Copolymerization Of Methyl Methacrylate Research Articles

Metal Affinity Immobilization of the Processive Endoglucanase EG5C-1 from Bacillus subtilis on a Recyclable pH-Responsive Polymer

Establishing a suitable immobilization strategy to improve the accessibility of immobilized cellulase for insoluble cellulose and subsequently recover the enzyme from the remaining substrate is crucial to promote the industrialization of biofuels. Here, using iminodiacetic acid (IDA) and Ni2+ ions, a novel metal-chelated copolymer of methacrylic acid and methyl methacrylate was prepared for the immobilization of His-tagged processive endoglucanase EG5C-1 via affinity interaction between polyhistidine tag and Ni2+. The optimum loading capacity of the functionalized polymer (Eud-IDA-Ni2+) for EG5C-1 was about 280 mg/g, where more than 80% of the activity was recovered. Immobilized EG5C-1 exhibited improved thermal and pH stability and better reusability than the free one, and after five cycles of usage, the hydrolysis productivity remained above 70% of the initial value. The Eud-IDA-Ni2+/EG5C-1 biocomposite displayed reversibly soluble–insoluble characteristics with pH change, which was in the soluble state during the enzyme reaction process but could be recovered in an insoluble form by lowering the pH after the reaction. Thus, the yield obtained from the hydrolysis of an insoluble phosphoric acid-swollen cellulose substrate was similar for the free and immobilized form of EG5C-1. Our combined results suggested that a metal-ion-chelated, pH-responsive polymer had the potential for His-tagged cellulase immobilization to improve both the operational efficiency and economic benefit of the cellulosic biorefinery industry.

Exploring novel carrier for improving bioavailability of Itraconazole: Solid dispersion through hot-melt extrusion

Kollicoat® Smartseal (Methyl methacrylate and diethylaminoethyl methacrylate copolymer dispersion) which is used for taste masking and moisture protection, has shown the ability for forming solid dispersion. The present study aimed to check its feasibility for improvement of pharmacokinetics when studied in-vivo in comparison to model high melting point drug-like Itraconazole. Hot-melt extrusion (HME) is a very well commercially accepted technology for solubility enhancement. However, there are limited polymers that can be utilized due to narrow processing window, low thermoplastic behavior or impart stability to the formed amorphous solid dispersion. Thus, having a carrier, which can address all these concerns, will give the industry an additional choice of the carrier for the development of formulations. Thus, the authors have tried to address this issue and demonstrated the ability of the novel carrier to be exploited into HME technology. Solid dispersions of Itraconazole were prepared, characterized, and tested for in-vivo performance in rats. The results indicated that the carrier exhibited good thermoplastic behavior over a temperature range of 120 °C–220 °C. Itraconazole had a plasticizing effect on the carrier. The in-vitro results indicated 20 fold improved solubility over plain Itraconazole. The results of thermal analysis fosters the possibility of the formation of solid solution which converts into an amorphous form. Kollicoat® Smartseal has shown high potential as a carrier to be used in HME for solubility enhancement of highly insoluble drugs like Itraconazole. It offered no processing challenges and the in-vivo results are in good agreement with in-vitro studies.

RADICAL INITIATED COPOLYMERIZATION OF METHYL METHACRYLATE AND ACRYLONITRILE IN PRESENCE OF IRON COMPLEXES

This article represents data on the effect of organometallic iron complexes: ferrocene, dicarbonyl dimer of cyclopentadienyl iron and tricarbonyl cyclooctatetraene iron on the copolymerization of methyl methacrylate (MMA) and acrylonitrile (AN) initiated by benzoyl peroxide. It is shown that the introduction of metal complexes and their structure affect the initial rate of copolymerization, the form of the diagrams of the composition of the obtained copolymers, and the values of the effective constants of the relative activities of the comonomers in the copolymerization of methyl methacrylate and acrylonitrile (system metallocomplex of iron – peroxide benzoyl: ferrocene – peroxide benzoyl: rММА = 1.58; rАН= 0.08 in 60 °С; rММА = 1.30; rАН = 0.05 in 50 °С; dicarbonyl dimer cyclopentadienyl iron–peroxide benzoyl: rММА = 1.36; rАН = 0.06 in 60 °С; rММА = 1.09; rАН = 0.14 in 50 °С; tricarbonyl cyclooctatetraene iron -peroxide benzoyl: rММА = 1.08; rАН = 0.15 in 60 °С; rММА = 1.14; rАН = 0.05 in 50 °С; peroxide benzoyl: rММА = 1.11; rАН = 0.07 in 60 °С; rММА = 1.11; rАН = 0.07 in 50 °С). The proportions of triadic sequences of units in copolymers, experimentally determined from 1H NMR spectroscopy, are given, as well as the calculated proportions of dyads. The presence of iron metal complexes affects the distribution of the proportions of the triad and dyad sequences of units, as well as their microstructure in copolymers. These changes are explained by the formation of macromolecules, both with the participation of free radicals and the stereospecific coordination active centers of polymerization that are formed in the presence of iron complexes.

Oxygen barrier property of synthesized polyacrylate coatings containing inter‐chain cross‐linking architecture on PET film

AbstractA series of coatings which applied for improving the oxygen barrier property of polyethylene terephthalate (PET) film were prepared based on the copolymerization of methyl methacrylate, methyl acrylate, diallyl maleate, and maleic acid (MA). The chemical structures of the coatings were characterized by Fourier Transform Infrared spectrometer. The curing behavior was analyzed by differential scanning calorimetry. The oxygen permeability (Po2) was measured by gas permeability tester. The molecular weight was investigated by gel permeation chromatography (GPC). Po2 is inversely proportional to the oxygen barrier property that the decrease of Po2 indicates the improvement of oxygen barrier property. The coating containing inter‐chain cross‐linking structure formed by the dehydration of carboxylic acid improves the oxygen barrier property of PET film greatly. With the increasing content of MA, the oxygen barrier capability of coated PET film is enhanced according to the Po2 decreasing from 1.450 to 0.8956. The Po2 of coated PET film is minimized by selecting N‐methyl pyrrolidone as solvent for polymerization. The GPC results indicate that the oxygen barrier of novel coated PET film can be obtained when the weight average molecular weight (Mw) is up to the stipulated value.

Post-chemical grafting poly(methyl methacrylate) to commercially renewable elastomer as effective modifiers for polylactide blends

A novel poly(epichlorohydrin-co-ethylene oxide)-g-poly(methyl methacrylate) copolymer (ECO-g-PMMA) was successfully synthesized from a commercially renewable elastomer via the ATRP method. The graft copolymer was investigated as a toughening agent and compatibilizer for polylactide (PLA) and PLA/ECO blends, respectively. Binary blending PLA with the copolymers (5–15 wt%) significantly improved the strain at break of PLA above 200% without a great strength loss. More importantly, the ternary PLA/ECO/ECO-g-PMMA copolymer blends exhibited a remarkably high impact strength of 96.9 kJ/m2 with non-broken behaviors. An interesting phase structure transformation from a typical sea-island structure to a unique quasi-continuous network structure was observed with varying the content of ECO-g-PMMA from 0 to 15 wt% in the ternary blends. The native toughening mechanism analysis indicated the synergistic toughening effect of the good interfacial adhesion and unique quasi-continuous morphology endowed the ternary blends with excellent mechanical performance.

In situ encapsulation of praziquantel through methyl methacrylate/diethylaminoethyl methacrylate and MMA/DMAEMA miniemulsion copolymerizations in presence of distinct ionic surfactants

AbstractSchistosomiasis is a neglected tropical disease that affects primarily the poorest and most vulnerable populations. Although praziquantel (PZQ) is the drug used most frequently for treatment of schistosomiasis, PZQ presents unpleasant bitter taste and low solubility in water, which prejudice the implementation of pediatric treatments. For this reason, the main purpose of the present work was the production of stable nanoparticles loaded with PZQ through in situ miniemulsion copolymerizations of methyl methacrylate (MMA) with diethylaminoethyl methacrylate (DEAEMA) or dimethylaminoethyl methacrylate (DMAEMA). Due to the cationic nature of the comonomers, the use of different ionic surfactants was also investigated. Nanoparticles with narrow particle size distributions, characteristic average diameters ranging from 50 nm to 110 nm, and loaded with 20 wt% of PZQ were manufactured successfully PZQ encapsulation efficiencies were higher than 97 wt% and PZQ was homogeneously dispersed in the final polymer matrix. Finally, the use of a cationic surfactant with DEAEMA cationic comonomer led to more stable latexes because of the high absolute value of the zeta potential.

Structural design and characterization of tricycloalkyl-containing methacrylate with methyl methacrylate copolymers

Three types of tricycloalkyl-containing methacrylate with methyl methacrylate copolymers, poly(adamantyl methacrylate-co-methyl methacrylate) [P(ADMA-co-MMA)], poly(tricyclodecyl methacrylate-co-methyl methacrylate) [P(TCDMA-co-MMA)] and poly(adamantyl methacrylate-co-tricyclodecyl methacrylate-co-methyl methacrylate) [P(ADMA-co-TCDMA-co-MMA)] were synthesized via the free-radical polymerization method. The effects of structural design on the thermal, mechanical, dielectric and optical properties of the synthesized copolymers were investigated. The results showed that the tricycloalkyl-containing methacrylate copolymers increased the thermal stability, mechanical strength and transparency in the UV–visible region as compared with PMMA. Additionally, a lower water absorption and dielectric constant were obtained. These results demonstrated that tricycloalkyl-containing methacrylate copolymers are promising candidates for use as high value-added optical plastics in microelectronics and optoelectronics applications.

Fireproofing wood using borate and vinyl phosphorus compounds and its water resistant treatment using copolymer of dimethyl vinylphosphonate and methyl methacrylate

Vinyl phosphorus compounds such as poly (vinyl phosphonic acid) (PVPA), poly (dimethyl vinyl phosphonate) (PDMVP) impart high flame retardancy to wood comparable to conventional fireproofing wood by combined use of sodium polyborate (SPB) in contrast to their single use. The differential thermal analysis and thermogravimetry (DTA/TG) suggest a synergy effect between SPB and PVPA. The water resistance of the treated wood is improved by copolymerization of dimethyl vinyl phosphonate (DMVP) with methyl methacrylate (MMA) inside the wood after the impregnation of SPB, and the incombustibility of the wood is mostly maintained after leaching tests. The combustion residues of the wood treated with DMVP and MMA after SPB show high compressive strength, and their SEM images suggest that the strength is due to formed charcoal.

Effect of shell phase composition on the dielectric property and energy density of core‐shell structured BaTiO3 particles modified poly(vinylidene fluoride) nanocomposites

AbstractDielectric nanocomposites have attracted much attention due to their wide applications in electronics and electrical industry. Recently, incorporating core‐shell nanoparticles into polymer matrix to improve the dielectric properties of nanocomposites has been widely reported. Tailoring the interfacial region between the polymer and the nanoparticles plays a crucial role in achieving the desired dielectric and energy storage properties of nanocomposites. However, the effect of shell structure in the interface region on the dielectric and energy storage properties is rarely studied. Based on this, core‐shell BaTiO3 nanoparticles with two different shell polymers, a “hard‐soft” copolymer of methyl methacrylate and butyl acrylate (P[MMA‐BA]) and a “hard” homopolymer of methyl methacrylate (PMMA), were prepared in this paper. The effect of core‐shell BaTiO3 nanoparticles with different shell structures on the dielectric and energy storage properties of poly(vinylidene fluoride) (PVDF) was investigated in depth. Due to the formation of a tight interfacial region between P(MMA‐BA)@BT and PVDF matrix, P(MMA‐BA)@BT/PVDF nanocomposites not only have low dielectric loss but also higher energy efficiency than PMMA@BT/PVDF nanocomposites. This study suggests a potential strategy that fabricating a “hard‐soft” copolymer shell on BaTiO3 surface can obtain desirable energy storage efficiency than the single “hard” shell structure in dielectric nanocomposites.

Synthesis of D-Limonene Loaded Polymeric Nanoparticles with Enhanced Antimicrobial Properties for Potential Application in Food Packaging.

Mini-emulsion polymerization was applied for the synthesis of cross-linked polymeric nanoparticles comprised of methyl methacrylate (MMA) and Triethylene Glycol Dimethacrylate (TEGDMA) copolymers, used as matrix-carriers for hosting D-limonene. D-limonene was selected as a model essential oil, well known for its pleasant odor and its enhanced antimicrobial properties. The synthesized particles were assessed for their morphology and geometric characteristics by Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM), which revealed the formation of particles with mean diameters at the nanoscale (D[3,2] = 0.135 μm), with a spherical shape, while the dried particles formed larger clusters of several microns (D[3,2] = 80.69 μm). The percentage of the loaded D-limonene was quantified by Thermogravimetric Analysis (TGA), complemented by Gas Chromatography-Mass Spectrometry analysis coupled with a pyrolysis unit (Py/GC-MS). The results showed that the volatiles emitted by the nanoparticles were composed mainly of D-limonene (10% w/w of dry particles). Particles subjected to higher temperatures tended to decompose. The mechanism that governs the release of D-limonene from the as-synthesized particles was studied by fitting mathematical models to the release data obtained by isothermal TGA analysis of the dry particles subjected to accelerated conditions. The analysis revealed a two-stage release of the volatiles, one governed by D-limonene release and the other governed by TEGDMA release. Finally, the antimicrobial potency of the D-limonene-loaded particles was demonstrated, indicating the successful synthesis of polymeric nanoparticles loaded with D-limonene, owing to enhanced antimicrobial properties. The overall performance of these nanoparticles renders them a promising candidate material for the formation of self-sterilized surfaces with enhanced antimicrobial activity and potential application in food packaging.

Copolymerization of butyl acrylate with methyl methacrylate in a bubble column reactor and the use of copolymer in corrosion protection

In this paper, copolymerization of methyl methacrylate (MMA) with n-butyl acrylate (BA) in a bubble column reactor using benzoyl peroxide as free radical initiator, at a temperature over 85 °C, is presented. This mode of copolymerization keeps an inert atmosphere throughout the entire reaction and contributes to proper mixing of the monomers. Higher pressure of the bubbling ensures the faster contact of the species, and a higher conversion was obtained in a shorter reaction time. The conversion of monomer at 124 Pa after 210 min is total, which is particularly noteworthy due to the absence of residual monomer that represents hazardous compounds, with negative impact upon employees and end-user safety. Higher conversions are obtained at 96 °C, 124 Pa nitrogen bubble pressure, 60/40% moles monomer ratio BA/MMA and 2% POB. The molar mass Mw, Mn and PDI decrease with the increase in temperature quite linearly. In the absence of nitrogen bubbling, the copolymer composition is approximately the same as in the feeding mixture. The corrosion protection efficiency of steel painted with these acrylic coatings was carried out by means of OCP and potentiodynamic polarization testing and electrochemical impedance spectroscopy (EIS).

Antibacterial Amphiphilic Copolymers of Dimethylamino Ethyl Methacrylate and Methyl Methacrylate to Control Biofilm Adhesion for Antifouling Applications.

Amphiphilic copolymers are recognized as important biomaterials and used as antibacterial agents due to their effective inhibition of bacterial growth. In current study, the amphiphilic copolymers of P(DMAEMA-co-MMA) were synthesized using free radical polymerization by varying the concentrations of hydrophilic monomer 2-dimethylamino ethylmethacrylate (DMAEMA) and hydrophobic monomer methyl methacrylate (MMA) having PDI value of 1.65–1.93. The DMAEMA monomer, through ternary amine with antibacterial property optimized copolymers, P(DMAEMA-co-MMA), compositions to control biofilm adhesion. Antibacterial activity of synthesized copolymers was elucidated against Gram-positive Staphylococcus aureus (ATCC 6538) and Gram-negative Escherchia coli (ATCC 8739) by disk diffusion method, and zones of inhibition were measured. The desired composition that was PDM1 copolymer had shown good zones of inhibition i.e., 19 ± 0.33 mm and 20 ± 0.33 mm for E. coli and S. aureus respectively. The PDM1 and PDM2 have exhibited significant control over bacterial biofilm adhesion as tested by six well plate method. SEM study of bacterial biofilm formation has illustrated that these copolymers act in a similar fashion like cationic biocide. These compositions viz. PDM1 and PDM2, may be useful in development of bioreactors, sensors, surgical equipment and drug delivery devices.

Effects of side chains in compatibilizers on interfacial adhesion of immiscible PLLA/ABS blends

A series of poly (methyl methacrylate) (PMMA)-type and comb-like polymers were synthesized by copolymerizing methyl methacrylate (MMA), glycidyl methacrylate (GMA) and MMA macromer. The effects of PMMA side chains, which were derived from the MMA macromer, on the interfacial adhesion of the immiscible poly (l-lactide)/acrylonitrile-butadiene-styrene (PLLA/ABS) system were thoroughly investigated. The peel strength of the PLLA/ABS interface determined from a T-peel test increased proportionately with the number of side chains. In addition, when the comb-like compatibilizers were applied in the PLLA/ABS system, the morphology of the blends, which was measured by the interface perimeter per unit area of dispersed phase domains, also increased linearly with the number of side chains in compatibilizers. The mechanical properties of the compatibilized PLLA/ABS blends were improved concomitantly with the increment of side chains. Specifically, the fracture strain of the PLLA/ABS blends compatibilized by the compatibilizer with two PMMA side chains was about 3 times greater than by the compatibilizer with no side chain.

Weathering and Biological Degradation of a Bioglycerol-Based Thermoset Material

Waste glycerol from biodiesel production (bioglycerol) can be used for obtaining rigid thermoset materials. In order to gain insights into applicability and final disposition of these renewable materials it is necessary evaluate their long-term behavior under environmental conditions as well as their biodegradability performance. A methyl methacrylate copolymer obtained from bioglycerol was subjected to weathering and biological degradation processes. The first stage of weathering degradation was evaluated using 340-nm light during 216–540 h. The material was affected slightly after 540 h aging, evidencing little chemical changes such as chains scissions as well as the formation of double bonds and hydroxyl groups due photodegradation. In the second stage of biodegradation, the polymer samples were exposed to microbial action of Aspergillus flavus or Aspergillus fumigatus strains. The material showed evidences of fungi colonization and adherence to polymer surface as well as surface damage, after 30 days exposure.

Enhancement in bonding strength and ageing resistance of polychloroprene solvent-base adhesives through graft copolymerization

In this research, graft copolymerization of Methyl methacrylate (MMA; hereafter) on to Polychloroprene rubber (CR; hereafter) has been processed in the presence of hydrogen peroxide as an initiator. Grafting reaction has been carried out in a mechanical mixer, and factors such as time, temperature, monomer, and initiator’s concentration were investigated and optimized. FTIR confirmed the grafting reaction occurred in the CR polymer as evident from a peak of a carbonyl group. The adhesive strength of grafted adhesive was analyzed by standard peel testing on canvas–canvas and leather–leather substrates. The effect of variation in environmental conditions such as storage time, exposure to elevated temperature, and immersion of adhesively joined substrates in the water on the peel strength of adhesive bonding was also studied. The results were compared with the strength of commercially available adhesives in local market. The solid content of grafted adhesive (55%) showed their greater applicability and high strength characteristics. The maximum peel strength achieved was 79 N/mm for canvas–canvas while 73 N/mm for leather–leather substrates. The percentage fall in peel strength after exposure to different environmental conditions was shallow as compared to commercially available adhesives. ‘GA-13’ the grafted adhesive has a high potential for the Leather-base industry and other applications.

The preparation and mechanism of permanently flame retardancy, antistatic, good toughness and high transparent poly(methyl methacrylate)

AbstractA novel kind of poly(methyl methacrylate) (PMMA) copolymer, P(MMA‐co‐HEMAP), with permanently flame retardancy, antistatic, good toughness and high transparency properties was synthesized through the addition of 2‐hydroxyethyl 2‐methyl‐2‐propenoate phosphated (HEMAP), which was chosen as the flame retardant and the antistatic agent. The included phosphine group is necessary for flame retardancy and acryl phosphate group that could absorb water to realize antistatic property while having good compatibility with methyl methacrylate (MMA). Different from the significantly reduction of transparency happened in traditional modification method, the optical property of the P(MMA‐co‐HEMAP) copolymers keeps almost unchanged comparing to that of neat PMMA in the visible range. And the peak Heat Release Rate (pHRR) and Total Heat Release (THR) of the 30PhrHEMAP were significantly reduced by 40% and 36.2%, respectively, while the Limiting Oxygen Index (LOI) increased from 17.8 to 24.5%. The HEMAP decomposed during the combustion process to form polyphosphoric acid, which promotes dehydration and carbonization of polymer matrix to form a cross‐linking yield char and it would reduce fire spread. Besides, the surface resistance of the 30PhrHEMAP could be reduced down to 1010Ω which could achieve antistatic effect. The hydrophilic groups, acryl phosphate on the surface of copolymer was able to absorb moisture from the air for antistatic effects. Furthermore, the toughness of the copolymers was also greatly improved compared to that of neat PMMA. This research provided a method for preparing PMMA copolymer and the resultant P(MMA‐co‐HEMAP) copolymers can significantly improve the three properties simultaneously for the first time.

Rheological characterization of polymeric solutions used in spray drying process

The present works contributes with a rheological characterization of the most commonly used polymers and solvents to formulate amorphous solid dispersions by means of spray drying process: copovidone, hydroxypropyl methylcellulose (HPMC), hydroxypropyl methylcellulose acetate succinate (HPMCAS) and a copolymer of methacrylic acid and methyl methacrylate (1:1 ratio and commercially known as Eudragit L100). The organic-based solutions are characterized in terms of surface tension, shear viscosity and relaxation time. HPMC and HPMCAS solutions exhibit shear thinning behaviour, i.e. decrease of shear viscosity with the increasing shear rate imposed, while the samples with Eudragit L100 can be considered Boger fluids, showing a constant viscosity but maintaining its viscoelastic character. Under uniaxial extensional flow, these polymers solutions exhibit a viscoelastic behavior with an increasing relaxation time with an increasing concentration, and in some cases showed a ‘beads-on-string’ effect. In contrast, copovidone showed a Newtonian fluid behavior, with the absence of elasticity. The fundamental understanding and characterization of the present work may be further applied to atomization modelling and support and expedite spray drying process development.

Diels-Alder Polymer Networks with Temperature-Reversible Cross-Linking-Induced Emission.

A novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.

Diels–Alder Polymer Networks with Temperature‐Reversible Cross‐Linking‐Induced Emission

AbstractA novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.

Innenrücktitelbild: Diels–Alder Polymer Networks with Temperature‐Reversible Cross‐Linking‐Induced Emission (Angew. Chem. 1/2021)

A novel synthetic strategy gives reversible cross-linked polymeric materials with tunable fluorescence properties. Dimaleimide-substituted tetraphenylethene (TPE-2MI), which is non-emissive owing to the photo-induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross-link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE-2MI in DMF showed reversible fluorescence with "on/off" behavior depending on the Diels-Alder (DA)/retro-DA process, which is easily adjusted by temperature. At high temperatures, the retro-DA reaction is dominant, and the fluorescence is quenched by the photo-induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE-2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent "turn on/off" behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.