Structure of friedel-crafts crosslinked polystyrene and sulfonated resins thereof

Summary A new method of crosslinking of polystyrene using difunctional chloromethylated crosslinking agents is reported. The solution crosslinking took place in dichloroethane with SnCl₄ as a catalyst at 80°C and with molar ratios of polystyrene to crosslinking agent ranging from 12 to 121. The crosslinked networks prepared by this method had thermal transitions considerably affected by the degree of crosslinking. Ion-exchange resins were prepared by sulfonation of these networks. Water swelling ratios as high as 16.2 were measured leading to indications about the physical structure of these networks.     

Comparison of thermal,thermomechanical, and rheological properties of blends of divinylbenzene-based hyperbranched and linear functionalized polymers

A range of polymer blends were prepared via a solvent-based film casting process using highly/hyperbranched (HB) polydivinylbenzenes (PDVB) polymers of two different molecular weights, linear functionalized (LF), hydrogenated hyperbranched (H-HB2) PDVB, and linear polystyrene (LP). The thermal, thermomechanical, and rheological properties of the pure polymers and blends were then investigated and the results related to the concentration of “branched” polymer in the blend and the level of branching/polymer end groups present in the “branched” polymers used. Differential scanning calorimetry (DSC) analysis revealed an increase of the glass transition temperature (T_g) for the blends containing the nonhydrogenated HBs (~108 °C compared to ~102 °C for LP), which was attributed to crosslinking via the unsaturated reactive chain end/pendant groups in the HB ( CHCH₂). In contrast at the blends, containing the hydrogenated polymers H-HB2, exhibited the same T_g as LP (~102°C) due to absence of crosslinking from the (H-HB2) polymer. As the unsaturated HBs were found to be thermally curable, curing temperature rheology measurements were carried out employing a temperature ramp. No specific T_gel (the temperature at which HB gets crosslinked) was identified for LP-HB1 and LP-HB2 blends, which might be suggested to be due to the fact that both chain entanglement from linear polystyrene. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48547.     

Preparation and performance of crosslinked poly(arylene ether)s containing azobenzene chromophores

A series of novel poly(arylene ether)s with crosslinked groups and different azobenzene chromophores contents (azo-CPAEs: PAE-allyl20%-azo20%, PAE-allyl20%-azo40%, PAE-allyl20%-azo60%) were synthesized from a new bisfluoro monomer, (2,6-difluorophenyl)-(4-hydroxyphenyl)methanone. Their chemical structures were characterized by means of UV-vis and FI-IR. The thermal properties of the polymers were investigated by TGA and DSC, indicating the polymers had high glass transition temperatures (T_g > 147 °C) and good thermal stability (T_d5 > 360 °C) even when the contents of azobenzene chromophores was high to 60%. And the influence of thermal crosslinking on the performance of PAE-allyl20%-azo20%, a typical one of the series, was investigated. T_g of PAE-allyl20%-azo20% increased with the increase of heating time when heat-treated at 250 °C for 20, 40 and 60 min, indicating the crosslink degree of the polymer increased. After heat-treated for 60 min, T_g of PAE-allyl20%-azo20% increased to 175 °C from 147 °C before thermal crosslinking. Upon irradiation with a 532 nm neodymium doped yttrium aluminum garnet (Nd:YAG) laser beam, the remnant value of the polymer PAE-allyl20%-azo20% before and after the thermal crosslinking were 81 and 96%, respectively, meaning that the PAE-allyl20%-azo20% after thermal crosslink showed more stable photoinduced alignment than that before thermal crosslinking.     

Poly(phenylene oxide) composites containing crosslinked polystyrene microspheres. II. Dark crosses observed in microscope

Extinction phenomena observed between crossed polaroids in microscope were classified into three groups: (1) Poly(2, 6-dimethyl-1, 4-phenylene oxide)/polystyrene composite with crosslinked polystyrene microspheres. Negative dark crosses were observed in the shells of the spheres, the cores of the spheres were completely extinct. The crosses disappeared at 170°C, which is 20°C above T_g of the matrix polymer. (2) Polycarbonate composite with glass beads. The dark crosses were positive and outside the glass beads. The crosses disappeared at 130°C, which is 20°C below T_g of the matrix polymer. (3) In situ polymerized composites with crosslinked polystyrene microspheres. The dark crosses were the same size of the spheres. They were negative in poly(methyl methacrylate) and poly(vinyl acetate) and positive in polystyrene. The disappearing temperatures of the crosses were 150, 110, and 285°C, respectively. The first two groups of phenomena are explained as the photoelastic effects caused by the thermally induced stresses. The last group is due to the inhomogeneous swelling or contracting of polystyrene networks in the matrices.     

Confinement effects on the kinetics of formation of sequential semi-interpenetrating polymer networks

Summary Peculiarities of formation kinetics of sequential semi-interpenetrating polymer networks based on crosslinked polyurethane with different cross-linking density and linear polystyrene and polybutylmethacrylate have been studied. Polyurethane networks were synthesized differing in molecular mass M_c of the chains between cross-links. Monomeric styrene and butyl methacrylate were introduced into these networks by swelling them in monomers up to equilibrium. The kinetics of polymerization of monomers in swollen networks was investigated. The experimental data show the dependence of the kinetic parameters of polymerization on M_c, this dependence being different for various monomers. Sharp discrepancy in molecular mass distribution of polymers formed in various matrices has been observed. The differences in dependencies of reaction kinetics and molecular mass distribution are supposed to be connected to various dependence of the chain growth and termination of various monomers on the density of network, i.e. on the confinements imposed by the intranetwork space.     

Accelerant‐promoted free radical polymerization of methacrylates by stabilized nitroxide unimolecular initiators: synthesis and characterization

BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of M_n evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (T_g) for PMMA was 123–128 °C. The degradation temperature (T_d) for PMMA was 350–410 °C. T_d for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry     

Synthesis of a novel difunctional NLO azo‐dye chromophore and characterizations of crosslinkable copolymers with stable electrooptic properties

The synthesis and the nonlinear optical (NLO) properties of crosslinkable copolymers based on a novel NLO azo‐dye chromophore bearing two functions: one used the free‐radical copolymerization, that is, the methacrylate group, and the other one used for the crosslinking process, that is, the carboxylic acid function, are described. Copolymerization of this new monomer with glycidyl methacrylate leads to novel soluble crosslinkable NLO copolymers bearing free epoxy and carboxylic groups. The poling process, before crosslinking, is achieved at a temperature (T_p) close to the glass transition temperature, T_g (<70°C), of the copolymers. At this temperature, no reaction takes place between epoxy and carboxylic acid functions. In fact, crosslinking begins to start at a higher temperature, T_c (T_c ≫ T_p ≈ T_g). After the optimization of the poling and crosslinking processes, the NLO crosslinked polymer with 30 mol % of the chromophore exhibits a T_g of 157°C and a high quadratic susceptibility (d₃₃) of 30 pm/V at 1320 nm. This coefficient is stable at 85°C for several weeks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 974–982, 1999     

Photocuring and thermomechanical properties of multifunctional amide acrylate compositions derived from castor oil

The photopolymerization of multifunctional acrylate monomers synthesized from castor oil was investigated by photo-DSC. These studies revealed that the extent of photopolymerization depended on the double bond concentration and a greater degree of crosslinking occurred in monomer mixtures with higher difunctional content. The monomer mixtures displayed significantly higher maximum rate of polymerization (R_p^max) and shorter time to reach peak maximum than the pure monomers. DMTA studies of films showed good storage modulus and broad tan δ transitions indicating heterogeneity in the crosslinked networks. The films displayed sub-T_g transitions in the loss modulus curves were possibly due to the side chain motions of the monomer acrylates which increased with increasing triacrylate concentration. Glass transition temperature (T_g) of these networks depended on composition and shifted to higher values with increasing amount of triacrylate.     

Crosslinking characterization of a polyimide: AFR700B

Crosslinking in AFR700B polyimide was studied using several techniques. Crosslinking could not be detected using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Swelling in n-methyl pyrrolidone (NMP) showed network formation occurs at cure temperatures ≥325°C (617°F), but the reaction kinetics could not be determined from the data. Dynamic mechanical analysis (DMA) studies have shown that the storage modulus (G′) increased with increasing cure temperature up to 350°C (662°F), and was constant above 350°C (662°F), indicating that crosslinking via the reverse Diels-Alder reaction was occurring. A broad secondary transition was seen in the loss modulus (G″) curves, centered between 150 and 180°C (302 and 356°F). This secondary transition appeared at a cure temperature of 300°C (572°F) and became more dominant with increasing temperature and time. This secondary transition was not seen for cures <300°C (572°F) when the chains have not crosslinked. Therefore, this is likely due to a crosslink bond rather than one in the backbone. At 1 atm, crosslinking followed second-order kinetics based on the increase in glass transition temperature (T_g). The Arrhenius plot of the rate constant showed a break in the slope, possibly indicating a change in reaction mechanism. At 1.38 MPa (200 psi), the T_g data was too scattered to determine the kinetics.     

Crosslinking reaction and properties of two‐component waterborne polyurethane from terpene‐maleic ester type epoxy resin

A two‐component waterborne polyurethane (2K‐WPU) is prepared with the terpene‐maleic ester type epoxy resin‐based polyol dispersion and a hydrophilically modified hexamethylene diisocyanate tripolymer. Laser particle size analyzer and transmission electron microscopy are used to characterize the particle size distribution and the micromorphology of the 2K‐WPU. Crosslinking reaction kinetics of the 2K‐WPU is examined by fourier transform infrared spectrometry (FTIR) spectra. In the preliminary stage of the crosslinking reaction, it shows a very good fit with a second order reaction kinetics, and the apparent activation energy is 94.61 kJ mol^?1. It is also shown from the FTIR spectra that the complete crosslinking reaction of the 2K‐WPU needs 7 h at 70°C. The crosslinked products of the 2K‐WPU have good thermal resistant properties, with glass‐transition temperatures (T_g) in the range of 35–40°C and 10% weight loss temperatures (T_d) in the range of 275–287°C. The films obtained from the crosslinked products have good water‐resistance, antifouling, blocking resistance properties and impact strength of >50 cm, flexibility of 0.5 mm, adhesion of 1 grade, pencil hardness of HB‐2H. The pencil hardness and thermal‐resistant properties of the crosslinked products increase with the molar ratio of isocyanate (? NCO) group to hydroxyl (? OH) group. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modification of DGEBA with diimide–diacids derived from bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and crosslinking study

Epoxy resins derived from diimide–diacids obtained from bicyclo[2.2.2.]oct-7-en-2,3,5,6-tetracarboxylic dianhydride and diglycidyl ether of bisphenol A were synthesized and characterized by spectroscopic techniques and thermal analyses. A further crosslinking using hydroxylic groups using dianhydride or diisocyanate as a hardener was also carried out. These processes led to crosslinked materials, but a DSC study does not show a straightforward relationship between the amount of hardener used and reaction enthalpiies, which suggests a complicated reaction mechanism. On the other hand only a slight increase in T_g values was observed during the curing process. No substantial differences between the thermal characteristics of linear and crosslinked polymers wer observed. © 1996 John Wiley & Sons, Inc.     

Synthesis,curing behavior and thermal properties of silicon‐containing hybrid polymers with Si−C≡C units

Three novel kinds of linear silicon‐containing hybrid polymers with Si?C≡C units were synthesized by polycondensation reactions using the Grignard reagent method. All the polymers were thermosetting, highly heat‐resistant, moldable and easily soluble in common organic solvents. The structure, curing behavior, thermal and oxidative properties were characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The results obtained can provide theoretical guidance for determining the curing of the resin system. In addition, the cured polymers exhibit excellent thermal and oxidative stabilities with temperatures of 5% weight loss (T_d5) above 480 °C and 450 °C in nitrogen and air respectively; the residues at 1000 °C were above 70.0% and 45.0% respectively. The thermal and oxidative stabilities of the polymers are attributed to a crosslinking reaction between the Si?H and C≡C bonds or C≡C bonds. These polymers have the potential for use as high‐temperature‐resistant resins and ceramic precursors. © 2013 Society of Chemical Industry     

Synthesis and characterization of air‐stable magnetic Fe composites microspheres of narrow size distribution

Air‐stable Fe magnetic nanoparticles entrapped within carbon and porous crosslinked polystyrene microspheres of narrow size distribution were prepared by the following sequential steps: (1) Polystyrene/poly(divinyl benzene) and polystyrene/poly(styrene‐divinyl benzene) uniform micrometer‐sized composite particles were prepared by a single‐step swelling of uniform polystyrene template microspheres dispersed in an aqueous continuous phase with emulsion droplets of dibutyl phthalate containing the monomers divinyl benzene and styrene and the initiator benzoyl peroxide. The monomers within the swollen polystyrene template microspheres were then polymerized by raising the temperature to 73°C; (2) Porous poly (divinyl benzene) and poly(styrene‐divinyl benzene) uniform crosslinked microspheres were prepared by dissolution of the polystyrene template part of the former composite particles; (3) Uniform magnetic poly(divinyl benzene)/Fe and poly(styrene‐divinyl benzene)/Fe composite microspheres were prepared by entrapping Fe(CO)₅ within the porous crosslinked microspheres, by suction of the Fe complex into the dried porous particles, followed by decomposition of the encapsulated Fe(CO)₅ at 200°C in Ar atmosphere; (4) Uniform magnetic air‐stable C/Fe composite microspheres were prepared similarly, apart from changing the decomposition temperature from 200 to 600°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Glass transition temperature of ideal polymeric networks

Measurements of the glass transition temperature (T_g) have been carried out on polystyrene networks prepared by the anionic copolymerization of styrene and divinylbenzene, and star-shaped polystyrene of varying functionality. The results show a linear variation of T_g versus $\text{M}\text{?}{}^{\mathrm{?1}}{}_{\mathrm{n}}$ in all cases. The value of the slope interpreted in terms of the free volume theory shows that the glass transition temperature depends closely on the average functionality of the crosslinks. In order to study the influence of free chains on the glass transition of crosslinked polymers a series of networks were contaminated with increasing ratios of linear polystyrene chains, slightly polydisperse.     

Network structure/mechanical property relationship in crosslinked dimethacrylates of different chain lengths

In this article, the syntheses of three novel dimethacrylates of different chain lengths as well as the mechanical and thermal properties of their copolymers with methyl methacrylate and styrene were studied. The monomers were prepared by the reaction of glycidyl methacrylate with dicarboxylic acid esters obtained from maleic anhydride and ethylene, 1,4‐butylene and 1,6‐hexylene glycols. The addition reaction of glycidyl methacrylate and the acidic compound was carried out in the presence of basic catalyst, tetraethylammonium bromide. The monomers were UV‐copolymerized with methyl methacrylate and styrene in the presence of a photoinitiator which was 2,2‐dimethoxy‐2‐phenyloacetophenone. The prepared polymers were subjected to different studies concerning evaluation of their flexural properties, thermal stability, dynamic mechanical behavior as well as qualitative estimation of the content of unreacted double bonds. The dependence of glass transition temperatures (T_g) as well as degree of inhomogeneity on the crosslinking density has been examined in different copolymer systems. Evidence that the dependence of the T_g on the crosslinking density is not straightforward is presented. Dynamic mechanical measurements have demonstrated that the heterogeneity of the crosslinked polymers depends strongly on the crosslinking density of the system and the nature of methacrylate monomers used. Depending on the monomer size as well as its functionality, the resultant polymer may have features such as crosslinks or residual unsaturations that influence and define the properties of the materials. It is proved that the new dimethacrylates change their functionality in copolymerization with different monovinyl monomers. Also, the degree of unsaturated bonds conversion was found to be growing with the amount of monovinyl in the copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Flexible polybenzoxazine thermosets containing pendent aliphatic chains

The rich chemistry of polybenzoxazines allows a wide range of molecular structure design by using appropriate starting materials. A new class of polybenzoxazines has been developed from benzoxazine monomers containing pendent long aliphatic chains. The monomers have been synthesized by the reaction of phenol or bisphenol A with two different long‐chain aliphatic amines. The chemical structure of the monomers was confirmed by ¹H nuclear magnetic resonance and Fourier transform infrared spectroscopy. The polymerization behavior of the monomers studied by differential scanning calorimetry shows exothermic peaks due to the ring‐opening polymerization of benzoxazine monomers centered at 247–255 °C. Dynamic mechanical analysis indicated that the glass transition temperatures T_g were in the range 81–92 °C. The thermal stability of the polymers was also examined by thermogravimetric analysis, demonstrating that the weight loss temperatures decreased in comparison with that of traditional polybenzoxazine. Copyright © 2011 Society of Chemical Industry     

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     

A structure–property rationalization of some poly(carboxyl–epoxy) thermosets

The glass transition temperatures, T_g, and strength properties have been determined for an acrylic-based prepolymer containing 25 mole-% carboxyl functionality crosslinked with five different diepoxides. The T_g values vary from 100° to 200°C, and ultimate elongations of 2% to 7% at 25°C are observed with the different crosslinking agents. These variations are rationalized in terms of the structural elements present in the diepoxides. Thermosets possessing rigid structural units at the crosslink points connected by flexible segments have the best all-around combination of T_g and tensile properties. A decline in these properties was noted when the epoxide/carboxyl ratio exceeded unity owing to the formation of mixed networks and free chain ends.     

Network properties: 3. A pulsed n.m.r. study of molecular motions in some AB-crosslinked polymers

This paper presents the results of a pulsed n.m.r. study of molecular motions in poly (methyl methacrylate) (PMMA) and poly (methyl acrylate) (PMA) chains in a series of multicomponent network polymers consisting of poly (vinyl trichloroacetate) (PVTCA) crosslinked with PMMA and with PMA, with emphasis on segmental motions. Results of ancilliary broad line n.m.r. and dilatometric studies are included; the latter demonstrate that in PMA containing polymers microphase separation of the components is complete while in PMMA containing polymers a mixed microphase of PVTCA and PMMA and a pure PMMA microphase are formed. α-Methyl group rotations in PMMA chains and segmental motions in both PMMA and PMA chains are modified with respect to those in the corresponding homopolymers. Modifications to the segmental motions in the crosslinking chains are attributed to the fact that their chain ends are attached to PVTCA chains. It is considered that the comparative rigidity of PVTCA chains (T_g ～ 60°C) reduces segmental motions in at least portions of the PMA chains (T_g ～ 5°C) while the comparative mobility of PVTCA enhances segmental motions in PMMA (T_g ～ 100°C). Thus the molecular mobility of chains of one polymer is to some extent transmitted to chains of another polymer to which it is attached.     

Correlating structure with ionic conductivity in bis(phosphonium)‐containing [NTf2] thiol–ene networks

Thiol–ene photopolymerization was employed in order to prepare a series of covalently crosslinked bis(phosphonium)‐containing poly(ionic liquid) (PIL) networks. While the counteranion was held constant (NTf₂), the structure of the bis(phosphonium)‐containing ‘ene’ monomer was varied in order to explore the breadth of thermal, mechanical and conductive properties available for this system. Towards this end, it was determined that more flexible spacers within the cationic monomer led to PIL networks with lower T_g values and higher conductivities. Most notable was a two‐ to three‐orders‐of‐magnitude increase in ionic conductivity (from 10^?9 to 10^?6 S cm^?1 at 30 °C, 30% relative humidity) when the R group on phosphonium was changed from phenyl to isopropyl. Changing the functional group ratio to off‐stoichiometry also led to a slight increase in conductivity. Although the thermal stability (T_d5%) of the phosphonium ionic liquid monomers was found to be significantly higher (>400 °C) than that of analogous imidazolium monomers, this improvement was not observed to directly transfer over to the polymer where a two‐step decomposition pathway was observed. The first step is attributed to the thiol monomer backbone while the second step correlates well with decomposition of the phosphonium portion of the PIL. © 2019 Society of Chemical Industry