SIMULTANEOUS POLYMER NETWORK

Hyperbranched polyurethanes are constmcted using phenol-blocked trifunctional monomers in combination with 4-methylbenzyl alcohol for end capping (11). Polyurethane interpenetrating polymer networks (IPNs) are mixtures of two cross-linked polymer networks, prepared by latex blending, sequential polymerization, or simultaneous polymerization. IPNs have improved mechanical properties, as weU as thermal stabiHties, compared to the single cross-linked polymers. In pseudo-IPNs, only one of the involved polymers is cross-linked. Numerous polymers are involved in the formation of polyurethane-derived IPNs (12). 

Over the years many blends of polyurethanes with other polymers have been prepared. One recent example is the blending of polyurethane intermediates with methyl methacrylate monomer and some unsaturated polyester resin. With a suitable balance of catalysts and initiators, addition and rearrangement reactions occur simultaneously but independently to give interpenetrating polymer networks. The use of the acrylic monomer lowers cost and viscosity whilst blends with 20% (MMA + polyester) have a superior impact strength. 

Silicone co-polymer networks and IPNs have recently been reviewed.321 The development of IPNs is briefly described, and the definitions of the main (non-exclusive) classes of the IPNs are cited. Examples of latex IPNs, simultaneous and sequential IPNs, semi-IPNs, and thermoplastic IPNs are provided. The use of silicone-silicone IPNs in studies of model silicone networks is also illustrated. Networks in which siloxane and non-siloxane components are connected via chemical bonds are considered co-polymer networks, although some other names have been applied to such networks. Today, some of the examples in this category should, perhaps, be discussed as organic-inorganic hybrids, or nanocomposites. Silicone IPNs are discussed in almost all of the major references dealing with IPNs.322-324 Silicone IPNs are also briefly discussed in some other, previously cited, reviews.291,306... 

The first type, termed sequential IPN s, involves the preparation of a crosslinked polymer I, a subsequent swelling of monomer II components and polymerization of the monomer II in situ. The second type of synthesis yields materials known as simultaneous interpenetrating networks (SIN s), involves the mixing of all components in an early stage, followed by the formation of both networks via independent reactions proceeding in the same container (10,11). One network can be formed by a chain growth mechanism and the other by a step growth mechanism. 

Simultaneous Interpenetrating Networks. An interpenetrating polymer network, IPN, can be defined as a combination of two polymers in network form, at least one of which was polymerized or synthesized in the presence of the other (23). These networks are synthesized sequentially in time. A simultaneous interpenetrating network, SIN, is an IPN in which both networks are synthesized simultaneously in time, or both monomers or prepolymers mixed prior to gelation. The two polymerizations are independent and non-interfering in an SIN, so that grafting or internetwork crosslinking is minimized (23-26). 

This is a theoretical study on the structure and modulus of a composite polymeric network formed by two intermeshing co-continuous networks of different chemistry, which interact on a molecular level. The rigidity of this elastomer is assumed to increase with the number density of chemical crosslinks and trapped entanglements in the system. The latter quantity is estimated from the relative concentration of the individual components and their ability to entangle in the unmixed state. The equilibrium elasticity modulus is then calculated for both the cases of a simultaneous and sequential interpenetrating polymer network. 

This is a theoretical study on the entanglement architecture and mechanical properties of an ideal two-component interpenetrating polymer network (IPN) composed of flexible chains (Fig. la). In this system molecular interaction between different polymer species is accomplished by the simultaneous or sequential polymerization of the polymeric precursors [1 ]. Chains which are thermodynamically incompatible are permanently interlocked in a composite network due to the presence of chemical crosslinks. The network structure is thus reinforced by chain entanglements trapped between permanent junctions [2,3]. It is evident that, entanglements between identical chains lie further apart in an IPN than in a one-component network (Fig. lb) and entanglements associating heterogeneous polymers are formed in between homopolymer junctions. In the present study the density of the various interchain associations in the composite network is evaluated as a function of the properties of the pure network components. This information is used to estimate the equilibrium rubber elasticity modulus of the IPN. 

Interpenetrating polymer networks are defined in their broadest sense as an intimate mixture of two or more pol)Mners in network form [1,2]. Ideally, they can be synthesized by either swelling the first crosslinked polymer with the second monomer and crosslinker, followed by in-situ polymerization of the second component (sequential IPN s) or by reacting a pair of monomers and crosslinkers at the same time through different, non-interfering reaction mechanisms, simultaneous interpenetrating networks, SIN s. In fact, many variations of these ideas exist in both the scientific and the patent literature. In any case, at least one of the two components must have a network structure, as an IPN prerequisite. ... 

Polyurethane-acrylic coatings with interpenetrating polymer networks (IPNs) were synthesized from a two-component polyurethane (PU) and an unsaturated urethane-modified acrylic copolymer. The two-component PU was prepared from hydroxyethylacrylate-butylmethacrylate copolymer with or without reacting with c-caprolactonc and cured with an aliphatic polyisocyanate. The unsaturated acrylic copolymer was made from the same hydroxy-functional acrylic copolymer modified with isocyanatoethyl methacrylate. IPNs were prepared simultaneously from the two-polymer systems at various ratios. The IPNs were characterized by their mechanical properties and glass transition temperatures. 

Note 2 Semi-interpenetrating polymer networks may be further described by the process by which they are synthesized. When an SIPN is prepared by a process in which the second component polymer is formed or incorporated following the completion of formation of the first component polymer, the SIPN may be referred to as a sequential SIPN. When an SIPN is prepared by a process in which both component polymers are formed concurrently, the SIPN may be referred to as a simultaneous SIPN. (This note has been changed from that which appears in ref [4] to allow for the possibility that a linear or branched polymer may be incorporated into a network by means other than polymerization, e.g., by swelling of the network and subsequent diffusion of the linear or branched chain into the network.). 

The importance of crosslinked polymers, since the discovery of cured phenolic formaldehyde resins and vulcanized rubber, has significantly grown. Simultaneously, the understanding of the mechanism of network formation, the chemical structure of crosslinked systems and the motional properties at the molecular level, which are responsible for the macroscopic physical and mechanical properties, did not accompany the rapid growth of their commercial production. The insolubility of polymer networks made impossible the structural analysis by NMR techniques, although some studies had been made on the swollen crosslinked polymers. 

The simultaneous hydrosilylation and ring-opening polymerization process provides a powerful method for the construction of a variety of novel polymer networks including comb, block and graft polymers, e.g. 272 (equation 102)271. 

The cyanates are mixed with thermoplastic polymers. They can be also dissolved in a monomer and then a simultaneous polymerization is carried out. So-called SINs (Simultaneous Interpenetrating Networks) are obtained. 

Jordhamo GM, MansonJA, Sperling LH (1986) Phase continuity and inversion in polymer blends and simultaneous interpenetrating networks. Poly Eng Sci 26 517... 

Zhou P, Xu Q, Frisch HL (1994) Kinetics of simultaneous interpenetrating polymer networks of poly(dimethylsiloxane-urethane)/poly(methyl methacrylate) formation and studies of their phase morphology. Macromolecules 27(4) 938-946... 

An interpenetrating polymer network (IPN) consisting of an epoxy and an elastomer has been developed by Isayama.29 This is a two-component adhesive-sealant where the components are simultaneously polymerized. It consists of the MS polymer, developed in Japan by Kanegafuchi and commonly used in sealant formulations, with the homopolymerization of DGEBA using a phenol catalyst and a small amount of silane as a graft site to connect the MS polymer and epoxy homopolymer networks. 

Simultaneous Mixing or Reacting. One of the advantages of the proposed nomenclature is the preservation of the time sequence of polymer reactions. Examples include grafting reactions and interpenetrating polymer networks. In some cases, like the blends or random copolymerization, the time sequence has no meaning. 

A novel approach to IPN synthesis was reported by Sperling and Arnts (I). They synthesized two polymer networks by simultaneous yet independent reactions in the same container at the same time. Complicated interactions were eliminated in the SIN s by combining free radical (acrylate) and condensation (epoxy) polymerization. The present work uses the basic technique of Sperling and Amts. 

Independent Variables. Simultaneous synthesis of two polymer networks is a complex process. Many independent variables are available for study and not all could be explored in a limited investigation. The emphasis in the present study centers on those variables whose predominant effect is to influence the relative rates or gelation times of the reactions. Three independent variables were selected (a) the concentration of di-tert-butyl peroxide initiator was changed to vary the rate of polymerization of n-butyl acrylate (b) the epoxy mix was allowed to prereact for different lengths of time before the acrylate mix was added, and (c) the amount of DEGDM added to the acrylate mix was varied to control the gel time of the acrylate without significantly affecting its rate of polymerization. 

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