Structure of comb-like polyfluoroalkyl acrylates and methacrylates

Budovskaya, L.D.; Ivanova, V. N.; Oskar, Liron; Lukasov, S. V.; Baklagina, Yu. G.; Sidorovich, A. V.; Nasledov, D.M.

doi:10.1016/0032-3950(90)90138-v

Cited by 21 publications

(25 citation statements)

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“…A melting peak of PFsA appeared at 65~ and a broad crystallization peak appeared at 22~ whereas the shape of these peaks was changed to normal in successive DSC measurements. It can be seen from this result that the side chain crystallization of PFsA is not so easy, because the degree of ordering in crystal may be directly related to the number of CF 2 groups, as reported by Budovskaya et al [8]. Although PFsMA and PF6MA are a powder or a bulk solid at room temperature, DSC measurements of PFsMA and PF6MA could not give a clear informa- tion, probably because the side-chain crystallization is not possible for these comblike polymers.…”

Section: Resultssupporting

confidence: 62%

“…The comb-like polymers containing long fluorocarbon chains in the side chains have been interested from the viewpoint of new functional polymers with special electrical and chemical properties, and also self-organizing property [7]. Budovskaya et al formed some monomer molecules containing long fluorocarbon chains which have a tendency to make a layered structure [8] and the functional groups for polymerization would be arranged in an optimum orientation allowing a conformational freedom. In this study, thermal properties of acrylate and methacrylate monomers containing long fluorocarbon chains and their polymers have been examined by differential scanning calorimetry (DSC) 34.6~ FIoMA and F10A were used after purification by recrystallization from the ethanol solution, but FsA, FaMA and F6MA were used as received, because melting points of these monomers are too low for a usual recrystallization.…”

Section: Introductionmentioning

confidence: 99%

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DSC and X-ray studies on side-chain crystallization of comb-like polymers

Shibasaki

Saitoh

Chiba

1997

Journal of Thermal Analysis

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Thermal properties of acrylate and methacrylate monomers containing long-fluorocarbon chains (H(CF2)nCH2OCOCH=CH2, (F.A)and H(CF2)nCH2OCOC(CH3)=CH2, (FnMA), where n=6, 8, 10) and their comb-like polymers have been investigated by differential scanning calorimeter (DSC) and X-ray diffraction. The comb-like polymers (PF10 A and PF10MA ) with sufficiently long-fluorocarbon chains showed a simple melting and crystallizing behavior. For the fusion of PFIoA in 1st heating, enthalpy change AHf was 18 kJ mo1-1 and entropy change ASf was 45 J K -1 mo1-1, while for PF10MA the values AHf and ASf were 5.3 kJ mol -l and 14 J K -1 mol -I, respectively. Melted PFsA crystallized slowly, whereas PFsMA with same fluorocarbon chain and also both of PF6A and PF6MA with shorter fluorocarbon chains can hardly crystallize by the aggregation of side-chains. Effects of the length of side-chain and the flexibility of main chain on the side-chain crystallization of comb-like polymers are clear. Crystallization process of the methacrylate monomers was sensitively affected by the scanning rate of DSC measurement and the length of fluorocarbon chains.

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Section: Resultssupporting

confidence: 62%

Section: Introductionmentioning

confidence: 99%

DSC and X-ray studies on side-chain crystallization of comb-like polymers

Shibasaki

Saitoh

Chiba

1997

Journal of Thermal Analysis

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“…When n number was 12, the FA/AA copolymer had 1 peak at 2 ϭ 18°and When n numbers were 16 and 18, the FA/AA copolymers had two peaks at 2 ϭ 18°and 22°, respectively. These peaks were caused by the side-chain R f groups 16 and alkyl groups packing, 17 respectively. Thus, when n numbers were below 8, the FA/AA copolymers were in the rubbery state and had high mobility; however, when n numbers were above 12, they were in the crystalline state and had low mobility.…”

Section: Dynamic Contact Anglementioning

confidence: 99%

Surface properties of perfluoroalkylethyl acrylate/n-alkyl acrylate copolymers

Morita

Ogisu

Kubo

1999

J. Appl. Polym. Sci.

129

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Wetting behavior of perfluoroalkylethyl acrylate (FA)/n-alkyl acrylate (AA) copolymers with the various length of side chains of the AAs is discussed from a standpoint of surface molecular mobility. The copolymerization reactivity ratio indicates that these polymers are random copolymers. The surface properties were studied by measuring dynamic contact angle, static contact angle and freeze-dried X-ray photoelectron spectroscopy, and the bulk properties by wide-angle X-ray diffraction and differential scanning calorimetry. The advancing contact angles for water were independent of side-chain length of AAs and were almost constant at 120°. We have attributed this phenomenon to the orientation of perfluoroalkyl groups (R f groups, C x F 2xϩ1 ) in air, which is independent of side-chain length of AAs. On the contrary, the receding contact angles showed small values of about 45°when n numbers below 8 and increased when n numbers above 12. This can be explained as follows. High wettability during the receding process at the n numbers below 8 results from regression of R f groups at the water-solid interface caused by minimization of the interface free energy. The low wettability during the receding process at the n numbers above 12 shows that R f groups cannot regress due to its crystallization. This mechanism is also supported by other measurements.

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“…In contrast, no ordered phase is seen for the polymer with (CH 2 ) 2 (CF 2 ) 6 F (F6) side groups. 4 The change in bulk order from isotropic to nematic to smectic A is accompanied by a change in surface energy from 10.0 dyn/cm (F6) to 9.0 dyn/cm (F7) to 8.0 dyn/cm (F8) at 20°C. Therefore, the three PFPMs are well-suited to investigate the relationship between bulk order, surface order, and surface energies.…”

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confidence: 99%

Correlation of Surface and Bulk Order in Low Surface Energy Polymers

et al. 2001

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Low surface energy coatings or antiwetting agents play an essential role in microelectronics, antifogging, and antifouling applications and even have promising medical applications. 1 Currently, perfluoroalkyl-substituted polymethacrylates (PFPMs) are widely in use, and the antiwetting properties of these and related polymers 2,3 are believed to arise from the segregation of CF 3 groups to the surface. Such polymers are known to exhibit various ordered bulk phases (crystalline, smectic A, smectic B, nematic, and isotropic), depending on the number of CF 2 units in the side groups. 4,5 So far, the search for possible correlations between the bulk structure/order and the surface energy 3,6 has been impeded by a missing link, namely, knowledge of the surface structure. It is clear that the surface energies are determined by the structures present in the top layer (1 nm or less from the air surface), and such information has been lacking for all but a few systems. 7 Thus, in lieu of a scientific understanding of how bulk structures and properties influence surface energies, the design of improved coatings has been largely empirical.We have investigated polymers with the same polymethacrylate backbone but with different perfluoroalkyl side groups of the form The polymer with (CH 2 ) 2 (CF 2 ) 8 F side groups (F8) exhibits a smectic A order at room temperature. Around 80°C it undergoes a smectic A to a nematic (or cybotactic nematic) transition and around 120°C a nematic to isotropic transition. In comparison, the polymer with (CH 2 )(CF 2 ) 7 F (F7) exhibits a nematic phase at room temperature and a nematic to isotropic transition around 75°C. In contrast, no ordered phase is seen for the polymer with (CH 2 ) 2 (CF 2 ) 6 F (F6) side groups. 4 The change in bulk order from isotropic to nematic to smectic A is accompanied by a change in surface energy from 10.0 dyn/cm (F6) to 9.0 dyn/cm (F7) to 8.0 dyn/cm (F8) at 20°C. Therefore, the three PFPMs are well-suited to investigate the relationship between bulk order, surface order, and surface energies.The polymer samples were prepared by atom transfer radical polymerization (ATRP) of the monomers, obtained from an esterification reaction of methacryloyl chloride with corresponding alcohols, to obtain high molecular weight samples with a relatively narrow molecular weight distribution. 8 The polymers were soluble in hexafluorobenzene and purified by reprecipitation in chloroform and methanol. The intrinsic viscosities of the polymers in hexafluorobenzene were found to be high, ca. 1.5 dL/g at 30°C, indicating high molecular weight characteristics (>100 000). Thin polymer films were deposited on silicon wafers by spincoating using hexafluorobenzene as solvent. We do not observe any thickness effects in the studied range of some 10 nm to a few microns.The surface energy was determined with the Zisman plot method from the measured contact angles for several liquids. 9 The contact angles remained constant over time for the F8 and F7 samples, but the value for the F6 sample had t...

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Structure of comb-like polyfluoroalkyl acrylates and methacrylates

Cited by 21 publications

References 1 publication

DSC and X-ray studies on side-chain crystallization of comb-like polymers

DSC and X-ray studies on side-chain crystallization of comb-like polymers

Surface properties of perfluoroalkylethyl acrylate/n-alkyl acrylate copolymers

Correlation of Surface and Bulk Order in Low Surface Energy Polymers

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