, we investigated in detail the effects of the content of compositions in the initial solution, OP-4-AC, SDS and AM, on their tensile mechanical properties on the basis of the proposed network structure. The results clearly indicate their tensile strength, fracture energy, elastic modulus, and elongation strongly depended on their composition content.     

Poly(2‐hydroxyethyl acrylate) hydrogels reinforced with graphene oxide: Remarkable improvement of water diffusion and mechanical properties

A series of hybrid hydrogels of poly(2‐hydroxyethyl acrylate), PHEA, and graphene oxide, G? O, with G? O content up to 2 wt % has been prepared by in situ polymerization. Because PHEA has been used as biomaterial in various applications, has a side chain with the hydroxyl functional group and its mechanical properties are poor, it is a good candidate for reinforcement with G? O. Fourier transform (infrared) spectroscopy, atomic force microscopy, differential scanning calorimetry, the thermal, mechanical, and water sorption properties of neat PHEA and PHEA/G? O composites have been studied in order to elucidate the dispersion and interaction between both components. An increase in the water diffusion coefficient and dramatic changes in its mechanical properties are the most remarkable results. Thus, at a nanofiller load of 2 wt %, the novel materials present an increased diffusion coefficient higher than 380% and the elastic modulus is enhanced by more than 650% in dry state and by more than 100% in swollen state, both compared to neat PHEA. These results have been attributed to the excellent interaction between the matrix, PHEA, and the reinforcement, G? O, and could open the door to new applications in the field of biomaterials with higher structural requisites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46158.     

Optimization of mechanical properties of PP/Nanoclay/CaCO3 ternary nanocomposite using response surface methodology

Response surface method of experimental design was applied to optimize the mechanical properties of polypropylene (PP)/nanoclay/CaCO₃ hybrid ternary nanocomposite using three different levels of melt flow index (MFI) of PP, nanoclay, and CaCO₃ contents. The samples were prepared by melt mixing in a lab scale corotating twin screw extruder. The main effect of each parameter on the tensile modulus, tensile strength, and impact strength was extensively discussed. The structure of obtained nanocomposite was studied using X‐ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) techniques. Tensile modulus and impact resistance of prepared ternary nanocomposite were correlated to considered parameters using a second‐order polynomial model. Also, the optimum values of studied variables were determined using contour plots. The obtained results show that increasing the nanoclay and CaCO₃ contents improve the tensile modulus up to 45%, whereas the optimum value of impact strength, about 54%, is achieved at low concentrations of nanoclay (2 wt %) and CaCO₃ (8 wt %). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Network structure and mechanical properties of hydrophobic association hydrogels: Surfactant effect I

Three series hydrophobic association hydrogels (HA‐gels) with different concentration of sodium dodecyl sulfate (SDS) were prepared by free radical micellar copolymerization. The backbone of HA‐gels was based on the copolymer of acrylamide and a little octylphenol polyoxyethylene ether acrylate with 10 ethoxyl units (OP10～AC). Their mechanical properties were determined by tension tests. It was found that the properties of all three series HA‐gels presented a very similar variation tendency with increasing R, the molar ratio of SDS to OP10～AC. In the medium region of R (around 1.23), higher effective crosslinked density and proper match between shorter and longer chains were achieved, so that the HA‐gels exhibited better mechanical strengths. In lower R region, it is prone to form the unstable aggregation of OP10～AC with little SDS, while in higher R region some of co‐micelles could not act as crosslinkers. Both would reduce the effective crosslinked density and the mechanical strength of HA‐gel. In the condition of fixed R, the change of OP10～AC content would remodel the topological structure of network. The HA‐gels with better properties could be obtained as the OP10～AC content was varied from 1 to 2% at the proper R. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41222.     

Hydroxyalkyl methacrylates: hydrogel formation based on the radical copolymerization of 2-hydroxyethylmethacrylate and 2,3-dihydroxypropylmethacrylate

The synthesis of hydrogels by radical copolymerization of mixtures of 2,3-dihydroxypropylmethacrylate (DHPM) and 2-hydroxyethylmethacrylate (HEMA) has been performed using ethylene dimethacrylate (DME) as crosslinking agent, in the presence of 2,2′-azobisisobutyronitrile (AIBN) or of a redox system as initiator. The hydrophilicity of the obtained materials increases as the proportion of 2,3-dihydroxypropylmethacrylate increases. The maximum swelling degree of poly (HEMA) hydrogels is limited by thermodynamic effects whereas the equilibrium swelling degree of materials with high DHPM unit content is structure dependent. The gels obtained have been characterized by their equilibrium swelling degrees in water or in organic solvents and by the determination of their elastic modulus by uniaxial compression measurements. All the materials are of great interest as potential biomaterials especially for soft contact lens manufacture.     

Physical properties of poly(n-alkyl acrylate) copolymers. Part 1. Crystalline/crystalline combinations

The physical properties of n-alkyl acrylate copolymers containing two crystallizeable monomers, including thermal characteristics, structure as determined by small angle X-ray scattering, and gas permeability as a function of temperature, were examined in detail and compared to the corresponding homopolymers. The copolymers exhibit co-crystallization and, thus, for a given average side-chain length have comparable melting temperatures as the corresponding homopolymers. For a given side-chain length, the copolymers have somewhat lower heats of fusion than the corresponding homopolymers because of a reduction in crystallite size as revealed by SAXS. This depression in crystallinity is reflected in the permeability data for the copolymers. Poly(n-alkyl acrylates) exhibit a ‘jump’ in their gas permeability at the T_m of the side-chain lengths that is mainly caused by a switch in the side-chain morphology from crystalline to amorphous upon melting. The depression in crystallinity for the copolymers results in a smaller permeation jump. The jump breadth correlates with the melting endotherms for these polymers as determined by DSC. Ultimately, the melting endotherms for these copolymer systems provide an excellent tool for predicting permeability changes across the melting region.     

Physical properties of poly(n-alkyl acrylate) copolymers. Part 2. Crystalline/non-crystalline combinations

The physical properties of n-alkyl acrylate copolymers containing one crystallizeable monomer and one non-crystallizeable or slightly crystallizeable monomer, including thermal characteristics, structure as determined by small angle X-ray scattering, and gas permeability as a function of temperature, were examined in detail and compared to the corresponding homopolymers and copolymer systems containing two crystallizeable comonomers. The current copolymers exhibit melting point depression and, for a given average side-chain length, have lower heats of fusion than the corresponding homopolymers and crystalline/crystalline copolymers. Limited SAXS experiments revealed an increase in the d-spacings, above and below the melting point, with side-chain length consistent with expectations. The crystallites predominantly exhibit end-to-end packing similar to other poly(n-alkyl acrylates) previously studied. Poly(n-alkyl acrylates) exhibit a ‘jump’ in their gas permeability at the T_m of the side-chain lengths that is mainly caused by a switch in the side-chain morphology from crystalline to amorphous upon melting. The reduced crystallinity of the crystalline/non-crystalline copolymers results in a smaller permeation jump, which in some cases were extremely broad. All jump breadths correlate with the melting endotherms for these copolymers as determined by DSC similar to that for homopolymers and crystalline/crystalline copolymers. The magnitude of the jump correlates with the heat of fusion, irrespective of the comonomer type, in all cases.     

纤维表面处理对复合材料力学性能的影响

本文研究了碳纤维表面处理方法对纤维-基体界面剪切强度的影响．研究结果表明，相对于未进行表面处詈的碳纤维-所采用的胺基化处理和偶联剂处理两种表面处理方法都能够提高碳纤维界面的剪切强度，从而提高复合材料整体的抗拉强度和弹性模量。并且偶联剂处理方法具有更好的工艺性．     

Physical properties of hydrogels of poly(2‐hydroxyethyl methacrylate) and copolymers with mono‐methyl itaconate synthesized by bulk and solution polymerization

The physical properties found during the swelling process of poly(2‐hydroxyethyl methacrylate) (PHEMA) and of copolymers of HEMA with mono‐n‐methyl itaconate, synthesized by solution and bulk polymerization, are reported. The swelling kinetics were followed at four different temperatures (295, 300, 305 and 310 K). Experimental data follow second‐order swelling kinetics, from where the kinetic rate constant k_∞ and the swelling capacity at equilibrium W_∞ were calculated as a function of temperature. The kinetic rate constant obeys Arrhenius behaviour. The following network parameters were determined for the hydrogels: Young's moduli E, effective crosslinking density v_e, molar mass per crosslink M_C, volume fraction ϕ₂ and polymer‐liquid interaction parameter χ. © 2000 Society of Chemical Industry     

Epoxy-based divinyl ester resin/styrene copolymers: Composition dependence of the mechanical and thermal properties

Epoxy-based divinyl ester resins (DVER) were obtained by reacting diglycidyl ether of bisphenol A (DGEBA) with methacrylic acid (MA) and characterized by FTIR and ¹H-NMR spectroscopies and gel permeation chromatography (GPC). The densities and viscosities of the DVER in styrene (S) solutions were measured at different temperatures, 25, 40, and 60°C and compositions, 3.4 to 100% by weight of styrene. Dynamic mechanical measurements (DMA) and differential scanning calorimetry (DSC) were used to determine the glass transition temperatures of the homopolymers and the DVER/S copolymers: 20, 40, 60, and 80% by weight of styrene. The values obtained are in the range limited by the homopolymers glass transition, 100°C for polystyrene and 173°C for the cured DVER. The data were well fitted if two contributions to the glass transition are taken into account: the “linear copolymer” contribution (Fox eq.) and the “crosslinking” contribution (Nielsen model). Uniaxial static compression tests were carried out to determine the modulus, yield stress, and ultimate stress in samples with different compositions. All the mentioned properties decrease with an increase in the styrene concentration in the final copolymer. It was found that the volumetric contraction during curing increases with styrene concentration. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1059–1066, 1997     

表面强化交联聚(N-异丙基丙烯酰胺) 水凝胶的温敏和浓缩分离性能

为了提高聚(N-异丙基丙烯酰胺)(PNIPA)凝胶粒子的浓缩分离效果,以过硫酸铵/N,N,N,N,-四甲基乙二胺为引发体系,N,N′-亚甲基双丙烯酰胺(BIS)和二乙烯苯(DVB)为复合交联剂,通过反相悬浮聚合合成了表面强化交联的PNIPA凝胶粒子.考察了凝胶颗粒形态、温敏特性及其浓缩分离聚乙二醇/水性能.发现得到的凝胶为紧密珠状粒子,低临界溶解温度为32℃;随着溶质聚乙二醇相对分子质量增大或浓度减小,凝胶对聚乙二醇/水的分离效率提高;增加合成PNIPA凝胶时的BIS用量,可提高凝胶对聚乙二醇/水的分离效率,但溶胀率显著下降;增加DVB用量,分离效率大幅提高,而凝胶溶胀率基本不变.     

Dynamic mechanical properties of polymer-fluid systems: characterization of poly(2-hydroxyethyl methacrylate) and poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogels

The complex shear moduli of crosslinked poly(2-hydroxyethyl methacrylate) and poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogels were measured as a function of water content, temperature and frequency using dynamic mechanical spectroscopy. The effect of increasing water content on both the storage and loss moduli is to lower the temperatures at which mechanical transitions occur. There is a significant decrease in the storage moduli and increase in the loss moduli dispersions with increasing water content. These data could be well correlated by a multiple-mechanism, time-temperature superposition procedure. Between 2% and 28% water content in the copolymer sample, the relaxation spectra and shift function characterizing the glassy-rubbery state transition become independent of water content when properly referenced to the observed transition temperature. At lower temperatures where the β transition occurs, the mechanical viscoelastic spectra depend much more strongly on water content although the shift factors collapse to a single curve when referenced to the observed β transition temperature.     

Engineering hydrophobically associated hydrogels with rapid self-recovery and tunable mechanical properties using metal-ligand interactions

In this contribution, hydrophobic association and metal-ligand coordination have been employed in a dual physical crosslinking strategy to access hydrogels based on micellar copolymerization of acrylamide and a hydrophobic acrylic monomer (containing terpyridine (terpy) for metal-ligand interaction). The mechanical properties of these hydrogels are strongly influenced by the thermodynamic stability and kinetic lability of the metal-terpy crosslinks present in these materials. While the hydrogel tensile strength and stability on water exposure are enhanced by choosing stronger Fe²⁺-terpy crosslinks, the weaker and more kinetically labile Zn²⁺-terpy coordination bonds enable significantly higher energy dissipation under tensile loading and self-healing in the resultant hydrogels.     

环境刺激响应型高强度智能水凝胶研究进展

环境刺激响应型智能水凝胶能够对外界环境因素的变化产生显著的体积或其他特性的变化,且其性质和结构与生物组织类似,有望应用于人工软骨、人造肌肉、组织工程等领域,引起了广泛的关注。提高环境刺激响应型智能水凝胶的力学性能是智能水凝胶应用研究的重要方向之一。本文综述了近年来环境刺激响应型高强度智能水凝胶的研究进展,简述了高强度智能水凝胶的网络结构的构建策略与方法,分析了其具备高力学性能的机理,重点介绍了4类不同结构的高强度智能水凝胶,即超低交联结构水凝胶、纳米颗粒复合水凝胶、拓扑结构水凝胶以及双网络结构水凝胶,最后讨论了环境刺激响应型高强度智能水凝胶在面向应用的研究过程中仍然需要解决的关键科学问题,如智能水凝胶的环境刺激与力学性能的博弈效应以及响应环境刺激前后的力学性能差异等。     

Effects of antimicrobial agents on the thermal and mechanical properties of acrylate hydrogel matrices

Polymer materials with antimicrobial activity are prepared by UV polymerization of acrylate and methacrylate mixture at room temperature. The antimicrobials are silver acetate and copper (II) acetate, used without pretreatment. Their chemical stability in the acrylate matrix and their effect on the thermal and mechanical properties of the polymer matrix are investigated as a function of their concentration up to 15 wt %. Physico‐chemical, thermal, rheological, and morphological analyses as well as the surveillance of metal salts release in aqueous medium are conducted. A significant decrease in the thermal stability of the salts introduced into the acrylate matrix is observed after UV treatment. The metal salts also have significant effects on the properties of the matrix. A plasticization and densification of the material associated with an aggregation of salts up to the percolation at the highest concentration are highlighted. At equal concentrations, the effects are more pronounced in the presence of copper salts. The latter was released more slowly than silver salts from acrylate material. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43501.     

Infiltration of laponite: An effective approach to improve the mechanical properties and thermostability of collagen hydrogel

Rapid aggregate precipitation of collagen and laponite in solution restricted the development of corresponding hybrid materials. Herein, a facile method of immerging collagen hydrogel into laponite dispersion was adopted to prepare hybrid collagen/laponite hydrogel, avoiding the precipitation. Collagen hydrogel shrunk and water content decreased dramatically after laponite solution treatment. According to the images of Scanning electron microscopy and energy dispersive system, the uniformly dispersed laponite in collagen hydrogel was observed, demonstrating infiltration of laponite into collagen hydrogel. X-ray photoelectron spectroscopy results revealed that coordination bonds generated between magnesium in laponite and collagen. Thermogravimetric analysis and Differential scanning calorimetry results displayed thermal decomposition temperature of collagen hydrogel increased from 321 to 342°C, and denaturation temperature rose from 43.8 to 50.8 °C after laponite infiltration. Rheological and compressive tests showed the elastic modulus, fracture stress, compressive modulus and rupture point of hydrogel treated by 10% laponite were 695.2 Pa, 253.3 kPa, 13.5 kPa and 76.7%, respectively, which were about 3.5, 5.5, 45.0, and 1.4 times larger than those of pristine collagen hydrogel. Besides, enzyme degraded rate of collagen was decelerated, and the hydrogel was still nontoxic with the infiltration of laponite. The promising data demonstrated infiltration of laponite was an effective way to fabricate collagen/laponite hybrid materials with desirable properties.     

Synthesis,characterization, and reactivity ratios of copolymers derived from 4‐nitrophenyl acrylate and n‐butyl methacrylate

Free‐radical copolymerization of 4‐nitrophenyl acrylate (NPA) with n‐butyl methacrylate (BMA) was carried out using benzoyl peroxide as an initiator. Seven different mole ratios of NPA and BMA were chosen for this study. The copolymers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectral studies. The molecular weights of the copolymers were determined by gel permeation chromatography and the weight‐average (M _w) and the number‐average (M _n) molecular weights of these systems lie in the range of 4.3–5.3 × 10⁴ and 2.6–3.0 × 10⁴, respectively. The reactivity ratios of the monomers in the copolymer were evaluated by Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos methods. The product of r₁, r₂ lies in the range of 0.734–0.800, which suggests a random arrangement of monomers in the copolymer chain. Thermal decomposition of the polymers occurred in two stages in the temperature range of 165–505°C and the glass transition temperature (T_g) of one of the systems was 97.2°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1817–1824, 2003