Synthesis of poly(arylene benzimidazole) sulfone (PABIS) and preparation of hollow PABIS microspheres

4,4'‐Di(benzimidazolyl)benzene sulfone, as the monomer, is very readily available by the reaction of 4,4'‐dicarboxydiphenyl sulfone with o‐phenylenediamine, and poly(arylene benzimidazole) sulfone (PABIS) has been synthesized by the condensation polymerization of bis(4‐fluorophenyl) sulfone with di(benzimidazolyl)benzene sulfone via an N–C coupling reaction. The structure of the polymer was characterized by Fourier transform IR spectroscopy, ¹H NMR spectroscopy and elemental analysis, and the results showed agreement with the proposed structure. DSC and thermogravimetric measurements showed that PABIS possesses a high glass transition temperature (T_g = 321 °C) and good thermal stability with high decomposition temperature (T_d > 530 °C). Additionally, PABIS exhibits good solubility in most polar organic solvents. Based on the good chemical and physical properties, hollow PABIS microspheres with diameters in the range 0.3–1.8 mm were prepared by the micro‐liquid technique and the double‐layer latex technique. A new double T‐channel droplet generator was developed for continuous fabrication of controlled‐size hollow PABIS microspheres. The structures of the hollow PABIS microspheres were characterized, and they possessed equal wall thickness and good spherical symmetry. © 2013 Society of Chemical Industry     

Thermoresponsive hollow magnetic microspheres with hyperthermia and controlled release properties

Thermoresponsive hollow magnetic microspheres consisting of a hollow magnetic core, a carbon shell, and a smart polymer layer are presented in this article. A carbon nanomaterial was used as a steric stabilizer for Fe₃O₄ nanoparticles and a supporter for polymer. The thermoresponsive monomer, N‐isopropyl acrylamide, was grafted on the carbon‐encapsulate hollows by surface radical polymerization. The experimental results indicate that the composites had a phase‐transition temperature around 43°C and a saturation magnetization of 56.9 emu/g; this showed apparent thermosensitivity and magnetism. The performances in hyperthermia evaluated by an inductive magnetic field showed that the hybrid microspheres had a specific absorption rate of 240 W/g. The model drug, 5‐fluorouracil, was loaded in and released from the microspheres with different release rates at 35 and 50°C. This demonstrated that the as‐synthesized microspheres had a thermotriggered release ability and would be a good drug carrier in the biomedical field. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42617.     

Effect of hybrid hollow microspheres on thermal insulation performance and mechanical properties of silicone rubber composites

Hollow microspheres (HM) of ceramic, silica, and glass‐filled silicone rubber (SR) composites were prepared, and the effects of hybrid HM on thermal and mechanical properties of composites were investigated. The results indicate that hybrid HM can effectively improve the thermal insulation property of HM/SR composites. Especially, for sample 15S, the thermal conductivity and thermal degradation temperature reached 0.1273 W/m K and 521 °C (45 °C higher than that of neat SR), respectively. Besides, thermal insulation performance was improved, showing as a temperature of 103.2 °C after 15 min heating, which is 37.8 °C lower than that of SR. The tensile strength of composites was enhanced from 1.92 MPa at 11.56 vol % hollow silica microspheres (HSM) loading to 3.08 MPa at 21.88 vol % HSM loading. Moreover, the compressive strength was improved from 3.33 to 5.68 MPa by introducing more hollow ceramic microspheres into the matrix, in this case, from 7.79 to 15.33 vol %. Furthermore, the failure mechanism was analyzed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46025.     

Effect of nano‐titanium nitride on thermal insulating and flame‐retardant performances of phenolic foam

In this work, titanium nitride (TiN) nanoparticles were employed to achieve enhanced thermal insulation and flame retardance of phenolic foam (PF)/TiN nanocomposites (PFTNs) via in situ polymerization. The morphologies of PFTNs were observed by scanning electron microscope and the images showed that the PFTNs have more uniform cell morphologies compared with pure PF. Thermal insulating properties of PFTNs were evaluated by thermal conductivity tests. The introduction of TiN obviously decreased the thermal conductivities of PF over a wide temperature range (?20 to 60 °C). Significantly, the thermal conductivity of PFTNs gradually decreased as the temperature increased from 30 to 60 °C, showing a contrary tendency with that of pure PF. Moreover, the thermal stability and flame‐retardant properties of PFTNs were estimated by thermogravimetric analysis (TGA), UL‐94 vertical burning and limited oxygen index (LOI) tests, respectively. The TGA and LOI results indicated that PFTNs possess enhanced thermal stabilities and fire‐retardant performances with respect to the virgin PF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43765.     

Effects of highly exfoliated montmorillonite layers on the properties of clay reinforced terpolymer nanocomposite plugging microspheres

In this study, exfoliated montmorillonite (MMT) nanolayers were successfully encapsulated in acrylamide/acrylic acid/2‐acrylamido‐2‐methylpropanesulfonic acid (AM/AA/AMPS) terpolymer microspheres by in situ inverse suspension polymerization with the aid of the organic intercalation modification and the lateral groups of terpolymer chains. The introduction of well‐dispersed MMT nanolayers reveals a significant enhancement of the comprehensive properties of these nanocomposite microspheres, such as the viscoelasticity, thermal stability, and plugging ability. Compared with the pure terpolymer, the elastic modulus (G′) of terpolymer/2.0 wt % O‐MMT nanocomposites is 4.30 times higher and the decomposition temperature of these nanocomposites increases by 40 °C. The plugging rate reaches as high as 86.6%. Besides, surface morphology, swelling degree, and wetting behavior can be effectively tuned by varying the content of exfoliated MMT. The wetting angle increases to 82.0 ° which is suitable for modifying the formation channels. These selected nanocomposite microspheres can effectively enter and plug the high permeable microchannels. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44894.     

Ethylene polymerization with hybrid nickel diimine/Cp2TiCl2 catalyst: a new method to prepare blends of linear and branched polyethylene

Blends of linear polyethylene (LPE) and branched polyethylene (BPE) display very good mechanic properties that can be beneficial for various applications such as shear thinning and melt elasticity. LPE, BPE and amorphous polyethylene can be produced using nickel diimine (DMN) catalyst under various polymerization conditions, while LPE can be obtained using metallocene catalyst. Thus, LPE/BPE blends can be achieved by in situ polymerization using a hybrid DMN/metallocene catalyst. A novel hybrid catalyst made of DMN and Cp₂TiCl₂ was designed and used for ethylene polymerization. A synergistic effect of the two active sites in the hybrid DMN/metallocene catalyst was observed. Blends of linear and low branched polyethylene were synthesized when polymerization was conducted at low temperature (0 °C), while blends of linear and highly branched polyethylene were obtained at high temperature (50 °C). However, the miscibility of the polymers obtained at 50 °C was dramatically reduced as compared to those obtained at 0 °C. Mesoporous particles (MCM‐41) consisting of aluminosilicate with cylindrical pores were used to support the hybrid catalyst, in which MCM‐41 provides sufficient nanoscale pores to facilitate the polymerization in well‐controlled confined spaces. Blends of LPE and BPE were synthesized by in situ polymerization without adding comonomer and characterized. The miscibility of the polymer blends can be improved by supporting the hybrid catalyst on MCM‐41. Copyright © 2009 Society of Chemical Industry     

Nanocomposites of PBAT and cellulose nanocrystals modified by in situ polymerization and melt extrusion

Cellulose nanocrystals (CNC) were successfully grafted with a low molecular weight poly(butylene glutarate) through an in situ polymerization procedure. The grafting treatment decreased the CNC hydrophilic character and increased the onset of their thermal degradation by approximately 20°C, thus increasing the possibilities of CNC application. Composites of grafted and nongrafted CNC with a poly(butylene‐adipate‐co‐terephthalate) (PBAT) matrix were prepared by melt extrusion. The CNC addition led to an increase of 50% of the tensile elastic modulus of the PBAT. In addition, dynamic mechanical thermal analysis showed that the composite with CNC retained its high modulus even at temperatures far above the glass transition temperature of PBAT. At 60°C the storage modulus of the composite with CNC was approximately 200% higher than that of the pure PBAT. Thus, in this work, nanocomposites of improved properties were obtained through a combination of in situ polymerization and melt extrusion. POLYM. ENG. SCI., 56:1339–1348, 2016. © 2016 Society of Plastics Engineers     

Grafting of titanium dioxide microspheres with a temperature‐responsive polymer via surface‐initiated atom transfer radical polymerization without the use of silane coupling agents

Titania microspheres with narrow size distribution and diameters of about 1 µm were prepared and subsequently functionalized using surface‐initiated atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α‐bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface‐grafted poly(N‐isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X‐ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli‐responsive TiO₂ microparticles via a straightforward controlled surface‐initiated polymerization method.     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Accelerant‐promoted free radical polymerization of methacrylates by stabilized nitroxide unimolecular initiators: synthesis and characterization

BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of M_n evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (T_g) for PMMA was 123–128 °C. The degradation temperature (T_d) for PMMA was 350–410 °C. T_d for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry     

Expansion space and thermal stability of microencapsulated n‐octadecane

5.0–50.0 vt% of cyclohexane was mixed with 95.0–50.0 vt% of n‐octadecane as the oil‐phase during the emulsion process in the in situ polymerization of melamine‐formaldehyde. By heat‐treating the microcapsules in an oven at 100°C, the cyclohexane was removed and expansion space was formed inside the microcapsules. The microcapsules were characterized by using FTIR, SEM, DSC, TGA, and gas chromatography. When the microcapsules are heat‐treated at temperatures higher than 180°C, Tm, ΔHm, Tc, and ΔHc of the microcapsules decrease. The attenuation of enthalpy of the microcapsules containing expansion space is obviously lower than that of the control sample, however. The permeability of the microcapsule shell decreases with the increase of cyclohexane content. There is a maximum between the thermal stabilities of the microcapsules and the cyclohexane contents. The microcapsules synthesized with 30.0–40.0 vt% of cyclohexane have the highest thermal stabilities, with 230°C and 289°C in air and nitrogen atmosphere, respectively. The thermal stable temperatures are approximately 67°C and 102°C higher than that of the control sample, respectively. The expansion space inside the microcapsules allows the n‐octadecane to expand in the temperature rising process and exert lower pressure to the shell, therefore keeping the shell intact and increasing the thermal stabilities of the microcapsules. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 390–396, 2005     

Preparation of high‐molecular‐weight poly(N‐vinylcarbazole) by the photoinduced low‐temperature solution polymerization of N‐vinylcarbazole in 1,1,2,2‐tetrachloroethane

For the preparation of high‐molecular‐weight (HMW) poly(N‐vinylcarbazole) (PVCZ) with a narrow molecular weight distribution, N‐vinylcarbazole (VCZ) was solution‐polymerized in 1,1,2,2‐tetrachloroethane (TCE) at ?20, 0, and 20°C with photoinitiation. The effects of the polymerization temperature and the concentrations of the polymerization solvent and photoinitiator on the polymerization behavior and molecular parameters of PVCZ were investigated. A low polymerization temperature with photoirradiation was successful in obtaining HMW PVCZ with a smaller temperature rise during polymerization than that for thermal free‐radical polymerization by azobisisobutyronitrile (AIBN). The photo‐solution‐polymerization rate of VCZ in TCE was proportional to [AIBN]^0.45. The molecular weight was higher and the molecular weight distribution was narrower for PVCZ made at lower temperatures. For PVCZ prepared in TCE at ?20°C with a photoinitiator concentration of 0.00003 mol/mol of VCZ, a weight‐average molecular weight of 920,000 was obtained, with a polydispersity index of 1.46, and the degree of transparency converged to about 99%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2391–2396, 2003     

Synthesis and characterization of poly(methyl methacrylate)/montmorillonite nanocomposites by in situ bulk polymerization

Poly(methyl methacrylate)/montmorillonite (MMT) nanocomposites were prepared by in situ bulk polymerization. The results showed that the silicone coupling agent affected the structure and properties of hybrid materials. XRD analysis showed that the dispersion of clay in nanocomposites with silicone‐modified organophilic MMT was more ordered than that in nanocomposites with unmodified organophilic MMT. The glass transition temperature (T_g) of the nanocomposites was 6–15°C higher and the thermal decomposition temperature (T_d) was 100–120°C higher than those of pure PMMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2256–2260, 2003     

A new macroinitiator for the synthesis of triblock copolymers PA12‐b‐PDMS‐b‐PA12

A new PDMS macroinitiator is proposed for the anionic ring‐opening polymerization of lactams. This α,ω‐dicarbamoyloxy caprolactam PDMS macroinitiator was readily obtained in quantitative yield, by an original synthesis scheme in two steps, which involved the scarcely reported reaction of isocyanates with silanol groups. It was then shown that this bifunctional macroinitiator enabled to synthesize triblock copolymers PA12‐b‐PDMS‐b‐PA12 by polymerization of lauryl lactam (LL) at high temperature (200°C) in inert atmosphere under conditions compatible with reactive extrusion processes. Another related high molar weight α,ω‐diacyllactam PDMS macroinitiator was also successfully used in the polymerization of LL under the same conditions, therefore overcoming the limitations formerly reported for this type of macroinitiators during the polymerization ε‐caprolactam (ε‐CL) at a much lower temperature (80°C). Triblock copolymers with a wide range of PA12 /molar weights (M_n: ～ 10,800–250,000 Da) were eventually obtained by using both types of macroinitiators. DMTA and DSC analyses showed that their thermal properties were strongly dependent upon their respective contents in soft and hard blocks. Such triblock copolymers already appear very promising for the highly effective in situ compatibilization of PA12/PDMS blends as shown by recent complementary results obtained in our laboratory. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2818–2831, 2006     

Properties of poly(ethylene terephthalate) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane

Poly(ethylene terephthalate) (PET) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS) was prepared by melt‐mixing and in situ polymerization methods. The melt‐mixed composite showed phase separation while the in situ polymerized composite did not, based on SEM characterization. During melt mixing, the reaction between the epoxy groups of POSS and hydroxyl groups of PET occurred, based on DSC results. DSC results on the in situ polymerization product showed formation of a lower‐melting component compared with PET. The tensile strength and modulus of the melt‐mixed composite fiber decreased compared with those properties of PET, whereas those of the in situ polymerized composite showed slightly higher values than PET despite the relatively small amounts (1 wt%) of POSS used. Dynamic mechanical analysis results showed an increase in storage modulus for the in situ polymerized composite of POSS and PET compared with PET over the temperature range of 40 °C to 140 °C. Copyright © 2004 Society of Chemical Industry     

One‐pot synthesis of monodispersed phosphazene‐containing microspheres with active amino groups

An amine‐terminated nucleophile Hexakis (4‐aminophenoxy) cyclotriphosphazene (HACP) was synthesized. Its chemical structure was identified by ¹H NMR and ³¹P NMR. Novel monodispersed phosphazene‐containing microspheres with active amino groups on the surface have been successfully prepared through a one‐pot precipitation polymerization of hexachlorocyclotriphosphazene with HACP. Just by single step, the microspheres were synthesized without stirring, surfactant and ultrasonic irradiation. The diameter of the obtained microspheres ranged from 0.1 to 0.5 μm with the rough surface. And, the onset of the thermal‐degradation temperature was 460°C, which is attributed to the highly cross‐linked structure and the introduced of the cyclotriphosphazene rings. Moreover, the products at variable stages of polymerization were measured by TEM. The formation mechanism was proposed which is corresponding with an oligomeric species absorbing mechanism. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43336.     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

In situ intercalation green polymerization,characterization, and kinetics of poly(lactic acid)/zinc oxide pillared saponite nanocomposites

Poly(lactic acid) (PLA)/Zinc oxide (ZnO) pillared saponite nanocomposites were prepared with ZnO pillared saponite as the green catalyst and lactic acid as monomer through in situ intercalation polymerization method. The optimum polymerization parameters were as follows the addition content of ZnO pillared saponite was 1% (wt) and the reaction was running at 180°C for 7 h. The Fourier transform infrared and ¹H NMR results showed that the polymerization sample was PLA; Gel permeation chromatography result showed the PLA had a narrow molecular weight distribution, which arranged from 3,000 to 5,000 and the polydispersity index of PLA was 1.2. Differential scanning calorimetry showed ZnO pillared saponite improved the crystallinity of PLA. Thermogravimetric analysis showed the thermal stability of PLA‐based nanocomposites were improved by ZnO pillared saponite. It was shown that in situ intercalative polymerization kinetics model of PLA/ZnO pillared saponite nanocomposites accorded with third order, and the activation energy of polymerization reaction was 49.3 kJ/mol under the polymerization reaction conditions as follows: the vacuum degree was 0.085 MPa, the temperature was 130°C, and the reaction extent was 2.35∼47.69%, the content of ZnO pillared saponite catalyst was 1 wt%. POLYM. COMPOS., 35:1023–1030, 2014. © 2013 Society of Plastics Engineers     

Infrared study on in situ polymerization of zinc dimethacrylate in poly(α‐octylene‐co‐ethylene) elastomer

An infrared spectroscopic method was used to follow the course of in situ polymerization of zinc dimethacrylate (ZDMA) in poly(α‐octylene‐co‐ethylene) elastomer (POE). The integral intensity of the 831 cm^?1 band, ie the out‐of‐plane deformation mode of ?CH, was used to determine the residual amount of ZDMA in composites cured at 165°C for different times, through which the course of in situ polymerization of ZDMA in POE was traced and the dynamic curve determined. The curing course of the ZDMA/POE/peroxide system at 165°C was examined with a rheometer and compared with the course of in situ polymerization. The results surprisingly show that the in situ polymerization of ZDMA is almost complete at the beginning stage of curing, and that substantial crosslinking starts subsequently. Scanning electron microscopy and transmission electron microscopy observations on morphologies of ZDMA/POE composites cured at 165°C for different times were carried out and confirmed the results of infrared experiments. Combining all the investigations, it was deduced that a competition exists between in situ polymerization and crosslinking in the composites. Covalent crosslinking rather than ionic bond crosslinks are the major types of crosslinks structures in ZDMA/POE composites, and its total density is lower than that of carbon‐ black‐reinforced POE. Copyright © 2004 Society of Chemical Industry     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.