Bisphenol diamine

Curing Systems. The most commonly used vulcanizing agent for the polyethers not containing AGE, that is, ECH and ECH—EO, is 2-mercaptoimidazoline, also called ethylenethiourea [96-45-7]. Other commercially appHed curing agents include derivatives of 2,5-dimercapto-l,3,4-thiadiazole, trithiocyanuric acid and derivatives, bisphenols, diamines, and other substituted thioureas. 

Cyanate esters may be modified by co-reaction with monomers or oligomers that contain active hydrogens (e.g., water, phenols, bisphenols, diamines, diepoxides, ethers, esters, etc) [2-6], The PCN modified with reactive monomers usually have a homogeneous single phase, with properties proportional to the ratio of the two components. 

Polyetherimide synthesis has been achieved by reaction of a dianhydride containing an ether linkage with a diamine, reaction of a diamine containing an ether linkage with a dianhydride, or nucleophilic displacement of halo or nitro groups of a bisimide by bisphenol dianion (19,20). Such Pis exhibit good thermal stabiUty and melt processibiUty. 

Diamine curatives were the first cross-linking agents for fluorocarbon mbbers. They are corrosive to mild steel molds and have been replaced in many appHcations by the bisphenol or other more recent cure systems. Nevertheless, some diamines are stiU used for food-contact appHcations of fluorocarbon mbbers and in zinc-free cures of halobutyl mbbers for pharmaceutical stoppers. Methylene dianiline and triethylene tetramine are cross-linking agents for ethylene—acryflc elastomers. 

In addition to electrical uses, epoxy casting resins are utilized in the manufacture of tools, ie, contact and match molds, stretch blocks, vacuum-forrning tools, and foundry patterns, as weU as bench tops and kitchen sinks. Systems consist of a gel-coat formulation designed to form a thin coating over the pattern which provides a perfect reproduction of the pattern detail. This is backed by a heavily filled epoxy system which also incorporates fiber reinforcements to give the tool its strength. For moderate temperature service, a Hquid bisphenol A epoxy resin with an aHphatic amine is used. For higher temperature service, a modified system based on an epoxy phenol novolak and an aromatic diamine hardener may be used. 

Dehydrofluorination by primary and secondary aliphatic amines occurs at room temperature and is the basis of diamine cross linkmg, which occurs by dehydrofluonnation and subsequent nucleophihc substitution of the double bond The locus of dehydrofluonnation is a VDF unit flanked by two perfluoroolefin units This selectively base-sensitive methylene group also undergoes elimination as the first step in phase-transfer-catalyzed cross-hnking with quaternary ammo mum or phosphomum salts, bisphenols, and morganic oxides and hydroxides as HF acceptors [31, 32]... 

Phenothiophosphine ring-containing polyamides and polyesters were also prepared by the polycondensation of 2,8-bischloroformyl-lO-phenylphenothiophos-phine 5,5, 10-trioxide with aromatic diamines such as 4,4 -diaminodiphenyl ether and 4,4 -diaminodiphenyl-methane, and bisphenols such as 4,4 -dihydroxybiphe-nyl and 4,4 -dihydroxydiphenylmethane, respectively [159]. These polymers are soluble in polar aprotic solvents and also exhibit good heat and fire resistance. Phosphorus containing high performance polymers are shown in Table 6. 

Figure 2. Solid-state spectra of four different epoxies (hosed on the resin diglycidyl ether of bisphenol-A) are compared with the liquid-state spectra of their respective unreacted components, The chemical compositions are in Table I. Here the epoxies are identified by their main curing agent (a) PIP—piperidine (b) MPDA—metaphenylene diamine (c) HHPA—hexahydro-phthalic anhydride (d) NMA—nadic methyl anhydride.

Statistical copolymerization of ethylene glycol and 1,4-butanediol with dimethyl ter-ephthalate results in products with improved crystallization and processing rates compared to poly(ethylene terephthalate). Polyarylates (trade names Ardel, Arylon, Durel), copolymers of bisphenol A with iso- and terephthalate units, combine the toughness, clarity, and proce-sibility of polycarbonate with the chemical and heat resistance of poly(ethylene terephthalate). The homopolymer containing only terephthalate units is crystalline, insoluble, sometimes infusible, and difficult to process. The more useful copolymers, containing both tere- and isophthalate units, are amorphous, clear, and easy to process. Polyarylates are used in automotive and appliance hardware and printed-circuit boards. Similar considerations in the copolymerization of iso- and terephthalates with 1,4-cyclohexanedimethanol or hexa-methylene diamine yield clear, amorphous, easy-to-process copolyesters or copolyamides,... 

Polyetherimides (PEI) are polyimides containing sufficient ether as well as other flexibi-lizing structural units to impart melt processability by conventional techniques, such as injection molding and extrusion. The commercially available PEI (trade name Ultem) is the polymer synthesized by nucleophilic aromatic substitution between 1,3-bis(4-nitrophthalimido) benzene and the disodium salt of bisphenol A (Eq. 2-209) [Clagett, 1986]. This is the same reaction as that used to synthesize polyethersulfones and polyetherketones (Eq. 2-206) except that nitrite ion is displaced instead of halide. Polymerization is carried out at 80-130°C in a polar solvent (NMP, DMAC). It is also possible to synthesize the same polymer by using the diamine-dianhydride reaction. Everything being equal (cost and availability of pure reactants), the nucleophilic substitution reaction is probably the preferred route due to the more moderate reaction conditions. 

In a similar way as has been described for syntheses of type al, the majority of examples of type b involve polycondensation of a,ea bifunctional, small molecule reaction partners. Some examples are the reaction of AIBN or AIBN derivatives with 1,4-cyclohexane bismethyl diamine78), 1,2-ethylene diamine78), 1,6-hexamethylene diamine 78-80 , bisphenol A 78,81 and mono-, di- and tetraethylene glycol 55-64 . In almost all case using the AIBN derivative 4,4 -azobis(4-cyano valeryl chloride), an interfacial polymerization was employed. These polymeric azo compounds could be used as initiators for radical block copolymerizations. 

For many usual, moderately polar networks, such as epoxides of the diglycidyl ether of bisphenol A (DGEBA) diamine type, or vinyl esters, Hs —Hw, so that the equilibrium concentration appears almost temperature-independent. For most of the less polar networks such as polyesters or anhydride-cured epoxies, Coo (or Wro) increases slightly with temperature AW /AT 0.01 0.02% K 1 between 20 and 50°C. 

Fluorocarbon elastomers based on VDF/HFP and VDF/HFP/TFE can be cured by bis-nucleophiles, such as bisphenols and diamines. The mechanism, proposed in Reference 17, is outlined below ... 

The detailed description is in Figure 5.2,18 where the bis-nucleophile Nu-R-Nu represents a bisphenol or diamine cross-linking agent. 

JP 62246978 (Japanese) 1987 Heat-resistant adhesives containing siloxanes and imide-containing resins Shin-Etsu Chemical Industry Co. Ltd., Japan S Ueno, N Nakanishi, S Hoshida Adhesives showed good adhesion and flexibility useful in the preparation of flexible laminates Resin was prepared from the reaction product of bismaleimides, diamines, amino-terminated siloxanes and a bisphenol A cyanate adduct. The adhesive formulation was used on polyimide films... 

Transition metal-catalysed carbon-heteroatom coupling reactions primarily comprise the carbonylation polycondensation of dibromoarenes with aromatic diamines and bisphenols in the presence of carbon monoxide... 

Palladium- or nickel-catalysed carbonylation polycondensation of dibromoar-enes with bifunctional nucleophilic monomers such as aromatic diamines and bisphenols in the presence of carbon monoxide appeared to be a new promising method for the synthesis of aromatic polyamides [scheme (15)] and polyesters [scheme (16)] respectively [162-170], The first successful example was the synthesis of high molecular weight polyaramide according to scheme (15) (Ar1 = m-C6H4-, Ar2 = p-C6H4 O C6H4 ) [162],... 

Linear polymers were obtained by the polyaddition of dicyanates with the compounds, which contain active protons primary and secondary amines, glycols and bisphenols. The reaction with diamines given polyisoureas [30, 31] (Scheme 8). 

As an additional component, various thermoplastic polymers can be used. As a binder for copper clad laminates, a solution of solid epoxide resin (Epikote 1001), BPA/DC prepolymer, Zn acetate and poly(phenylene sulfide) was used [83], Other binders for reinforced plastics contain polysulfone. Such compositions consist of liquid BPA/ECH epoxide resin, BPA/DC prepolymer, polysulfone and bis(4-hydro-xyphenyl)sulfone [85]. Bis(4-aminophenyl)sulfone can be also added [86]. In such systems the bisphenol reacts with the epoxide resin as a chain extension agent, whereas the diamine crosslinks the diepoxide. The Tg values are close to 200 °C. They can be increased a little, if the BPA/ECH epoxide resin is replaced by the tetra-epoxide A,A,A, A -tetrakis(2,3-epoxypropyl)diaminodiphenylmethane [87]. 

Fire resistant polymers were obtained from brominated epoxynovolak resin, BPA/DC prepolymer, BMI, Zn acetate and benzoyl peroxide [103] or from an oligo-aspartimide (BMI-diamine reaction product), BPA/DC, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane (i.e. Tetrabromo-Bisphenol A) and 2-ethyl-4-methylimi-dazole [104]. A mixture of BPA/DC, BMI and epoxide resin with brominated polycarbonate, copoly[oxy-2,6-dimethylphenylene)-(oxy-2,3,6-trimethylphenylene)] and a catalyst was also suggested [105],... 

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