Functionalized and Functionalizable Fluoropolymer Membranes

Solid–Liquid Europium Ion Extraction via Phosphonic Acid-Functionalized Polyvinylidene Fluoride Siloxanes

“…Purified poly(VDF- ter -VTEOS- ter -VDMP) terpolymers were analyzed by 1 H, 19 F, 31 P, and 29 Si NMR spectroscopies. The 1 H NMR spectrum ( Figure 1 ) of the poly(VDF- ter -VDMP- ter -VTEOS) terpolymer ( P 20 ) exhibits eight characteristic signals, mainly at: (i) 0.40 to 0.70 ppm assigned to the methine proton adjacent to the Si atom, (ii) 1.10 to 1.30 ppm for the three CH 3 groups of the triethoxysilyl units, (iii) 1.70 ppm corresponding to the CH group adjacent to the PO group, (iv) 1.90 ppm singlet of the CH 3 protons in the dimethyl phosphonate side group, (v) 2.15 to 2.40 ppm range attributed to the reverse (tail-to-tail, T-T) addition of VDF repeat units (−CF 2 C H 2 −C H 2 CF 2 −) [ 83 , 86 , 87 , 88 , 89 , 90 , 91 , 92 ], (vi) 2.70 to 3.10 ppm assigned to normal (head-to-tail, H-T) addition of VDF (−C H 2 CF 2 −C H 2 CF 2 −) [ 83 , 86 , 87 , 88 , 89 , 90 , 91 , 92 ], (vii) 2.80 ppm for protons of ethylene in VDF and VTEOS or VDMP dyad, and finally (viii) 3.65 ppm corresponding to the CH 2 of triethoxysilane group. However, this last signal overlaps with that of DMC which cannot be removed due to the highly viscous terpolymers.…”

Vinylidene Fluoride-Based Polymer Network via Cross-Linking of Pendant Triethoxysilane Functionality for Potential Applications in Coatings

“…The 1 H NMR spectrum of the poly­(VDF- co -MAF-cyCB) copolymers (Figure ) mainly exhibits seven characteristic signals: (i) in the 2.15–2.40 ppm range attributed to the reverse (tail-to-tail, T–T) addition of VDF repeat units (−CF 2 C H 2 –C H 2 CF 2 −), ,,− ,,, (ii) a small signal at 2.62 ppm assigned to the [−CH 2 CF 2 –C H 2 C­(CF 3 )­{CO 2 CH 2 CH­(O)­CH 2 O}−]; (iii) a broad signal ranging between 2.70 and 3.20 ppm corresponding to normal (head-to-tail, H–T) addition of VDF (−C H 2 CF 2 –C H 2 CF 2 −), ,,− ,,, (iv) at 3.73 ppm attributed to one of the two protons in −CO 2 CH 2 CH­(O)­C H 2 O in the cyclic carbonate function, − (v) between 4.2 and 4.55 ppm characteristic of the −CO 2 C H 2 CH­(O)­CH 2 O, − (vi) at around 4.6 ppm attributed to the second proton of −CO 2 CH 2 ­CH­(O)­C H 2 O, − and (vii) at 5.07 ppm assigned to −CO 2 CH 2 C H ­(O)­CH 2 O in the cyclic carbonate function. A tiny triplet of triplets, centered at 6.3 ppm, corresponding to −CH 2 CF 2 – H end-group, suggested negligible backbiting or any transfer to monomer, solvent, or copolymer …”

“…The 1 H NMR spectrum of the poly(VDF-co-MAF-cyCB) copolymers (Figure 2) mainly exhibits seven characteristic signals: (i) in the 2.15−2.40 ppm range attributed to the reverse (tail-to-tail, T−T) addition of VDF repeat units (−CF 2 CH 2 −CH 2 CF 2 −), 5,9,[12][13][14][15]17,18,59 (ii) a small signal at 5,9,[12][13][14][15]17,18,59 (iv) at 3.73 ppm attributed to one of the two protons in −CO 2 CH 2 CH(O)CH 2 O in the cyclic carbonate function, 27−32 (v) 52 or any transfer to monomer, solvent, or copolymer. 17 The microstructures of the resulting copolymers were determined by 19 F NMR spectroscopy (see Experimental Section for details).…”

“…However, extensive use of PVDF as adhesion promoting agents, printer inks, and paints is often restricted by some disadvantages: (i) high crystallinity leading to costly processing, (ii) low solubility, and (iii) laborious tuning properties for targeted applications (especially due to the lack of functionality). ,, However, these drawbacks can be overcome by (i) the incorporation of functional vinyl monomers such as acetoxy, thioacetoxy, hydroxyl, esters, ethers, halogens, carboxylic acid, , or phosphonic acid or (ii) cross-linking via cure site comonomers containing trialkoxysilane and by using bisamines or bisphenates . These approaches can lead to improvement of some of the properties of the resulting copolymers such as adhesion, thermal stability, proton conductivity, or hydrophobicity …”

Phosphorus-Containing Fluoropolymers: State of the Art and Applications

“…Thus, these specialty polymers exhibit high thermal, chemical, aging, and weather resistance, excellent inertness to solvents, to hydrocarbons, to acids, low surface energy (high oil and water repellencies), low dielectric constants, low flammability, low refractive index, and moisture absorption. These outstanding properties enabled them to be used in building, petrochemical and automotive industries, aerospace and aeronautics, chemical engineering, optics, textile treatment, stone, and microelectronics. − Though most were used as homopolymers, the copolymerization of commercially available fluoromonomers with other co-monomer bearing a functional group has gained a lot of interest. − These co-monomers introduce a (bulky) functional group that induces disorder in the macromolecule, thus reducing the high crystallinity of the homopolymer. − In addition, these co-monomers present a functional group such as acetoxy, hydroxyl, esters, ethers, halogens, cyclic carbonates, or carboxylic acid , to name a few. These functions can also improve some of the properties of the resulting copolymers such as thermal stability, proton conductivity , or hydrophobicity compared to pristine homopolymers.…”