CTBN copolymers

Figure 8.1 Cloud-point temperatures versus volume fraction of modifier, for mixtures of diglycidyl ether of bisphenol A, DGEBA (n = 0.15) with two CTBN copolymers with different acrylonitrile content 18 and 10 wt%. (Reprinted from Verchere et ai, 1989, Copyright 2001, with permission from Elsevier Science)...

Epoxy-nitrile Nitrile-epoxy adhesives are composed of solid epoxy resin modified with carboxyl-terminated butadiene nitrile (CTBN) copolymer. The CBTN is introduced into die epoxy resin at elevated temperatures. The modification provides toughness and high peel strength without sacrificing heat and chemical resistance. The film adhesives are widely used in the aerospace industry in the construction of jetliners. 

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. )...

Two chemically dissimilar polymers will naturally attempt to phase separate and the structure that is formed will reflect the way in which this process occurs and the driving forces associated with the process. Phase separation is used to achieve rubber toughening in thermoset resin systems. Low molar mass CTBN copolymer is soluble in the simple mixtures of monomers used to create amine-cured epoxy resins systems. However, as the molecular mass of the epoxy resin increases so the balance of entropy and enthalpy of mixing of these components changes and a driving force for phase separation is created. 

Piperidine and carboxyl terminated butadiene acrylonitrile copolymer (CTBN) at 75 °C. 

A 3300 molecular weight carboxyl terminated 80-20 butadiene-acrylonitrile random copolymer designated CTBN (I) (Figure 3). 

It is obvious from these data that CTBN (the carboxyl terminated butadiene-acrylonitrile copolymer) is the most effective modifier, and therefore it was selected for further study. As the concentration of the elastomer was increased to levels up to 100 parts, the impact also increased. The data in Table II show that the room temperature impact of ERL-4221 increased from 40 inch-lbs to greater than 320 inch-lbs by adding 100 phr or 33 wt % of CTBN. At very low temperatures ( —160°F) the impact of the system modified with 60 parts, or 23 wt %, of CTBN was 120 inch-lbs. These impact improvements appear to be directly proportional to the concentration of the elastomer modifier. 

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. 

Figure 13.8 Fracture energy of epoxy networks cured with DDS (diamino dipheny sulfone) versus the initial DGEBA (diglycidyl ether of bisphenol A) ( ) neat systems ( ) with 10% CTBN (27% AN). Rubber = CTBN carboxy-terminated butadiene acrylonitrile random copolymer. (Pearson and Yee, 1989 with kind permission from Kluwer Academic Publisher.)... 

The epoxy-nitrile adhesives were introduced commercially in the late 1960s. They consisted primarily of DGEBA epoxy resin modified with carboxyl-terminated butadiene nitrile (CTBN) rubber. These first nitrile copolymers were available from B.F. Goodrich under the trade name of Hycar. The most convenient form of epoxy nitrile adhesive, especially when one is bonding large parts (aircraft structures), is a supported film. However, solvent solutions of epoxy-nitrile adhesives have also been commercially available. 

However, newer adhesives systems having moderate temperature resistance have been developed with improved toughness but without sacrificing other properties. When cured, these structural adhesives have discrete elastomeric particles embedded in the matrix. The most common toughened hybrids using this concept are acrylic and epoxy systems. The elastomer is generally a amine- or carboxyl-terminated acrylonitrile butadiene copolymer (ATBN and CTBN). 

Siebert and Riew (4) described the chemistry of the in situ particle formation. They proposed that the composition of the particle is a mixture of linear CTBN-epoxy copolymers and crosslinked epoxy resin. The polymer morphology of the CTBN toughened epoxy systems was investigated by Rowe (5) using transmission electron microscopy by carbon replication of fracture surfaces. Riew and Smith (6) supported the... 

Materials. Hycar CTBN is a registered trade name of a carboxyl-terminated, liquid copolymer of butadiene and acrylonitrile (B. F. Goodrich Chemical Co.). For most purposes it can be represented structurally as ... 

The separate phases will be rich in one component but may have the other present as a minor component. In order to control compatibility the elastomer may have reactive end groups to enhance interfacial adhesion. A common example in epoxy-resin technology is the carboxy-terminated butadiene-acrylonitrile copolymer (CTBN). The structure is shown in Scheme 1.47. In this resin the solubility in the epoxy resin is conferred by the acrylonitrile group, and an increase in the fraction present decreases the upper critical solution temperature, with 26% acrylonitrile conferring total miscibility of CTBN with a DGEBA-based epoxy resin (Pascault et al, 2002). 

PCL with CTBN or CTBR APS Ellipsometric methods. A1 = 3 nm without APS and 6 nm with APS (a reactively generated copolymer) Okamoto and Inoue, 1993... 

Liquids, butadiene-acrylonitrile copolymers (Hycar ATBN or CTBN, B.F. Goodrich)... 

The incorporation of elastomers into epoxy resins has been an active area of research over the past decade (1-11). The primary reason for this interest has been the improved toughness of the modified materials. We have limited our work to the carboxy-terminated butadiene-acrylonitrile copolymers (CTBN) produced by... 

Thus, with two equations and two unknowns, a unique solution to X and Y can be calculated. Carboxy-terminated copolymers of butadiene and acrylonitrile (CTBN) can be incorporated into the epoxy resin through a simple esterification reaction. One equivalent of carboxylic acid is esterified by one equivalent of epoxide. This reaction is again catalyzed by triphenylphosphine. Since, for our reactions, the limiting reagent in the esterification is the CTBN elastomer, the product is an elastomer capped with an epoxy resin. The epoxy terminated rubber is then capable of reacting in the usual manner with curing agents or in the previously discussed advancement reaction (Reaction Scheme 2). 

Thermoplastic rubber block copolymers, with completely new adhesive performance, were developed in 1965 [21]. The first commercial product was Shell Chemical s Kraton 101, of styrene polybutadiene-styrene composition. This development led to the carboxy-terminated nitrile (CTBN) rubber modifiers used to flexibilize epoxy and other brittle resin adhesives in the late 1960s. Today, the thermoplastic rubber block copolymer adhesives are used in hot melt-, solvent- and water-based adhesives, and as hot melt- and solvent-based sealants. Major applications are as pressure-sensitive adhesives, construction adhesives and sealants, and general assembly adhesives. 

The abbreviations mean amino-, epoxy-, carboxyl- and non-functional end-capped polybutadiene-acrylonitrile copolymers, respectively, of the same molar mass and 18% AN content. The polarity of rubbers changes in the same order except for CTBN. Lower values of CTBN miscibility in comparison with ATBN and ETBN can possibly be caused by the great self-association effect of carboxyl groups through hydrogen bonding with the formation of high molar mass chains. 

Fig. 13. Experimental CPC (A) and calculated binodal (broken curve) and spinodal (dotted curve) curves for a binary system composed of a DGEBA-based epoxy monomer (M = 479 gmol ) and a carboxyl-terminated butadiene-acrylonitrile rubber (CTBN) (Reprinted from Polymer, 30, D. Verchere, H. Sautereau, J.P. Pascault, S.M. Mos-chiar, C.C. Riccardi, R.J.J. Williams, Miscibility of epoxy monomers with carboxyl-terminated butadiene-acrylonitrile random copolymers, 107 -115, Copyright (1989), with kind permission from Butterworth-Heinemann journals, Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington 0X5 1GB, UK)...

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. 

The B. F. Goodrich Chemical Company produces monopolymers and copolymers with acrylonitrile. These are known as the Hylar series. Acrylonitrile increases the viscosity and imparts oil resistance, adhesion, and compatibility with epoxy resins. Carboxy-terminated butadiene-acrylonitrile copol)uner (CTBN) improves impact strength, low-temperature shear strength, and crack resistance in epoxy formulations. 

Synonyms Acrylonitrile-butadiene copolymer, carboxyl-terminated Butadiene-acrylonitrile copolymer carboxylated Butadiene-acrylonitrile copolymer, carboxyl-terminated Carboxylated butadiene-acrylonitrile copolymer CTBN... 

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