Glass‐Transition‐, Melting‐, and Decomposition Temperatures of Tailored Polyacrylates and Polymethacrylates: General Trends and Structure–Property Relationships

Fleischhaker, Friederike; Haehnel, Alexander P.; Misske, Andrea M.; Blanchot, Mathieu; Haremza, Sylke; Barner‐Kowollik, Christopher

doi:10.1002/macp.201400062

Cited by 55 publications

(55 citation statements)

References 13 publications

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“…This finding may be explained by the different hydrodynamic behavior of the polymer chains in solution. None of the copolymers show a glass transition temperature ( T g ), but an endothermic peak at ≈ −35 to −42 °C (Figure S22, Supporting Information), which can be explained with the side‐chain crystallization of PLMA chains . All copolymers are thermally stable up to at least ≈200 °C.…”

Section: Resultsmentioning

confidence: 99%

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Enke

Jehle

Bode

et al. 2017

Macro Chemistry & Physics

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Histidine-zinc interactions are believed to play a key role in the self-healing behavior of mussel byssal threads due to their reversible character. Taking this as inspiration, the authors synthesize here histidine-rich copolymers, as well as model histidine compounds and characterize them using isothermal titration calorimetry (ITC). With this approach, the influence of two different zinc(II) salts and the role in the complex formation of the amine function of the imidazole ring are investigated in detail. The extracted metal-ligand ratios are utilized to design novel self-healing metallopolymers. For this purpose, n-lauryl methacrylate is copolymerized with the histidine monomer via reversible addition-fragmentation chain transfer polymerization. The copolymers are crosslinked using different zinc salts, and the resulting coatings are characterized with Raman spectroscopy to investigate the metal coordination behavior and with scratch healing tests to investigate the self-healing capacity. Finally, the selfhealing behavior of the different materials is correlated with the metal-ligand binding affinity measured by ITC. 2 (2.5 g, 5.52 mmol) was dissolved in 40 mL dry dichloromethane. Triethylamine (1.53 mL, 11.06 mmol) and acetic anhydride (0.52 mL, 5.52 mmol) was added dropwise. After complete conversion, which was monitored by thin layer chromatography (TLC), the solvent and the triethylamine were evaporated in vacuo. The residue was dissolved in 50 mL chloroform and washed with 0.1 m NaHCO 3 solution and afterward with deionized water. The organic layer was dried over Na 2 SO 4 . Finally, the crude product was purified by silica gel chromatography (MeOH/CHCl 3 1:9, R f = 0.5).Yield: 2.0 g (4.04 mmol) of a white solid, 73%. Melting point: 76-77 °C. 1 H NMR (300 MHz, CDCl 3 ): δ = 0.85-0.89 (t, 3H, CH 3 ), 1.22-1.46 (m, 4H, CH 2 CH 2 CH 3 ), 1.93-2.04 (m, 4H, CH 3 Macromol. Chem. Phys. , , 1600458 M. Enke et al.

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Section: Resultsmentioning

confidence: 99%

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Enke

Jehle

Bode

et al. 2017

Macro Chemistry & Physics

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“…At a molar ratio larger than 1, the amine likely reacts with the ester group to form amides and free glycerol. The latter may act as a plasticizer and consequently lead to a reduction in the T g …”

Section: Resultsmentioning

confidence: 99%

Synthesis and properties of cross‐linked polymers from epoxidized rubber seed oil and triethylenetetramine

Abduh

Iqbal

Picchioni

et al. 2015

J of Applied Polymer Sci

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A series of epoxidized oils were prepared from rubber seed, soybean, jatropha, palm, and coconut oils. The epoxy content varied from 0.03 to 7.4 wt %, in accordance with the degree of unsaturation of the oils (lowest for coconut, highest for rubber seed oil). Bulk polymerization/curing of the epoxidized oils with triethylenetetramine (in the absence of a catalyst) was carried out in a batch setup (1 : 1 molar ratio of epoxide to primary amine groups, 100°C, 100 rpm, 30 min) followed by casting of the mixture in a steel mold (180°C, 200 bar, 21 h) and this resulted in cross‐linked resins. The effect of relevant pressing conditions such as time, temperature, pressure, and molar ratio of the epoxide and primary amine groups was investigated and modeled using multivariable nonlinear regression. Good agreement between experimental data and model were obtained. The rubber seed oil‐derived polymer has a Tg of 11.1°C, a tensile strength of 1.72 MPa, and strain at break of 182%. These values are slightly higher than for commercial epoxidized soybean oil (Tg of 6.9°C, tensile strength of 1.11 MPa, and strain at break of 145.7%). However, the comparison highlights the potential for these novel resins to be used at industrial/commercial level. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42591.

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“…We next investigated thermal properties of PNFHMAs of different MWs by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). In contrast to polymers of lower MWs ( M n =7.52×10 3 and 1.61×10 4 Da, green and red lines in Figure a,b), the UHMW counterpart ( M n =1.78×10 6 Da, blue lines) exhibited a glass transition temperature ( T g ) and decomposition temperature ( T d ) of 8 °C and nearly 100 °C higher, respectively, displaying clearly improved thermal stability achieved by increasing MW …”

Section: Resultsmentioning

confidence: 96%

Precise Synthesis of Ultra‐High‐Molecular‐Weight Fluoropolymers Enabled by Chain‐Transfer‐Agent Differentiation under Visible‐Light Irradiation

Gong

Zhao

et al. 2019

Angew Chem Int Ed

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Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.

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Glass‐Transition‐, Melting‐, and Decomposition Temperatures of Tailored Polyacrylates and Polymethacrylates: General Trends and Structure–Property Relationships

Cited by 55 publications

References 13 publications

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Synthesis and properties of cross‐linked polymers from epoxidized rubber seed oil and triethylenetetramine

Precise Synthesis of Ultra‐High‐Molecular‐Weight Fluoropolymers Enabled by Chain‐Transfer‐Agent Differentiation under Visible‐Light Irradiation

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