Tung oil‐based thermosetting polymers for self‐healing applications

Several bio‐renewable thermosetting polymers were successfully prepared from tung oil through cationic polymerization for the use as the healing agent in self‐healing microencapsulated applications. The tung oil triglyceride was blended with its methyl ester, which was produced by saponification followed by esterification. The changes in storage modulus, loss modulus, and glass transition temperature as functions of the methyl ester content were measured using dynamic mechanical analysis. In addition, the fraction of cross‐linked material in the polymer was calculated by Soxhlet extraction, while proton nuclear magnetic resonance, Fourier transform infrared spectroscopy and TEM were used to investigate the structure of the copolymer networks. The thermal stability of the thermosets as a function of their methyl ester blend contents was determined by thermogravimetric analysis. Finally, the adhesive properties of the thermosets were studied using compressive lap shear and the fracture surfaces were analyzed using SEM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40406.     

Polyurethane foams from chlorinated and non‐chlorinated metathesis modified canola oil polyols

The product of 1‐butene metathesis of canola triacylglycerol (CMTAG), with shortened structures, terminal double bonds (50% of the total), and oligomers (40% dimer and trimer, and 10% higher oligomers) was used to synthesize novel polyols and polyurethane foams. A non‐chlorinated (Pol‐1) and a chlorinated polyol (Pol‐2) having OH value (170 and 190 mg KOH/g, respectively) were synthesized from CMTAG by epoxidation followed by hydroxylation, and epoxidation followed by hydrogenation, respectively. Both polyols remained liquid below ambient temperature and demonstrated physical characteristics such as viscosity which allowed for the facile preparation of polyurethane foams. The foam obtained with Pol‐1 was relatively soft (～0.32 MPa at 10% strain) and very flexible (recovery ～90%); whereas, the foam obtained with Pol‐2 was semi‐rigid (～1.1 MPa at 10% strain and recovery of 64%). The higher strength and rigidity of Pol‐2 foam compared to Pol‐1 foam is chiefly attributable to the effect of the bulky chlorines on the crosslink density. Importantly, this work highlights that one can improve and control jointly the mechanical properties and deformation recovery ability of bio‐based foams by combining primary functional groups, oligomers, and high molar volume molecules in the polyols. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46616.     

Epoxidized pine oil‐siloxane: Crosslinking kinetic study and thermomechanical properties

In this study, a novel approach to toughen biobased epoxy polymer with different types of siloxanes was explored. Three different modified siloxanes, e.g., amine‐terminated polydimethyl siloxane (PDMS‐amine), glycidyl‐terminated polydimethyl siloxane (PDMS‐glycidyl), and glycidyl‐terminated polyhedral oligomeric silsesquioxane (POSS‐glycidyl) were used as toughening agents. The curing and kinetics of bioepoxy was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. The mechanical, thermal, and morphological properties of the cured materials were investigated. Rheological characterization revealed that the inclusion of POSS‐glycidyl slightly increased the complex viscosity compared to the neat resin. The morphology of the cured bioresin was characterized by transmission electron microscopy and scanning electron microscopy. The inclusion of POSS‐glycidyl to bioepoxy resin resulted in a good homogeneity within the blends. The inclusion of PDMS‐amine or PDMS‐glycidyl was shown to have no effect on tensile and flexural properties of the bioresins, but led to a deterioration in the impact strength. However, the inclusion of POSS‐glycidyl enhanced the impact strength and elongation at break of the bioresins. Dynamic mechanical analysis showed that the siloxane modified epoxy decreased the storage modulus of the bioresins. The thermal properties, such as decomposition temperature, coefficient of linear thermal expansion, and heat deflection temperature were improved by inclusion of POSS‐glycidyl. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42451.     

Synthesis and characterization of a soybean oil‐based macromonomer

An acrylate‐functional soybean oil‐based macromonomer (SoyAA‐1) was synthesized in high yields utilizing sequential amidation and acrylation processes to serve as an internal plasticizer in emulsion polymers. The structure and structure–property relationships of this unique macromonomer were validated with FTIR, NMR, and LC‐MS. The viability of SoyAA‐1 as a comonomer in emulsion polymerization was established via copolymerization with methyl methacrylate (MMA) at varying copolymer weight compositions. The effect of increasing SoyAA‐1 levels and concomitantly higher allylic functionality was measured through film coalescence, minimum film forming temperature, and initial and progressively increasing glass transition temperature(s). The results indicate that synthetic modification of a renewable resource, soybean oil, can yield a valuable monomer that can be copolymerized in high yields via emulsion polymerization to produce practical and mechanically stable latexes for a variety of coatings applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40249.     

Biobased thermosetting resins composed of L‐lysine methyl ester and bismaleimide

Lysine methyl ester (LME), which was generated in situ by the reaction of lysine methyl ester dihydrochloride and triethylamine in dimethyl sulfoxide (DMSO), was prepolymerized with 4,4′‐bismaleimidodiphenylmethane (BMI) at 80°C for 2 h in DMSO. Then, the formed prepolymer was precipitated in water. The obtained LME/BMI prepolymers with molar ratios of 2:2, 2:3, and 2:4 were compression‐molded at a final temperature of 230°C for 2 h to produce cured lysine methyl ester/4,4′‐bismaleimidodiphenylmethane resins (cLBs; cLB22, cLB23, and cLB24, respectively). Fourier transform infrared (FTIR) analyses revealed that the Michael addition reaction of amino groups to the C?C bonds of the maleimide group occurred in addition to the homopolymerization of the maleimide group. The glass‐transition temperature (T_g) and 5% weight loss temperature (T₅) of the cured resin increased with increasing BMI feed content, and cLB24 showed the highest T_g (343°C) and T₅ (389°C). The flexural strengths (131–150 MPa) and moduli (3.0–3.6 GPa) of the cLBs were comparable to those of the conventionally cured resins of BMI and 4,4′‐diaminodiphenylmethane. Field emission scanning electron microscopy analysis revealed that there was no phase separation for all of the cured resins. Although cLB23 and cLB24 were not biodegradable, cLB22 had a biodegradability of 8.5% after 30 days in an aerobic aqueous medium containing activated sludge. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40379.     

Development of vegetable‐oil‐based polymers

The utilization of renewable resources for the preparation of new materials is an alternative option for reducing the high demand of fossil feedstocks. Vegetable oils are potential bioresources that are renewable and abundantly available. Triglyceride‐based vegetable oils, such as soybean, jatropha, linseed, sunflower, palm, castor, nahar seed, and canola oil, are being considered as precursors in the production of polymers. In this article, we attempt to summarize advancements in processes and technologies for the synthesis of polymers from various kinds of vegetable oils. The advantages and disadvantages of these biobased polymers with respect to traditional monomer‐based ones are also highlighted. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40787.     

Photocross-linked polymers based on plant-derived monomers for potential application in optical 3D printing

Photocross linking of the resins composed of plant-derived monomers, acrylated epoxidized soybean oil (AESO), myrcene (MYR) and vanillin dimethacrylate (VDM) or divinylbenzene (DVB, for comparison), was performed using 2,2-dimethoxy-2-phenylacetophenone as photoinitiator. Photocross-linking rate and properties of the crosslinked polymers depended on the resin compositions. The higher amount of MYR caused not only the better homogenization and lower viscosity of the resin but also the reduction of polymerization rate and the worse mechanical and thermal properties of the resulting polymers. The higher amount of aromatic component (VDM or DVB) improved mechanical and thermal properties of polymers. Moreover, the use of VDM instead of DVB in the system led to the higher photocross-linking rate and higher yield of insoluble fraction. The resin composed of only plant-derived monomers AESO/MYR/VDM, molar ratio 1:1:3, showed characteristics comparable to those of commercial petroleum-derived photoresins and was selected as a potential renewable photoresin for application in optical 3D printing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48708.     

Oil‐spill cleanup: The influence of acetylated curaua fibers on the oil‐removal capability of magnetic composites

A magnetic resin based on cardanol, furfural, and curaua fibers was prepared and characterized. The material could be used in oil‐spill cleanup processes, because of its aromatic/aliphatic balance. The resin was prepared through bulk polycondensation of cardanol and furfural in the presence of curaua fibers and maghemite nanoparticles. Hydrophobicity of the curaua fibers was improved by acetylation, increasing the oil‐absorbing capability of the composites. The obtained magnetic composites were studied by Fourier‐transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. Degree of cure, magnetic force, and oil‐removal capability tests were also performed. The results show that the composites possess an elevated cure degree in addition to a considerable magnetic force. The materials exhibit a good oil removal capability in the presence of a magnetic field, which is improved by the use of acetylated curaua. In the best case, the composite filled with maghemite and curaua can remove 12 parts of oil from water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41732.     

Organic–inorganic hybrid linseed oil‐based urethane oil wood coatings

To prepare alkoxysilane‐functionalized urethane oil (AFUO) using linseed oil, 3‐aminopropyltriethoxysilane (APTES) was first reacted with diisocyanate to obtain an NCO‐terminating oligomer. The reaction was continued by adding linseed oil glyceride to form an AFUO prepolymer. The auto‐oxidative drying coating was obtained after adding a metal dryer to the AFUO prepolymer. Urethane oil (UO) coating, as a control, was obtained by the same procedure as that for AFUO, but without containing alkoxysilane‐functional groups in the formation. Siloxane hybrid urethane oil (SHUO) wood coatings were prepared by mixing tetraethyl orthosilicate (TEOS) solutions, as an external crosslinking agent by sol–gel process, with the AFUO and UO coatings. We found that introducing of APTES into the molecular chains of the UO coating resulted in a film with superior impact and abrasion resistance, and it is the most efficient process to enhance the UO films. The addition of TEOS into AFUO coatings shortened the curing time and further improved the crosslinking density of the AFUO films; however, the physical properties like impact resistance, bending resistance, and gloss were even worse than AFUO films. Mixing of TEOS and UO coating also shorten the curing time and improved the heat resistance, lightfastness, and hardness of the UO coating. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44562.     

Water‐resistant plant protein‐based nanofiber membranes

Developing green and sustainable alternative materials to replace petroleum based ones is the need of the day. Such green materials are becoming popular because they can be composted once their useful life is over. In the current research, protein‐based nanofibers were fabricated without the use of any toxic cross‐linking agent. Defatted soy flour was purified using an acid‐wash process to obtain material with higher protein content, blended with gluten, and successfully electrospun into nanofibers with the help of polyvinyl alcohol. Oxidation of sucrose with hydrogen peroxide (H₂O₂) was carried out to synthesize oxidized sugar‐containing aldehyde (—CHO) groups and used as green cross‐linker. The cross‐linking quality of protein‐based nanofibers modified by oxidized sugar was found to be similar to nanofibers cross‐linked using toxic glyoxal and show good resistance to water. These novel green protein‐based nanofibers can be useful in fabricating inexpensive products with very high specific surface area and highly porous structure. © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41852.     

Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol

A bio‐based thermoset resin has been synthesized from glycerol reacted with lactic acid oligomers of three different chain lengths (n): 3, 7, and 10. Lactic acid was first reacted with glycerol by direct condensation and the resulting branched molecule was then end‐functionalized with methacrylic anhydride. The resins were characterized by Fourier‐transform infrared spectroscopy (FT‐IR), by ¹³C‐NMR spectroscopy to confirm the chemical structure of the resin, and by differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA) to obtain the thermal properties. The resin flow viscosities were also measured using a rheometer with different stress levels for each temperature used, as this is an important characteristic of resins that are intended to be used as a matrix in composite applications. The resin with a chain length of three had better mechanical, thermal, and rheological properties than the resins with chain lengths of seven and 10. Also, its bio‐based content of 78% and glass transition temperature of 97°C makes this resin comparable to commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40488.     

Cure kinetics of an acrylated epoxidized hemp oil‐based bioresin system

In this work, the cure kinetics of a novel acrylated epoxidized hemp oil (AEHO)‐based bioresin was investigated for the first time by differential scanning calorimetry (DSC) using both isothermal and nonisothermal conditions. This new bioresin was synthesized by the acrylation of a previously epoxidized hemp oil (EHO) bioresin. The curing of the AEHO bioresin showed an autocatalytic behavior with the vitrification phenomenon preventing the conversion reaching unity for all the temperatures studied. It was found that the curing behavior can be modeled with high accuracy using a modified Kamal autocatalytic model that takes into account the vitrification phenomenon. Dynamic activation energies were determined from the Kissinger and Ozawa–Flynn–Wall methods, resulting in 58.87 and 62.02 kJmol^?1, respectively. In addition, activation energies associated with the autocatalytic model constants, k₁ and k₂, were established to be equal to 58.94 and 45.32 kJmol^?1, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Recyclable bio‐based crosslinked polyurethanes with self‐healing ability

We report the synthesis of a linear bio‐based polyurethane (bio‐PU) containing furan ring by using renewable polylactide copolymer diol and 2,5‐furandimethanol as a soft segment and chain extender, respectively, in which the reversible crosslinked covalent bonds between hard segments were incorporated via Diels–Alder (D‐A) reaction between the furan ring of the chain extender and bismaleimide (BM) crosslinker. By simply controlling the amount of BM, mechanical properties of the obtained crosslinked bio‐PUs (CBPUs) were varied widely. In particular, the CBPU100 sample shows the highest tensile strength of 10.8 MPa, Young's modulus of 193 MPa, and an elongation of 155%. The differential scanning calorimetry experiments verify the recycle property of the CBPUs by the D‐A/retro‐D‐A reaction at the proper temperature. The thermal recyclability and remolding ability of these materials are demonstrated by two kinds of polymer processing methods, i.e., solution casting and hot‐compression molding. The recycled CBPUs display almost identical elongation and slightly decreased tensile strength compared to the as‐synthesized samples. Furthermore, the CBPUs also exhibit excellent self‐healing ability. Therefore, the resulting CBPUs possess tunable mechanical properties, good thermal recyclability, re‐mending, and self‐healing ability, which makes the bio‐based materials more eco‐friendly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46272.     

Characterization of multiwalled carbon nanotube filled,palm‐oil‐based polyalkyds: Effects of loading and in situ reaction

In this study, the contribution of multiwalled carbon nanotubes (MWCNTs) was studied for the evaluation of the performances of polyalkyd‐based films produced from dehydrated palm oil. Initially, different percentages of MWCNTs, including 0.5, 1.0, and 1.5 wt %, were considered for loading into the resin with the help of sonication. Additionally, a 1.0 wt % loading was considered for in situ conditions during the esterification process to achieve better dispersion and obtain improved properties of the film. The loading was evaluated by different performance tests, such as those of tensile, elongation, pencil hardness, swelling ratio, gel content, wettability, chemical resistivity, adhesion, and surface morphology. The results of mechanical testing showed that the addition of 1.0 wt % MWCNTs enhanced the tensile strength by 50%, whereas in situ conditions were found to be favorable for significantly improving the tensile strength by 75%. Moreover, the wettability, surface morphology, and thermal properties were also found to be in favor of in situ conditions for the dispersion of the MWCNTs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42934.     

Performance of palm oil‐based dihydroxystearic acid as ionizable molecule in waterborne polyurethane dispersions

Waterborne polyurethane dispersions (WPUDs) containing a renewable palm oil‐based 9,10‐dihydroxystearic acid (DHSA) as an isocyanate‐reactive compound bearing ionizable carboxylic group to incorporate hydrophilic groups into the polymer chain have been successfully prepared. The WPUDs were prepared by using polyether and polyester polyols of 2000 molecular weight, DHSA and its traditional petroleum‐based counterpart 2,2‐bis(hydroxymethyl)‐propionic acid (DMPA), and an aliphatic diisocyanate (isophorone diisocyanate, IPDI). A comparison was made between the properties of WPUDs obtained using blends of DHSA and DMPA at different molar ratios and a reference WPUD based on DMPA. The particle size of polyester type WPUDs containing DHSA was reduced at a 0.5 to 0.5 molar ratio of DMPA to DHSA. A lower initial temperature was used in the preparation of NCO‐prepolymers with DHSA as compared to DMPA and this eased the preparation of WPUDs. The effect of molar ratio of DMPA to DHSA on the properties of films and coatings prepared with WPUDs was evaluated. The best properties were obtained with WPUDs prepared with a 0.5 to 0.5 molar ratio of DMPA to DHSA. The incorporation of renewable palm oil‐based DHSA into WPUDs improved water resistance (lower water uptake) and exhibited good combination of properties including hardness, adhesion strength, tensile strength, and elasticity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43614.     

Processing and characterization of bio‐based poly (hydroxyalkanoate)/poly(amide) blends: Improved flexibility and impact resistance of PHA‐based plastics

One of the most significant limitations to widespread industrial implementation of emerging bioplastics such as poly(lactic acid) and poly(hydroxyalkanoate) (PHA) is that they do not match the flexibility and impact resistance of petroleum‐based plastics like poly(propylene) or high‐density poly(ethylene). The basic goal of this research is to identify alternative, affordable, sustainable, biodegradable materials that can replace petroleum‐based polymers in a wide range of industrial applications, with an emphasis on providing a solution for increasing the flexibility of PHA to a level that makes it a superior material for bioplastic nursery‐crop containers. A series of bio‐based PHA/poly(amide) (PA) blends with different concentrations were mechanically melt processed using a twin‐screw extruder and evaluated for physical characteristics. The effects of blending on viscoelastic properties were investigated using small‐amplitude oscillatory shear flow experiments to model the physical character as a function of blend composition and angular frequency. The mechanical, thermal, and morphological properties of the blends were investigated using dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and tensile tests. The complex viscosity of the blends increased significantly with increasing concentration of PHA and reached a maximum value for 80 wt % PHA blend. In addition, the tensile strength of the blends increased markedly as the content of PHA increased. For blends containing PA at >50 wt %, samples failed only after a very large elongation (up to 465%) without significant decrease in tensile strength. The particle size significantly increased and the blends became more brittle with increasing concentration of PHA. In addition, the concentration of the PA had a substantial effect on the glass relaxation temperature of the resulting blends. Our results demonstrate that the thermomechanical and rheological properties of PHA/PA blends can be tailored for specific applications, and that blends of PHA/PA can fulfill the mechanical properties required for flexible, impact‐resistant bio‐based nursery‐crop containers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42209.     

Effect of five saturated fatty acids on the properties of sweet‐potato‐starch‐based films

To fully explore the influences of saturated fatty acids (SFAs) on the properties of sweet‐potato‐starch (SPS)‐based films, five SFAs were chosen to add to SPS. The SPS‐based films were prepared by casting. The microstructure, mechanical, optical, water vapor barrier, and thermal properties of the films were investigated. The 2.0% (w/w, on the basis of starch) SFA significantly changed the SPS pasting characteristics in the peak viscosity, breakdown, and other feature point viscosity values as determined by a Rapid Visco Analyser. The amylose molecular weights decreased as measured by high‐performance size exclusion chromatography. A thermal study with differential scanning calorimetry suggested that the addition of SFA increased the onset temperature and peak temperature. Scanning electronic microscope (SEM) images showed a continuous and uniform structure in the films with SFA. The SPS–SFA composite films showed lower light transmission and elongation at break than the control. Compared with the control films, the addition of SFA increased the tensile strength and decreased the water vapor permeability of the films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41380.     

Swelling kinetics of linseed oil‐based polymers

Kinetics of swelling and sorption behavior of copolymers (based on linseed oil, styrene, divinylbenzene, and acrylic acid via cationic and thermal polymerization) is studied in tetrahydrofuran (THF) at different temperatures. The values of n in the transport equation are found to be below 0.4, showing non‐Fickian or pseudo‐Fickian transport in the polymers. The dependence of diffusion coefficient on the composition and temperature has also been studied for the linseed oil‐based polymers. The diffusion coefficient in cationic samples decreases with an increase in the oil contents in the samples. In case of thermal samples, the diffusion coefficient first increases up to 30% oil contents and then decreases. The diffusion coefficient decreases with an increase in temperature for all of the linseed oil polymer samples. The sorption coefficient increases with an increase in the oil contents for all samples. The crosslink density (calculated from the THF swelling) ranges from 20.16 to 92.34 × 10⁶ mol/cm³ for cationic samples and 20.62 to 86.01 × 10⁶ mol/cm³ for thermal samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of CaO in the thermal crosslinking of maltodextrin and citric acid: A cooperative action of condensation and ionic interactions

The study of the effect of CaO in the thermal crosslinking of maltodextrin with citric acid demonstrates that the addition of small amount of this compound enhances the crosslinking of the cured system under processing conditions. This enhancement of the crosslinking leads to a noticeable improvement of the mechanical properties. The mechanism of the enhanced crosslinking reaction has been deeply analyzed by rheology, FT‐IR, and TGA. The rheological results show that CaO contributes to the crosslinking. This contribution would allow decreasing 10 °C the temperature of curing process. The enhancement of the crosslinking and consequent improvement of mechanical properties is explained by the contribution of the interactions between the Ca²⁺ and citric acid and the polycondensate network formed between maltodextrin and citric acid. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44203.     

Fully bio‐based poly(ɛ‐capolactone)/poly(lactide) alternating multiblock supramolecular polymers: Synthesis,crystallization behavior,and properties

Supramolecular poly(?‐capolactone)/poly(lactide) alternating multiblock copolymers were prepared by UPy‐functionalized poly(lactide)‐b‐ poly(?‐capolactone)‐b‐ poly(lactide) copolymers. The prepared supramolecular polymers (SMPs) exhibit the characteristic properties of thermoplastic elastomers. The stereo multiblock SMPs (sc‐SMPs) were formed by blending UPy‐functionalized poly(l ‐lactide)‐b‐ PCL‐b‐ poly(l ‐lactide) (l ‐SMPs) and UPy‐functionalized poly(d ‐lactide)‐b‐ PCL‐b‐ poly(d ‐lactide) (d ‐SMPs) due to stereocomplexation of the PLLA and PDLA blocks. Sc‐SMPs with low content of d ‐SMPs (≤20%) are transparent, elastic solids, while those having high d ‐SMPs content are opaque, brittle solids. The effects of l ‐SMPs/d ‐SMPs mixing ratios on thermal, crystallization behaviors, crystal structure, mechanical and hydrophilic properties of sc‐SMPs were deeply investigated. The incorporation of UPy groups depresses the crystallization of polymer, and the stereocomplex formation accelerates the crystallization rate. The used initiator functionalized polyhedral oligomeric silsesquioxanes causes a different effect on the crystallization of PLA and PCL blocks. The tensile strength and elongation at break of l _d /d _d ‐SMPs (d represents the initiator diethylene glycol) are significantly larger than that of l _p /d _p ‐SMPs (p represents the initiator polyhedral oligomeric silsesquioxanes), and their heat resistance and hydrophilicity can be also modulated by the l ‐SMPs/d ‐SMPs mixing ratios and the different initiators. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45575.