Oligomers, resins

Although HR-600/Thermid-600 provided promising neat resin and composite properties, major processing problems have plagued these as well as other acetylene-terminated oligomers. Resin flow and wetting is inhibited due to the reaction of the terminal ethynyl groups prior to the formation of a complete melt or soft state. This becomes even more severe due to heat transfer problems as... 

Figure 1. DSC trace of uncured BCB oligomer resin, the initial...

Oligomer Resin 25-90 Film Formation and Basic Properties... 

PAFO phenol-aniline-formaldehyde oligomer (resin)... 

Chem. Descrip. Solid grade oligomer resin Uses Resin for ulfra low VOC pkg. inks, overprinf varnishes, aq. pigmenf disps. 

Features Fast cure response good surf, cure low color and odor in cured films optimum absoq). 250-334 nm Pre rties Clear liq. completely sol. in most org. soivs., monomers, oligomers, resins pract. insol. in water sp.gr. 1.053 vise. 55,000 cps (20 C) b.p. 310 C flash pt. 140 C Use Level 4-10%... 

Resin A resin is an amorphous polymer or oligomer. Resin is increasingly used for low-molecular-mass materials, such as natural resins. 

These condensation products are of low molecular weight (consisting of a small number of monomer units) and are therefore considered to be oligomer resins (not high polymers). Because the alkylated phenol feedstocks are alkylated at the para position, they produce non-heat-reactive resins that are not thermosetting. 

The production of formo-phenolic materials is always carried out in two steps. The first one corresponds to the formation of an oligomer (resin) that is used as prepolymer, and its molecular structure depends on the pH of the reaction medium. The mechanism of these reactions is described in Section 7.4.2. 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

Resins. As mentioned above, both furfural and furfuryl alcohol are widely used in resin apphcations. Another resin former, 2,5-furandimethanol [1883-75-6] (BHME), is prepared from furfuryl alcohol by reaction with formaldehyde. It is usually not isolated because oligomerization occurs simultaneously with formation (competing reaction). Both the monomer and oligomers are very reactive owing to difuntionahty, and are used primarily as binders for foundry sand (72) and fiberglass insulation (147,148). 

TetrabromobisphenolA. TBBPA is the largest volume reactive flame retardant. Its primary use is in epoxy resins (see Epoxyresins) where it is reacted with the bis-glycidyl ether of bisphenol A to produce an epoxy resin having 20—25% bromine. This brominated resin is typically sold as a 80% solution in a solvent. TBBPA is also used in the production of epoxy oligomers which are used as additive flame retardants. 

Formaldehyde—Alcohol Solutions. These solutions are blends of concentrated aqueous formaldehyde, the alcohol, and the hemiacetal. Methanol decreases the average molecular weight of formaldehyde oligomers by formation of lower molecular weight hemiacetals. These solutions are used to produce urea and melamine resins the alcohol can act as the resin solvent and as a reactant. The low water content can improve reactivity and reduce waste disposal and losses. Typical specifications for commercially available products are shown in Table 7 (117). 

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. 

Terpene Copolymers. Terpenes are routinely polymerized with other terpenes or with nonterpene-type monomers (97—102). The AlCl catalyzed polymerization of P-pinene, dipentene, and terpene oligomers (oily dimers and trimers) has been found to yield resins with softening points ranging from 0—40°C (103). 

A second type of uv curing chemistry is used, employing cationic curing as opposed to free-radical polymerization. This technology uses vinyl ethers and epoxy resins for the oligomers, reactive resins, and monomers. The initiators form Lewis acids upon absorption of the uv energy and the acid causes cationic polymerization. Although this chemistry has improved adhesion and flexibility and offers lower viscosity compared to the typical acrylate system, the cationic chemistry is very sensitive to humidity conditions and amine contamination. Both chemistries are used commercially. 

Miscellaneous Copolymers. VP has been employed as a termonomer with various acryUc monomer—monomer combinations, especially to afford resins usehil as hair fixatives. Because of major differences in reactivity, VP can be copolymerized with alpha-olefins, but the products are actually PVP grafted with olefin or olefin oligomers (151,152). Likewise styrene can be polymerized in the presence of PVP and the resulting dispersion is unusually stable, suggesting that this added resistance to separation is caused by some grafting of styrene onto PVP (153). The Hterature contains innumerable references to other copolymers but at present (ca 1997), those reviewed in this article are the only ones known to have commercial significance. 

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