Lack of polymerization of fluorinated acrylates

McElroy, Kermit T.; Purrington, Suzanne T.; Bumgardner, Carl L.; Burgess, Jason P.

doi:10.1016/s0022-1139(99)00019-6

Cited by 45 publications

(43 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The homopolymerization of VAc initiated by 2,2′‐azobis (4‐methoxy‐2,4‐dimethylvaleronitrile) (V‐70) in the presence of [Co(acac) 2 ] at 40 °C produced PVAc with controlled molar mass ( M n = 28 200 g mol −1 ) and low dispersity ( Đ = 1.16), as previously described (entry 1 in Table S1 and Figure S1, Supporting Information). In contrast, attempts to obtain a MAF‐TBE homopolymer under the same conditions failed (entry 2, Table S1, Supporting Information), as expected, since MAF‐TBE does not homopolymerize under radical conditions …”

Section: Resultssupporting

confidence: 52%

“…2‐(Trifluoromethyl)acrylic acid (MAF) and alkyl 2‐trifluoromethacrylate (MAF‐esters) are very interesting monomers. Although homopolymers can be produced anionically, these monomers do not homopolymerize under radical conditions, but can be copolymerized together with electron‐donating monomers such as vinyl ethers . MAF‐ and MAF‐esters containing fluorinated copolymers led to suitable materials for molecularly imprinted polymers, microlithography, polymer electrolyte membranes for fuel cells and for Li‐ion batteries .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

Banerjee

Ladmiral

Debuigne

et al. 2017

Macromol. Rapid Commun.

View full text Add to dashboard Cite

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly(VAc-alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (≤1.24) and molar masses up to 57 000 g mol . These copolymers have a precise 1:1 alternating structure over a wide range of comonomer feed compositions. The reactivity ratios are determined as r = 0.01 ± 0.01 and r = 0 at 40 °C. Remarkably, from a feed containing >50% molar VAc content, poly(VAc-alt-MAF-TBE)-b-PVAc block copolymers are produced via a one-pot synthesis. Such diblock copolymers exhibit two glass transition temperatures attributed to the alternating and homopolymer sequences. The OMRP of this fluorine-containing alternating monomer system may provide access to a wide range of new polymer materials.

show abstract

Section: Resultssupporting

confidence: 52%

Section: Introductionmentioning

confidence: 99%

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

Banerjee

Ladmiral

Debuigne

et al. 2017

Macromol. Rapid Commun.

View full text Add to dashboard Cite

show abstract

“…Actually, acrylic acid (AA) is too reactive (its propagation rate, k p , is very high compared with that of VDF) to lead to satisfactory poly(VDF‐ co ‐AA) copolymers, but α‐trifluoromethacrylic acid (TFMA) has already evidenced an appropriate reactivity with VDF 23, 26. In addition, the free radical terpolymerization of TFMA with VDF and hexafluoropropylene23 was successfully carried out in organic solvent while TFMA radical homopolymerization failed 27, 28. These reactions were carried out in solution, and the present challenge deals with an emulsion process without any surfactant, under controlled radical polymerization in aqueous medium.…”

Section: Introductionmentioning

confidence: 99%

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Boyer

Améduri

2009

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

The synthesis of poly(VDF-co-TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and a-trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1-perfluorohexyl iodide (C 6 F 13 I) and 1,4-diodoperfluorobutane (IC 4 F 8 I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF-co-TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1 H and 19 F NMR to assess the amount of each comonomer, and the molecular weights and the end-groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, \10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for r TFMA and r VDF were 0 and 1.6 at 80 C, respectively. V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: [4710][4711][4712][4713][4714][4715][4716][4717][4718][4719][4720][4721][4722] 2009

show abstract

“…These values were quite similar, but higher than, that exhibited by T. The lower polymerization rate of T could be possibly be due to the strongly electron‐withdrawing substituent groups of the fluoroalkyl (CF 3 ) in the penultimate unit of the T radicals in comparison with the alkyl (CH 3 or CH 2 CH 3 ) groups possessed by MMA or EMA. The electron‐withdrawing effect of the trifluoromethyl group would stabilize the radical through the captodative effect, thus causing a loss of monomer reactivity 52, 53…”

Section: Resultsmentioning

confidence: 99%

Statistical fluorinated copolymers from heterogeneous atom transfer radical copolymerization of styrene and 2,2,2‐trifluoroethyl methacrylate with similar reactivity ratios

Zhang

et al. 2013

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

Fluorinated copolymers with statistical structure of azeotropic or gradient composition were prepared from heterogeneous atom transfer radical copolymerizations of styrene (S) and 2,2,2-trifluoroethyl methacrylate (T). The polymerization kinetic studies show that while the propagation rate constant of S increased with a decreasing S content in the comonomer feed ratio, the propagation rate of T decreased with decreases of the S content in the comonomer feed ratio. The polymerization rate and controllability of the heterogeneous ATRP of S and T were regulated by the solubility of Cu(II)/ligand in the reaction mixture, based on a mechanistic analysis and solubility tests of the Cu(II)/ligand system in the reaction media. The reactivity ratios of S and T were 0.22 and 0.35, as evaluated from kinetic analysis of monomer conversions higher than 35%. These statistical polymers self-assembled in T to form giant vesicles GVs) with broad diameter distribution in the range of 1-10 lm. Unlike the methods normally used to prepare gradient copolymers by spontaneous controlling with feeding model or batch polymerization of comonomers with obvious differences in the reactivity ratio, in this contribution, we report a novel synthetic strategy for preparing gradient copolymers can also be prepared from both monomers with very similar reactivity ratio.

show abstract

Lack of polymerization of fluorinated acrylates

Cited by 45 publications

References 11 publications

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Statistical fluorinated copolymers from heterogeneous atom transfer radical copolymerization of styrene and 2,2,2‐trifluoroethyl methacrylate with similar reactivity ratios

Contact Info

Product

Resources

About