Amorphous Polymers Research Articles

Review on Polymer Materials for Solid Desiccant Cooling System

AbstractAs an alternative form of vapor compression air conditioning devices, solid desiccant cooling (SDC) techniques have increasingly been explored recently. The overall performances of SDC primarily rely on the capability of dehumidification and regeneration of desiccant. A desiccant with a great uptake capability and excellent regeneration potential is preferred in an SDC system. Although traditional desiccants like silica gels and zeolites are able to absorb moisture at moderate levels, hygroscopic polymers show a superior ability in moisture sorption and desorption. Significant research has been conducted to investigate the hygroscopic polymers in SDC for household and industrial applications. Here, first, an introduction to SDC systems is presented, and then hygroscopic polymers from natural and synthetic origins are discussed. Synthetic polymers discussed are metal–organic frameworks (MOFs), covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), amorphous porous organic polymers (POPs), polyelectrolytes, and polymer‐based composites. Their dehumidification behaviors in SDC systems, primarily desiccant‐coated heat exchanger (DCHE) systems, are compared and summarized. Binders employed in SDC systems are also summarized, as a proper binder enhances the overall performance of the desiccant system. It can be anticipated that hygroscopic polymers and binder materials would witness extensive applications in the future.

Melanin biopolymers from microbial world with future perspectives-a review.

Melanin is an amorphous polymer made of heterogeneous functional groups synthesized by diverse organisms including fungi, bacteria, animals, and plants. It was widely acknowledged for its biological processes and its key role in the protection of organisms from environmental stress. Recently, melanin clutches attention in the field of nanobiotechnology, drug delivery, organic semiconductors and bioelectronics, environmental bioremediation, photoprotection, etc., Furthermore, melanin from natural sources like microbial community shows antimicrobial, fighting cancer, radical scavenging, cosmeceuticals, and many therapeutic areas as well. Though the multipotentiality nature of melanin has been put forth, real-world applications still flag fall behind, which might be anticipated to the inadequate and high price essence of natural melanin. However, current bioprocess technologies have paved for the large-scale or industrial production of microbial melanin, which could help in the replacement of synthetic melanin. Thus, this review emphasizes the various sources for melanin, i.e., types-based on its pathways and its chemical structures, functional efficiency, physical properties, and conventional and modern methods of both extraction and characterization. Moreover, an outlook on how it works in the field of medicine, bioremediation, and other related areas provides perspectives on the complete exploitation of melanin in practical applications of medicine and the environment.

Fabrication and Characterization of Hybrid and Tunable ZnO@Ag Flexible Thin Films Used as SERS Substrates

Flexible substrates have known increased popularity over rigid ones due to their use in surface-enhanced Raman scattering (SERS). They provide irregular surfaces, ideal for in situ sensing. In this context, we report the SERS performance of hybrid ZnO@Ag thin films deposited by magnetron sputtering (MS) on flexible, thermoplastic substrates. This physical deposition method is acknowledged for obtaining high-quality and reproducible ZnO films that can be embedded in (bio)sensing devices with various applications. Three types of thermoplastic-based, commercially available substrates with different glass transition temperatures (Tg) were chosen for the variation in flexibility, transparency, and thickness. Zeonor® (Tg = 136 °C, thickness of 188 μm) and two types of Topas (Topas®: Tg = 142 °C, thickness of 176 μm; Topas2: Tg = 78 °C, thickness of 140 μm) thermoplastic sheets are nonpolar and amorphous cyclo-olefin polymer (COP) and cyclo-olefin copolymers (COC), respectively. Their thicknesses and different values of Tg can greatly affect the topographical and roughness properties of films with small thicknesses and, thus, can greatly influence the enhancement of the Raman signal. The ZnO films deposited on top of Zeonor® or Topas® have identical morphological properties, as shown by the scanning electron microscopy (SEM) characterization. Subsequently, by using the MS technique, we tuned the thickness of the deposited silver (Ag) films in the range of 7–30 nm to assess the growth influence on the morphology and the SERS signal amplification of the substrates with and without the ZnO intermediate layer. The SEM analysis showed that the Ag atoms migrated both into the interstitial areas, filling the voids between the ZnO granular structures, and over the latter, forming, in this case, isolated Ag clusters. SERS analysis performed on the ZnO-Ag hybrid films using crystal violet (CV) molecule revealed a limit of detection (LOD) of 10−7 M in the case of 15 nm thick Ag/Zeonor® interlayer films ZnO and relative standard deviation (RSD) below 10%.

A constitutive model for amorphous thermoplastics from low to high strain rates: Formulation and computational aspects

In this paper, a recently proposed finite strain visco-elastic visco-plastic (three-dimensional) constitutive model is extended to predict the nonlinear response of amorphous polymers from low to high strain rates. The model accounts for the influence of distinct molecular mechanisms, which become active at different deformation rates. Therefore, the constitutive equations include two relaxation phenomena to describe the strain rate sensitivity of amorphous polymers. Well-established rheological elements are adopted to define visco-elasticity (generalized Maxwell elements) and visco-plasticity (Eyring dashpots). In addition, strain hardening is modeled with a plasticity-induced (nonlinear) hardening element which is extended to distinguish between the contribution of the two transitions. From a computational viewpoint, a fully implicit integration algorithm is derived, and a highly efficient implementation is obtained. It is shown that it is possible to reduce the return mapping system of equations to only two independent (scalar) nonlinear equations. A four-stage optimization-based calibration procedure is proposed to identify the model’s material parameters in a completely unsupervised way. The predictive capability of the constitutive model is validated against literature results for polycarbonate and poly(methyl methacrylate), accounting for temperature and strain rate dependencies under different loading conditions. The results show that the model can capture the transition in the yield behavior and predict the post-yield large strain behavior over a wide range of strain rates. The efficiency of the calibration procedure and the overall numerical strategy is also demonstrated. Despite the adiabatic conditions observed under high strain rates, the model replicates the associated effect of temperature through strain rate dependency.

Characterization of Viscoelastic Properties of EPDM Molding Compound for Door Grommet Component Using Molecular Dynamics and Phenomenological Modeling

Abstract The automotive industry is evolving by incorporating innovative tools to improve production processes. A proper manufacturing process influences the behavior of the door grommet during its lifetime. In this paper, molecular dynamics simulations are conducted to evaluate the chemical and physical crosslinking of the EPDM rubber over a range of temperatures using a COMPASS force field. Then, once the ethylene propylene diene monomer (EPDM) model was equilibrated and all possible crosslinks were formed, additional simulations were performed on the model to explore its mechanical behavior. Subsequently, using the superposition principle, viscosity and curing kinetics were evaluated using phenomenological models. To validate the results of the simulations, three injection tests of the door grommet were performed at different temperature conditions. The results indicate that the viscosity and elastic properties increase with increasing levels of crosslink density and that the critical gel point decreases with temperature. Molecular dynamics superposition results in phenomenological models are in reasonable agreement with the kinetic and viscoelastic behavior of EPDM during and after the injection process. The results presented in this paper provide novel molecular-level findings on the crosslinking mechanisms of amorphous polymers and their influence on viscoelastic behavior, which could facilitate the design of the injection process for door grommet applications.

Influence of interfacial compatibility on the crystallization behavior of electrospun core–sheath fibers

Core–sheath fibers composed of a crystalline polymer [poly(ethylene oxide) (PEO)] in the core and amorphous polymers [polystyrene (PS) and poly(methyl methacrylate) (PMMA)] in the sheath were fabricated through coaxial electrospinning. Because the melting temperature of PEO is lower than the glass transition temperatures of PS and PMMA, PEO crystallization was hard-confined within the immobile sheath. In immiscible PEO/PS fibers and miscible PEO/PMMA fibers, hard confinement reduced the crystallizability of PEO; therefore, its crystallite size, degree of crystallinity, and crystallization kinetics decreased with decreases in the degree of confinement. Confinement hindered PEO crystallization to a greater extent when the core and sheath polymers were miscible than when they were not. The favorable interaction between PEO and PMMA facilitated their interdiffusion during electrospinning, which caused the increased confinement of PEO in the core. Furthermore, when the compatibility between the solvents used for coaxial electrospinning increased, they enhanced the interdiffusion of the core and sheath polymers, which hindered PEO crystallization. However, the compatibility between polymers influenced the crystallization behavior of PEO to a considerably greater extent than did the compatibility between solvents.

Spinodal dynamics of metastable glass transition domains in amorphous polymer towards thermomechanically tailorable shape memory effect

Spinodal dynamics of metastable glass transition domains in amorphous polymer towards thermomechanically tailorable shape memory effect

The Mechanical Properties of Geopolymers from Different Raw Materials and the Effect of Recycled Gypsum

Geopolymers are amorphous inorganic polymers that are mainly used in the construction industry as an environmentally friendly alternative to ordinary cement. This study compared selected mechanical properties (setting time, shrinkage, strength) of geopolymer specimens made from different main raw materials, mainly at room temperature, and investigated the effects of recycled gypsum on these. A structural analysis of the specimens was conducted with XRD and SEM. Also, the leaching of aluminium, silicon, and calcium from the specimens was investigated. According to this study, raw materials have a significant impact on the properties of geopolymers. Recycled gypsum affected the setting time of the geopolymers, but the effect was not the same for all specimens. It increased the setting time of specimens made from calcium-rich raw materials, for example, and the ground-granulated blast furnace slag specimens hardened as fast as ordinary Portland cement (about 300 min), but the addition of gypsum decreased it to 1300 min. Gypsum-containing specimens, based on Ca-deficient metakaolin or fly ash, hardened even faster than OPC, in 100–150 min. Recycled gypsum significantly reduced the plastic shrinkage of most of the 28 d specimens to lower values than those achieved for OPC (0.07%). The only exceptions were the fly-ash-based specimens. However, gypsum had no effect on the drying shrinkage, which accounted for a larger proportion of the total shrinkage in most specimens. Therefore, it had no significant effect on the total shrinkage of the geopolymer specimens. The reducing effect of gypsum on the plastic shrinkage of geopolymers was attributed to ettringite, which was observed in all gypsum-containing specimens analysed with XRD. In this study, recycled gypsum decreased the compressive strength of the specimens, which could be prevented by using a finer gypsum powder.

Vapor Deposition of p‐Hexadecylstyrene by Ion‐ and Electron‐Assisted Methods

Thin films of p‐hexadecylstyrene (C16Sty) are prepared by an ion‐assisted deposition (IAD) and an electron‐assisted deposition (EAD) methods. The IAD enhances polymerization of C16Sty molecules by irradiating argon ions on the substrate surface, while the EAD initiates radical polymerization by irradiating electrons to the C16Sty vapor. The polymerization by these methods renders the films to be amorphous, whereas the conventional vapor deposition produces polycrystalline films consisting of C16Sty monomers. Upon thermal stress, the amorphous polymer films by IAD and EAD undergo morphological change at temperatures lower than that observed for the vapor‐deposited polycrystalline film. However, the polymer films retain smooth structure without coagulation upon heating. The deposited films have surface energy lower than that of polyethylene. Especially, the films deposited by EAD have a surface energy comparable to that of a normal alkane. The IAD and EAD of C16Sty are promising methods for preparing inert surfaces by dry processes.

A bridging model of a water-triggered shape-memory effect in an amorphous polymer undergoing multiple glass transitions

Hydrothermally-driven shape memory polymers (SMPs) have been extensively studied due to their advantage of having multiple response capabilities. In these SMPs,bound water reduces their glass transition temperatures (T g) by plasticizing the soft segments to achieve a water-triggered shape-memory effect (SME). However, the effect of bound water on hard segments, which has a synergistic effect on the T g and water-triggered SME of the soft ones, remains largely unexplored. In this study, we propose a new model to explore the working principles and hydrothermally-driven shape memory behaviors of amorphous SMPs. The bound water molecules are first divided into bridging and non-bridging bound water, and then a bridging effect is proposed to convert hard segments into soft ones, thus affecting the T g and water-triggered shape memory behavior in SMPs. An extended Gordon–Taylor model is formulated to identify the effects of bound water weight fraction and T g. Furthermore, a constitutive relationship between strain and relaxation time has been developed to describe the effects of temperature and bound water weight fraction on the hydrothermally-driven shape memory behaviors. Finally, the effectiveness of the proposed models is verified using the experimental results of amorphous SMPs reported in the literature.

Poly(ethylene 2,5-thiophenedicarboxylate-co-2,5-furandicarboxylate) copolyesters with improved ductility and PEF-comparable high performance

Poly(ethylene 2,5-furandicarboxylate) (PEF) is an important biobased polyester with not only high glass transition temperature (Tg), excellent strength and rigidity but also superior gas barrier properties. However, its poor ductility could limit its applications. In this study, 2,5-thiophenedicarboylic acid (TDCA) was used to modify PEF by copolycondensation. By introducing 10–40 mol% TDCA, poly(ethylene 2,5-thiophenedicarboxylate-co-2,5-furandicarboxylate) (PEThF) copolyesters with intrinsic viscosity of 0.63–0.77 dL/g were synthesized and characterized with 1H NMR, DSC, TGA, etc. The copolyesters are all amorphous polymers. Brittle-ductile transition was observed during tensile testing of PETh10F (PEThF containing 10 mol% 2,5-thiophenedicarboxylate unit). PEThFs containing 20–30% 2,5-thiophenedicarboxylate unit showed not only clearly improved ductility but also well-maintained performance advantages of PEF including high Tg (84–81 °C), modulus (∼3.2 GPa), strength (yielding 95 MPa, breaking 60 MPa) and oxygen barrier (5.4–5.0 times PET).

Synthesis and mesomorphic properties of swallow-tailed liquid crystal monomers and polymers

In this article, we designed and synthesized two novel swallow-tailed liquid crystal monomers (M1 and M2) with different chain lengths and rigidities centered on 3,4,5-trihydroxybenzoic acid and two series of side-chain liquid crystals polymers PN1 and PN2. All liquid crystal monomers and polymers were conformed to the molecular designs by FT-IR and NMR. The liquid crystal properties were tested by DSC and POM, and the results showed that M1 and M2 were thermotropic enantiotropic nematic liquid crystals and the side-chain liquid crystal polymers PN1 and PN2 series were typical amorphous liquid crystal polymers. With the increase of monomer content, the glass transition temperatures and clearing points of PN1 and PN2 series enhanced. With the increase of the number of mesogens in the liquid crystal monomer, the rigidity was enhanced, and the liquid crystal performance of the polymer was better.

Predicting self-diffusion coefficients in semi-crystalline and amorphous solid dispersions using free volume theory

The self-diffusion coefficient of active ingredients (AI) in polymeric solid dispersions is one of the essential parameters for the rational formulation design in life sciences. Measuring this parameter for products in their application temperature range can, however, be difficult to realise and time-consuming (due to the slow kinetics of diffusion). The aim of this study is to present a simple and time-saving platform for predicting the AI self-diffusivity in amorphous and semi-crystalline polymers on the basis of a modified version of Vrentas’ and Duda’s free volume theory (FVT) [A. Mansuri, M. Völkel, T. Feuerbach, J. Winck, A.W.P. Vermeer, W. Hoheisel, M. Thommes, Modified free volume theory for self-diffusion of small molecules in amorphous polymers, Macromolecules. (2023)]. The predictive model discussed in this work requires pure-component properties as its input and covers the approximate temperature range of T < 1.2 Tg, the whole compositional range of the binary mixtures (as long as a molecular mixture is present), and the whole crystallinity range of the polymer. In this context, the self-diffusion coefficients of the AIs imidacloprid, indomethacin, and deltamethrin were predicted in polyvinylpyrrolidone, polyvinylpyrrolidone/vinyl acetate, polystyrene, polyethylene, and polypropylene. The results highlight the profound importance of the kinetic fragility of the solid dispersion on the molecular migration; a property which in some cases might entail higher self-diffusion coefficients despite an increase in the molecular weight of the polymer. We interpret this observation within the context of the theory of heterogeneous dynamics in glass-formers [M.D. Ediger, Spatially heterogeneous dynamics in supercooled liquids, Annu. Rev. Phys. Chem. 51 (2000) 99–128] by attributing it to the stronger presence of “fluid-like” mobile regions in fragile polymers offering facilitated routes for the AI diffusion within the dispersion. The modified FVT further allows for identifying the influence of some structural and thermophysical material properties on the translational mobility of AIs in binary dispersions with polymers. In addition, estimates of self-diffusivity in semi-crystalline polymers are provided by further accounting for the tortuosity of the diffusion paths and the chain immobilisation at the interface of the amorphous and crystalline phases.

Thermomechanical shape memory testing of 4D printed novel material rhombus-shape structure

4D printing of functional energy generation/absorption structures by material extrusion technique can capitalize on the exciting applications in intelligent damping devices and patterns to deform spontaneously. This paper investigated the capitalization of this acquired knowledge by studying the shape memory effects of a functional rhombus shape structure. Initially, the shape memory characteristics of energy absorption and dissipation capacity were analyzed using dynamic mechanical testing to develop databases to gather thermophysical data before expressing the material behavior and recovery performances of printed shape memory structures. Then a complete thermomechanical cycle (shape programming and recovery) on 4D printed amorphous and semi-crystalline shape memory polymers exhibited deep insights into shape memory performance. The performance factors (i.e., recovery and fixity ratios) are influenced by variable printing parameters (i.e., layer height, printing temperature, and speed) and stimuli-based testing conditions. Results reveal both materials have significant shape memory effects with a maximum recovery ratio of up to 92.30 ± 0.32% from the programmed configuration. The amorphous polymer was extremely affected by printing temperature, whilst the semi-crystalline was influenced heavily by the interaction of all three parameters. Finally, shape memory effects predicted by a high-order design model and compared with experimental results showed negligible error. The analyses and assessments presented in this paper are adequate to understand the shape memory behavior under process control parameters to establish a data-driven model of a 4D printed semi-crystalline and amorphous polymer reactive to thermal stimuli.

Ultra-small PdAuIr nanoparticles on amine-functionalized porous organic polymers for efficient dehydrogenation from FA at room temperature

Formic acid (FA) is a prospective hydrogen storage agent, which has attracted much attention for its low toxicity and stability and plays a significant role in the comprehensive implementation of the hydrogen economy. In this regard, it is very important to utilize additive free FA dehydrogenation, for which few heterogeneous catalysts are available. Herein, we report ultra-small PdAuIr nanoparticles (NPs) supported on amine-based amorphous porous organic polymers (POPs), which exhibit excellent FA dehydrogenation activity with an initial total turnover number (TOF) of 9635 h−1 without additives at room temperature and apparent activation energy (Eaapp) of 36.5 kJ/mol. The results show that the excellent performance can be attributed to the synergistic effect of trimetallic alloys and strong metal-support interaction effect (SMSI), as well as to the amine groups (-NH2) grafted on POPs which facilitates the O–H bond splitting on FA. Overall, the simple and efficient synthetic strategy provides a new method for the selective dehydrogenation of FA.

Ionic transport in solid-state composite poly(trimethylene carbonate)–Li6.7Al0.3La3Zr2O12 electrolytes: The interplay between surface chemistry and ceramic particle loading

The ionic transport in solid-state composite electrolytes based on poly(trimethylene carbonate) (PTMC) with LiTFSI salt and garnet-type ion-conducting Li6.7Al0.3La3Zr2O12 (LLZO) ceramic particles is here investigated for a range of different compositions. Positive effects on ionic conductivity have previously been reported for LLZO incorporated into poly(ethylene oxide) (PEO), but the origin of these effects is unclear since the inclusion of particles also affects polymer crystallinity. PTMC is, in contrast to PEO, a fully amorphous polymer, and therefore here chosen for the design of a more straight-forward composite electrolyte (CPE) system to study ionic transport. With LLZO loadings ranging from 5 to 70 wt%, the CPE with 30 wt% of LLZO exhibits the highest ionic conductivity with a cationic transference number of 0.94 at 60 °C. This is significantly higher than for the pristine PTMC polymer electrolyte. Generally, low to moderate LLZO loadings display a gradual increase of the ionic conductivity, transference number and also of the polymer-cation coordination number. The combined contributions of ionic transport along polymer-ceramic interfaces and Lewis acid-base interaction between the LLZO particles and the LiTFSI salt can explain this enhancement. With loadings of LLZO above 50 wt%, a detrimental effect on the ionic conductivity was however observed. This could be explained by agglomeration of ceramic particles, and by a partial coverage of LLZO particles with a Li2CO3 layer. Consequently, inner polymer-particle interfaces become more resistive, and Li+conduction is prevented along interfacial pathways. The presence of Li2CO3 has more detrimental impact at higher LLZO loadings, since inter-particle connectivity will be hampered, and this is vital for efficient ionic transport. This suggests that there is an interplay between the LLZO particle surface chemistry with its loading, which ultimately controls the Li-ion transport.

A reaction-diffusion framework for hydrolytic degradation of amorphous polymers based on a discrete chain scission model

Hydrolytic degradation of polymers involves the scission of long chain molecules, leading to molecular weight reduction and mass loss. The precise degradation response however depends on the scission probability of individual bonds along the polymer backbone. In particular, bonds near the chain ends are considered to be more susceptible to hydrolysis than inner bonds. In this paper, we incorporate a discrete chain scission model that can handle arbitrary bond scission probabilities within a continuum reaction-diffusion framework. Overall hydrolysis kinetics (including autocatalysis) is described independently of the chain scission model. By decoupling the description of the chain scission mechanism from kinetics, our framework enables the identification of the chain scission mechanism from molecular weight reduction and mass loss curves commonly reported in experimental degradation studies. We further propose a reduced continuum model which is better suited for large-scale simulations while retaining the predictive capability of the full discrete-continuum model. The model capability is illustrated in representative case studies based on experimental data from the literature for different materials and geometries. Statement of significanceMany models have been proposed to predict the evolution of molecular weight and mass loss in biodegradable polymers undergoing hydrolytic degradation. However, existing models remain limited in their ability to describe the degradation mechanism, autocatalytic kinetics and short chains diffusion simultaneously. Moreover, existing models often rely on empirical relations and a large number of fitting parameters. Here, we propose a conceptually simple discrete-continuum mathematical framework with a small number of parameters which all have a clear physical meaning. Model calibration against experimental data is simplified, and further provides insights into the degradation mechanisms at play, namely random scission, chain-end scission, or a combination of both. The framework can serve as a basis for future generalisations, including a description of evolving crystallinity, or other degradation mechanisms, such as thermal oxidation or photo-degradation.

Further Step in the Transition from Conventional Plasticizers to Versatile Bioplasticizers Obtained by the Valorization of Levulinic Acid and Glycerol.

In the last two decades, the use of phthalates has been restricted worldwide due to their well-known toxicity. Nonetheless, phthalates are still widely used for their versatility, high plasticization effect, low cost, and lack of valuable alternatives. This study presents the fully bio-based and versatile glycerol trilevulinate plasticizer (GT) that was obtained by the valorization of glycerol and levulinic acid. The mild-conditions and solvent-free esterification used to synthesize GT was optimized by investigating the product by Fourier transform infrared and NMR spectroscopy. An increasing content of GT, from 10 to 40 parts by weight per hundred parts of resin (phr), was tested with poly(vinyl chloride), poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(lactic acid), and poly(caprolactone), which typically present complicated processability and/or mechanical properties. GT produced a significant plasticization effect on both amorphous and semicrystalline polymers, reducing their glass-transition temperature and stiffness, as observed by differential scanning calorimetry measurements and tensile tests. Remarkably, GT also decreased both the melting temperature and crystallinity degree of semicrystalline polymers. Furthermore, GT underwent enzyme-mediated hydrolysis to its initial constituents, envisioning a promising prospective for environmental safety and upcycling. Furthermore, 50% inhibitory concentration (IC50) tests, using mouse embryo fibroblasts, proved that GT is an unharmful alternative plasticizer, which makes it potentially applicable in the biomedical field.

Photoproduction of High Molecular Weight Poly (N-methylpyrrole) under Green Conditions

A novel and green photochemical polymerization method of N-methylpyrole is reported. Spectral and chromatographic characterizations revealed the formation of high molecular weight polymer (1436 kg/mol) having light absorption in the near-infrared region (~750 nm), high fluorescence emission in the visible region, high conductivity (0.062 S/cm) and good thermal stability. Powder X-ray diffractogram identified a totally amorphous polymer. According to cyclic voltammetry studies the polymer formed (PMPy) possess a relatively low electronic band gap (1.39 eV) which is very important for the (opto)electronic device applications of such materials.

Achieving Tunable Organic Afterglow and UV Irradiation-Responsive Ultralong Room-Temperature Phosphorescence from Pyridine-Substituted Triphenylamine Derivatives.

Amorphous polymers with ultralong room-temperature phosphorescence (RTP) are highly promising for various applications. Particularly, polymer-based RTP materials with multiple functions such as color-tunability or stimulus-responsiveness are highly desirable for multilevel anti-counterfeiting but are rarely reported. Herein, we present a facile strategy to achieve a series of polymer-based RTP materials with ultralong lifetime, multicolor afterglow, and reversible response to UV irradiation by simply embedding pyridine-substituted triphenylamine derivatives into the polymer matrix poly(vinyl alcohol) (PVA) and poly(methyl methacrylate) (PMMA), respectively. Notably, the pyridine group with the capabilities of promoting intersystem crossing and forming hydrogen-bonding interactions is essential for triggering ultralong RTP from the doping PVA system, among which the doping film TPA-2Py@PVA exhibits excellent RTP property with an ultralong lifetime of 798.4ms and a high quantum yield of 15.2%. By further co-doping with the commercially available fluorescent dye, multicolor afterglow is obtained via phosphorescence energy transfer. While the doping PMMA system exhibits reversible photo-activated ultralong RTP properties under continuous UV irradiation. Finally, we demonstrate potential applications of these doping PVA and PMMA systems with ultralong lifetime, multicolor afterglow, and photo-activated ultralong RTP in multi-dimensional anti-counterfeiting. This article is protected by copyright. All rights reserved.