Acrylonitrile-butadiene rubber epoxy-modified

ABA ABS ABS-PC ABS-PVC ACM ACS AES AMMA AN APET APP ASA BR BS CA CAB CAP CN CP CPE CPET CPP CPVC CR CTA DAM DAP DMT ECTFE EEA EMA EMAA EMAC EMPP EnBA EP EPM ESI EVA(C) EVOH FEP HDI HDPE HIPS HMDI IPI LDPE LLDPE MBS Acrylonitrile-butadiene-acrylate Acrylonitrile-butadiene-styrene copolymer Acrylonitrile-butadiene-styrene-polycarbonate alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy Acrylic acid ester rubber Acrylonitrile-chlorinated pe-styrene Acrylonitrile-ethylene-propylene-styrene Acrylonitrile-methyl methacrylate Acrylonitrile Amorphous polyethylene terephthalate Atactic polypropylene Acrylic-styrene-acrylonitrile Butadiene rubber Butadiene styrene rubber Cellulose acetate Cellulose acetate-butyrate Cellulose acetate-propionate Cellulose nitrate Cellulose propionate Chlorinated polyethylene Crystalline polyethylene terephthalate Cast polypropylene Chlorinated polyvinyl chloride Chloroprene rubber Cellulose triacetate Diallyl maleate Diallyl phthalate Terephthalic acid, dimethyl ester Ethylene-chlorotrifluoroethylene copolymer Ethylene-ethyl acrylate Ethylene-methyl acrylate Ethylene methacrylic acid Ethylene-methyl acrylate copolymer Elastomer modified polypropylene Ethylene normal butyl acrylate Epoxy resin, also ethylene-propylene Ethylene-propylene rubber Ethylene-styrene copolymers Polyethylene-vinyl acetate Polyethylene-vinyl alcohol copolymers Fluorinated ethylene-propylene copolymers Hexamethylene diisocyanate High-density polyethylene High-impact polystyrene Diisocyanato dicyclohexylmethane Isophorone diisocyanate Low-density polyethylene Linear low-density polyethylene Methacrylate-butadiene-styrene... 

Fig. 35. Dependence of fracture energy on the modifier composition (CTBN 1300 X 9 = carboxyl-tenninated acrylonitrile, acrylic acid and butadiene rubber with 18% acrylonitrile and 2% acrylic acid contents CTBN 1300x 13 = carboxyl-terminated acrylonitrile, butadiene rubber with 26% acrylonitrile content) (Reprinted from Journal of Materials Science, 27, T.K. Chen, Y.H. Jan, Fracture mechanism of toughened epoxy resin with bimodal rubber-particle size distribution, 111-121, Copyright (1992), with kind permission from Chapman Hall, London, UK)...

With the increased usage of 120°C cured, rubber modified epoxy structural adhesives for aluminum airframes, certain service problems have been observed which have been attributed to environmental factors. The problems associated with the combined effects of sustained load, elevated temperature and high humidity upon the aluminum substrate, corrosion inhibiting primers, and the structural epoxy adhesive matrix are discussed. A particular type adhesive matrix, based on acrylonitrile/butadiene rubber modified bisphenol type epoxy systems is discussed in detail, and important advances in the preparation of more moisture resistant aluminum (oxide) surfaces are reviewed. 

The material used was a diglycidyl ether of bisphenol A (DGEBA) based epoxy resin (Ciba-Geigy, GY250) cured using stoichiometric amounts of 4,4 -diamin-odiphenyl sulfone (DDS). The rubber used for the modifications was Hycar car-boxy-teminated butadiene-acrylonitrile (CTBN) rubber (1300 x 13). The curing schedule for all the rubber-modified epoxy-DDS systems was as follows first the rubber and then DDS were mixed with the epoxy resin and stirred at 135 °C until the DDS was dissolved the systems were cured for 24 h at 120 °C and then postured for 4 h at 180 °C. The control epoxies were cured according to the same schedule. 

The morphology of ruber modified epoxy photopolymers was found to depend on the cure conditions as well as the nature and concentration of rubber. The commercially available acrylonitrile-butadiene copolymer rubber modifiers with varying percentages of acrylonitrile content were used. They were polymerized using a photocationic initiator involving a UV exposure followed by a thermal cure. Transmission electron micrographs of osmium tetroxide stained specimens, coupled with dynamic mechanical measurements indicated that phase separation and particle size distribution depended not only on rubber concentration and compatibility, but also on the cure conditions. 

Chen and Jan [133] showed that bimodal distributions could be obtained by using two different rubbers as modifiers of a DGEBA-based epoxy resin cured with piperidine. The rubbers were two acrylonitrile-butadiene copolymers (CTBNs), with different AN content, i.e. 18 and 26%. The miscibility with the epoxy resin (and the corresponding cloud-point conversion) increased with the AN content. Therefore, when 10 wt% of CTBN (26% AN) was used as modifier, a high concentration (Cp == 13.4 pm ) of small particles (D = 0.2 pm) was obtained. When the same amount of CTBN (18% AN) was used as modifier. 

Epoxies modified with butadiene acrylonitrile copolymers with (32) amine or carboxy end groups have disadvantages. They are susceptible to thermal and oxidative degradation and also have poor hot/wet properties, i.e., they soften when exposed to heat and moisture for long periods. Polysiloxane rubbers such as polydimethylsiloxane have been considered as a possible alternative. 

More recently Crosbie and Philips [85,86] investigated the toughening effect of several reactive liquid rubbers (carboxyl terminated butadiene-acrylonitrile, vinyl terminated butadiene-acrylonitrile, hydroxyl terminated polyether, polyepichlorohydrin) and an unspecified experimental reactive liquid rubber developed by Scott Bader Ltd. on two different polyester resins a flexibilized isophthalic-neopentyl glycol polyester resin, PVC compatible and an epoxy modified polyester resin, which is preaccelerated. The results of these studies are summarized as follows ... 

A wide variety of well-known polymers are currently rubber modified, always with the intent of improving the toughness of the material either at ambient temperature, or, often, at sub-ambient. Most well known is high impact polystyrene (HIPS) which, in terms of composition, is polystyrene containing 5-10% polybutadiene rubber. ABS (acrylonitrile/butadiene/styrene) is similar to HIPS except the glassy polymer is the more heat and solvent resistant poly(styrene-co-acrylonitrile). Poly(vinyl chloride) (PVC), polypropylene (PP), epoxy resins, and nylons are all available in rubber-... 

Studies of the particle—epoxy interface and particle composition have been helpful in understanding the rubber-particle formation in epoxy resins (306). Based on extensive dynamic mechanical studies of epoxy resin cure, a mechanism was proposed for the development of a heterophase morphology in rubber-modified epoxy resins (307). Other functionalized mbbers, such as amine-terminated butadiene—acrylonitrile copolymers (308) and tf-butyl acrylate—acrylic acid copolymers (309), have been used for toughening epoxy resins. 

Effect of Molecular Configuration of Elastomer. The extent of the impact and strength improvements of ERL-4221 depends on the chemical structure and composition of the elastomer modifier. The data shown in Table I indicate that the carboxyl terminated 80-20 butadiene-acrylonitrile copolymer (CTBN) is the most effective toughening and reinforcing agent. The mercaptan terminated copolymer (MTBN) is considerably less effective as far as tensile strength and heat distortion temperature are concerned. The mercaptan groups are considerably less reactive with epoxides than carboxyls (4), and this difference in the rate of reaction may influence the extent of the epoxy-elastomer copolymerization and therefore the precipitation of the rubber as distinct particles. 

For epoxy networks modified by liquid reactive rubbers, it is not so easy to discuss these parameters separately, because they are interdependent. For example, an increase in the acrylonitrile content of the carboxy-termi-nated butadiene acrylonitrile rubber (CTBN) induces a size reduction of the rubbery domains but also a higher miscibility with the epoxy-rich phase, leading to a higher amount remaining dissolved in the matrix at the end of cure (Chapter 8). It is not possible to separate the influence of these two effects on toughness. 

Figure 13.7 Variation of yield stress (

Fig. 13. TXT cure diagram temperature of cure vs. the times to phase separation (doud point), gelation and vitrification for a neat and two rubber-modified systems. of the neat system is also included. The systems studied were DER331/TMAB O, gelation , vitrificaticm modified with IS parts rubber per hundred parts epoxy 1) pr eacted carboxyl-terminated butadiene-acrylonitrile (CTBN) copolymer containing 17% acrylonitrile (K-293, Spencer Kellog Co.) A, phase separation , gelation , vitrification, and 2) polytetramethylene oxide terminated with anmiatic amine (ODA2000, Polaroid Corp.) A. phase separation O, gelation O, vitrification. (DER331/TMAB/ K-293 data from Ref. )...

The polyester resin used in this study, MR 13006 (Aristech Corporation), was supplied as a 60-wt% solution in styrene monomer. The epoxy resin, a digly-cidyl ether of bisphenol A (Epon 828), was obtained from Shell Chemical Company. The reactive liquid rubber, an amino-terminated butadiene-acrylonitrile copolymer (ATBN 1300 x 16), was provided by the BFGoodrich Company. The resin was mixed with additional styrene monomer to maintain the ratio of reactive unsaturation in the polyester-to-styrene monomer at 1 to 3. We added 1.5 wt% of tert-butylperbenzoate initiator to the solution, which we then degassed under vacuum. The mixture was poured between vertical, Teflon-coated, aluminum plates and cured under atmospheric pressure at 100 °C. In the modified compositions, the rubber was first dissolved in the styrene monomer, and then all the other components were added and the solution cured as described. In all the compositions, the ratio of the amine functions with respect to the epoxy functions was kept at 1 to ensure complete cure of the epoxy. 

Recent work has shown that the addition of epoxy-terminated butadiene-acrylonitrile (ETBN) liquid rubbers to elastomer-modified VER gives a fivefold increase in fracture energy over that of elastomer-modified VER (3). 

---