Monomer-polymer reaction

Theoretical Model for Determining Monomer-Polymer Reaction Stoichiometry from Equilibrium Gel Partition... 

Transition metal compound Main group metal compound Monomer Polymer Reaction conditions... 

The problems of monomer recovery, reaction medium viscosity, and control of reaction heat are effectively dealt with by the process design of Montedison Fibre (53). This process produces polymer of exceptionally high density, so although the polymer is stiU swollen with monomer, the medium viscosity remains low because the amount of monomer absorbed in the porous areas of the polymer particles is greatly reduced. The process is carried out in a CSTR with a residence time, such that the product k jd x. Q is greater than or equal to 1. is the initiator decomposition rate constant. This condition controls the autocatalytic nature of the reaction because the catalyst and residence time combination assures that the catalyst is almost totally expended in the reactor. 

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

A substantial fraction of commercially prepared methacrylic polymers are copolymers. Monomeric acryUc or methacrylic esters are often copolymerized with one another and possibly several other monomers. Copolymerization greatiy increases the range of available polymer properties. The aH-acryhc polymers tend to be soft and tacky the aH-methacryhc polymers tend to be hard and brittie. By judicious adjustment of the amount of each type of monomer, polymers can be prepared at essentially any desired hardness or flexibiUty. Small amounts of specially functionalized monomers are often copolymerized with methacrylic monomers to modify or improve the properties of the polymer directiy or by providing sites for further reactions. Table 9 lists some of the more common functional monomers used for the preparation of methacrylic copolymers. 

Copolymers. There are two forms of copolymers, block and random. A nylon block copolymer can be made by combining two or more homopolymers in the melt, by reaction of a preformed polymer with diacid or diamine monomer by reaction of a complex molecule, eg, a bisoxazolone, with a diamine to produce a wide range of multiple amide sequences along the chain and by reaction of a diisocyanate and a dicarboxybc acid (193). In all routes, the composition of the melt is a function of temperature and more so of time. Two homopolyamides in a moisture-equiUbrated molten state undergo amide interchange where amine ends react with the amide groups. 

Emulsion Polymerization. Emulsion and suspension reactions are doubly heterogeneous the polymer is insoluble in the monomer and both are insoluble in water. Suspension reactions are similar in behavior to slurry reactors. Oil-soluble initiators are used, so the monomer—polymer droplet is like a small mass reaction. Emulsion polymerizations are more complex. Because the monomer is insoluble in the polymer particle, the simple Smith-Ewart theory does not apply (34). 

Bulk polymerisation is heterogeneous since the polymer is insoluble in the monomer. The reaction is autocatalysed by the presence of solid polymer whilst the concentration of initiator has little effect on the molecular weight. This is believed to be due to the overriding effect of monomer transfer reactions on the chain length. As in all vinyl chloride polymerisation oxygen has a profound inhibiting effect. 

The use of light olefins, diolefins, and aromatic-based monomers for producing commercial polymers is dealt with in the last two chapters. Chapter 11 reviews the chemistry involved in the synthesis of polymers, their classification, and their general properties. This book does not discuss the kinetics of polymer reactions. More specialized polymer chemistry texts may be consulted for this purpose. 

Lack of termination in a polymerization process has another important consequence. Propagation is represented by the reaction Pn+M -> Pn+1 and the principle of microscopic reversibility demands that the reverse reaction should also proceed, i.e., Pn+1 -> Pn+M. Since there is no termination, the system must eventually attain an equilibrium state in which the equilibrium concentration of the monomer is given by the equation Pn- -M Pn+1 Hence the equilibrium constant, and all other thermodynamic functions characterizing the system monomer-polymer, are determined by simple measurements of the equilibrium concentration of monomer at various temperatures. 

Chain transfer is the reaction of a propagating radical with a non-radical substrate (X-Y, Scheme 6.1) to produce a dead polymer chain and a new radical (Y ) capable of initiating a polymer chain. The transfer agent (X-Y) may be a deliberate additive (e.g. a thiol) or it may be the initiator, monomer, polymer, solvent or an adventitious impurity. 

The first patent of Edwards and Robinson147 claims the condensations of pyromel-litic acid and aliphatic diamine salt to prepare polyimide. Recently, that approach has been revisited, and biphenyl tetracarboxylic and pyromellitic acids give a salt monomer by reaction with 1 mol of an aliphatic diamine (octamethylene diamine and dodecamethylene diamine). The salts were polymerized under 250 MPa at 250°C for 5 h in closed reaction vessels (Fig. 5.32) giving crystalline polymers.148 By reaction of pyromellitic tetraacid with oxydianiline, it has been possible to isolate a monomeric salt. It was polymerized under 30 MPa giving a PMDA-ODA polyimide with water elimination. 

Decreasing as the reaction temperature exceeded the glass transition temperature of the monomer polymer mixture. 

Monomeric actin binds ATP very tightly with an association constant Ka of 1 O M in low ionic strength buffers in the presence of Ca ions. A polymerization cycle involves addition of the ATP-monomer to the polymer end, hydrolysis of ATP on the incorporated subunit, liberation of Pi in solution, and dissociation of the ADP-monomer. Exchange of ATP for bound ADP occurs on the monomer only, and precedes its involvement in another polymerization cycle. Therefore, monomer-polymer exchange reactions are linked to the expenditure of energy exactly one mol of ATP per mol of actin is incorporated into actin filaments. As a result, up to 40% of the ATP consumed in motile cells is used to maintain the dynamic state of actin. Thus, it is important to understand how the free energy of nucleotide hydrolysis is utilized in cytoskeleton assembly. 

In the field of materials synthesis, T8[CH = CH2]8 has been used to prepare three-dimensional (meso)porous polymers with high surface area via reactions with TgHg or T8[OSiMe2H]8 in the presence of a Pt catalyst as described in Section Xu et al. prepared a POSS-based monomer by reaction... 

Another classification system, first suggested by Carothers in 1929, is based on the nature of the chemical reactions employed in the polymerisation. Here the two major groups are the condensation and the addition polymers. Condensation polymers are those prepared from monomers where reaction is accompanied by the loss of a small molecule, usually of water, for example polyesters which are formed by the condensation shown in Reaction 1.1. 

The authors concluded that the side reactions normally observed in amine-initiated NCA polymerizations are simply a consequence of impurities. Since the main side reactions in these polymerizations do not involve reaction with adventitious impurities such as water, but instead reactions with monomer, solvent, or polymer (i.e., termination by reaction of the amine-end with an ester side chain, attack of DMF by the amine-end, or chain transfer to monomer) [11, 12], this conclusion does not seem to be well justified. It is likely that the role of impurities (e.g., water) in these polymerizations is very complex. A possible explanation for the polymerization control observed under high vacuum is that the impurities act to catalyze side reactions with monomer, polymer, or solvent. In this scenario, it is reasonable to speculate that polar species such as water can bind to monomers or the propagating chain-end and thus influence their reactivity. 

All important electronically conducting polymers, except perhaps for polyacetylene, can be prepared electrochemically by anodic oxidation of the monomers. The reaction is initiated by splitting off two hydrogen atoms from the monomer molecule (H—M—H), which subsequently polymerizes by interconnecting thus activated sites ... 

Recently, Kolel-Veetil and Keller have modified this system to produce elastomeric networked polymers. The ambient-condition hydrosilation reactions between monomeric vinyl- or ethynyl-terminated carboranylenesiloxane and three different monomeric branched siloxane cross-linkers in hexane yielding these systems were catalyzed by the Karstedt catalyst.134 The reactions involving the vinyl-carboranylenesiloxane were reported to produce a set of completely hydrosilated networked polymers (105) (Fig. 65). In the case of the ethynyl monomer, the reactions were carried out at two different ratios, yielding a partially (106) and a com-... 

Shapiro remained true to his role of critical observer at the ISSOL conference in 2002 in Mexico there he expressed the opinion that the beginnings of life did not involve polymers at all (be they nucleic acids or proteins, or their hypothetical precursors pre-nucleic acids or pre-proteins), but initially involved interactions between monomers, the polymeric biomolecules being formed in later phases of molecular evolution. In this monomer world , reactions were supported by small biocatalysts (Shapiro, 2002). 

Chemical Crosslinking. Only linear polymers are produced from bifunctional monomers. The reaction system must include a polyfunctional monomer, i.e., a monomer containing 3 or more functional groups per molecule, in order to produce a crosslinked polymer. However, the polyfunctional reactant and/or reaction conditions must be chosen such that crosslinking does not occur during polymerization but is delayed until the fabrication step. This objective is met differently depending on whether the synthesis involves a chain or step polymerization. In the typical... 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

This second molecule might be a monomer, polymer, or solvent. Because of chain transfer the end of one polymer chain might be a hydrogen atom, and the beginning of the next the radical formed by removing the hydrogen atom from the solvent molecule. In the same paper, he proposed the two most probable chain termination reactions, mutual combination and disproportionation. 

Figure 2. Log-log plots of the conversion curves of acrylic acid in methanol solutions (4). Monomer concentrations (volume per cent) (1) 100% (2) 80% (3) 75% (4) 60% (5) 50% (6) 25% (7) 15%. The polymer precipitates as a fine powder for monomer concentrations of 100-75% it forms a swollen gel for 75—50% monomer the reaction medium is homogeneous for less than 50%...

Auto-acceleration is determined by a "catalytic" action of the polymer formed in the early stages of the reaction. The monomer selectively "solvates" the polymer to form a pre-oriented monomer-polymer complex in which propagation occurs at a much higher rate. At this point it seems difficult to determine to what extent the conclusions reached above can be generalized to other systems. Experiments along these lines are in progress. 

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