Hydroxymethylation and polymerization of plant oil triglycerides

The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100°C to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free‐radical–initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by ¹H‐NMR, ¹³C‐NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass‐transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40°C for soybean‐based polymer and 30°C for sunflower‐based polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4037–4046, 2004     

Synthesis and polymerization of the bromoacrylated plant oil triglycerides to rigid,flame‐retardant polymers

Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N‐bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, ¹H‐NMR, ¹³C‐NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oil–styrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glass‐transition temperatures were also determined and soybean oil–based polymer and sunflower oil–based polymer showed a glass transition at 55–65 and 20–30°C, respectively. The storage moduli of the soybean‐based and sunflower‐based polymers at room temperature were approximately 1.0 × 10¹⁰ and 1.1 × 10⁸ Pa, respectively. Photopolymerization was also carried out by using 2,2‐dimethoxy‐2‐phenyl‐acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713‐78 and was found to be 5 B at 2.00 mm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:2700–2710, 2004     

Synthesis and characterization of copolymers of bromoacrylated methyl oleate

In this study, methyl oleate was bromoacrylated in the presence of N‐bromosuccinimide and acrylic acid in one step. Homopolymers and copolymers of bromoacrylated methyl oleate (BAMO) were synthesized by free radical bulk polymerization and photopolymerization techniques. Azobisisobutyronitrile (AIBN) and 2,2‐dimethoxy‐2‐phenyl‐acetophenone were used as initiators. The new monomer BAMO was characterized by FTIR, GC‐MS, ¹H, and ¹³C‐NMR spectroscopy. Styrene (STY), methylmethacrylate (MMA), and vinyl acetate (VA) were used for copolymerization. The polymers synthesized were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, and differential scanning calorimetry (DSC). Molecular weight and polydispersities of the copolymers were determined by GPC analysis. Ten different feed ratios of the monomers STY and BAMO were used for the calculation of reactivity ratios. The reactivity ratios were determined by the Fineman–Ross and Kelen–Tudos methods using ¹H‐NMR spectroscopic data. The reactivity ratios were found to be r_sty = 0.891 (Fineman–Ross method), 0.859 (Kelen–Tudos method); r_bamo = 0.671 (Fineman–Ross method), 0.524 (Kelen–Tudos method). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2475–2488, 2004     

Rigid,thermosetting liquid molding resins from renewable resources. I. Synthesis and polymerization of soy oil monoglyceride maleates

In this study, rigid thermoset polymers were prepared from radical copolymerization of the soybean oil monoglyceride maleates with styrene. In the first part of the study, soybean oil monoglycerides (SOMGs) were obtained from the reaction of soybean oil with glycerol at 220–240°C with an optimization of the reaction to maximize the monoglyceride yield. In the following step, SOMG were reacted with maleic anhydride at temperatures around 100°C to produce the SOMG maleate half esters. Different catalysts and different reaction conditions were examined to increase the maleate half esters' yields. The reactions were followed by IR and ¹H NMR, and the products were characterized by mass spectrometry. In the final step, the radical initiated copolymerization of the SOMG maleates with styrene produced rigid, thermoset polymers. The emulsion copolymerization of the SOMG maleates with styrene was also carried out successfully without the addition of an emulsifier. The obtained polymers were characterized by IR and the crosslinked network structure of the copolymers was examined with the swelling behavior in different solvents. Mechanical properties of the cured resin such as T_g, dynamic flexural modulus, and surface hardness were also determined. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 69–77, 2001     

A simple one‐step synthesis and polymerization of plant oil triglyceride iodo isocyanates

In this study, a novel and simple route for the synthesis of the iodine isocyanate (INCO) adduct of soybean oil triglycerides is described. Soybean oil iodo isocyanate (ISONCO) was synthesized by the reaction of iodine isocyanate and soybean oil at room temperature. ISONCO was then polymerized with polyols, such as, castor oil, pentamethylene glycol, and glycerol to give the corresponding polyurethanes and with polyamines, such as, ethylene diamine, hexamethylene diamine, and triethylene tetramine to give corresponding polyureas. The structures of the monomer and the polymers were determined by FTIR and ¹H‐NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150°C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a T_g around ?50°C. The mechanical properties of the polymers were determined by tensile tests. Among the polymers synthesized, castor oil polyurethane showed the highest elongation at break and the lowest tensile strength of 140 KPa. The highest tensile strength of 900 KPa was observed in the pentamethylene glycol polyurethanes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. I. Synthesis and characterization

The cationic copolymerization of regular soybean oil, low‐saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃·OEt₂) or related modified initiators provides viable polymers ranging from soft rubbers to hard, tough, or brittle plastics. The gelation time of the reaction varies from 1 × 10² to 2 × 10⁵ s at room temperature. The yields of bulk polymers are essentially quantitative. The amount of crosslinked polymer remaining after Soxhlet extraction ranges from 80 to 92%, depending on the stoichiometry and the type of oil used. Proton nuclear magnetic resonance spectroscopy and Soxhlet extraction data indicate that the structure of the resulting bulk polymer is a crosslinked polymer network interpenetrated with some linear or less‐crosslinked triglyceride oil–styrene–divinylbenzene copolymers, a small amount of low molecular weight free oil, and minor amounts of initiator fragments. The bulk polymers possess glass‐transition temperatures ranging from approximately 0 to 105°C, which are comparable to those of commercially available rubbery materials and conventional plastics. Thermogravimetric analysis (TGA) indicates that these copolymers are thermally stable under 200°C, with temperatures at 10% weight loss in air (T₁₀) ranging from 312 to 434°C, and temperatures at 50% weight loss in air (T₅₀) ranging from 445 to 480°C. Of the various polymeric materials, the conjugated LoSatSoy oil polymers have the highest glass‐transition temperatures (T_g) and thermal stabilities (T₁₀). The preceding properties that suggest that these soybean oil polymers may prove useful where petroleum‐based polymeric materials have found widespread utility. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 658–670, 2001     

Synthesis and characterization of styrene–acrylic ester copolymers

Homopolymers and copolymers of styrene and different acrylic esters (i.e., acrylates) were synthesized by the free‐radical solution polymerization technique. Feed ratios of the monomers styrene and cyclohexyl acrylate/benzyl acrylate were 90 : 10, 75 : 25, 60 : 40, 50 : 50, 40 : 60 and 20 : 80 (v/v) in the synthesis of copolymers. All 6 homopolymerizations of acrylic ester synthesis were carried out in N,N(dimethyl formamide) except for the synthesis of poly(cyclohexyl acrylate) (PCA), where the medium was 1,4‐dioxane. Benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) were used as initiators. The polymers synthesized were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and viscosity measurements. The reactivity ratios were determined by the Fineman–Ross method using ¹H‐NMR spectroscopic data. The reactivity ratios (r) for the copolymerization of styrene (r_S) with cyclohexyl acrylate (r_CA) were found to be r_S = 0.930 and r_CA = 0.771, while for the copolymerization of styrene with benzyl acrylate, the ratios were found to be r_S = 0.755 and r_BA = 0.104, respectively. The activation energies of decomposition (E_a) and glass‐transition temperature (T_g) for various homo‐ and copolymers were evaluated using TGA and DSC analysis. The activation parameters of the viscous flow, voluminosity (V_E) and shape factor (ν) were also computed for all systems using viscosity data. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1513–1524, 2001     

Sheet molding compound resins from soybean oil: Thickening behavior and mechanical properties

Thermosetting resins for sheet molding compound (SMC) and bulk molding compound applications were synthesized from soybean oil. The SMC resins were prepared from maleated hydroxylated soybean oil (MHSO) and maleated acrylated epoxidized soybean oil (MAESO) with styrene. When thickened with divalent cations such as MgO, these resins exhibited a substantial rise in viscosity at room temperature because of complexation of MgO with the terminal acid groups on maleic anhydride. The resulting high viscosity sheet upon heating rapidly reduced its viscosity as the labile MgO‐acid groups thermally disassociated. The flexural strength σ and moduli E of these polymers varied from 61 to 87 MPa and from 1.6 to 2.4 GPa, respectively and the tensile strength and moduli varied from 27 to 44 MPa and from 1.6 to 2.5 GPa, respectively. The mechanical and fracture properties of these polymers were related to the amount of functional groups f, on the fatty acid backbone, and followed the Rigidity Percolation and Twinkling Fractal Theories, σ ～ [Eν]^1/2, where ν ～ [f ? 1]. The fracture energy G_IC decreased significantly with increasing crosslink density, as G_IC ～ ν^?2 and the plastic zone r_p decreased as r_p ～ ν^?3. The new bio‐based resins possessed mechanical and thermal properties comparable with petroleum‐based unsaturated polyesters. POLYM. ENG. SCI., 47:1469–1479, 2007. © 2007 Society of Plastics Engineers     

Random copolymerization of 2,2‐dimethyltri methylene carbonate and ε‐caprolactone using a rare‐earth tris(4‐tert‐butylphenolate)s as a single‐component initiator

Highly random copolymers of 2,2‐dimethyltrimethylene carbonate (DTC) and ε‐caprolactone (CL) were synthesized by single component rare‐earth tris(4‐tert‐butylphenolate)s [Ln(OTBP)₃] for the first time. The influences of reaction conditions on the copolymerization initiated by La(OTBP)₃ have been examined in detail. The monomer reactivity ratios of DTC and CL determined by the Fineman–Ross method are 4.0 for r_DTC and 0.27 for r_CL. The microstructure of the copolymer was determined by the analyses of the diads DTC–DTC, DTC–CL, CL–DTC and CL–CL of the ¹H NMR spectra. The high degree of randomness of the chain structure was further confirmed by the ¹³C NMR spectra and differential scanning calorimetry. The thermal properties of the copolymers as a function of composition are reported. The mechanism investigated by ¹H NMR data indicates that the rare‐earth tris(4‐tert‐butylphenolate)s initiate the ring‐opening copolymerization of DTC and CL with acyl‐oxygen bond cleavages of the monomers. Copyright © 2004 Society of Chemical Industry     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. v. shape memory effect

A series of new shape memory polymers are synthesized by the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), and/or conjugated LoSatSoy oil with styrene and divinylbenzene, norbornadiene, or dicyclopentadiene initiated by boron trifluoride diethyl etherate or related modified initiators. The shape memory properties of the soybean oil polymers are characterized by the deformability (D) of the materials at temperatures higher than their glass‐transition temperatures (T_g), the degree to which the deformation is subsequently fixed at ambient temperature (FD), and the final shape recovery (R) upon being reheated. It is found that a T_g well above ambient temperature and a stable crosslinked network are two prerequisites for these soybean oil polymers to exhibit shape memory effects. Good shape memory materials with high D, FD, and R values are prepared by controlling the crosslink densities and the rigidity of the polymer backbones. The advantage of the soybean oil polymers lies in the high degree of chemical control over the shape memory characteristics. This makes these materials particularly promising in applications where shape memory properties are desirable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1533–1543, 2002; DOI 10.1002/app.10493     

Synthesis,characterization, and reactivity ratios of copolymers derived from 4‐nitrophenyl acrylate and n‐butyl methacrylate

Free‐radical copolymerization of 4‐nitrophenyl acrylate (NPA) with n‐butyl methacrylate (BMA) was carried out using benzoyl peroxide as an initiator. Seven different mole ratios of NPA and BMA were chosen for this study. The copolymers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectral studies. The molecular weights of the copolymers were determined by gel permeation chromatography and the weight‐average (M _w) and the number‐average (M _n) molecular weights of these systems lie in the range of 4.3–5.3 × 10⁴ and 2.6–3.0 × 10⁴, respectively. The reactivity ratios of the monomers in the copolymer were evaluated by Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos methods. The product of r₁, r₂ lies in the range of 0.734–0.800, which suggests a random arrangement of monomers in the copolymer chain. Thermal decomposition of the polymers occurred in two stages in the temperature range of 165–505°C and the glass transition temperature (T_g) of one of the systems was 97.2°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1817–1824, 2003     

Reactivity ratios of free monomers and their charge‐transfer complex in the copolymerization of N‐butyl maleimide and styrene

As for the charge‐transfer complex (CTC) formed by N‐butyl maleimide (NMBI) and styrene in chloroform, the complex formation constant was determined by ¹H‐NMR of Hanna–Ashbaugh. The copolymerization of NBMI (NBMI, M₁) and styrene (St, M₂) in chloroform using AIBN as an initiator was investigated. On the basis of the kinetic model proposed by Shan, the reactivity ratios of free monomers and CTC in the copolymerization were calculated to be r₁₂ = 0.0440, r₂₁ = 0.0349, r_1C = 0.00688, r_2C = 0.00476, and the ratios of rate constants were obtained to be k_1C/k₁₂ = 6.40, k_2C/k₂₁ = 7.33. In addition, the copolymer was characterized by IR, ¹H‐NMR, DSC, and TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3007–3012, 2002; DOI 10.1002/app.2330     

Ruthenium Catalyzed Oxidative Cleavage of High Oleic Sunflower Oil: Considerations Regarding the Synthesis of a Fully Biobased Triacid

Tricarboxylic acids are molecules of interest for the synthesis of highly cross-linked polymers, for instance, for the curing of epoxy resins. Herein, a synthesis route to a novel high oleic sunflower oil based triacid is described by applying a ruthenium catalyzed oxidative cleavage of its double bonds. A statistical concept is devised for the prediction of the yields of mono-, di-, and trifunctional derivatives that can be formed from high oleic sunflower oil, depending on the overall conversion of double bonds into this functional group and the overall oleic acid content of the used oil. This concept proved to be highly useful for the explanation of seemingly moderate triacid yields, which are inherently dependent on the unsaturated fatty acid content of the used oil. All obtained sunflower oil based polyacids are fully analyzed by attenuated total reflection infrared spectroscopy (ATR-IR), electrospray ionization mass spectrometry (ESI-MS), ¹H, ¹³C, and quantitative ³¹P nuclear magnetic resonance (NMR) spectroscopy. In addition, a more sustainable purification procedure is developed to obtain a polymerizable mixture of polyacids containing more than 2.0 carboxylic acids per molecule in average. Practical applications : Tricarboxylic acids are valuable monomers for the synthesis of cross-linked polymers. The herein reported procedure represents a hitherto unknown synthesis route towards a new triacid and polyacid mixture directly from high oleic sunflower oil.     

Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group—part 7. Copolymerization of tetrafluoroethylene with ω‐hydroxy trifluorovinyl monomers

The radical copolymerization of tetrafluoroethylene (TFE) and trifluorovinyl ω‐hydroxy comonomers [F₂CCF(CH₂)_mOH with m = 1 (FA1) and m = 3 (FA3)] for the synthesis of fluorinated polymers bearing hydroxy side groups is presented. FA1 was prepared by dehydrofluorination of 2,2,3,3‐tetrafluoropropanol, whereas FA3 was obtained in a three‐step scheme starting from the radical addition of 1,2‐dichloroiodotrifluoroethane to allyl alcohol. The copolymerization conditions (in bulk or in solution in di n‐butyl ether) and the polymer compositions considerably influenced the molecular weights, the molecular weight distributions, and the thermal properties of these copolymers. The kinetics of copolymerization of both couples enabled to determine the reaction order to the initiator (being 0.9) and the close values of apparent activation energies for [TFE/FA1 (E_a = 52.4 kJ · mol⁻¹) and for TFE/FA3 (E_a = 46.8 kJ · mol⁻¹)] couples. From the Tidwell and Mortimer method, the relative reactivity ratios were calculated by elemental analysis or by ¹⁹F‐NMR spectroscopy, showing a higher reactivity of the TFE to incorporate the copolymer (r_TFE = 2.47 and r_FA1 = 0.41; r_TFE = 1.57 and r_FA3 = 0.45). The high values of the reaction order to the initiator and low molecular weights of copolymers were associated to the allylic chain transfer of the hydroxy comonomers and a mechanism of copolymerization was proposed. The comonomer diad and triad distribution was determined by the statistic theory and allowed one to calculate the average length of the comonomer sequences. Finally, the thermal decomposition of these cooligomers showed that those containing FA3 units are more thermostable than those synthesized from FA1, and that the higher the fluorinated alcohol content, the faster the thermal decomposition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 189–202, 1999     

Optoelectronic properties of thiazole‐based polythiophenes

In this work, two thiazole‐containing monomers N‐(thiazol‐2‐yl)?2‐(thiophen‐3‐yl)acetamide (ThDBTH) and N,N′‐([4,4′‐bithiazole]‐2,2′‐diyl)bis(2‐(thiophen‐3‐yl)acetamide) (Th₂DBTH) were synthesized through amidification reaction of 2‐(thiophen‐3‐yl)acetyl chloride with aminothiazole derivatives and characterized by FTIR and ¹H and ¹³C‐NMR. The monomers were subjected to electrochemical polymerization and optoelectronic properties of the resultant conducting polymers were investigated. Additionally, copolymerization of ThDBTH in the presence of thiophene was achieved. PThDBTH, PTh₂DBTH, and P(ThDBTH‐Th) exhibited optical band gaps of 2.15, 2.30, and 1.95 eV, respectively. Switching time and optical contrast of the polymers were evaluated via kinetic studies. The P(ThDBTH‐Th) revealed satisfactory switching time and appropriate optical contrast of 1.27 s and 24.97%, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42206.     

New polymers from plant oil derivatives and styrene‐maleic anhydride copolymers

In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy‐anhydride and alcohol‐anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA‐epoxidized soy oil and SMA‐CO polymers are crosslinked rigid infusible polymers. SMA‐epoxidized soy oil and SMA‐CO showed T_g's at 70 and 66°C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA‐epoxidized methyl oleate, poly[styrene‐co‐(maleic anhydride)]‐graft‐(methyl ricinoleate), and SMA‐soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydrophobically modified acrylamide‐based polybetaines. I. Synthesis,characterization, and stimuli‐responsive solution behavior

Acrylamide‐based, hydrophobically modified (HM) polybetaines containing N‐butylphenylacrylamide (BPAM) and varying amounts of the sulfobetaine monomer 3‐(2‐acrylamido‐2‐methylpropanedimethylammonio)‐1‐propanesulfonate (AMPDAPS) or the carboxybetaine monomer 4‐(2‐acrylamido‐2‐methylpropyldimethylammonio)butanoate (AMPDAB) were synthesized by micellar copolymerization. The corresponding control (co)polymers lacking BPAM or betaine comonomers were also prepared. The terpolymers were characterized by ¹³C‐NMR and UV spectroscopy, classical light scattering, and potentiometric titration. Low charge density polymers contained 3.9–8.6 mol % betaine, whereas the high charge density systems contained 17–25 mol % betaine; the HM polymers contained up to 1.0 mol % BPAM as the hydrophobe. The weight‐average molecular weights of the polymers ranged from 4.19 × 10⁵ to 1.29 × 10⁶ g/mol, and most HM polymers exhibited negative second virial coefficients. The pK_a of the carboxybetaine moieties was found to increase with increasing levels of hydrophobic and betaine comonomer incorporation. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH and electrolyte concentration, was investigated using rheological analysis. The solution behavior of the polymers was characteristic of HM polyacrylamides and acrylamide‐based polyzwitterions. The high charge density HM polycarboxybetaine exhibited unusual solution behavior that can be explained in terms of electrostatic, hydrophobic, and hydrogen‐bonding associations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 647–657, 2004     

Synthesis of starch-based flocculant by multi-component grafting copolymerization and its application in oily wastewater treatment

The grafting copolymerization of methacryloxyethyl trimethyl ammonium chloride (DMC), acrylamide (AM) and polyaluminum chloride (PAC) on starch was initiated by KMnO₄, HIO₄ and H₂SO₄ composite system. The modification of starch was combined its best attributes with those of inorganic and organic polymers and therefore enhanced the flocculation effect when it was used as flocculants by increasing the charge neutralization, adsorption bridging and aggregation ability. The main influence factors on oil removal ratio were investigated through orthogonal experimental design, and the optimal preparation conditions were obtained. The grafted copolymer was characterized through a series of physicochemical techniques (i.e., SEC-MALS, ¹³C MAS NMR, ²⁷Al NMR, FTIR, SEM, and TGA and XRD), which indicated the PAC, PAM and PDMC were successfully grafted on the starch.     

Aminolysis reaction of poly(N-4-methylphenylitaconimide) and its graft copolymerization

Polyitaconimide and copolymers of itaconimide were transformed to macromolecules having diamido pendent groups via an aminolysis reaction. The polymers obtained were cast into films, which were then graft copolymerized with acrylamide (AAM) using ceric ion as an initiator. Radical homopolymerization and copolymerization of N-4-methylphenylitaconimide with methyl acrylate or ethyl acrylate were carried out at 60°C in benzene; high molecular weight polymer and copolymers (M?_n = 10⁴–10⁵) were obtained. The resulting polymer and copolymers were reacted with n-butylamine in order to produce polymers possessing a pendent 4-tolylcarbamoyl group (4-CH₃C₆H₄NHCO-), which can significantly promote the acrylamide (AAM) graft copolymerization initiated with ceric ion. Transparent films of the polymers were graft copolymerized with AAM in the presence of ceric ion at 45°C. The formation of graft polymers was verified by water absorption percentage, XPS and SEM.     

Synthesis and properties of novel crosslinkable second‐order nonlinear optical polymers based on 2,3,4,5,6‐pentafluorostyrene

Two crosslinkable second‐order nonlinear optical polymers were prepared by copolymerization of 2,3,4,5,6‐pentafluorostyrene, styrene (St), glycidyl methacrylate (GMA) and 1‐(4‐nitrophenyl)‐2‐(4‐{[2‐(methacryloyloxy) ethyl] ethylamino}‐phenyl) diazene (DR1M) via the sealed‐tube reaction technique. These polymers were characterized using ¹H, ¹³C and ¹⁹F NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The crosslinkable polymers have high molecular weights, good organosolubility, excellent film‐forming properties and high glass transition (106–110 °C) and thermal decomposition temperatures (290–350 °C) after being crosslinked. Furthermore, the polymer films possess not only high values (12–16 pm V^?1) of electro‐optical coefficient (r₃₃) at 1.3 µm wavelength but also low optical loss (1.7 dB cm^?1) at 1.55 µm wavelength, which is of interest for applications in electro‐optical devices. Copyright © 2004 Society of Chemical Industry