Solution-polymerized cement

Solution Polymerization. This method is not commercially important, although it is convenient and practical, because it provides viscous cements that are difficult to handle. Also, the choice of the solvent is a key parameter due to the high solvent chain-transfer constants for acrylates. 

Polymeric Calcium Phosphate Cements. Aqueous solutions of polymers such as poly(acryHc acid), poly(vinyl alcohol), gelatin, etc, and/or autopolymerizable monomer systems, eg, 2-hydroxyethyl methacrylate, glycerol dimethacrylate, calcium dimethacrylate, etc, have been used as Hquid vehicles (41,42,76) for the self-setting calcium phosphate cement derived from tetracalcium phosphate and dicalcium phosphate [7757-93-9J. 

Chemical Reactivity - Reactivity with Water Dissolves and forms a weak solution of hydrofluoric acid Reactivity with Common Materials In presence of moisture will corrode glass, cement and most metals. Flammable hydrogen gas may collect in enclosed spaces Stability During Transport Stable Neutralizing Agents for Acids and Caustics Flush with water, rinse with dilute solution of sodium of sodium bicarbonate or soda ash Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Organic peroxide-aromatic tertiary amine system is a well-known organic redox system 1]. The typical examples are benzoyl peroxide(BPO)-N,N-dimethylani-line(DMA) and BPO-DMT(N,N-dimethyl-p-toluidine) systems. The binary initiation system has been used in vinyl polymerization in dental acrylic resins and composite resins [2] and in bone cement [3]. Many papers have reported the initiation reaction of these systems for several decades, but the initiation mechanism is still not unified and in controversy [4,5]. Another kind of organic redox system consists of organic hydroperoxide and an aromatic tertiary amine system such as cumene hydroperoxide(CHP)-DMT is used in anaerobic adhesives [6]. Much less attention has been paid to this redox system and its initiation mechanism. A water-soluble peroxide such as persulfate and amine systems have been used in industrial aqueous solution and emulsion polymerization [7-10], yet the initiation mechanism has not been proposed in detail until recently [5]. In order to clarify the structural effect of peroxides and amines including functional monomers containing an amino group, a polymerizable amine, on the redox-initiated polymerization of vinyl monomers and its initiation mechanism, a series of studies have been carried out in our laboratory. 

Another development has been the advent of the dual-cure resin cements. These are hybrids of glass polyalkenoate cements and methacrylates that set both by an add-base cementation reaction and by vinyl polymerization (which may be initiated by light-curing). In these materials, the solvent is not water but a mixture of water and hydroxyethylmethacrylate which is capable of taking dimethacrylates and poly(acrylic add)-containing vinyl groups into solution. In the absence of light these materials set slowly and... 

The most common poly(alkenoic acid) used in polyalkenoate, ionomer or polycarboxylate cements is poly(acrylic acid), PAA. In addition, copolymers of acrylic acid with other alkenoic acids - maleic and itaconic and 3-butene 1,2,3-tricarboxylic acid - may be employed (Crisp Wilson, 1974c, 1977 Crisp et al, 1980). These polyacids are prepared by free-radical polymerization in aqueous solution using ammonium persulphate as the initiator and propan-2-ol (isopropyl alcohol) as the chain transfer agent (Smith, 1969). The concentration of poly(alkenoic add) is kept below 25 % to avoid the danger of explosion. After polymerization the solution is concentrated to 40-50 % for use. 

The most important of these are the refractory cements formed by the heat treatment of aluminium acid phosphate solutions. This subject has been well reviewed by Kingery (1950a), Morris et al. (1977), Cassidy (1977) and O Hara, Duga Sheets (1972). The chemistry of these binders is extremely complex as the action of heat on acid phosphates gives rise to polymeric phosphates, with P-O-P linkages, and these are very complex systems (Ray, 1979). 

Here we are concerned with the cement-forming reaction between orthophosphoric acid solutions and basic oxides and silicates where the reaction is much simpler. Polymeric phosphates are not involved, there are no P-O-P bonds, and the structural unit is the simple [POJ tetrahedron. 

We have noted earlier that aluminium is unusual in forming alumino-phosphate complexes in phosphoric acid solution which may be of a polymeric nature. Bearing in mind the analogies between aluminium phosphate and silica structures, it may well be that during cement formation an aluminium phosphate hydrogel is formed. Its character may be analogous to that of silica gel, where a structure is built up by the... 

There are six stabilization techniques currently available however, only two of them have found widespread application. These are cementation and stabilization through the addition of lime and fly ash.25 26 There is currently developmental work being undertaken to make use of bitumen, paraffin, and polymeric materials to reduce the degree to which metals can be taken into solution. Encapsulation with inert materials is also under development. 

Suspension polymerization also is used When acrylic monomers or their mixtures with other monomers are polymerized while suspended (usually in aqueous system), the polymeric product is obtained m the form of small beads, sometimes called pearls or granules. Bead polymers are the basis of the production of molding powders and denture materials. Polymers derived from acrylic or methacrylic acid furnish exchange resins of the carboxylic acid type. Solutions in organic solvents furnish lacquers, coatings and cements, while water-soluble hydrolysates are used as thickeners, adhesives, and sizes. 

The ampoules were removed from the bath at the desired time and opened. The polymerizations were shortstopped by quickly pouring the polymer cement into 30% of its volume of a 0.15M solution of ammonia gas in THF. This cement was then evaporated in air and finally dried in a vacuum oven to constant weight. 

These cements are formed by a similar process to the silicate minerals described in Chapter 1, the difference being the rate. Silicate minerals are formed at a rate lower by orders of magnitude compared with dental cements. In the case of dental cements, the phosphoric acid releases protons in the solution and lowers its pH. This decomposes the glass and releases silicon in the solution, and silicic acid forms as an intermediate product [26,27]. Simultaneously, cations such as Ap, Ca " ", and Na" " and the anion F are also released [28]. The cations and anions are attracted to each other, and neutral bonding phases form. Such a bonding network, especially that of aluminum, results in gelation and subsequent polymerization of a hard product. 

Preparation of the primary oligomeric clusters has been discussed in terms of the association of the ions in electrolyte solutions or condensation-mediated ion clustering. Dependent on the electrolyte concentration and the physicochemical state (P, T, pS, pH, pi, pCl, pc, pe) of the system, the ions associate to polymeric species or then the ion clusters may reach the critical size that enables them to grow to primary particles of some 100 mn in size. As discussed, they are probably a coagulate of cemented crystallites of 1 to 10 mn size. However, to be useful for further processing, these must be stabilized to sols, i.e., to a stable dispersion of particles of colloidal (10 to 1000 mn) size. There are basically two approaches for the stabilization ... 

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