ACRYLIC ESTER POLYMER

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 

Historically, the development of the acrylates proceeded slowly they first received seiious attention from Otto Rohm. Acrylic acid (propenoic acid) was first prepared by the ah oxidation of acrolein in 1843 (1,2). Methyl and ethyl acrylate were prepared in 1873, but were not observed to polymerize at that time (3). In 1880 poly(metliyl acrylate) was reported by G. W. A. Kahlbaum, who noted that on dry distillation up to 320°C the polymer did not depolymerize (4). Rohm observed the remarkable properties of acrylic polymers while preparing for his doctoral dissertation in 1901 however, a quarter of a century elapsed before he was able to translate his observations into commercial reality. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Robin s laboratory, the first limited production of acrylates began in 1927 by the Rohm and Haas Company in Darmstadt, Germany (6). Use of this class of compounds has grown from that time to a total U.S. consumption in 1989 of approximately 400,000 metric tons. Total worldwide consumption is probably twice that. 

To a large extent, the properties of acrylic ester polymers depend on the nature of the alcohol radical and the molecular weight of the polymer. As is typical of polymeric systems, the mechanical properties of acrylic polymers improve as molecular weight is increased however, beyond a critical molecular weight, which often is about 100,000 to 200,000 for amorphous polymers, the improvement is slight and levels off asymptotically. 

Glass Transition. The glass-transition temperature T reflects the mechanical properties of polymers over a specified temperature range. 

Below T polymers are stiff, hard, brittle, and glass-like above 7. if the molecular weight is high enough, they are relatively soft, limp, stretchable, and can be somewhat elastic. At even higher temperatures they flow and are tacky. Methods used to determine glass-transition temperatures and the reported values for a large number of polymers may be found in References 7—9. Values for the T of common acrylate homopolymers are found in Table 1. 

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ACRYLONITRILEPOLYMMRS - SURVEY AND SAN (STYRENE-ACRYLONITRILECO-POLYMMRS)] (Vol 1) -acrylic ester copolymerization [ACRYLIC ESTER POLYMERS - SURVEY] (Vol 1)... 

The polymeric products can be made to vary widely in physical properties through controlled variation in the ratios of monomers employed in thek preparation, cross-linking, and control of molecular weight. They share common quaHties of high resistance to chemical and environmental attack, excellent clarity, and attractive strength properties (see Acrylic ester polymers). In addition to acryHc acid itself, methyl, ethyl, butyl, isobutyl, and 2-ethylhexyl acrylates are manufactured on a large scale and are available in better than 98—99% purity (4). They usually contain 10—200 ppm of hydroquinone monomethyl ether as polymerization inhibitor. 

Acrylic Ester Polymers, 2-Cyanoacrylic Ester Polymers" ia ECT 3rd ed., VoL 1, pp. 408—413, by H. W. Coover, Jr., andj. M. Mclatire, Tennessee Eastman Company. 

Anaerobic stmctural adhesives are typically formulated from acryhc monomers such as methyl methacrylate [80-62-6] C Hg02, and methacrylic acid [79-41-4] (see Acrylic ester polymers). Very often, cross-linking agents such as dimethacrylates are also added. A peroxide, such as cumene... 

The medium is the binder which provides for the adhesion of pigments. The most important types are the temper media (glue, egg, and gum), the oils, and wax. In addition, for wall painting there is the tme fresco technique, where the pigments are laid down in a fresh, wet plaster preparation layer. Several other media have been used, but much less frequendy, eg, casein temper. In modem paints, a number of synthetic resins are used for this purpose. Contemporary artist paints are often based on acryhc polymers (see Acrylic ester polymers Paints). 

The most common VI improvers are methacrylate polymers and copolymers, acrylate polymers (see Acrylic ester polymers), olefin polymers and copolymers, and styrene—butadiene copolymers. The degree of VI improvement from these materials is a function of the molecular weight distribution of the polymer. VI improvers are used in engine oils, automatic transmission fluids, multipurpose tractor fluids, hydrautic fluids, and gear lubricants. Their use permits the formulation of products that provide satisfactory lubrication over a much wider temperature range than is possible using mineral oils alone. 

Itaconic acid, anhydride, and mono- and diesters undergo vinyl polymerization. Rates of polymerization and intrinsic viscosities of the resulting homopolymers ate lower than those of the related acrylates (see Acrylic ester polymers) (8,9). 

AH-acryHc (100%) latex emulsions are commonly recognized as the most durable paints for exterior use. Exterior grades are usuaHy copolymers of methyl methacrylate with butyl acrylate or 2-ethyIhexyl acrylate (see Acrylic ester polymers). Interior grades are based on methyl methacrylate copolymerized with butyl acrylate or ethyl acrylate. AcryHc latex emulsions are not commonly used in interior flat paints because these paints typicaHy do not require the kind of performance characteristics that acryHcs offer. However, for interior semigloss or gloss paints, aH-acryHc polymers and acryHc copolymers are used almost exclusively due to their exceUent gloss potential, adhesion characteristics, as weU as block and print resistance. 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

Acrylic ESTER POLYMERS Acrylonitrile POLYMERS Cellulose esters). Engineering plastics (qv) such as acetal resins (qv), polyamides (qv), polycarbonate (qv), polyesters (qv), and poly(phenylene sulfide), and advanced materials such as Hquid crystal polymers, polysulfone, and polyetheretherketone are used in high performance appHcations they are processed at higher temperatures than their commodity counterparts (see Polymers containing sulfur). 

Polymerization of Butyl Acrylate. An aqueous solution of K2S20g and a solution of butyl acrylate [141-32-2] and catalytic amounts of Ahquat 336 in ethyl acetate are heated at 55°C (28) (see Acrylic Ester Polymers). 

The thermoplastic or thermoset nature of the resin in the colorant—resin matrix is also important. For thermoplastics, the polymerisation reaction is completed, the materials are processed at or close to their melting points, and scrap may be reground and remolded, eg, polyethylene, propjiene, poly(vinyl chloride), acetal resins (qv), acryhcs, ABS, nylons, ceUulosics, and polystyrene (see Olefin polymers Vinyl polymers Acrylic ester polymers Polyamides Cellulose ESTERS Styrene polymers). In the case of thermoset resins, the chemical reaction is only partially complete when the colorants are added and is concluded when the resin is molded. The result is a nonmeltable cross-linked resin that caimot be reworked, eg, epoxy resins (qv), urea—formaldehyde, melamine—formaldehyde, phenoHcs, and thermoset polyesters (qv) (see Amino resins and plastics Phenolic resins). 

In the adhesives market growth has been slower than in other segments. Increasing competition from other materials, most notably polyurethanes and acryhcs, is affecting the market (see Acrylic ester polymers Urethane polymers). 

A large number of organic acrylic ester polymer have been prepared in the laboratory. Poly (methyl acrylate) is tough, leathery and flexible. With increase in chain length there is a drop in the brittle point but this reaches a minimum with poly-(n-octyl acrylate) (see Figure 15.12.). The increase in brittle point with the higher acrylates, which is similar to that observed with the poly-a-olefins and the poly(alkyl methacrylate)s, is due to side-chain crystallisation. 

COLUMN SELECTION AND RELATED ISSUES FOR ACRYLIC ACID AND ACRYLATE ESTER POLYMERS... 

YHiile THF is the solvent of choice for ordinary acrylate ester polymers, there are numerous monomers that can be incorporated into those acrylic polymers that cause problems either with solubility or with adsorption onto the stationary phase. In some cases, these problems can be overcome by switching to a solvent other than THF. 

Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterifying alkyl acrylate polymers with 4-morpholinethanol or alkanolamines and fatty alcohols or alkoxyl-ated alkylphenols and neutralizing with phosphoric acid. This polymer salt (pH of a 10% aqueous solution = 5.1) was used as an emulsifying agent for oils and waxes [70]. 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

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