Polymers from Renewable Resources. Xviii. Thermal Properties of the Interpenetrating Polymer Networks Derived from Castor Oil Based Polyurethane-4-Acetyl Phenyl Acrylate

Abstract

4-Acetyl-phenyl acrylate was prepared by reacting 4-hydroxy acetophenone with acryloyl chloride. It was then polymerized using benzoyl peroxide (BPO) as initiator to give the homopolymer. Both the vinylmonomer and its homopolymer were characterized by FTIR spectra. The polyurethane obtained from castor oil and TDI (Toluene-2,4-diisocyanate) with varying NCO/OH ratio was reacted with the new monomer 4-acetyl phenyl acrylate to give a large number of interpenetrating polymer networks (IPNs) using divinyl benzene as cross-linker and BPO as initiator. The thermogravimetric studies of the IPNs have been carried out and the kinetic parameters have been evaluated.     

Synthesis and crosslinking of hyperbranched poly(n‐nonyl acrylate) to form organogels

(2‐Bromo‐n‐nonan‐1‐oxycarbonyl)ethyl acrylate was synthesized as an inimer for self‐condensing vinyl polymerization (SCVP) to produce hyperbranched poly(n‐nonyl acrylate), either as a homopolymer or as a copolymer with n‐nonyl acrylate. The inimer was homopolymerized and copolymerized by atom transfer radical polymerization (ATRP) and activator generated by electron transfer ATRP to produce soluble polymers with broad polydispersities (up to ? = 9.91), which is characteristic of hyperbranched polymers produced by SCVP. The resulting hyperbranched (co)polymers were crosslinked by atom transfer radical coupling in both one‐pot and two‐step procedures. The radical–radical crosslinking reaction is extremely efficient, resulting in hard plastic particles from the homopolymer of (2‐bromo‐n‐nonan‐1‐oxycarbonyl)ethyl acrylate synthesized in bulk. Crosslinked organogels that swell in tetrahydrofuran were formed when the rate of crosslinking decreased using acetonitrile solutions. Dynamic shear and stress relaxation experiments demonstrated that the dry network behaves as a covalently crosslinked soft gel, with a glass transition at ?50 °C according to differential scanning calorimetry. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2399–2410     

Thermal stability of copolymers of vinyl acetate and methyl acrylate

The thermal degradation of a series of copolymers of vinyl acetate and methyl acrylate and the two homopolymers poly(vinyl acetate) and poly(methyl acrylate) obtained using Ce(IV) as initiator has been investigated using differential thermal analysis (DTA) and thermogravimetry (TGA) in dynamic nitrogen. The kinetic parameters E, n, and A have been obtained following several methods of thermogravimetric analyses. The stability increases as the methyl acrylate content in the copolymer composition increases. The incorporation of 5 mol % of vinyl acetate in the copolymer produces a marked decrease in stability compared to the homopolymer poly(methyl acrylate). There is evidence for an intramolecular lactonization process in vinyl acetate—methyl acrylate copolymers.     

Chemical modification of methyl cellulose with HMDI to modulate the thickening properties in castor oil

This work deals with the selective incorporation of reactive isocyanate groups into methyl cellulose in order to be used as reactive thickening agent in castor oil. Resulting gel-like dispersions may have potential applications as green lubricating greases formulated from renewable resources. Two different isocyanate-functionalized methyl cellulose-based polymers were obtained by reaction of methyl cellulose with 1,6-hexamethylene diisocyanate. The functionalization degree, from fully functionalized to a certain number of free hydroxyl groups (58:36:6 ratio between –OMe, –NCO and free –OH groups), was controlled by modifying the reagents molar ratio. These polymers were characterized through nuclear magnetic resonance of protons (¹H-NMR), Fourier transform infrared spectroscopy and thermogravimetric analysis (TGA). Thermal and rheological responses of oleogels prepared by dispersing these polymers in castor oil were studied by means of TGA analysis and small-amplitude oscillatory shear measurements. The evolution of linear viscoelasticity functions with frequency of the oleogel containing isocyanate-functionalized methyl cellulose with lower –NCO content is quite similar to that found for traditional lithium lubricating greases. In relation to long-term stability of these oleogels, the values of viscoelastic functions significantly increase during the first 7 days of ageing and then remain almost constant.     

Synthesis of Phenacylmethacrylate: Its Characterization and Polymerization

Abstract

Phenacylmethacrylate (PAMA), a new monomer containing two carbonyl groups (C[dbnd]O), was obtained from phenacyl chloride and sodium methacrylate. The homopolymer of PAMA and its copolymer with styrene were prepared in dioxane by using benzoylperoxide (Bz₂O₂) as initiator. IR, ¹H-NMR and ¹³C-NMR techniques were used to identify the structure of the monomer and polymers. The density of monomer, homopolymer and copolymer were found to be 1.13; 1.35 and 1.10 gr/ml respectively. Also, limit viscosity numbers, solubility parameters, glass transition and decomposition temperatures of polymers were determined.     

Thermal degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl acrylate copolymers

Vinylidene chloride polymers containing comonomer units capable of consuming evolved hydrogen chloride to expose good radical-scavenging sites might be expected to display greater thermal stability than similar polymers containing simple alkyl acrylates as comonomer. Incorporation of a comonomer containing the phenyl t-butyl carbonate moiety into a vinylidene chloride polymer has the potential to afford a polymer with pendant groups which might interact with hydrogen chloride to expose phenolic groups. Copolymers of vinylidene chloride with [4-(t-butoxycarbonyloxy)phenyl]methyl acrylate have been prepared, characterized, and subjected to thermal degradation. The degradation has been characterized by thermal and spectroscopic techniques. The degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl acrylate copolymers is much more facile than the same process for similar copolymers containing either [4-(isobutoxycarbonyloxy)phenyl]methyl acrylate or methyl acrylate, a simple alkyl acrylate, as comonomer. During copolymer degradation, [4-(t-butoxycarbonyloxy) phenylmethyl acrylate units are apparently converted to acrylic acid units by extensive fragmentation of the sidechain. Thus, the phenyl t-butyl carbonate moiety does function as a labile acid-sensitive pendant group but its decomposition in this instance leads to the generation of a phenoxybenzyl carboxylate capable of further fragmentation.     

Submicron Size Formulation of Linseed Oil Containing Omega-3 Fatty Acid for Topical Delivery

The aim of the present study was to design and develop topical submicron size gel formulation of linseed oil with enhanced permeation through the skin for the management of psoriasis. Linseed oil contains significant amount of α-linolenic acid (ALA) an omega-3 fatty acid, which is responsible for its pharmacological actions. In order to enhance permeation through skin, microemulsion based gel formulation was prepared and characterized. Microemulsions were prepared by aqueous phase titration method, using linseed oil, Unitop 100, PEG 400, and distilled water as the oil phase, surfactant, cosurfactant and aqueous phase, respectively. Selected formulations were subjected to physical stability studies and consequently in vitro skin permeation studies. Surface morphology studies of optimized formulation were done by transmission electron microscopy (TEM). The droplet size of microemulsions ranged from 70 to 500 nm with average particle size 186 nm. The optimized microemulsion was converted into hydrogel using carbopol 971 which had a viscosity of 498 ± 0.04 cps. During in vitro permeation study the flux of microemulsion formulation and gel was found to be 19.05 and 10.2 µg/cm²/hr, respectively, which indicated better penetration of linseed oil through the skin. These result indicated that the developed ME formulation may be a good approach for topical therapy for the management of psoriasis.     

Preparation and characterization of a viscosity index improver for naphthenic and paraffinic base oils

Copolymers of -methyl styrene and 2-ethylhexyl acrylate were prepared in a benzene solution. The presence of the copolymers were confirmed by solubility, IR and NMR tests. The molecular weight and the polydispersity of the polymers were estimated by GPC. The copolymers obtained were blended with paraffinic and naphthenic base oils. The viscosity, the viscosity index (VI) the Q value as well as the stability to shear and oxidation were obtained for these blends. The results are compared with the results obtained with an oil blend containing a commonly used high temperature additive. Two of the copolymers obtained have shown to be good alternatives for specific applications.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Ring‐opening metathesis polymerization of a modified linseed oil with varying levels of crosslinking

A commercial norbornyl‐functionalized linseed oil, blended with a bicyclic norbornene‐based crosslinking agent (at loadings ranging from 0 to 50 wt %) undergoes ring‐opening metathesis polymerization with the 1st generation Grubbs' catalyst to form a biorenewable polymer network. Comonomers are characterized, the thermal and mechanical properties of the cured systems are investigated by dynamic mechanical analysis, and thermal decomposition is evaluated by thermogravimetric analysis. The resin is shown to consist of a modified linseed oil and small oligomers of cyclopentadiene. Broad tan δ peaks suggest inhomogeneous phase morphologies, which result in complex crosslinking behaviors. The thermal stability of the polymers increases with increasing crosslinker content. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6851–6860, 2008     

Synthesis and rheological behavior of poly[acrylamide–acrylic acid–<Emphasis Type="Italic">N</Emphasis>-(4-butyl)phenylacrylamide] hydrophobically modified polyelectrolytes

Hydrophobically modified polyelectrolytes were prepared by an aqueous micellar copolymerization technique from acrylamide, N-(4-butyl)phenylacrylamide, and a third monomer, sodium acrylate. The amounts of surfactant and anionic monomers used in the synthesis have great effects on the molecular structures and the association behaviors of the resultant polymers. Rheological properties have been studied as a function of polymer concentration, ionic strength, temperature, shear rate, viscoelasticity, and so on. As expected, the copolymers exhibit improved thickening properties owing to the strong synergistic viscosification effects of the ions and the hydrophobic groups of the polymer molecules. Atomic force microscope studies were used to explore the aggregation morphology and association mechanism of such polymers.     

Synthesis and characterization of highly stable blue‐light‐emitting hyperbranched conjugated polymers

Polyfluorene homopolymer ( P1 ) and its carbazole derivatives ( P2 – P4 ) have been prepared with good yield by Suzuki coupling polymerization. P2 is an alternating copolymer based on fluorene and carbazole; P3 is a hyperbranched polymer with carbazole derivative as the core and polyfluorene as the long arms; P4 is a hyperbranched polymer with carbazole derivative as the core and the alternating fluorene and carbazole as the long arms. These polymers show highly thermal stability, and their structures and physical properties are studied using gel permeation chromatography, ¹H NMR, ¹³C NMR, elemental analysis, Fourier transform infrared spectroscopy, thermogravimetry, UV–vis absorption, photoluminescence, and cyclic voltammetry (CV). The influence of the incorporation of carbazole and the hyperbranched structures on the thermal, electrochemical, and electroluminescent properties has been investigated. Both carbazole addition and the hyperbranched structure increase the thermal and photoluminescent stability. The CV shows an increase of the HOMO energy levels for the derivatives, compared with polyfluorene homopolymer ( P1 ). The EL devices fabricated by these polymers exhibit pure blue‐light‐emitting with negligible low‐energy emission bands, indicating that the hyperbranched structure has a strong effect on the PLED characteristics. The results imply that incorporating carbazole into polyfluorene to form a hyperbranched structure is an efficient way to obtain highly stable blue‐light‐emitting conjugated polymers, and it is possible to adjust the property of light‐emitting polymers by the amount of carbazole derivative incorporated into the polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 790–802, 2008     

One-dimensional order in atactic polyacrylates containing aromatic side groups

To help in the understanding of the relations between chemical structure and morphological order in polymers of the type of poly(p-biphenyl acrylate) (PPBA), some polymers of similar structure have been synthesized and some of their physical properties studied. These polymers are: poly(p-biphenyl methacrylate), poly(vinyl p-phenyl benzoate), poly(p-phenyl benzyl acrylate), poly(p-benzyl phenyl acrylate) and poly(p-cyclohexyl phenyl acrylate) (PPCPA). Only PPCPA has been shown to possess a one-dimensional order in the solid state for reasons which are briefly discussed.The effect of copolymerization on the structural order of PPBA has also been given preliminary study. Copolymers of p-biphenyl acrylate (PBA) with p-biphenyl methacrylate (PBMA), N-vinyl carbazole (NVC) and p-cyclohexyl phenyl acrylate (PCPA) have been prepared and their properties have been studied by DSC and X-ray techniques. Small concentrations of PBMA or NVC units are sufficient to cancel the order of PPBA. On the contrary, copolymers of PBA and PCPA of any composition display morphological order in the solid state.     

Synthesis and Characterization of Novel Poly(Arylene Ether)s from 1,3‐bis(4‐Hydroxyphenyl) Benzene

Abstract

Several poly(aryl ether)s have been prepared by the condensation of 1,3‐bis(4‐hydroxy phenyl) benzene with different trifluoromethyl activated bis‐fluoro compounds. IR, ¹H and ¹³C NMR, and elemental analyses have established the resulting polymer structures. The properties of the polymers have been evaluated by DSC, TGA, dynamic mechanical analysis (DMA) and stress–strain analysis. The polymers 1a and 1c showed semi‐crystalline behavior as evident by sharp crystalline melting peaks at 299°C and 330°C along with glass transitions at 202°C and 216°C, respectively. The polymers showed very good thermal stability in air, high modulus, and high tensile strength with low elongation at break.     

用双硫酯链转移法合成嵌段聚合物

研究了以双硫酯为链转移剂进行的均聚和嵌段共聚物的合成 .首先合成大分子链转移剂 ,得到分子量可控、多分散性系数较小的均聚物PMMA、PBMA、PEMA、PEA、PBA、PMA、PSt,多分散性系数一般小于 1 30 .在相同的条件下 ,甲基丙烯酸酯类的聚合速度最快 ,苯乙烯其次 ,丙烯酸酯类最慢 .用末端带有双硫酯基团的PSt、PBMA、PBA为链转移剂 ,加入多种第二单体聚合得到实测分子量与理论分子量接近 ,且多分散性系数较小的两嵌段聚合物 .在链转移剂和引发剂的比例为 3∶1～ 6∶1的范围内 ,聚苯乙烯同样可以作为第一嵌段得到和其它酯类单体的两嵌段聚合物 .1 H NMR方法证明了聚合物的末端带有双硫酯基团 .嵌段聚合时必须加入微量的自由基引发剂以形成大分子自由基 ,达到较好的控制聚合效果     

Synthesis,Characterization and Electrorheological Properties of Polyindene/Kaolinite Composites

In this study, synthesis, characterization and electrorheological (ER) properties of polyindene (PIN) and polyindene/kaolinite composites were carried out by cationic radical polymerization using FeCl₃ as the oxidizing agent. The homopolymer and composites, containing different amounts of PIN were characterized by FTIR spectroscopy, thermo‐gravimetric (TGA) analyses, scanning electron microscopy (SEM) and dynamic light scattering (DLS) methods. The conductivity and dielectric properties of PIN and PIN/kaolinite composites were determined. Suspensions of PIN and PIN/kaolinite composites were prepared in silicone oil (SO), at a series of concentrations (c=5–25 m/m %). The effects of concentration, shear rate, electric field strength, frequency, temperature and promoter on ER activities of suspensions were investigated.     

Homopolymers and copolymers of acrylates and methacrylates of homoterpenylmethyl carbinol and α-campholenol

Acrylates and methacrylates of homoterpenylmethyl carbinol and α-campholenol were homopolymerized. Copolymers with each other and acrylonitrile were studied. Terpolymers of the acrylate of homoterpenylmethyl carbinol and the acrylate of α-campholenol with butadiene and styrene or acrylonitrile were also prepared. The lactone ring in the homopolymer of methacrylate of homoterpenylmethyl carbinol was opened up under basic conditions at room temperature, yielding a water-soluble polymer. Films of this polymer were cast from a water solution. The acrylate of homoterpenylmethyl carbinol gave a high molecular weight copolymer with acrylonitrile which could be molded into a transparent, extremely tough, film. The terpolymers of the acrylate of homoterpenylmethyl carbinol with butadiene and styrene or acrylonitrile were obtained in high yield and could be molded into strong, rubbery films. Several polymers were epoxidized and cured with p-phenylenediamine.     

Synthesis and Properties of New Polyphenylquinoxaline-imide-amides

Abstract

New thermostable polymers containing imide and phenylquinoxaline units have been prepared by solution polycondensation of diaminophenylquinoxaline coupled by ether, methylene, or sulfone linkages with diacid chlorides containing preformed imide rings. Solubility, thermal stability, and electroinsulating properties of these compounds are discussed and compared with those of related heterocyclic polymers previously reported.     

Synthesis,characterization and performance evaluation of long chain methacrylate-octene copolymer for lubricant formulation

Abstract

In this study, the authors synthesized myristyl methacrylate monomers by esterification reaction of methacrylic acid and myristyl alcohol using conc. H₂SO₄ as catalyst. Homopolymer of the prepared ester was synthesized and a series of copolymers were prepared by varying the ratio between the ester and 1-octene by free radical polymerization using azobisisobutyronitrile as initiator. All the synthesized polymers were characterized by spectral studies (FT-IR and NMR) and their average molecular weights were determined by gel permeation chromatography (GPC). Thermogravimetric analysis (TGA) was selected as the method to investigate the thermal behavior of the polymers at high temperature. Performances of the polymers as additives, and their responses as flow improvers and viscosity modifiers in the base fluid were carefully assessed by standard methods in terms of pour point and viscosity index. In addition, photo micrographic image was employed to examine the wax crystallization behavior of the additives. The results of the experimental work showed that although the copolymers were thermally more stable than the homopolymer, the latter showed better flow improving efficiency and induced better viscosity modification. The viscosity modification and the pour point performance of the additives also depend on the concentration of the additives in the base fluid.     

Oil-in-gold nanoparticle solution emulsion stabilized with amphiphilic polymers and its stability under NIR irradiation

Oil-in-water emulsions were prepared by emulsifying mineral oil in gold nanoparticle (GNP) solution using amphiphilic polymers as an emulsifier. Poly(2-hydroxyethyl acrylate) (PHEA) and poly(2-hydroxyethyl acrylate-co-propyl methacryate) (P(HEA/PMA)) having different PMA contents (2.98%, 3.29%, 6.1%, and 8.59% (mole/mole)) were prepared by a free radical polymerization, confirmed by ¹H NMR spectroscopy. According to the optical density change of the polymer solution (2% (w/v)) at 20°C–80°C, only P(HEA/PMA) having a PMA content of 3.29 mole % showed its lower solution critical temperature around 31°C. The air/water interfacial activity of the amphiphilic polymers was higher as the PMA content was higher. GNP was prepared by reducing gold ions in water. The mean hydrodynamic diameter was 22.2?nm and it appeared sphere-like on TEM photo. The emulsion prepared using PHEA maintained its stability above 80% for 190 hours, whereas it was destabilized rapidly upon 60 minutes of near-infrared (NIR) irradiation and its stability decreased to below 20% in 20 hours. As the PMA content was higher, the stability of the emulsions prepared using P(HEA/PMA) became lower and NIR irradiation accelerated the destabilization more effectively.     

Synthesis and Characterization of Polymeric Materials from Vegetable Oils

Although the petrochemical polymers have revolutionized the technological development, the intensive use of these materials have contributed to the global pollution. In this context, researches involving ecofriendliness materials are growing up, as well as, a current interest in developing materials from inexpensive and renewable resources, such as vegetable oils. In this work, is described the synthesis of polymeric materials by thermal polymerization from linseed oil (Linum usitatissimum L.) and passion fruit oil (Passiflora edulis) and their characterization by gas chromatographic (GC), Fourier transform infrared (FTIR) spectroscopy, solubility in organic solvents, thermogravimetry (TG), differential scanning calorimetry (DSC) and Raman spectroscopy. The TG curve shows that those polymeric materials present two stages of decomposition. DSC plots of the vegetable oils showed some endothermic and exothermic transitions which are not present in the DSC curves corresponding to oil-based polymers. The Raman spectra of the polymers indicate declining of absorbance in the region of CC stretching (∼1600 cm⁻¹). This absorption was used to estimate the degree of polymerization (79% and 67.5% for linseed and passion fruit oils, respectively).