Amine-terminated polybutadiene

The successful synthesis of such materials requires that, Initially, telechelic tertiary amine terminated polybutadiene be prepared quantitatively. Alternative routes are therefore being sought, two of which are outlined In this paper. 

To a lesser extent, amine-terminated polybutadiene/acrylo-nitrile (ATBN) liquids are also used by epoxy formulators. This polymeric disecondary amine is employed in admixture with amines, amldoamlnes or fatty polyamides of choice (10, 11). Thus, one admixes chemical and polymeric amines to create a novel toughening or flexibilizing hardener package. 

A number of rubbery materials have been added to lightly crosslinked epoxies in order to make them more fiacture resistant. These include polybutadiene/aciylonitrile elastomer of phenol-formaldehyde epoxies, carboxy terminated and amine terminated polybutadiene/aciylonitrile resins, terpolymers, siloxanes, and aciylic, as well as other types of rubbers. 

Drs. K.Rieu and R.Drake, the B.F.Goodrich Chem. Co., for kindly supplying the amine-terminated polybutadiene. They also wish to thank Messrs. Guan-Wen Chen and Y.Hata, Department of Polymer Chemistry, Kyoto University, for their contribution. 

Analogously to their preparation of aziridine- and amine-terminated polybutadiene, Phillips has also prepared epoxide-terminated polyhutadiene [288]. Either glycilaldehyde or various diepoxides were added to polyhutadiene carbanion ... 

Polybutadienes, polycaprolactones, polycarbonates, and amine-terminated polyethers (ATPEs) are shown in Scheme 4.4 as examples of other commercially available polyols. They are all specialty materials, used in situations where specific property profiles are required. For example, ATPEs are utilized in spray-applied elastomers where fast-reacting, high-molecular-weight polyamines give quick gel times and rapid viscosity buildup. Polycarbonates are used for implantation devices because polyuredtanes based on them perform best in this very demanding environment. Polycaprolactones and polybutadienes may be chosen for applications which require exceptional light stability, hydrolysis resistance, and/or low-temperature flexibility. 

These results indicate that if polydienes and similar polymers can be prepared quantitatively with tertiary amine terminal groups, then they can be combined with other halogen functional polymers using established techniques to create interesting new block copolymer systems. For example, consider the reaction between telechelic pyridine terminated polybutadiene and monofunctional bromine terminated polystyrene (equation 4) -the latter has been prepared in 95% yield. >it The product would be an ABA... 

Figure 11.10 Examples of dissipation spectra (1 Hz frequency), (a) amine-epoxy network containing a carboxyl-terminated polybutadiene. The rubber a peak (arrow) is superimposed on the p peak of epoxy, (b) unsaturated polyester containing polyvinylacetate. The a peak (arrow) is at the onset of the p—a dissipation band.

Polynoxylin. See Urea-formaldehyde resin Polyoctadecylmethylsiloxane. SeeStearyl methicone Polyoctylmethylsiloxane. See Polymethyloctylsiloxane Polyoil, epoxidized. See Epoxidized polybutadiene Polyol, flexible Polyol, flexible, amine-terminated Polyol, rigid. See Polyether polyol... 

Gallot et al. published one of the earliest reports on the preparation of PLL-based hybrid block copolymers. The synthetic segments in these copolymers were primary amine-terminated polystyrene or polybutadiene that were used to initiate the ROP of ZLL-NCA. The authors intended to use the hybrid conjugates as a model for biological membranes. In the following years, several reports emerged on the synthesis of PLL hybrid block copolymers based on macroinitiators prepared by vinyl monomer polymer-ization. ° The pH and temperature dependence of the copolymer vesicles formed in solution was investigated. ... 

Waterborne polyurethane resins are produced from maleinised monoglyceride (MMG) of sunflower oil, hydroxy-terminated polybutadiene, toluene diisocyanate and ethylene diamine. The carboxylic acid groups of MMG are neutralised by triethyl amine, making the resin water dispersible. The monoalkylated castor oil (MCO) or dehydrated castor oil (DCO) is treated with a polyether glycol at 120°C, followed by the addition of IPDI and DBTDL. To obtain a series of aqueous polyurethanes, butane diol and dimethylol propionic acids (DMPA) are added and the mixture heated to 70°C for two hours to produce a NCO-terminated pre-polymer which forms salt with triethylamine, giving a water-soluble polymer. The reaction mixture is dispersed in water and a chain extender, ethylene diamine, is added. Two aqueous polyurethanes, MCPU and DCPU, are finally obtained from MCO and DCO, respectively. 

Epoxy structural adhesives which employ carboxylic polybutadiene/acrylonitrile solid and liquid (CTBN) elastomers as modifiers have increased in number and proliferated in use since their introduction in the mid- 60 s. Such adhesive systems are now used in aircraft, electronics, automotive and industrial bonding operations. In the mid- 70 s, amine-reactive versions of the liquid polymers (ATBN) were issued, thereby offering another way to introduce rubber modification into a cured epoxy network. References are cited which provide detailed discussions of nitrile rubber, carboxylic nitrile rubber and both carboxyl- and amine-terminated nitrile liquid polymers (1-4). ... 

Blends of carboxylic acid-terminated polybutadiene and amine-terminated PDMS have been prepared by Fleischer et al. (1994). A copolymer with block-like structure was postulated to form. Blends were characterized using pendant drop tensiometry and FTIR. 

The novel liquid polymers are characterized by having reactive terminal vinylidene groups and are prepared from liquid carboxyl-terminated polybutadiene polymers using an amine catalyst [50]. 

Two separate series of experiments were carried out in order to study the reactivity of EPR-g-SA towards low Mw diols with or without the addition of a tertiary amine as catalyst, and the reactivity of EPR-g-SA towards a long-chain hydroxyl-terminated polybutadiene (HTPB). For both of them, the same experimental procedure was followed to ensure an intimate mixing of the reactants, they were all dissolved in a common solvent at room temperature and in a certain stoichiometric amount (in solution, the kinetics of esterification is very slow, thus the degree of reaction is negligible). Subsequently, the solvent is quickly removed by evaporation under vacuum at room temperature directly onto KBr disks to obtain a film which is used for IR analysis. 

Synthesis. The polyvinyl block [polybutadiene or polystyrene) is synthesized by anionic polymerization, then the chemical modification of the living ends provides a polymer terminated by a primary amine function which is used to initiate the polymerization of the NCA of the desired a amino acid [7,8). 

Living polybutadiene prepared with a tertiary amine functionalized alkyl lithium initiator is terminated by an a-chloro-[Pg.8209]

Low molecular weight polybutadiene and butadiene-acrylonitrile copolymers terminated with carboxyl, vinyl, amine, epoxy, phenol, and hydroxyl groups have been widely used as toughening agents both for epoxy and polyester resins. Thermally reactive isoprene-acrylonitrile and ethylacrylate-butylacrylate copolymers have also been used [82,83]. 

The synthesis of block copolymers can be easily carried out if functional groups such as acid chloride ( COCl), amines ( -NH2), or alcohols (-"UH) are present at chain ends. This way, a polymer of one kind (say, polystyrene or polybutadiene) with dicarboxylic acid chloride (ClCO COCl) terminal groups can react with a hydroxy-terminated polymer (OH> OH) of the other kind (say, polybutadiene or polystyrene), resulting in an AB type block copolymer, as follows ... 

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