Organotin polymers. IV. Binary and ternary copolymerizations of tributyltin acrylate and methacrylate with styrene, allyl methacrylate, butyl methacrylate, butyl acrylate, and acrylonitrile

Pomogailo A.D., Kestelman V.N., Dzhardimalieva G.I.

Polymerization of unsaturated metal carboxylates is a unique method of synthesis of metallopolymers with a metal atom included in each monomeric unit. In utmost cases, metallopolymers of the type under consideration are prepared by radical polymerization, which comprises the same elementary steps as for conventional monomers. The rate of radical polymerization.(w) is described by the known equation:

Al-Deyab S.S., Al-Hazmi A.M., El-Newehy M.H.

Organotin monomers containing dibutyltin groups – dibutyltin citraconate (DBTC) as a new monomer and dibutyltin maleate (DBTM) – were synthesized. Free radical copolymerizations of the organotin monomers with styrene (ST) and butyl acrylate (BA) were performed. The overall conversion was kept low (≤15% wt/wt) for all studied samples and the copolymers composition was determined from tin analysis using the Gillman and Rosenberg method. The reactivity ratios were calculated from the copolymer composition using the Fineman-Ross (FR) method. The synthesized monomers were characterized by elemental analysis, 1H-, 13C-NMR and FTIR spectroscopy.

Iyer B.D., Mathakiya I.A., Shah A.K., Rakshit A.K.

Tercopolymers of acrylamide (AM), acrylic acid (AA) and acrylonitrile (AN) synthesized by free radical solution polymerization have been characterized using 13C NMR and thermal analysis (DSC) techniques. Incorporation of the above three monomers was confirmed by 13C NMR analysis. The tercopolymers have similar polymer backbone structures, and a limited branching in the main chain was found as evidenced by DSC analysis. Microbiological observations of polymer-dependent growth and of respiration studies using a soil bacterial isolate, suggested that these tercopolymers were used as growth substrate and were therefore biodegradable. © 2000 Society of Chemical Industry

Vallee-Rehel K., Mariette B., Hoarau P.A., Guerin P., Langlois V., Langlois J.Y.

Environmental concerns have led to a progressive withdrawal of antifouling paints containing organotin derivatives. Resanbio®, a cooperative research program, plans to develop new antifouling paints that are more compatible with living species. In the first stage, we studied specific acrylic polymers with a variable hydrophilic/hydrophobic balance and, in some cases, pendant hydrolyzable functions. To evaluate the ability of these materials for hydrolysis, biocides release, and erosion, test panels with formulated films were prepared and immersed in sea water. An analytical protocol was established to characterize the polymeric material, to reveal chemical reactions that occur during erosion and antifouling action, and to understand the influence of the resin chemical structure on the paint’s antifouling efficiency. The degradation of these binders was revealed by the appearance of a product resulting from the hydrolysis. This product was identified and quantified by GC-MS. The release of cuprous oxide as model molecule, due to its water solubility and biocide activity, was quantified by inductively coupled plasma. The different processes used are explained and illustrated by an example of an efficient, erodable, antifouling paint following 22 months of immersion.

Joshi R.R., Gupta S.K.

A new organotin monomer, p -acryloamino tributyltin benzoate, has been synthesized by the reaction of p -amino tributyltin benzoate and acryloyl chloride in the presence of dry pyridine. The monomer is polymerized by free radical polymerization using azobisisobutyronitrile as initiator in dimethylformamide and 1–4 dioxane at 55 ± 0.1 °C. The monomer and the unfractionated homopolymer have been characterized by tin analysis, solubility, i.r. and NMR spectral studies and viscosity measurements. The thermal properties were examined by thermogravimetry (TG), and differential thermal analysis (DTA). Biotoxicity testing of the premonomer, monomer and homopolymer was performed with two bacterial and one larval species. The antifouling property of the homopolymer was tested in a marine environment. The newly developed monomer and its homopolymer were compared with tributyltin acrylate (TBTA), tributyltin methacrylate (TBTMA), tributyltin α-chloroacrylate (TCA) and α-methyl p -acryloxy tributyltin benzoate (MATE) and their homopolymers.

Siah L., Das V.G., Gan S.

Shukla P., Srivastava A.K.

Solution terpolymerization of styrene, acrylonitrile and chromium acrylate has been carried out in dimethylformamide at 85°C using styrene-arsenic sulfide complex as radical initiator. 1H nuclear magnetic resonance (n.m.r.), infra-red (i.r.) and elemental analysis have been used to characterize the terpolymer. Data from 1H n.m.r., elemental analysis and gravimetric analysis have been used to evaluate terpolymer composition. Reactivity ratios (calculated from Finemann-Ross method as r1(Sty) = 5 ± 2 r2(AN + CrA) = 0.15 + 0.02) and composition confirm its random origin. The terpolymer was highly thermally stable and has a glass transition temperature of 96°C as evaluated from differential scanning calorimetry studies.

Mahmoud A.A., Azab M.M., Messiha N.N.

Radical copolymerizations of p -acryloyloxy-tri-n-butyltin benzoate (ABTB) with allyl methacrylate, N -vinyl pyrrolidone and vinyl acetate were carried out in solution at 70° using 1 mol% azobisisobutyronitrile as initiator. The copolymer compositions were determined from tin analyses. The monomer reactivity ratios for copolymerizations of ABTB (monomer-1) with allyl methacrylate, N -vinyl pyrrolidone and vinyl acetate have been found to be r 1 = 0.28, r 2 = 0.89; r 1 = 0.07; r 2 = 0.40 and r 1 = 0.92, r 2 = 0.99, respectively. The Q and e values for the organotin monomer were calculated.

Mahmoud A.A., Shaaban A.F., Azab M.M., Messiha N.N.

p -Acryloyloxybenzoic acid (ABA) and N -methacryloyloxytetrabromophthalimide (NMTP) were prepared. The monomer reactivity ratios for the copolymerization of tri-n-butyltin acrylate (monomer-1) with ABA and NMTP have been found to be r 1 , = 1.01, r 2 = 0.40 and r 1 , = 0.69, r 2 = 0.90 respectively; those for tri-n-butyltin methacrylate (monomer-l) with ABA and NMTP were r 1 = 2.21, r 2 = 0.87 and r 1 = 0.85, r 2 = 1.35 respectively. Copolymerizations were carried out in solution at 70° using 1 mol% azobisisobutyronitrile as initiator. The structures of the monomers were investigated by i.r. and 1 H-NMR.

Shi L., Zhou G., Deng Y., Han Z., Wu P.

The crystal and molecular structure of (C6H5)3SnOCOCCH2CH3 has been determined by a single crystal X-ray diffraction study. The crystal is monoclinic with space group P21/c,a=11.902(3),b=10.104(4),c=16.721(2) Å,β=97.56(1)°,V=1930.4 Å3,Z=4 andD c =1.495 g/ cm3,F(0,0,0)=872,λ(CuKα)=1.5418 Å. The structure was solved by the heavy-atom method and refined by full-matrix least-squares procedures to anR factor of 0.060 based on 2157 independent reflections. The results showed that the Sn-O bond distance is 2.064(4) Å. The average Sn-C bond distance is 2.126 Å. There is a weak coordination through the O of the CO group of the methacrylate residue (Sn-O(2) 2.774(5) Å) except for four normal coordinations. The coordination number at the Sn4+ is 5.

Ayoub M.M., Abdel Malek M.M., Messiha N.N.

An organotin copolymer with tin content of 22% was prepared by the reaction of methyl methacrylate and tri‐n‐butyltin methacrylate. The prepared copolymer was incorporated into a paint formulation containing cuprous oxide as an external toxin. Laboratory evaluation of the formulation showed that the average value of the leaching rate of Cu was 7 µg/cm2/day, while the leaching rate of tin was found to be in the range of 0.033 µg/cm2/day. The antifouling performance of the prepared formulation was tested as painted areas on the hull of a trading ship. After about one year's running period through the Mediterranean and Red Sea harbours the tested areas showed good antifouling efficiency compared with the commercial antifouling paint.

Shaaban A.F., Arief M.M., Mahmoud A.A., Messiha N.N.

The monomer reactivity ratios for the copolymerization of di-(tri-n-butyltin) itaconate (M1) with methyl acrylate (M2), ethyl acrylate (M2), N-vinyl pyrrolidone (M2) and acrylonitrile (M2) were found to be r1 = 0.387, r2 = 0.671; r1 = 0.555, r2 = 0.958; r1 = 0.033, r2 = 0.185 and r1 = 0.441, r2 = 0.425, respectively. Copolymerization reactions were carried out in solution at 60°C using 1 mol% AIBN, with copolymer compositions being determined by tin analysis. The Q and e values for di-(tri-n-butyltin) itaconate were calculated from the monomer reactivity ratios determined in the present and previous studies. The sequence distribution of the triad fractions for the systems studied were calculated at azeotropic compositions.

Blunden S.J., Hill R.

Stationary or mobile structures immersed in sea-water, such as off-shore platforms, drilling rigs, buoys, ships’ hulls or submarines, are subject to fouling, arising from the settlement, attachment and growth of marine plants and animals. Fouling also occurs in fresh-water, but this does not produce the severe undesirable effects observed in the oceans and seas. The most practical method of dealing with this problem involves the application of a suitable antifouling coating which incorporates chemical(s) poisonous to the settling stages of aquatic organisms. Triorganotin compounds are proving themselves to be highly effective toxicants in these systems (Table 1), some 3500 tons being currently used for this application.1

Peng F.M.