Aromatic monomer resins

Aromatic monomer resins which are highly saturated and purified are light in color and have excellent heat, light and oxygen resistance. Some examples of these products are Kristalex and Piccotex resins (Hercules Chemicals). 

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Catalysts used in the polymerization of C-5 diolefins and olefins, and monovinyl aromatic monomers, foUow closely with the systems used in the synthesis of aHphatic resins. Typical catalyst systems are AlCl, AIBr., AlCl —HCl—o-xylene complexes and sludges obtained from the Friedel-Crafts alkylation of benzene. Boron trifluoride and its complexes, as weU as TiCl and SnCl, have been found to result in lower yields and higher oligomer content in C-5 and aromatic modified C-5 polymerizations. 

The conversion of aromatic monomers relative to C-5—C-6 linear diolefins and olefins in cationic polymerizations may not be proportional to the feedblend composition, resulting in higher resin aromaticity as determined by nmr and ir measurements (43). This can be attributed to the differing reactivity ratios of aromatic and aHphatic monomers under specific Lewis acid catalysis. Intentional blocking of hydrocarbon resins into aromatic and aHphatic regions may be accomplished by sequential cationic polymerization employing multiple reactors and standard polymerization conditions (45). 

G-9 Aromatic Petroleum Resins. Feedstocks typically used for aromatic petroleum resin synthesis boil in the approximate range of 100—300°C at atmospheric pressure, with most boiling in the 130—200°C range. The C-9 designation actually includes styrene (C-8) through C-10 hydrocarbons (eg, methylindene). Many of the polymerizable monomers identified in Table 1 for coumarone—indene type cmdes from coal tar are also present in aromatic fractions from cracked petroleum distillates. Therefore, the technology developed for the polymerization of coal-tar cmdes is also appHcable to petroleum-derived aromatic feedstocks. In addition to availabiHty, aromatic petroleum resins offer several advantages over coumarone—indene resins. These include improved color and odor, as weU as uv and thermal stabiHty (46). 

In order to increase the solubiUty parameter of CPD-based resins, vinyl aromatic compounds, as well as other polar monomers, have been copolymerized with CPD. Indene and styrene are two common aromatic streams used to modify cyclodiene-based resins. They may be used as pure monomers or contained in aromatic steam cracked petroleum fractions. Addition of indene at the expense of DCPD in a thermal polymerization has been found to lower the yield and softening point of the resin (55). CompatibiUty of a resin with ethylene—vinyl acetate (EVA) copolymers, which are used in hot melt adhesive appHcations, may be improved by the copolymerization of aromatic monomers with CPD. As with other thermally polymerized CPD-based resins, aromatic modified thermal resins may be hydrogenated. 

Styrene [100-42-5] (phenylethene, viaylben2ene, phenylethylene, styrol, cinnamene), CgH5CH=CH2, is the simplest and by far the most important member of a series of aromatic monomers. Also known commercially as styrene monomer (SM), styrene is produced in large quantities for polymerization. It is a versatile monomer extensively used for the manufacture of plastics, including crystalline polystyrene, mbber-modifted impact polystyrene, expandable polystyrene, acrylonitrile—butadiene—styrene copolymer (ABS), styrene—acrylonitrile resins (SAN), styrene—butadiene latex, styrene—butadiene mbber (qv) (SBR), and unsaturated polyester resins (see Acrylonithile polya rs Styrene plastics). 

The generic name hydrocarbon resins designates several families of low molar mass polymers (M from 600 to 104) obtained by polymerization of petroleum, coal tar, and turpentine distillates [80-82], In most cases, these products are obtained by cationic polymerization of mixtures either of aliphatic and/or aromatic mono and diolefins present in the more or less enriched Cs and C9 feedstreams, or of pure aromatic monomers generally of the styrene type. They are complex mixtures of polymers ranging from viscous liquids and tacky fluids to hard, brittle thermoplastics, and are used as additives in adhesives, printing inks, rubbers, coatings, etc. [80-82], They are obviously amorphous and are characterized by their softening point (0 to —150° C), determined by standardized methods (i.e.,... 

Synthesis in presence of phenol and alkylphenols, which leads to Friedel-Crafts alkylation by the cationic propagating chain ends (Aromatic C9, 1C, pure monomer resins, polyterpenes). 

There are more than 35 producers all over the world an exhaustive list was provided in a recent review [82]. World consumption of hydrocarbon resins has been estimated —750 kt in 1994 which corresponds to an increase of 7.8% with respect to 1993. About 65% of the resins were used in adhesive formulations. Production was 350 kt for aromatic (C9 + IC) resins, 274 kt for aliphatic (C5 + DCPD), and 128 kt for the more rapidly developing water-white pure monomer resins, which corresponds on average to about 80% of world plant capacities [95]. Production of polyterpene resins appears limited to 25-30 kt per year. 

Shear yielding is well established as the principal deformation mechanism and source of energy dissipation in both uiunodified and rubbo -toughened epoxy resins [2,3,27,83,121]. As molecular mobility in the epoxy resin network chains decreases, the ability of the matrix to deform by shear yielding is reduced. This is the reason why epoxy resins become both more brittle and more difficult to toughen as the epoxy resin crosslink density increases and/or as the network chains increase in rigidity, e.g. by use of highly aromatic epoxy resin monomers (see Section 19.7.1.1). 

The structural element of a coumarone-indene resin is relatively similar to that for aromatic hydrocarbon resins, as they differ only in the proportion of indene-type structures which are present in higher concentration in the coumarone-indene resins. The main monomers in the aromatic resins are styrene and indene. Styrene produces the atactic conformation of the resins, whereas indene introduces rigidity into the polymer chain. A typical structural element of an aromatic resin is given in Fig. 11. 

Water-white resins are a recent commercial development. They are made by the homo- or copolymerization of pure vinyl aromatic monomers such as styrene or alpha-methylstyrene. Polymerization is carried out in aromatic solvents using BF3 or complexes of BF3 at 15-40°C. A controlled amount of water is added in order to improve initiation efficiency. The molecular weight of the product is low as a result of the extensive chain transfer processes at this temperature. Water-white resins are used where color stability is important. 

Pri ce. The price of a thermoplastic resin is basically determined by the cost of preparation, which in turn strongly depends on the cost of reagents (monomers, catalysts, etc), the complexity of the manufacturing process, and the dimension of production plants. Aliphatic polyketones, for instance, are made from very cheap raw molecules as ethylene, propylene, and CO their cost is determined by the need for expensive catalysts, based on Pd complexes, and the relatively complex production plant. On the other hand, PEN, which can easily be prepared in the same reactors used for PET, suffers from the difficult availability of its basic monomer dimethyl 2,6-naphthalene dicarboxylate. Most engineering polymers contain aromatic monomers, which are difficult to synthesize and polymerize, with slow and sophisticated mechanisms (condensation, substitution, oxidative coupling). 

Typically, a solid epoxy of 3000 to 4000 EEW (Epikote 1007 or 1009 types or an analogue material manufactured by the chain extension of a lower M liquid epoxy resin) is modified to provide an acid functional epoxy. In general, the acid functionality ctm be conferred by two methods, acid capping (see resin 1 and resin 2) of the oxirane groups or by the graft polymerisation of an epoxy with a carbonyl functional co-polymer (see resin 3). The co-polymer can consist of Ae reaction product of a free radical polymerisation of any approved ethylenic unsaturated monomers containing carbon-carbon unsaturadon, e.g. carboxyl functional acrylic monomers, (acrylic add, methacrylic acid, etc.), the lower alkyl esters, vinyl monomers (acrylamides), vinyl esters (vinyl acetate, vinyl butyrate), vinyl aromatic monomers (styrene, a methylstyrene) etc. The acrylic caj ing resin is add fimctional, being based upon either methacrylic or acrylic acid. The former is normally preferred. An acid value of 50-100 mg KOH/g would be typical. 

Eor most hydrocarbon resins where numerous stmcturaHy different monomers are polymerized, nmr is typically used as a general tool to quantify the aromatic and/or olefinic content of a resin. In conjunction with gpc and ftir, nmr measurements are used to identify and quantify particular functionaHties or monomers present in hydrocarbon resins. 

Petroleum resins are low molecular weight thermoplastic hydrocarbon resins synthesized from steam cracked petroleum distillates. These resins are differentiated from higher molecular weight polymers such as polyethylene and polypropylene, which are produced from essentially pure monomers. Petroleum resin feedstocks are composed of various reactive and nonreactive aliphatic and aromatic components. The resins are usually classified as C-5... 

A common procedure for the preparation of vinylated alkyds is as foUows. A base alkyd resin is brought to the desired endpoint. The resin is then cooled to about 160°C and often diluted with aromatic thinner. The desired monomer is added, usually at about 20 —60% based on the final product, foUowed by an appropriate amount of a free radical initiator. Alternatively, a premix of the monomer and the initiator is added at a controUed rate over most of the reaction. The reaction is brought to monomer reflux, until the residual monomer content has fallen below a specified level. Residual monomer, if any, is stripped away before the product is diluted in a solvent, filtered, and packaged. 

Only a few commercial uses for TDA per se have been found. In epoxy curing appHcations, 2,4- I DA has been used as a component of a eutectic mixture with short chain aUphatic glycidal ether resins (46) as well as by itself (46,47) TDA (46) and single isomers (47) are also used as amine curatives. TDA can be used as a chain extender in polyurethanes (48,49). TDA is cited as a monomer in making aromatic polymers with unique properties, eg, amorphous polyamides (50), powdered polyamides (51), and low melting, whoUy aromatic polyamides (52). 

OC-Methylstyrene. This compound is not a styrenic monomer in the strict sense. The methyl substitution on the side chain, rather than the aromatic ring, moderates its reactivity in polymerization. It is used as a specialty monomer in ABS resins, coatings, polyester resins, and hot-melt adhesives. As a copolymer in ABS and polystyrene, it increases the heat-distortion resistance of the product. In coatings and resins, it moderates reaction rates and improves clarity. Physical properties of a-methylstyrene [98-83-9] are shown in Table 12. 

Commercial engineering thermoplastic nylons are mainly crystalline resins. Nylon-6,6 [32131 -17-2] is the largest volume resin, followed by nylon-6 (48). Other commercially available but much lower volume crystalline nylons are -6,9, -6,10, -6,12, -11, and -12. The crystallinity of the molded part decreases with chain size (49). A few truly amorphous commercial nylon resins contain both aromatic and ahphatic monomer constituents (50). For example, Trogamid T resin is made from a mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamines and terephthahc acid (51). 

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