Fuel Cell Membranes Based on Grafted and Post‐Sulfonated Glycidyl Methacrylate (GMA)

Glycidyl methacrylate (GMA) was pre‐irradiation grafted into ETFE base film of 25 μm thickness up to graft levels of 300%. The grafted films were sulfonated using a mixture of sulfite and bisulfite. FTIR and SEM–EDX analysis of the synthesized films and membranes was performed to confirm the grafting and the sulfonation. A pronounced front mechanism for grafting of GMA into ETFE was found. Regarding ex situ fuel cell relevant properties, conductivities of up to 0.25 S cm^–1 were attained. For the first time, fuel cell testing of this type of membrane is reported. These grafted membranes performed comparable to a commercial benchmark membrane (Nafion® 212) and better than a styrene‐based grafted membrane with similar conductivity. Post‐test FTIR analysis showed that a fraction of the grafted chains was lost during the test under constant current conditions, yet the membrane still exhibited superior durability compared to a styrene‐based grafted membrane. Hydrolysis of the methacrylate groups was shown not to be the principle cause of the loss of sulfonic acid groups.     

Preparation and properties of sulfonated ETFE‐g‐polyvinyltoluene membranes for application in fuel cells

A new polymer electrolyte membrane prepared by radiation grafting of vinyltoluene into poly(ethylene‐co‐tetrafluoroethylene) (ETFE) film and subsequent sulfonation was developed for application in fuel cells. The effect of grafting condition on the degree of grafting was investigated in detail. Results indicated that the degree of grafting can be controlled over a wide range. The grafted films were sulfonated in a chlorosulfonic acid solution to obtain the polymer electrolyte membranes, which were characterized with respect to their use in fuel cells. It is concluded that the substituted methyl group on the vinyltoluene can improve the chemical stability of the resulting membranes, and the crosslinked ETFE‐g‐poly(vinyltoluene‐co‐divinylbenzene) membranes can be proposed for the future development of alternative low‐cost and high‐performance membranes for fuel cells. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2661–2667, 2006     

Irradiation grafting of methyl methacrylate monomer onto ultra‐high‐molecular‐weight polyethylene: An experimental design approach for improving adhesion to bone cement

The grafting of methyl methacrylate (MMA) onto ultra‐high‐molecular‐weight polyethylene (UHMWPE) and chromic acid etched UHMWPE was conducted with a preirradiation method in air in the presence of a Mohr salt and sulfuric acid. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, a gravimetric method, differential scanning calorimetry, scanning electron microscopy (SEM), and interfacial bonding strength measurements. The FTIR results showed the presence of ether and carbonyl groups in the MMA‐grafted UHMWPE (MMA‐g‐UHMWPE) samples. The Taguchi experimental design method was used to find the best degree of grafting (DG) and bonding strength. The efficient levels for different variables were calculated with an analysis of variance of the results. SEM micrographs of MMA‐g‐UHMWPE samples showed that with increasing DG and chromic acid etching, the MMA‐g‐UHMWPE rich phase increased on the surface; this confirmed the high interfacial bonding strength of the grafted samples with bone cement. The grafting of the MMA units onto UHMWPE resulted in a lower crystallinity, and the crystallization process proceeded at a higher rate for the MMA‐g‐UHMWPE samples compared to the initial UHMWPE; this suggested that the MMA grafted units acted as nucleating agents for the crystallization of UHMWPE. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of ultrasonic irradiation on ceric‐salt‐initiated grafting of methyl methacrylate onto regenerated cellulose film

Effect of ultrasonic irradiation on ceric salt (Ce⁴⁺)‐initiated grafting of methyl methacrylate (MMA) on regenerated cellulose film (thickness = 20 μm) was investigated under an air atmosphere in water solvent at 60°C. The grafting system with the ultrasonic irradiation was characterized by higher percentage of grafting and graft efficiency than the system without the irradiation. Reaction of cellulose with Ce⁴⁺ was also accelerated by the ultrasonic irradiation. No accelerating effect of grafting due to the ultrasonic irradiation was observed for the system under reduced pressure of 5 torr. The effect of the ultrasonic irradiation on the average molecular weight of MMA‐grafted chains was also studied. Moreover, the surface layer of the resulting grafted films was examined by attenuated total reflection–infrared (ATR–IR) measurement and scanning electron microscopy (SEM) observation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 251–258, 1999     

Functionalization of poly(tetrafluoroethylene‐co‐ethylene) film by radiation‐induced graft copolymerization

To introduce functional moieties to Tefzel film, a copolymer of tetrafluoroethylene and ethylene, graft copolymerization of vinyl monomers such as acrylonitrile (AN) and methacrylonitrile (MAN) was attempted by a preirradiation method in aqueous medium. Optimum conditions for obtaining the maximum percentage of grafting have been evaluated for both monomers. Maximum grafting of AN (52.2%) and MAN (77.7%) is obtained at a total dose of 3.14 and 2.69 × 10⁴ Gy, respectively, using [AN] = 3.018 mol/L and [MAN] = 1.177 mol/L in 10 mL of water. The effect of aliphatic alcohols of varying chain length, such as methanol, ethanol, isopropanol, n‐butanol, and cyclohexanol, on percentage add‐on of AN and MAN has also been studied. It has been found that all the alcohols decreased the percentage of grafting. Characterization of Tefzel and grafted Tefzel films has been carried out by IR spectroscopy and thermogravimetric analysis. Grafted Tefzel film has been found to have improved thermal resistance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1171–1178, 2000     

Polymer electrolyte membranes having sulfoalkyl grafts into ETFE film prepared by radiation‐induced copolymerization of methyl acrylate and methyl methacrylate

Polymer electrolyte membranes (PEMs) containing alkylsulfonic acid grafts can be prepared by radiation‐induced graft copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) into a poly(ethylene‐co‐tetrafluoroethylene) film followed by sulfonation of the MA units in the copolymer grafts using an equimolar complex of chlorosulfonic acid and 1,4‐dioxane (ClSO₃H‐Complex). PEMs with MA/MMA copolymer grafts that are 33%–79% MA units were prepared by preirradiation with a dose of 20 kGy and grafting in bulk comonomers at 60°C. The grafted films are treated with ClSO3H‐Complex to obtain PEMs with ion exchange capacity of 0.36‐0.81 mmol/g (sulfonation degrees of 20%–40%) and proton conductivity of 0.04‐0.065 S/cm. These values can be controlled by changing the MA content the sulfonation occurring at an α‐carbonyl carbon. The PEMs with higher MMA content showed higher durability in water (80°C) and under oxidative conditions (3% H₂O₂) at 60°C. This is because the PMMA grafts in the PEMs have no proton at an α‐carbonyl carbon, which is considered to be a trigger of the degradation of grafting polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel graft copolymers by radiation‐induced grafting

The radiation‐induced graft copolymerization of N‐vinyl‐2‐pyrrolidone (NVP), 4‐vinyl pyridine (4VP), and 2‐vinyl pyridine (2VP) monomers onto poly (ethylene‐alt‐tetrafluoroethylene) (ETFE) was investigated. The influence of synthesis conditions particularly the solvent was studied. Various solvents, such as n‐propanol, isoproponol, benzyl alcohol, methanol, ethanol, cyclohexanone, tetrahydrofuran (THF), nitromethane, 1,4‐dioxane, and n‐heptane were examined for this purpose. Graft copolymers were characterized by Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical analysis (DMA), and scanning electron microscopy‐energy dispersive spectroscopy (SEM‐EDAX). It was found that the nature of the solvent had profound influence over the grafting reaction. Cyclohexanone, n‐propanol, and isoproponol for 4VP/ETFE grafting, THF and 1,4‐dioxane for NVP/ETFE grafting, and benzyl alcohol and methanol for 2VP/ETFE grafting were found to be the suitable solvents yielding highest graft levels. Isoproponol and n‐propanol are promising in terms of both graft level and mechanical properties for 4VP/ETFE. Grafting of NVP, 4VP, and 2VP onto ETFE were verified through FTIR spectroscopy. Storage modulus and glass transition temperature of the copolymers were found to increase as graft level increased. Surface profile of representative films was also investigated by viewing the distribution of elemental nitrogen using SEM‐EDAX. Results indicated that copolymers of 4VP, NVP, and 2VP are considerably different from each other. 4VP‐based copolymers exhibited relatively more homogenous grafting over the surface compared with NVP‐ and 2VP‐based copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of Radiation‐Induced Grafting Process on Mechanical Properties of ETFE‐Based Membranes for Fuel Cells

The mechanical stability is, in addition to thermal and chemical stability, a primary requirement of polymer electrolyte membranes in fuel cells. In this study, the impact of grafting parameters and preparation steps on stress–strain properties of ETFE‐based proton conducting membranes, prepared by radiation‐induced grafting and subsequent sulphonation, was studied. No significant change in the mechanical properties of the ETFE base film was observed below an irradiation dose of 50 kGy. It was shown that the elongation at break decreases with increasing both the crosslinker concentration and graft level (GL). However, the tensile strength was positively affected by the crosslinker concentration. Yield strength and modulus of elasticity are almost unaffected by the introduction of crosslinker. Interestingly, yield strength and modulus of elasticity increase gradually with GL without noticeable change of the inherent crystallinity of grafted films. The most brittle membranes are obtained via the combination of high GL and crosslinker concentration. The optimised ETFE‐based membrane (GL of ∼25%, 5% DVB v/v), shows mechanical properties superior to those of Nafion® 112 membrane. The obtained results were correlated qualitatively to the other ex situ properties, including crystallinity, thermal properties and water uptake of the grafted membranes.     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Thermal properties of proton-conducting radiation-grafted membranes

Proton-exchange membranes are required to exhibit chemical, mechanical, and thermal stability for fuel cell applications. The present investigation has been carried out to explore the thermal behavior of poly(ethylene-alt-tetrafluoroethylene) (ETFE)-based proton-conducting membranes, both uncrosslinked and crosslinked, prepared by radiation grafting and subsequent sulfonation. The influence of preparation steps (irradiation, grafting, sulfonation, crosslinking) on the thermal degradation, crystallinity, and melting behavior of membranes with varying degree of grafting was examined. ETFE base film and grafted films were studied as the reference materials. Furthermore, poly(tetrafluoroethylene-co-hexafluoropropylene)-based grafted films and membranes were investigated as well for comparison. Membrane preparation steps, degree of grafting, crosslinking, type of base polymer have considerable influence on the thermal properties of membranes. The crystallinity of the films decreases slightly by grafting, while a significant decrease was observed after sulfonation. For instance, crystallinity decreased from 37% (pristine ETFE) to 36% (uncrosslinked grafted film) and 23% (uncrosslinked ETFE-based membrane). On the other hand, the melting temperature of the base polymer was almost unaffected by irradiation and grafting. The crosslinked ETFE-based membranes exhibit a slightly higher melting temperature (262.5°C) than their corresponding grafted films (261.3°C) and the base film (260.6°C). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

γ‐Radiation‐Induced Graft Copolymerization of Ethyl Acrylate onto Hydroxypropyl Methylcellulose

Summary: Graft copolymerization of EA onto water‐soluble HPMC was carried out using γ‐radiation using both simultaneous and preirradiation in an aqueous medium. The effects of radiation environment, radiation dose, monomer concentration, and reaction temperature on percentage of grafting (G) and grafting efficiency (G_E) were investigated. For preirradiation, the observed values for G and G_E were higher in air than in a nitrogen atmosphere. G and G_E values are obviously higher for preirradiation; their maximum values were obtained for a radiation dose of 1.8 kGy. The grafting parameters increase for increasing monomer concentration up to 0.15 mol · L^?1, where they reach their saturation values. In the case of preirradiation, the largest grafting parameters are obtained at 65 °C. The graft copolymers obtained were characterized by FTIR spectroscopy, TEM, SEM, and XRD methods. The method of irradiation significantly affects the mechanical properties of the grafted HPMC samples. Samples prepared by simultaneous irradiation show superior mechanical properties. In addition, the equilibrium humidity adsorption behaviors of the grafted copolymers were also studied, and the humidity resistance behavior of HPMC was enhanced through the grafting copolymerization.

Transmission electron micrograph of the HPMC‐g‐PEA water dispersion.     

Electrical properties of modified‐grafted polypropylene

The electrical properties of polypropylene (PP), grafted polypropylene (PP‐g‐PVP), and modified‐grafted PVP with α‐cyano‐β‐(2‐thienyl) crotononitrile were investigated. Also, the electrical characteristic of the modified‐grafted PVP subjected to γ‐irradiation (60 kGy) was studied. The results show that the σ of trunk polymer undergoing different degree of grafting generally increases as function of the grafting yield. The grafting yield between 64.1 and 149% resulted in a progressive decrease in ΔE_σ value. Inclusion of sulfur‐containing substrate in different films, having various grafting yields, leads to both increase and decrease in σ values. A significant increase in σ values is observed upon inclusion of sulfur‐containing substrate having maximum grafting yield (149%). These changes are accompanied by fluctuation in σ values. The exposure of sulfur‐containing substrate in grafting film to a dose of 60 kGy results in a significant decrease in ΔE_σ values for the films undergoing a grafting yield between 64.1 and 149%. The observed changes in ΔE_σ of different films investigated could be attributed mainly to corresponding changes in σ values. The observed improvement in electrical properties is mainly because of possible increase in concentration of charge carrier and/or their mobilities. The scanning electron micrographs of some selected films show significant changes in the morphology of the films investigated due to changing the grafting yield, inclusion of sulfur‐containing substrate, and exposure to γ‐irradiation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3797–3803, 2007     

High temperature surface neutralization process with random copolymers for block copolymer self‐assembly

Hydroxyl terminated poly(styrene‐r ‐methyl methacrylate) (P(S‐r ‐MMA )) random copolymers (RCPs ), with molecular weight (M _n) spanning from 1700 to 69 000 g mol^?1 and equal styrene unit content, were grafted at different temperatures onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder forming polystyrene‐b ‐poly(methyl methacrylate) (PS ‐b ‐PMMA ) block copolymer thin films. When the grafting temperature increases from 250 to 310 °C, a substantial increase in the grafting rate is observed. In addition, an increase in the surface neutralization efficiency occurs thus resulting in an increase in the robustness of the surface neutralization step. These data revealed that the neutralization of the substrate is the result of a complex interplay between RCP film characteristics and underlying substrate properties that can be finely tuned by properly adjusting the temperature of the grafting process. © 2016 Society of Chemical Industry     

Structural characterization of alpha methyl styrene‐butyl acrylate‐grafted polyetheretherketone films

Radiation‐induced graft copolymerization of alpha methyl styrene (AMS)‐butyl acrylate (BA) mixture onto poly(etheretherketone) (PEEK) was carried out to develop films of varying copolymer compositions. The characterization of films was carried out with fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The presence of AMS and BA units within the film matrix was confirmed by FTIR. The intensity of the characteristic peaks for AMS and BA increased with the increasing grafted component in the films. The crystallinity of the films as observed from DSC and XRD decreased with the increasing graft levels. On the other hand, the melting temperature of the base polymer was almost unaffected by irradiation and the grafting process. The glass transition temperature (T_g) of the grafted film increased as compared to the virgin PEEK. Ungrafted film showed a stable thermogram up to ～500°C. However, the grafting introduced a new decomposition range in the copolymer, due to the presence of the AMS/BA. AFM images showed the formation of domains on the grafted PEEK film surface. The SEM also showed domain formation of the grafted component within the PEEK matrix. However, the fracture analysis did not show any prominent phase separation. Mechanical characterization of films in terms of tensile strength, elongation, and modulus was also carried out. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface modification of polypropylene film by radiation‐induced grafting and its blood compatibility

To endow blood‐compatible properties onto polypropylene (PP) film, we grafted 2,3‐epoxypropyl methacrylate (EPMA) to PP film with a preirradiation grafting technique and then introduced various functional groups onto the grafted PP film. The EPMA grafting extent was dependent on the absorbed dose, reaction time, and temperature. The reactions of hydroxylation, iminodiacetation, sulfonation, phosphonation, and amination were performed under various conditions to introduce functional groups into the epoxy group of EPMA‐grafted PP films, respectively. We also immobilized heparin on aminated PP film to compare blood compatibility with various functionalized samples. The grafting, functionalization, and heparinization reaction were confirmed by Fourier transform infrared spectroscopy in the attenuated total reflectance mode and electron spectroscopy for chemical analysis. The blood compatibility of various functional groups and heparin‐introduced samples as well as control samples was examined by the determination of platelet adsorption and thrombus formation. For the examination of the blood compatibility of functionalized PP samples, acid citrate dextrose human whole blood and platelet‐rich plasma were used. The amount of the formed thrombus and the adherent platelets on functionalized PP sample surfaces were evaluated by an in vitro method following Imai and Nose's technique and by scanning electron microscopy, respectively. The blood compatibility of various functional‐group‐introduced PP films after grafting was better than that of the PP control. Phosphoric‐acid‐group‐ and heparin‐introduced PP films had especially good blood compatibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1726–1736, 2003     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. I. Effect of grafting conditions

The simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied at room temperature. The effects of grafting conditions (type of solvent, irradiation dose, dose rate, and monomer concentration) were investigated. The degree of grafting was found to be dependent on the investigated grafting conditions. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be of 0.5 and 1.3 orders, respectively. The results suggest that grafting proceeds by the so‐called front mechanism in which the grafting front starts at the surface of the film and moves internally toward the middle of the film by successive diffusion of styrene through the grafted layers. Some selected properties of the grafted films were evaluated in correlation with the degree of grafting. We found that the grafted FEP films possess good mechanical stability, which encourages their use for the preparation of proton exchange membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 220–227, 2000     

Simultaneous radiation grafting of vinylbenzyl chloride onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films

In this study, we demonstrated that vinylbenzyl chloride (VBC), a versatile monomer with reactive a chloromethyl group could be grafted onto a poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) film without a degradation of the chloromethyl group during a simultaneous irradiation process. The effects of various irradiation conditions such as the total dose, dose rate, solvent, and VBC concentration on the degree of grafting of VBC onto a FEP film were also investigated. The prepared PVBC‐grafted films were characterized using FTIR, TGA, and SEM EDX. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of the radiation grafting conditions on the cross‐sectional distribution of poly(vinylbenzyl chloride) grafted polymer onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films

Poly(vinylbenzyl chloride) (PVBC)‐grafted poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films were prepared as precursors for ion‐exchange membranes with a radiation grafting technique. A scanning electron microscopy–energy dispersive X‐ray spectroscopy (SEM‐EDX) instrument was used to investigate the effects of the radiation grafting conditions on the distribution profiles of the grafts in the FEP‐g‐PVBC films because the properties of the ion‐exchange membranes were largely affected not only by the degree of grafting (DOG) but also by the distribution of the graft chain. These results indicate that the distribution profile of the grafts largely depended on the grafting parameters, such as the solvent, monomer concentration, film thickness, and irradiation dose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Synthesis and evaluation of fluorosilicone‐modified starch for protection of historic stone

Starch is sensitive to moisture and is weak to durability in the protection application to ancient relics. Therefore, two fluorosilicone‐modified starches are firstly prepared and evaluated for the protection of historic stones. The fluoro‐silicone copolymer grafted starch of P(VTMS/12FMA)‐g‐starch is synthesized by grafting copolymer of vinyltrimethoxysilane (VTMS) and dodecafluoroheptyl methacrylate (12FMA) onto starch. While the fluoro‐silicone starch latex of VTMS‐starch@P(MMA/BA/3FMA) is obtained by emulsion polymerization of VTMS primarily grafted‐starch (VTMS‐starch) with methyl methacrylate (MMA), butyl acrylate (BA) and 2,2,2‐trifluoroethyl methacrylate (3FMA). The grafting fluorosilicone copolymer onto starch improves obviously their hydrophobic and thermal properties. Comparatively, VTMS‐starch@P(MMA/BA/3FMA) film performs higher water contact angle (107°) and thermal stability (350–430°C) than p(VTMS/12FMA)‐g‐starch film (72°, 250–420°C) due to the migration of fluorine‐containing group onto the surface of film during the film formation. Therefore, VTMS‐starch@P(MMA/BA/3FMA) shows much better protective performance in water‐resistance, and salt/freeze‐thaw resistance for stone samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41650.