Catalyst polyester resin

The IPN elastomers were synthesized by the mixing of two components. In the case of two-component PU/E IPN elastomers, one component contained Nlax 31-28, Isonol-100, T-12 and epoxy catalyst (BFs-etherate, Eastman Chemical). The other component contained epoxy resin (DER-330, Dow Chemical) and Isonate-143L. Whereas In the case of three-component IPN elastomers composed of PU/E/UPE, polyester resin catalyst (TBPB) and unsaturated polyester resin were Incorporated, respectively. In the former and latter components. 

As a dibasic acid, malic acid forms the usual salts, esters, amides, and acyl chlorides. Monoesters can be prepared easily by refluxing malic acid, an alcohol, and boron trifluoride as a catalyst (9). With polyhydric alcohols and polycarboxyUc aromatic acids, malic acid yields alkyd polyester resins (10) (see Alcohols, polyhydric Alkyd resins). Complete esterification results from the reaction of the diester of maUc acid with an acid chloride, eg, acetyl or stearoyl chloride (11). 

The second largest use at 21% is for unsaturated polyester resins, which are the products of polycondensation reactions between molar equivalents of certain dicarboxyhc acids or thek anhydrides and glycols. One component, usually the diacid or anhydride, must be unsaturated. A vinyl monomer, usually styrene, is a diluent which later serves to fully cross-link the unsaturated portion of the polycondensate when a catalyst, usually a peroxide, is added. The diacids or anhydrides are usually phthahc anhydride, isophthahc acid, and maleic anhydride. Maleic anhydride provides the unsaturated bonds. The exact composition is adjusted to obtain the requked performance. Resins based on phthahc anhydride are used in boat hulls, tubs and spas, constmction, and synthetic marble surfaces. In most cases, the resins contain mineral or glass fibers that provide the requked stmctural strength. The market for the resins tends to be cychcal because products made from them sell far better in good economic times (see Polyesters,unsaturated). 

Uses. About 35% of the isophthahc acid is used to prepare unsaturated polyester resins. These are condensation products of isophthahc acid, an unsaturated dibasic acid, most likely maleic anhydride, and a glycol such as propylene glycol. The polymer is dissolved in an inhibited vinyl monomer, usually styrene with a quinone inhibitor. When this viscous hquid is treated with a catalyst, heat or free-radical initiation causes cross-linking and sohdification. A range of properties is possible depending on the reactants used and their ratios (97). 

Polyester resins can also be rapidly formed by the reaction of propylene oxide (5) with phthaUc and maleic anhydride. The reaction is initiated with a small fraction of glycol initiator containing a basic catalyst such as lithium carbonate. Molecular weight development is controlled by the concentration of initiator, and the highly exothermic reaction proceeds without the evolution of any condensate water. Although this technique provides many process benefits, the low extent of maleate isomerization achieved during the rapid formation of the polymer limits the reactivity and ultimate performance of these resins. 

Catalyst Selection. The low resin viscosity and ambient temperature cure systems developed from peroxides have faciUtated the expansion of polyester resins on a commercial scale, using relatively simple fabrication techniques in open molds at ambient temperatures. The dominant catalyst systems used for ambient fabrication processes are based on metal (redox) promoters used in combination with hydroperoxides and peroxides commonly found in commercial MEKP and related perketones (13). Promoters such as styrene-soluble cobalt octoate undergo controlled reduction—oxidation (redox) reactions with MEKP that generate peroxy free radicals to initiate a controlled cross-linking reaction. 

Benzoin, [119-53-9] 2-hydroxy-2-phenylacetophenone, CgH CH(OH)COCgH (mp, 133—137°C bp, 343—344°C at 101.3 kPa), is formed by the self-condensation of benzaldehyde in the presence of potassium cyanide. It is used on a small scale as a polymerization catalyst in polyester resin manufacture. 

Cobalt salts are used as activators for catalysts, fuel cells (qv), and batteries. Thermal decomposition of cobalt oxalate is used in the production of cobalt powder. Cobalt compounds have been used as selective absorbers for oxygen, in electrostatographic toners, as fluoridating agents, and in molecular sieves. Cobalt ethyUiexanoate and cobalt naphthenate are used as accelerators with methyl ethyl ketone peroxide for the room temperature cure of polyester resins. 

This is also known as Bulk Moulding Compound (BMC). It is blended through a mix of unsaturated polyester resin, crosslinking monomer, catalyst, mineral fillers and short-length fibrous reinforcement materials such as chopped glass fibre, usually in lengths of 6-25 mm. They are all mixed in different proportions to obtain the required electromechanical properties. The mix is processed and cured for a specific time, under a prescribed pressure and temperature, to obtain the DMC. 

An interest has been developed in the use of vanadium naphthenates as accelerators. In 1956 the author found that if MEKP was added to a polyester resin containing vanadium naphthenate the resin set almost immediately, that is, while the peroxide was still being stirred in. Whereas this effect was quite reproducible with the sample of naphthenate used, subsequent workers have not always obtained the same result. It would thus appear that the curing characteristics are very dependent on the particular grade of resin and of vanadium naphthenate used. It was also observed by the author that the gelation rate did not always increase with increased temperature or accelerator concentration and in some instances there was a retardation. Subsequent workers have found that whilst the behaviour of the naphthenate varies according to such factors as the resin and catalyst used, certain vanadium systems are of value where a high productivity in hand lay-up techniques is desired. 

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. 

Unsaturated polyesters The formation of the coating occurs in situ by the reaction between polyester resin and styrene, activated by a catalyst such as organic peroxide. The main use as coatings is in the formation of glass fiber or glass flake, reinforced plastics. 

Coating materials may be based on short or medium-oil alkyds (e.g. primers for door and window frames) nitrocellulose or thermoplastic acrylics (e.g. lacquers for paper or furniture finishes) amino resin-alkyd coatings, with or without nitrocellulose inclusions, but with a strong acid catalyst to promote low temperature cure (furniture finishes) two-pack polyurethanes (furniture, flat boards) unsaturated polyester resins in styrene with free-radical cure initiated by peroxides (furniture) or unsaturated acrylic oligomers and monomers cured by u.v. radiation or electron beams (coatings for record sleeves paperback covers, knock-down furniture or flush interior doors). 

Paraplex Resin-Bonded Explosive. Usually consists of Paraplex P-43/RDX/Al/Styrene monomer/ Lupersol DDM (as a polymerization catalyst) in the following percentages, viz 6.0/65.0/ 20.0/9.0/0.5. Density 1.65g/cc. The material is mixed and polymerized using the usual procedure for polyester resins and Plastic Bonded Expls (see in this Vol)... 

An unsaturated polyester resin consists of a linear polyester whose chain contains double bonds and an unsaturated monomer such as styrene that copolymerizes with the polyester to provide a cross-linked product. The most common unsaturated polyester is made by step growth polymerization of propylene glycol with phthalic and maleic anhydrides. Subsequent treatment with styrene and a peroxide catalyst leads to a solid, infusible thermoset. 

It has been used as a room or low temp catalyst for polymerization of polyester resins Ref Lucidol Division, Novadel-Agene Corp, Buffalo, NY, Organic Peroxides, Data Sheets No 18 (1948) and No 32 (1950)... 

The ignition temperature of a sample of the mixture of KC104 with unsaturated polyester resin introduced into a thermostat heated to 296°C, in relation to time, is shown in Fig. 117 (curve I). The curve resembles that given by Roginskii for nitroglycerine heated at 41 °C in the presence of nitric acid as a catalyst (Vol. II,. Fig. 11, p. 48). Here the temperature of the sample just before the explosion was 298°C,... 

The binder itself (Genpol A-20 polyester resin, styrene and methyl acrylate) was combined with the necessary polymerization catalyst (methyl ethyl ketone peroxide) and an accelerator (cobalt octoate or naphthenate). 

Zinc Nitrate. See in Vol 8, N40-L and the following Addnl Refs 1) G.W. Batchelder G.A. Zimmerman, Smokeless Propellant Compositions Containing a Polyester Resin , USP 3653993 (1972) CA 79,77449 (1973) [The inventors claim that Zn nitrate acts as the burning rate catalyst in their propint formulation. Thus, the addn of 0.1% Zn nitrate to a propint contg AN (45), amm dichromate (5%), a polyester, styrene, methacrylate and lecithin increased this parameter from 0.07 to 0.11 indies/ sec] 2) Anon, Fire Protection. . . 7th Edition , NFPA, Boston (1979), 491M-445 [This source reports that Zn nitrate will expld if sprinkled on hot C. Also, that heat, shock and friction sensitive expls are formed when the nitrate is intimately mixed with the following finely divided materials Cu, metal sulfides, organic matter, P and S]... 

PS PSF PSU PTFE PU PUR PVA PVAL PVB PVC PVCA PVDA PVDC PVDF PVF PVOH SAN SB SBC SBR SMA SMC TA TDI TEFE TPA UF ULDPE UP UR VLDPE ZNC Polystyrene Polysulfone (also PSU) Polysulfone (also PSF) Polytetrafluoroethylene Polyurethane Polyurethane Poly(vinyl acetate) Poly(vinyl alcohol) poly(vinyl butyrate) Poly(vinyl chloride) Poly(vinyl chloride-acetate) Poly(vinylidene acetate) Poly(vinylidene chloride) Poly(vinylidene fluoride) Poly(vinyl fluoride) Poly(vinyl alcohol) Styrene-acrylonitrile copolymer Styrene-butadiene copolymer Styrene block copolymer Styrene butadiene rubber Styrene-maleic anhydride (also SMC) Styrene-maleic anhydride (also SMA) Terephthalic acid (also TPA) Toluene diisocyanate Ethylene-tetrafluoroethylene copolymer Terephthalic acid (also TA) Urea formaldehyde Ultralow-density polyethylene Unsaturated polyester resin Urethane Very low-density polyethylene Ziegler-Natta catalyst... 

C-4 Chemistry (Butanes, Butylenes, Butadiene). Maleic anhydride is the main chemical made from w-butane. A complex catalyst is used for the oxidation reaction. The major uses for maleic anhydride are the making of unsaturated polyester resins (by reaction with glycol and phthalic anhydride) and tetrahydrofuran (by hydrogenation). 

Two resins were used to do the first study on laminate construction. The first was a brominated epoxy vinyl ester resin with antimony pentoxide and the second was a brominated unsaturated polyester resin. They were both promoted to cure at room temperature with methyl ethyl ketone peroxide catalyst. The panels were then postcured at 250°F (121°C) for 8 h. Panels were prepared that varied in glass content from 25% to 70% and panel thickness varying from 0.05 in. to 0.25 in. and were tested at the same testing facility. A summary of the FSI test data for the first set of panels tested are shown in Figures 23.1 and 23.2. This graph in Figure 23.1 plots the FSI value versus the panel thickness. This data would indicate that the thickness of the test panel has no effect on the measured... 

Simultaneous IPN was obtained by dissolving BPA/DC in an unsaturated polyester resin (UPR) and crosslinking at elevated temperature using benzoyl peroxide and a zinc compound as cyclotrimerization catalyst. Prolonged post-curing at 180 °C was needed to reach elevated Tg values [132, 133],... 

Polyesterification. High molecular weight linear polyester resins, such as poly(ethylene terephthalate) (PET), poly(propylene terephthalate) (PPT), and poly(butylene terephthalate) (PBT), can be produced by either transesterification of dimethyl terephthalate (DMT) with an excess of the corresponding diol or by direct esterification of terephthalic acid (TPA). Tetraalkyl titanates, such as TYZOR TPT or —TYZOR TBT, have been found to be excellent catalysts for either of these reactions. However, in the case of PET, the residual titanate catalyst reacts with trace quantities of aldehydic impurities produced in the polymerization process to generate a yellow discoloration of the polymer (468,469). In the case of PPT and PBT, where the color of polymer is not as critical, organic titanates are the catalyst of choice because of their greater reactivity than antimony or tin (470). Numerous processing variations have been described in the literature to minimize formation of tetrahydrofuran in the PBT process (471—472). 

Dialkylperoxides are used as high temperature catalysts for suspension and bulk polymerization as well as hardeners for unsaturated polyester resins and for cross-linking polymers because of their good thermal stability. While the liquid di-tert-butylperoxide is relatively volatile at application temperatures, dicumylperoxide is much less volatile and has the disadvantage of forming decomposition products with intense odors (acetophenone)(Chapter 13). 

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