Fluorinated poly(butylene terephthalate): Preparation and properties (original) (raw)
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Unsaturated polyester resins modified with perfluoropolyethers
Journal of Applied Polymer Science, 1998
Telechelic macromers based on hydroxyterminated perfluoropolyethers (HO-R H -PFPE-R H -OH) with different molecular weights were used for the preparation of fluorine-containing unsaturated polyester resins (FUPR). The products resulting from the reaction of the monomers usually employed for the preparation of unsaturated polyesters with HO-R H -PFPE-R H -OH were in any case milky liquids. The degree of reaction of the hydroxyl terminal groups of HO-R H -PFPE-R H -OH was monitored by 1 H-NMR analysis on the fractions collected after sedimentation experiments; amount and composition of the sediment and sedimentation rate were found dependent on both the molecular weight of fluorinated macromer and the method used for polyesterification. The molecular weight of HO-R H -PFPE-R H -OH and the reaction conditions had also a strong influence on the final morphology of crosslinked polymers. A very poor interphase adhesion was observed when unreacted HO-R H -PFPE-R H -OH was blended with the unsaturated polyester. On the contrary, when the fluorinated macromer was allowed to react during polyesterification, the adhesion of the fluorine-rich dispersed phase to the unsaturated polyester matrix was good for low molecular weight HO-R H -PFPE-R H -OH and when the fluorinated prepolymer had been modified by a previous reaction with chlorendic anhydride, but it was poor, as for unreacted macromers, for high molecular weight HO-R H -PFPE-R H -OHs. FUPRs prepared using a low molecular weight HO-R H -PFPE-R H -OH exhibited a significant improvement of the flexural strength even at very low level of addition (3% by wt).
ACS applied materials & interfaces, 2017
Original perfluoropolyethers (PFPE)-based oligomeric polyesters (FOPs) of different macromolecular architecture were synthesized via polycondensation as low surface energy additives to engineering thermoplastics. The oligomers do not contain long-chain perfluoroalkyl segments, which are known to yield environmentally unsafe perfluoroalkyl carboxylic acids. To improve the compatibility of the materials with polyethylene terephthalate (PET) we introduced isophthalate segments into the polyesters and targeted the synthesis of lower molecular weight oligomeric macromolecules. The surface properties such as morphology, composition, and wettability of PET/FOP films fabricated from solution were investigated using atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. It was demonstrated that FOPs, when added to PET film, readily migrate to the film surface and bring significant water and oil repellency to the thermoplastic boundary. We have established ...
Journal of Polymer Research, 2020
Poly (dihydroferulic acid) (PHFA) from biorenewable vanillin was reported before as an alternative replacement of polyethylene terephthalate (PET). Thermal properties of PHFA were found to be very close to those of commercial polyethylene terephthalate (PET). However, PHFA was insoluble in common organic solvents, and it was difficult to measure molecular weight of the obtained polymer due to difficulty of performing gel permeation chromatography (GPC) analysis. In order to modulate the physical properties of PHFA, here we report a new kind of polyester synthesized from ethyl vanillin instead of vanillin as a starting material. Ethyl group on the monomer was found to disrupt the crystallinity, improve the thermal properties and increase the solubility of the obtained polymer. 3-(4-acetoxy)-3-ethoxyphenyl) propanoic acid (AEPPA) was obtained from the reaction between ethyl vanillin and acetic anhydride through Perkin reaction and subsequent hydrogenation. Polycondensation of AEPPA was achieved using zinc acetate catalyst and resulted in poly (3-(4-acetoxy)-3-ethoxyphenyl) propanoic acid) with 75% yield and high solubility in common organic solvents. Thermal transition temperatures of the obtained polymer are very close to those of commercial PET. Polycondensation was further extended to copolymerization of AEPPA and monomers derived from vanillin and syringaldehyde. Synthesized copolymers also showed higher solubility and tunable thermal properties compared to the PHFA from vanillin.
Synthesis of polyesters-perfluoropolyethers block copolymers
Polymer Bulletin, 1992
Multiblock-(A-B)n-copolymers containing polyester segments together with perfluoropolyether (PFPE) segments have been prepared by polymerizing dimethyl terephthalate (DM'r), or an oquimolar mixture of DMT and dimethyl isophthalate (DMI), with ethylene glycol (EG) in the presence of different telechelic perfiuoropolyethers in various amounts (5-30 wt%), using Ti(OBu)4 as the catalyst. Fomblin ZDEAL (a-COOCH3 terminated PFPE), Fomblin ZDOL (a PFPE having-CH2OH terminal groups), and Fomblin ZDOLI~X (a PFPE having-CH20(CH2CH20)yH terminal groups) were used as telechellc PFPEs. Fomblin ZDOLTX gave the best results: the highest yield in block copolymer (less sensitive to hydrolysis with respect to block copolymers prepared from the other PFPEs), a longer average length of polyester segments, and a relatively low fraction of PFPE lost by distillation during polymerization. In troduction Perfluoropolymers are characterized primarily for their excellent thermal and chemical stability, inertness, durability, low coefficient of friction, low wettability etc, and are widely used in special applications. These Include biomedical applications, lubrication of magnetic media, electrical insulation In the microelectronic indus1W etc. Perfluoropolyethers (PFPE), in particular, are viscous liquids characterized for their very low glass transition (Tg =-120oc). A series of telechelic pertluoropolyethers having different types of terminal groups has been made available under the trade name of Fomblln by Montefluos; these Include the types used in the present paper, namely, Fomblin ZDEAL, Fomblln ZDOL and Fomblin ZDOLTX, having formula I with X =-COOCH3, CH2OH and-CH20(CH2CH20)yH, respectively. X-CF20((C2F40)n-(CF20)m]CF2-X (1) These terminal groups make them potential comonomers for preparing block copolymers containing perfluoropolyether blocks. In previous papers(I,2) we characterized the polymeric materials obtained by polymerizing dimethyl terephthalate (DMT) and ethylene glycol (EG) in the presence of Fomblin ZDEAL under various experimental conditions. In any case, the polymeric materials consisted of poly(ethylene terephthalate) homopolymer (PET), PET-PFPE multlblock copolymers and unreacted PFPE. The fraction of unreacted PFPE decreased, relatively to the overall PFPE content, by decreasing the initial amounts of ZDEAL, however, even for an initial amount of ZDEAL as low as 5%, there was still a 50% of PFPE unreacted. Therefore, It is practically Impossible to obtain a large amount of PET-PFPE multiblock copolymer directly from polymerization when Fomblln ZDEAL Is used. Other drawbacks, connected with the use of FombUn ZDEAL, are a low hydrolytic stability of the ester bonds at the junction between polyester and PFPE segments, and the Inhibition of the catalytic activity of the catalysts(1,2) usually employed for the first stage, of transesterlfication, of polymerization of PET. For this last reason Fomblin ZDEAL has to be added when the first stage is completed, before starting the second stage. It was also Interesting to note that the very surface compastton of samples prepared with the polymeric materials obtained from the polymerization of PET In the presence of FombUn ZDEAL was much richer in fluorine than the bulk composition(3), and that the surface composition profile was dependent on the relative amount of unreacted PFPE(4). In order to verify the possibility of preparing samples with an high amount of polyester-PFPE multiblock copolymers, we have extended the study to other PFPEs, and in this paper we report the results of polymerizations of polyesters (PET) and copolyesters (from DMT, DMI and EG) carded out In the presence of Fomblin ZDEAL, Fomblin ZDOL and Fomblin ZDOLTX.
Poly(ethylene isophthalate)s: effect of the tert-butyl substituent on structure and properties
Polymer, 2004
A comparative study of the two isophthalic acid deriving homopolyesters poly(ethylene isophthalate) (PEI) and poly(ethylene 5-tert-butyl isophthalate) (PE t BI), including synthesis, crystal structure, and thermal and permeability properties, was carried out. The two polyesters were prepared by condensation polymerization in the melt. In both cases, minor amounts of cyclic dimers were observed to form, which were characterized by nuclear magnetic resonance and mass spectroscopy. PEI and PE t BI were thermally stable up to 400 8C and they appeared to be semicrystalline polyesters, having their melting temperatures between 130 and 135 8C. Their glass-transition temperatures were 62 and 94 8C, respectively. The crystal structure adopted by the two polyesters seemed to consist of a regularly folded conformation, clearly different from the almost extended conformation characteristic of poly(ethylene terephthalate). Gas permeability measurements for N 2 , O 2 , and CO 2 revealed that PE t BI is more permeable to these gases than PEI, in spite of having a higher T g : Furthermore, water vapor diffusion was found to be increased by the insertion of the tert-butyl group, whereas water absorption diminished. The differences in gas and water vapor transport properties observed for these two polyesters were discussed on the basis of their respective molecular structures. q
Langmuir : the ACS journal of surfaces and colloids, 2018
For decades, water and oil repellency of engineering thermoplastics has been achieved with introduction of long-chain perfluoroalkyl substances and moieties (C F, n ≥ 7). However, their bioaccumulative and toxicological impact is now widely recognized and, consequently, the substances have been phased out of industrial production and applications. To this end, we have synthesized fluorinated oligomeric triblock polyesters (FOPBs), which do not possess the long-chain perfluoroalkyl segments and serve as effective low-surface-energy additives to engineering thermoplastics. More specifically, we obtained original perfluoropolyether (PFPE)-based triblock copolymers, in which two identical fluorinated blocks were separated by a short nonfluorinated polyester block made of poly(ethylene isophthalate) (PEI). It was found that when FOPBs were added to poly(ethylene terephthalate), nylon-6, and poly(methyl methacrylate) films they readily migrate to the film surface and in doing so imparted ...
Polymer, 2000
Poly(butylene terephthalate-co-diethylene terephthalate) random copolymers of various compositions and molecular weights were synthesized in bulk and characterized in terms of chemical structure and thermal and rheological properties. All copolymers are partially crystalline and thermally stable up to about 300ЊC. The main effect of copolymerization is a decrease in melting and glass transition temperatures with respect to PBT homopolymer. The fusion temperatures are well correlated to composition by Baur's equation and the T m Њ and DH m Њ extrapolated values for PBT are in good agreement with those reported elsewhere. The presence of diethylene terephthalate units was found to influence slightly the rheological behaviour in the melt. ᭧ Poly(butylene-co-diethylene terephthalate) copolymers (PBTDEG) were synthesized starting from DMT, BD and DEG with Ti(OBu) 4 (about 0.7 g/kg of DMT) as catalyst, Polymer 41 (2000) 5297-5304 0032-3861/00/$ -see front matter ᭧