Bisphenol polyols

The basic metal salts and soaps tend to be less cosdy than the alkyl tin stabilizers for example, in the United States, the market price in 1993 for calcium stearate was about 1.30— 1.60, zinc stearate was 1.70— 2.00, and barium stearate was 2.40— 2.80/kg. Not all of the coadditives are necessary in every PVC compound. Typically, commercial mixed metal stabilizers contain most of the necessary coadditives and usually an epoxy compound and a phosphite are the only additional products that may be added by the processor. The requited costabilizers, however, significantly add to the stabilization costs. Typical phosphites, used in most flexible PVC formulations, are sold for 4.00— 7.50/kg. Typical antioxidants are bisphenol A, selling at 2.00/kg Nnonylphenol at 1.25/kg and BHT at 3.50/kg, respectively. Pricing for ESO is about 2.00— 2.50/kg. Polyols, such as pentaerythritol, used with the barium—cadmium systems, sells at 2.00, whereas the derivative dipentaerythritol costs over three times as much. The P-diketones and specialized dihydropyridines, which are powerful costabilizers for calcium—zinc and barium—zinc systems, are very cosdy. These additives are 10.00 and 20.00/kg, respectively, contributing significantly to the overall stabilizer costs. Hydrotalcites are sold for about 5.00— 7.00/kg. 

Specialty Epoxy Resins. In addition to bisphenol, other polyols such as aUphatic glycols and novolaks are used to produce specialty resins. Epoxy resins may also include compounds based on aUphatic, cycloaUphatic, aromatic, and heterocycHc backbones. Glycidylation of active hydrogen-containing stmctures with epichlorohydrin and epoxidation of olefins with peracetic acid remain the important commercial procedures for introducing the oxirane group into various precursors of epoxy resins. 

A rare example of cationic polymerization of emulsified epoxy resins has been reported by Walker et al.973 Polymerization of water emulsion of epoxy resins with a variety of superacids (triflic acid, HCIO4, HBF4, HPF6) results in polyols with two glycidyl units (294) in contrast to commercial epoxy resins with one unit separating the aromatic moieties. The level of residual glycidyl ether and Bisphenol-A units is also much lower than in conventional epoxy resins. 

Liquefaction of untreated wood can also be achieved at a lower temperature of 150°C and at atmospheric pressure in the presence of a catalyst [12]. Phenolsulfonic acid, sulfuric acid, hydrochloric acid, and phosphoric acid were used as catalysts. In this acid catalyst method, phenols and polyhydric alcohols can also be used for the coexisting organic solvents. Phenol, cresol, bisphenol A and F, and so forth are successfully adoptable as the phenols. Polyethylene glycols, polyether polyols (epoxide additionally reacted polyether polyol, polyethylene terephthalate polyol) have been found to liquify wood resulting in polyol solutions [13]. Liquefaction of wood in the presence of -caprolactone, glycerin, and sulfuric acid has also been accomplished. It was confirmed in this case that liquefaction and polymerization, the latter of which produces polycaprolactone, take place in the reaction system at the same time [14]. Besides the wood material, it has become apparent that trunk and coconut parts of palm, barks, bagasse, coffee bean wastes, and used OA papers can also be liquified [15]. 

The IPNs prepared were composed of a rubbery polyurethane and a glassy epoxy component. For the polyurethane portion, a carbodiimide-modified diphenyl-methane diisocyanate (Isonate 143L) was used with a polycaprolactone glycol (TONE polyol 0230) and a dibutyltin dilaurate catalyst (T-12). For the epoxy, a bisphenol-A epichlorohydrin (DER 330) was used with a Lewis acid catalyst system (BF -etherate). The catalysts crosslink via a ring-opening mechanism and were intentionally selected to provide minimum grafting with any of the polyurethane components. The urethane/epoxy ratio was maintained constant at 50/50. A number of fillers were included in the IPN formulations. The materials used are shown in Table I. 

Rapra Technology Ltd has undertaken a detailed investigation into the migration of species from different types of adhesives used with laminated multi-layer materials (Barber et al, 2003). Migration of aromatic amines, BADGE, bisphenol A and polyols were examined. A description of the samples used and a brief summary of some of the results obtained from this analytical work are given below. 

Epoxy resins based on glycidylation of bisphenols, cresol and phenol novolacs, polycarboxylic acids, polyols, amines, and aminophenols have been long known. Epoxidized linear and cyclic olefins have also been used as specialty epoxy resins. More recently, glycidylated heterocycles have been introduced, initially as specialty resins promising improved resistance to weathering. One heterocycle in particular, the hydantoin ring, has become of particular interest as an epoxy substrate (J ). 

The aromatic nuclei of the bisphenol A segment have a high affinity for the aromatic nuclei of styrene - ACN copolymer styrene units, the polyether chains having a strong interaction with the liquid poly ether medium. As an immediate consequence, the structure 6.15 assures a good steric stabilisation of polymeric dispersions in liquid polyether polyols (see the structure in Figure 6.6). 

The preferred polyol is a polyether triol (MW of 4700-5000 daltons), with a terminal poly[EO] block (13-15% EO). The preferred epoxy resin is a liquid one, the diglycidyl ether of bisphenol A (DGBA), and the hardener is ethylenediamine (EDA). The molar ratio of epoxy resin EDA is around 0.8-1 1. 

By solubilisation of propoxylated bisphenol A with the structure 15.28, in a sucrose-based polyether polyol for rigid foams, an homogeneous mixture is obtained [29]. The viscosities of these mixtures increase with the content of propoxylated bisphenol A. From these mixtures rigid PU foams were obtained. Due to the aromaticity introduced by the propoxylated bisphenol A, the physico-mechanical properties of the resulting rigid PU foams were superior to the rigid PU foams made with the sucrose-based poly ether polyol alone [29]. 

An excellent polyol for urethane isocyanuric foams is a diol based on bisphenol A, alkoxylated with 8-9 mols of EO or with 4 mols of PO and 4-5 mols of EO (structures 15.31 and 15.32). 

Bisphenol A is a compound with a melting point of around 157 °C, which is higher than the normal alkoxylation temperatures (90-120 °C). Bisphenol A can be alkoxylated in a liquid reaction medium such as an inert solvent (toluene, xylene) or in a reactive liquid reaction medium such as PO or in the final polyether polyol [28, 30]. 

A third process of solid bisphenol A alkoxylation is to use a suspension of solid bisphenol A in final polyether polyol (40-60% bisphenol A and 60-40% liquid polyether diol). This suspension, in the presence of a tertiary amine as catalyst, is ethoxylated at 80-95 °C, with 8-9 mols of EO/mol of bisphenol A. At the end of the reaction, all the solid bisphenol A was totally transformed into liquid polyether diols [30]. The resulting polyether diols are used successfully for production of urethane-isocyanuric foams with very good physico-mechanical properties and intrinsic fire resistance. 

Very interesting polyols for rigid PU foams are obtained by the simultaneous alkoxylation with PO (or EO) of a mixture from bisphenol A and a costarter, such as bisphenol A... 

Simultaneous alkoxylation of bisphenol A and an aromatic amine as second polyol is a variation used to obtain highly aromatic polyols. 

Antioxidants. Certain components of heat stabilizers (polyols, phosphites) also serve as antioxidants. The protection against oxidative attack is not as great in PVC as it is in certain ethylenically unsaturated materials. However, PVC compounds may require protection in the high-temperature service as in electrical wire insulation bisphenol A is often incorporated into the plasticizer for this purpose. Impact modifiers containing unsaturation such as acrylonitrile-butadiene-styrene polymers often require antioxidant protection. Hindered phenols such as butylated hydroxytoluene are often used for this purpose, especially when outdoor applications are involved. 

Methacrylate esters have been prepared by the reaction of methacrylic acid with epoxies such as the diglycidyl ethers of bisphenol A (XXXVII) [37]. Methacrylate esters suitable for anaerobic adhesives have also been prepared by the reaction of glycidyl methacrylate (XXXVIII) with a hydroxyl-terminated polyester [38]. The reaction of isocyanatoethyl methacrylate (XXXIX) with polyols resulted in monomers that could be formulated into anaerobic adhesives and sealants [39]. 

Chem. Descrip. Bisphenol A-based polyol Uses Diluent, wetting agent, flow aid, mar resist, aid, impact strengthener, pot life extender, adhesion promoter on substrates, flexibilizer for coatings, low-VOC applies. 

Chem. Descrip. Bisphenol A-based polyol (6 mole ethoxylate)... 

Using a mixture of castor oil and hydroxyether of bisphenol-A (HBA) as the polyol and reacting with TDI in the presence of DBTDL catalyst at 35°C, a series of polyurethanes are prepared in an air-circulating oven for 48 h. A series of poly(urethane urea)-vinyl polymer hybrid aqueous dispersions are prepared. Waterborne poly(urethane urea) is synthesised from castor oil and polyoxypropylene polyol M = 1000 g moL ), dimethylol propionic acid and isophorone diisocyanate and then neutralised with tertiary amine. The hybrid aqueous dispersion with high oil content poly(urethane urea) exhibits excellent compressive mechanical strength. Sunflower oil-modified waterborne polyurethane resin may also be prepared. The waterborne resin is synthesised from the monoglyceride of the oU, poly(propylene-ethylene) triol, tartaric acid and toluene diisocyanate, then neutralised with triethyl amine. 

A variety of poly/dihydric oils are used for the preparation of glyddyl ether-type epoxy resins. These include bisphenols, namely bisphenol-A (BPA), bisphenol-F (BPF), bisphenol-S (BPS) and bisphenol-H (BPH) and so on. Other aromatic diols and polyols such as phenolic resin, MF resins and hyperbranched polyol may also be used in the preparation of vegetable oil-based epoxy resins. Bisphenol-A (2,2-bis(4-hydroxyphenyl)propane) is one of the most widely used aromatic diols for the synthesis of epoxy resin. The resins are commonly used as lacquers for coated metal products such as food cans, bottle tops and water pipes. There are also reports on the use of bisphenol-S (BPS) (bis(4-hydroxyphenyl) sulphone), in the synthesis of epoxy resin. The advantages of resistance to deformation by heat and improvement of thermal stability were observed for such epoxy resins. The presence of sulphone group (BPS-based epoxy resin) in the epoxy resin exhibits better gel time than BPA-based epoxy. Another important diol, namely bis(4-hydroxydiphenyl)methane or bisphenol-F (BPF) is used for the synthesis of low viscosity epoxy resins. BPF generally comprises several isomers such as bis(2-hydroxylphenyl)methane (i.e. ortho-ortho isomer), bis(4-hydroxylphenyl)methane (i.e. para-para isomer) and... 

The base methacrylate monomers utilized were a polyethyleneglycol dimethacrylate (PEGMA - produced by Loctite), an ethoxylated bisphenol—A dimethacrylate (EBIPMA - produced by AKZO), a urethane methacrylated capped poly(butadiene acrylonitrile) polyol, and hydroxy-propyl methacrylate (HPMA - Rohm and Haas). The following maleimide capped monomer/prepolymers were examined N-phenyl maleimide (NPM), meta-phenylene dimaleimide (m-PDM), and a reaction product of methylenedi-aniline and excess methylenedianiline bismaleimide (P-MDA-2MDABM), sold by Rhodia Corp. under the tradename of Keramide... 

Miscellaneous Stabilizers. A variety of other stabihzers are vaguely mentioned in the literature, mainly by vendors. Polyols and organo-nitrogen compounds may be added to complex iron impurities in fillers and keep them from catalyzing degradation of PVC. Other additives are more secretive and their benefits less clear. Bisphenol is added to wire and cable insulation to stabilize the plasticizer rather than the PVC. UV stabilizers may be added for outdoor use, and biostabilizers are important to protect the plasticizer. 

---