Interpenetrating polymer networks from castor oil based polyurethanes and poly(ethyl acrylate)

Polyurethanes were obtained by the reaction of hydroxyl groups of castor oil with hexamethylene diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate using an NCO/OH ratio of 1.6. These polyurethanes were swollen in ethyl acrylate monomer and subsequently polymerized by radical polymerization initiated with benzoyl peroxide in the presence of the crosslinking agent ethylene glycol dimethacrylate. A series of interpenetrating polymer networks (PU/PEA IPNs) were obtained as tough films by casting in glass moulds. The characteristics of these films were determined: resistance to chemical reagents, thermal behaviour (DSC, TGA), tensile strength, Young's modulus, elongation at break (%) and Shore A hardness. The morphology was determined by scanning electron microscopy, and the dielectric properties such as electrical conductivity, dielectric constant (ε′), dielectric loss (ε″) and loss tangent (tan δ) were studied.     

Interpenetrating polymer network from castor oil-based polyurethanes and poly(methyl acrylate). XIV

Castor oil containing hydroxyl functionality was reacted with 4,4′-diphenylmethanediisocyanate under different stoichiometric ratios of NCO/OH to obtain liquid polyurethanes. These polyurethanes were subsequently interpenetrated with methyl acrylate monomer using ethylene glycol dimethacrylate as a crosslinker by radical polymerization using benzoyl peroxide as an activator. The polyurethane/poly(methyl acrylate) interpenetrating polymer networks (PU/PMA IPNs) were obtained as tough films by transfer molding techniques. All IPNs were characterized by their resistance to chemical reagents, optical properties, thermal behavior, and mechanical properties: tensile strength, Young's modulus, elongation at break (%) and hardness Shore A. The morphology of the IPNs was studied by scanning electron microscopy and dielectric properties: electrical conductivity (σ), dielectric constant (?′), dielectric loss (?″), and loss tangent (tan δ) at different temperatures.     

Interpenetrating polymer networks from caster oil-based-polyurethanes and poly(ethyl acrylate). VII

Liquid prepolyurethanes were synthesized from castor oil and toluene-2, 4-diisocyanate (TDI) under different experimental conditions and varying NCO/OH ratios. All these prepolyurethanes were subsequently reacted with ethyl acrylate/ethylene glycol dimethacrylate mixtures by radical polymerization using benzoyl peroxide as initiator to obtain interpenetrating polymer networks (IPNs) by transfer molding. The novel polyurethane/poly(ethyl acrylate) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents, thermal behavior (DSC, TGA), mechanical behavior including tensile strength, Young's modulus, and elongation. The dielectric properties, namely electrical conductivity (σ), dielectric constant (ε′), dielectric loss (ε″), and loss tangent (tan δ) were computed. The mechanothermal behavior was analyzed by dynamic mechanical spectroscopy. The morphological behavior was studied by scanning electron microscopy.     

Interpenetrating polymer networks of castor oil polyester and poly(methyl methacrylate)

The physical and mechanical properties of interpenetrating polymer networks (IPNs) and semi-I IPNs of the castor oil polyester network and poly(methyl methacrylate) were investigated. In the semi-I IPNs, the second component was a copolymer of poly(methyl methacrylate) and polystyrene (PS) or poly(methyl methacrylate) and poly(n-butyl acrylate) (PnBA). The dynamic mechanical properties indicated the semi-I IPNs to be more compatible than the IPNs. The degree of molecular mixing was higher than that for IPNs. The impact strength showed a gradual increase with the increase in the percentage of PS or PnBA in the copolymer. The effect of the copolymerization of the second component on transparency was investigated. The transparency of the semi-I IPNs increased with the increasing composition of PnBA, but reduced with the increasing composition of PS. These results are discussed in light of existing theories.     

Interpenetrating polymer networks from castor oil based polyurethane and poly(methyl methacrylate), III

Liquid prepolyurethanes (PPU) were obtained from castor oil and toluene-2,4-diisocyanate under different experimental conditions varying NCO/OH ratio. All these prepolyurethanes were subsequently interpenetrating with poly(methyl methacrylate) made by radical polymerization initiated with benzoyl peroxide. The novel PPU/PMMA interpenetrating polymer networks were obtained as though films by transfer moulding. They were characterized by thermal studies (DSC and TGA) and mechanical properties viz., tensile strength, modulus of elasticity, and percent elongation at break. The morphological behaviour was analyzed by scanning electron microscopy.     

Interpenetrating polymer networks from castor oil based polyurethanes,XI

Under different experimental conditions, various liquid polyurethanes (PU) were synthesized from castor oil and isophorone diisocyanate varying NCO/OH ratio. These polyurethanes were then subsequently interpenetrated with n-butyl acrylate (nBA) monomer and ethylene glycol di-methacrylate as crosslinker by radical polymerization using benzoyl peroxide as an initiator. This leads to the formation of novel PU/PnBA interpenetrating polymer networks (IPNs) by transfer molding. These IPNs were characterized by their resistance to chemical reagents, thermal behavior (TGA), mechanical properties, namely; tensile strength, Young's modulus, elongation at break (%) and hardness (Shore A). The morphology of the IPNs was studied by Scanning Electron Microscopy. The dielectric behavior was computed in terms of electrical conductivities, dielectric constant (ε′), loss tangent (tan δ) and dielectric loss (ε″).     

Fabrication and apparent kinetic study of poly(methyl methacrylate)/poly(octyl acrylate) and poly(octyl acrylate)/poly(methyl methacrylate) latex interpenetrating polymer networks

Two latex interpenetrating polymer networks (LIPNs) were synthesized with methyl methacrylate (MMA) and octyl acrylate (OA) as monomers, respectively. The apparent kinetics of polymerization for the LIPNs was studied. This demonstrates that network II does not have a nucleus formation stage. The monomers of network II were diffused into the latex particles of network I and then formed network II by in situ polymerization. It indicates that the polymerization of network I obeys the classical kinetic rules of emulsion polymerization. But the polymerization of network II only appears a constant‐rate stage and a decreasing‐rate stage. The apparent activation energies (E_a) of network I and network II of PMMA/POA were calculated according to the Arrhenius equation. The E_a values of POA as network I (62 kJ/mol) is similar to that of POA as network II PMMA/POA (60 kJ/mol). However, the E_a value of PMMA as network II POA/PMMA (105kJ/mol) is higher than that of PMMA as network I (61 kJ/mol). Results show that the E_a value of the network II polymerization is related to the properties of its seed latex. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interpenetrating polymer networks from castor oil-based polyurethanes and polystyrene,XXV

Interpenetrating polymer networks (IPNs) of castor oil-based polyurethanes and polystyrene were prepared by simultaneous polymerization. The liquid prepolyurethanes were formed by reacting the hydroxyl functionality of castor oil with isophorone diisocyanate using different stoichiometric NCO/OH ratios. These prepolyurethanes were mixed with styrene monomer and subsequently polymerized by free radical polymerization initiated by benzoyl peroxide in the presence of the crosslinker 1,4-divinyl benzene. The interpenetrating polymer networks. PU/PS IPNs, were obtained as tough and transparent films by the transfer moulding technique. These IPNs were characterized by the static mechanical properties (tensile strength, Young's modulus and % elongation), thermal properties and morphology. The dielectric relaxation properties (σ, E′, E″ and tanδ) of the IPNs at different temperatures were studied.     

Interpenetrating polymer networks based on thermoplastic polyurethanes (TPUS) and cis-1,4-polyisoprene

Semi-interpenetrating polymer networks based on two elastomers, cis-1,4-polyisoprene (PI) and thermoplastic polyurethane elastomers (TPUs) were prepared in varying compositions. The PI component was cross-linked using peroxide initiators. Modulus and mechanical properties were investigated as a function of composition and temperature. Slight synergisms were observed in mechanical properties, particularly for compositions containing 10% PI by weight. Little or no molecular mixing is shown by differential scanning calorimetry (DSC) for these two-phase materials. © 1994 John Wiley & Sons, Inc.     

Viscoelastic behavior of interpenetrating polymer networks: Poly(ethyl acrylate)–poly(methyl methacrylate)

The creep behavior of a series of poly(ethyl acrylate)–poly(methyl methacrylate) interpenetrating polymer networks was investigated. For comparison purposes, some stress relaxation data were included. Master curves containing a single broad transition covering approximately 20 decades of time were found for midrange compositions. Although the time–temperature superposition principle and the WLF equation should not strictly apply, reasonable agreement was found over a large portion of shift factor versus temperature plots. Application of a modified Tobolsky-Aklonis-Dupre glass–rubber theory suggested that the breadth of the transition could be attributed to a near continuum of phase compositions in the material, each phase composition making its specific contribution to the relaxation spectrum. Whether or not these phase regions are so small as to arise from random concentration fluctuations in an otherwise compatible polymer pair remains unknown.     

Interpenetrating polymer networks of poly(dimethylsiloxane): 1. Preparation and characterization

Model networks of ,ω-dihydroxy-poly(dimethylsiloxane) (PDMS) were prepared by tetrafunctional crosslinking agent tetraethyl orthosilicate (TEOS) and the catalyst stannous 2-ethylhexanoate. Hydroxylterminated chains of PDMS having molecular weights 15 × 10³ and 75 × 10³ g mol⁻¹ were used in the crosslinking reaction. Bimodal networks were obtained from a 50% (w/w) mixture of PDMS chains with M_n = 15 × 10³ and 75 × 10³ g mol⁻¹. A sequential interpenetrating network of these PDMS chains was also prepared. Physical properties of the elastomers were determined by stress-strain tests, swelling and extraction experiments, and differential scanning calorimetry measurements.     

Dielectric relaxations in poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate)

A comparative study is undertaken of the dielectric relaxation spectra of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate), taking into consideration the spectra of the corresponding polymers in the series of the polymethacrylates. The three polymers, PMA, PEA, and PBA, present an α relaxation zone clearly separated from the secondary relaxations. Its shape is not altered with temperature, and it is possible to construct a master curve. With increasing length of the side chain, its distribution of relaxation times broadens and the temperature of the maximum of the relaxation decreases. A β relaxation with decreasing intensity as the length of the side chain increases is clearly perceptible in PMA and PEA, but almost not perceptible at all in PBA. In PEA this relaxation appears split into two peaks. Computer simulation of restricted motions of the side chain discard an origin similar to that of the γ relaxation in PPA or PBA for the lowest temperature component of the relaxation, and suggests the conjunction of two rotation mechanisms in this relaxation for the polyacrylates. For the experimental temperatures of our tests a γ relaxation shows up only in PBA. Its apparent activation energy, higher than in related polymers of the polymethacrylate series, suggests that the tighter packing of monomeric units in polyacrylates leads to a significant increase in the intermolecular contribution to the potential energy barrier responsible for the relaxation.     

Interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of two or more chemically distinct networks are not only intrinsically interesting as examples of macromolecular chemical topological isomerism but are in practice useful means of controlling mutual miscibility and phase morphology in crosslinked polymers. We will first review briefly the synthesis and properties of such IPN systems. This will be followed by an outline of a phenomenological theory of the phase stability and linearised theory of spinodal decomposition of binary, chemically quenched, low crosslink density IPNs recently developed by K. Binder and the author. Finally, we will discuss some aspects of the synthesis of ternary IPNs and the thermochromic properties of IPNs containing a crosslinked polydiacetylene.     

Interpenetrating polymer networks based on carboxylated nitrile rubber and poly(alkyl methacrylate)s

A series of interpenetrating polymer networks (IPNs) based on carboxylated nitrile rubber (XNBR) and poly(alkyl methacrylate)s such as poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(butyl methacrylate) (PBuMA) were synthesized. The compositions of the IPNs were also varied by changing the swelling time of the rubber in the methacrylate monomer. The tensile and dynamic mechanical properties of the IPNs were studied. The dynamic mechanical properties in the range of 1–10⁵ Hz were obtained by the time‐temperature superposition of the data under multifrequency mode, which indicated high tanδ with good storage modulus in the entire frequency range. This indicates the suitability of these IPNs as vibration and acoustic dampers.     

Thermal stability of poly(methyl methacrylate-co-butyl acrylate) and poly(styrene-co-butyl acrylate) polymers

Thermal stability of poly(methyl methacrylate-co-butyl acrylate) and poly(styrene-co-butyl acrylate) modified with a small amount of acrylic acid and/or N-methylolacrylamide as a crosslinking agent was studied in this work. Programmed thermogravimetric analysis has been used to study the effect of copolymer composition on thermal stability, over a temperature range from 50 to 450°C, under a constant flow of nitrogen. Kinetic parameters of thermal degradation, activation energy, pre-exponential factor, and reaction order were obtained by using MacCallum-Tanner's approach. Kinetic data indicate that the thermal degradation of the investigated copolymer systems is the first order reaction, and that the increase of activation energy may be an indication of thermal stability changes in copolymer systems.     

Interpenetrating polymer networks of polyurethanes and epoxy resin,II. Compatibility and morphology

The interpenetrating polymer networks (IPN) of polyurethanes (PU) and a glycidyl ether of phenol formaldehyde (GEPF) were prepared by a simultaneous polymerization method. The dynamic mechanical properties and morphologies of the IPNs were investigated. It was found that multiphased morphology was formed in the PU/GEPF IPNs. With the PU based on polyester- or polyether-type polyols, the dynamic mechanical analysis (DMA) of these IPNs exhibited various shifts in the loss moduli (E″) of the high and low temperature transition domains depending upon the types and molecular weights of the polyols employed in the PU. Three distinct transition domains were observed as the PU content increased up to a certain level.     

Graft‐interpenetrating polymer networks of epoxy with polyurethanes derived from poly(ethyleneterephthalate) waste

Polyester polyurethanes derived from poly(ethyleneterephthalate) (PET) glycolysates were blended with epoxy to form graft‐interpenetrating networks (IPNs) with improved mechanical properties. Microwave‐assisted glycolytic depolymerization of PET was performed in the presence of polyethylene glycols of different molecular weights (600–1500). The resultant hydroxyl terminated polyester was used for synthesis of polyurethane prepolymer which was subsequently reacted with epoxy resin to generate grafted structures. The epoxy‐polyurethane blend was cured with triethylene tetramine under ambient conditions to result in graft IPNs. Blending resulted in an improvement in the mechanical properties, the extent of which was found to be dependant both on the amount as well as molecular weight of PET‐based polyurethane employed. Maximum improvement was observed in epoxy blends prepared with polyurethane (PU1000) at a loading of 10% w/w which resulted in 61% increase in tensile strength and 212% increase in impact strength. The extent of toughening was quantified by flexural studies under single edge notch bending (SENB) mode. In comparison to the unmodified epoxy, the Mode I fracture toughness (K_IC) and fracture energy (G_IC) increased by ～45% and ～184%, respectively. The underlying toughening mechanisms were identified by fractographic analysis, which generated evidence of rubber cavitation, microcracking, and crack path deflection. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40490.     

Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. VII. Polyurethane–poly(methyl acrylate) interpenetrating polymer networks

A series of polyurethane–poly(methyl acrylate) sequential interpenetrating polymer networks containing 40 wt % polyurethane were prepared. The triol/diol ratio used in the preparation of the first formed polyurethane network was changed so that the average molecular weight between crosslinks ranged from 9500 to 500 g/mol. In addition to decreasing this average molecular weight, changing the triol/diol ratio alters the hard segment content of the polyurethane. The extent of mixing of the components in these IPNs was investigated using electron microscopy, dynamic mechanical analysis, tensile testing, and sonic velocity measurements. The polyurethane networks were also characterized by swelling studies. It was concluded that, as the triol/diol ratio increased, the extent of mixing increased and there was evidence of phase separation of the hard segments of the polyurethane component at high triol/diol ratios.     

GPC calibration for poly(methyl acrylate)

Summary Electrophylic vinyl reagents can be reacted with a protonated tertiary amine supported by a polymeric chain. We determined the mechanism of this addition in the case of vinyl methyl ketone and poly (4 vinyl pyridinium bromide). The first step is the addition of the vinyl compound on the tertiary amine, then protonation of the intermediate species occurs. The velocity constant at 268 K is 0.087 1. mole^–1. mn^–1 and the activation energy is 10 kcal.mole^–1.