Utilisation of mangrove bark extracts in cold-setting wood adhesives
Extraction of mangrove bark with 4.0% aqueous sodium sulfite and 0.4% aqueous sodium carbonate at 100° and 2 hours gives 24-26% yields compared with extraction by water at 70° for 2 hours which gives 21%. The hot water extracts are more acidic (pH 3.6) than is the sulfite extract (pH 5.6); both are reasonably reactive toward formaldehyde (Stiasny number 70.6 using water and 85.4 using aqueous sulfite-carbonate). The 13C NMR spectra of R. mucronata shows this tannin to have phloroglucinolic A-rings with hydroxy groups at C-5 and C-7 and pyrogallolic B-rings with hydroxy groups at C-3', C-4', and C-5'. The interflavanoid linkages are C-4→C-8 and C-4→C-6. The 13C NMR spectra also indicate the presence of a considerable amount of carbohydrate which is shown to be mainly rhamnose, glucose, arabinose, and uronic acids. Sulfitation of R. mucronata bark reduces the total carbohydrate and the rhamnose extracted but increases the amount of arabinose and uronic acids. The bark storage period has significant effects on the pH and the reactivity of the aqueous tannin solution. Barks stored for <4 weeks produce higher extraction yields than those stored for > 6 weeks and contain significantly larger amount of reactive tannin and have shorter gel times. The reactivity of bark extracts towards formaldehyde can be controlled either by limiting the duration of bark storage to 4 weeks or by maintaining the aqueous tannin solution at pH <10.0. The aqueous tannin solution from R. mucronata exhibited properties such as viscosity, solubility and tackiness which were superior to those from the R. apiculata extract while the mixed R. mucronata-R. apiculata aqueous tannin solution had properties in between these. These barks could be used singly or together as a source of tannin without the bond strength of the resulting glued joints being significantly affected. The "honeymoon" bonding technique improved the bond strengths of joints made using sulfited tannin but is suitable only for tannin solutions containing > 4% aqueous sodium hydroxide. The viscosity of sulfited tannin adhesives is influenced by (a) the amount of aqueous sodium hydroxide added to the aqueous tannin solution, and (b) the lapse time, i.e. the period between the addition of sodium hydroxide to the aqueous tannin solution and the addition of phenol-resorcinol-formaldehyde (PRF) resin, hardener, and paraformaldehyde. The present study shows that with the addition of 5% w/w sodium hydroxide and at a curing temperature of 40° the sulfited tannin extracts from the bark of mangrove trees can replace about 50% w/w of the PRF resin in cold-setting wood adhesives with the production of bond strengths comparable to those produced by 100% PRF resin.