Tributyltin Acrylate Research Articles

Wood Preservation Based on In situ Polymerization of Bioactive Monomers. Part 2. Fungal Resistance and Thermal Properties of Treated Wood

Summary This paper is the second in a two-part series on in situ polymerization of bioactive monomers as an alternative to conventional preservative treatments. In this part of the study, bioactive monomers were evaluated for their ability to provide resistance to decay and protection against fire. Five bioactive monomers were synthesized: (1) pentachlorophenolyl acrylate (PCPA), (2) tributyltin acrylate (TBTA), (3) 8-hydroxyquinolyl acrylate (HQA), (4) 5,7-dibromo-8-hydroxyquinolyl acrylate (DBHQA), and (5) diethyl-N1N-bis (acryloxyethyl) aminomethyl phosphonate (Fyrol 6 acrylate, F6A). Southern pine sapwood samples were treated with acrylate solutions at different retention levels and with various amounts of crosslinker (trimethylolpropane trimethacrylate, TMPTM), then polymerized in situ. Methyl methacrylate (MMA) was used as the control. Biological resistance to the brown-rot fungus Gloeophyllum trabeum was determined on acetone-leached and unleached samples. PCPA showed some biological efficacy in the absence of crosslinker, but otherwise provided no more protection than did MMA alone. TBTA was biologically effective at all retention levels except with crosslinker concentration ≥10 %. HQA was biologically effective at ≥ 2% retention. F6A was not biologically effective, although unleached wood treated with 10% F6A and 5% or no crosslinker showed some resistance to decay. The 5% DBHQA plus 5% crosslinker treatment was biologically effective in both leached and unleached wood. The effects of the highest treatment level of each monomer, after polymerization, were also evaluated by thermogravimetric analysis. All treatments provided some resistance to fire. The best treatment was 10 % F6A, which resulted in the lowest mass loss (67.0 %) and the lowest maximum temperature of pyrolysis (308.5 °C).

Wood Preservation Based on In situ Polymerization of Bioactive Monomers. Part 1. Synthesis of Bioactive Monomers, Wood Treatments and Microscopic Analysis

Summary In situ polymerization of bioactive monomers was investigated as an alternative to conventional preservative treatments. The results are presented in a series of two papers. In Part 1 of the study, six acrylate monomers with covalently bonded, potentially bioactive moieties were synthesized: (1) pentachlorophenolyl acrylate (PCPA), (2) tributyltin acrylate (TBTA), (3) 8-hydroxyquinolyl acrylate (HQA), (4) 5,7-dibromo-8-hydroxyquinolyl acrylate (DBHQA), (5) diethyl-N1N-bis(acryloxyethyl) aminomethyl phosphonate (Fyrol 6 acrylate, F6A), and (6) tetrabromobisphenol A acrylate (TBBPAA). All of these acrylates, except F6A, were purified. Southern pine sapwood samples were treated with acrylate solutions (except TBBPAA) at different retention levels and various amounts of crosslinker (trimethylolpropane trimethacrylate, TMPTM), polymerized in situ, and then acetone leached. The relative amount and location of the polymer in earlywood and latewood of selected samples were determined by scanning electron microscopy and x-ray analysis. Distribution of the compounds varied with treatment. Biological and thermal properties of the treated wood are discussed in Part 2 of this series.

Synthesis, characterization, biotoxicity and antifouling study of a new organotin monomer and polymer

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.

Azeotropy in terpolymerisation reactions of tributyltin acrylate or methacrylate with itaconic acid or dimethylitaconate and N‐vinyl‐2‐pyrrolidone

AbstractTernary copolymerisations of tri‐n‐butyltin acrylate (TBTA) or tri‐n‐butyltin methacrylate (TBTMA) with itaconic acid (IA) or dimethylitaconate (DMI) and N‐vinyl‐2‐pyrrolidone (NVP) were carried out in solution at 70°C in the presence of a free radical initiator. Experimental, terpolymerisation data agreed with calculations based on the Alfrey‐Goldfinger equation. Ternary azeotropic compositions for TBTA‐IA‐NVP and TBTA‐DMI‐NVP systems were 52.60:14.80:32.60 and 56.60:26.60:16.80 mol%, respectively. Also ‘pseudoazeotropic’ regions were identified where the deviation between feed and polymer compositions is very small.

Organotin polymers. XV. Azeotropy in terpolymerization reactions of tributyltin acrylate or methacrylate with itaconic acid or dimethylitaconate and acrylonitrile

AbstractTernary copolymerization of tri‐n‐butyltin acrylate (TBTA) or methylacrylate (TBTMA) with itaconic acid (IA) or dimethyl itaconate (DMI) and acrylonitrile (AN) were carried out in solution at 70°C in the presence of a free radical initiator. Experimental terpolymerization data agreed well with calculations based on the Alfrey‐Goldfinger equation. Ternary azeotropic compositions for TBTA‐IA‐AN, TBTMA‐IA‐IA, and TBTMA‐DMI‐AN systems were 39.0 : 26.1 : 34.9, 51.7 : 10.5 :37.8, and 00.3 : 66.3 : 33.4 mol %, respectively. Also, “pseudo‐azeotropic” regions were indentified where the deviation between feed and polymer compositions is very small.

Ecotoxicity studies of some organotin compounds

The ecotoxicities of three organic compounds containing spacer groups, an intermediate organotin premonomer, four organotin monomers, their homopolymers and six copolymers of tributylin α‐chloroacrylate (TCA) are reported against two microorganisms viz., Pseudomonas aeruginosa and Sarcina lutea and a larval species Anemia salina (Nauplii II). The organic compounds containing spacer group were less toxic whereas the monomers were found to be highly toxic. The homopolymers were found to be more toxic than that of tributyltin acrylate (TBTAA), tributyltin methacrylate (TBTMA) and tributyltin α‐Chloroacrylate (TCA). The toxicity of TCA copolymers increased with the increase in tributyltin (TBT) content in the polymer. From this study it was not possible to establish any relationship between the chemical nature of the comonomer with its toxicity.

Biotoxicity of tributyltin acrylate polymers

AbstractThe biotoxicity of 3 tributyltin monomers, their homopolymers, and 8 copolymers of tributyltin α‐chloroacrylate (TCA) against 2 microorganisms (Pseudomonas aeruginosa, Sarcina lutea) and the larvae Artemia salina (Naupli II) is reported. Biotoxicity of the TCA monomer was found to be lower than that of the tributyltin acrylate (TBTAA) monomer. However, the toxicity of homopolymers of TCA was higher than that of TBTAA. The toxicity of copolymers increased with an increase in tributyltin content in the polymer. The biotoxicity could not be correlated with the chemical structure of the polymer.

Synthesis, characterization and biotoxicity study of α-methyl p-acryloyloxy tributyltin benzoate monomer and polymer

A new organotin monomer, α-methyl p-acryloyloxy tributyltin benzoate, has been synthesized by the reaction of p-ydroxy tributyltin benzoate and methacrylic acid in the presence of dicyclohexylcarbodiimide. The monomer is polymerized by radical polymerization using azobisisobutyronitrile as initiator in tetrahydrofuran and dimethylformamide at 60°. The monomer and the unfractionated homopolymer have been characterized by tin analysis, i.r. and NMR spectral studies, solubility and viscosity measurements. The thermal properties were examined by thermogravimetry, differential thermogravimetry and differential scanning calorimetry. Biotoxicity testing of the parent compound, premonomer, monomer and homopolymer was performed with two bacterial species. The newly developed monomer and its homopolymer were compared with tributyltin acrylate, tributyltin methacrylate and tributyltin α-chloracrylate and their homopolymers.

Light scattering characterization of organotin polymers: 1. Tributyltin acrylate copolymer Cutinox-1000

Laser light scattering including both elastic (integral) and quasielastic measurements, supplemented by intrinsic viscosity data, has been used to characterize a tributyltin acrylate copolymer commercially known as Cutinox-1000 in dilute solution. Four solvents differing in their thermodynamical quality and optical properties were used. Chemical composition heterogeneity of the investigated sample was estimated to be sufficiently small not to influence significantly results of light scattering measurements. Coupled integral and quasielastic light scattering methods were used to determine the molecular weight distribution function, from which the polydispersity of the investigated copolymer sample was estimated to be M¯ w/ M¯ n= 2.1. Determined molecular properties were in reasonable agreement with some theoretical predictions. Conformational parameters, such as the steric factor σ, statistical segment length and R¯ H/ R¯ G ratio, as compared with poly(methyl methacrylate) values suggest some small increase of the copolymer rigidity, probably due to steric hindrance caused by the large metalloorganic side groups.

Antifouling performance of some new organotin polymers in the Mediterranean and Red Sea

Three new organotin polymers with built-in organotin moieties were prepared from tributyltin acrylate and methacrylate with other vinyl monomers. The tin content of the prepared polymers was 19.5–22.5%. The antifouling performance of the polymers was tested as un-pigmented and pigmented coatings by raft exposure to the local fouling-intensive marine environment in the harbours of Alexandria and El-Ghardaqua. Formulations based on tri-n-butyltin methacrylate, methyl methacrylate, acrylonitrile and tri-n-butyltin acrylate showed good antifouling efficiency for more than 22 months.

Organotin polymers-V. Binary and ternary copolymerization reactions of tributyltin acrylate and methacrylate with vinyl acetate and N-vinylpyrrolidone

Copolymerization reactions were carried out in solution at 70°C in the presence of a free radical initiator, and the copolymer composition in each case was determined from tin analysis. The monomer reactivity ratios for the copolymerization reactions of tributyltin acrylate with vinyl acetate and N-vinylpyrrolidone were found to be: r 1 = 2.567, r 2 = 0.006 and r 1 = 0.513, r 2 = 0.610, respectively. Also, the copolymerization parameters of tributyltin methacrylate with vinyl acetate and N-vinylpyrrolidone were: r 1 = 4.408, r 2 = 0.017 and r 1 = 3.160, r 2 = 0.438, respectively. Four selected terpolymer feed compositions involving tributyltin acrylate or methacrylate with vinyl acetate or methyl methacrylate and N-vinylpyrrolidone or acrylonitrile, were polymerized to low conversion and the terpolymer composition in each case was calculated from tin and nitrogen analyses. The variations of terpolymer composition with conversion fit the experimental results over a wide range of conversion. The structure of the prepared co- and terpolymers was investigated by i.r. spectroscopy.

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

The monomer reactivity ratios for the copolymerization of tributyltin acrylate with styrene and allyl methacrylate have been found to be r1 = 0.213, r2 = 1.910 and r1 = 0.195, r2 = 2.257, respectively. Also, the copolymerization parameters of tributyltin methacrylate with styrene and allyl methacrylate were as follows: r1 = 0.256, r2 = 1.104 and r1 = 2.306, r2 = 1.013. Copolymerization reactions were carried out in solution at 70°C using 1 mole % AIBN, and the copolymer compositions were determined by tin analysis. Ternary copolymerization of the three systems butyl methacrylate–tributyltin methacrylate–acrylonitrile, butyl acrylate–tributyltin methacrylate–acrylonitrile, and styrene–tributyltin acrylate–acrylonitrile have been studied, and the terpolymer composition of each system was determined through tin and nitrogen analyses. The variation of instantaneous and average terpolymer composition with conversion fit satisfactorily the experimental results over a wide range of conversion.

Organotin polymers—III: Copolymerization and terpolymerization of tributyltin acrylate with methyl methacrylate, propyl methacrylate, butyl methacrylate and acrylonitrile

Copolymerizations of tri- n-butyltin acrylate (M 1) with (a) methyl methacrylate (M 2), (b) propyl methacrylate (M 3), (c) butyl methacrylate (M 4) and (d) acrylonitrile (M 5) in solution at 70 using AIBN as initiator led to monomer reactivity ratios as follows: (a) r 1 = 0.401 and r 2 = 2.199, (b) 0.323 and 1.713, (c) 0.196 and 1.65, and (d) 0.243 and 1.008. The variation of the average copolymer composition with conversion for two copolymers from M 1 with M 2 and M 4 were calculated and verified experimentally. Four terpolymer compositions involving M 1 and M 5 with M 2 or M 4 were prepared and the terpolymer compositions were calculated on the basis of tin and nitrogen analyses. The variations of instantaneous and average terpolymer composition with conversion fit satisfactorily the experimental results over a wide range of conversion.

Interfacial preparation and properties of poly(tributyltin acrylate) and related polymers

Journal of Applied Polymer ScienceVolume 19, Issue 10 p. 2911-2912 NoteFree Access Interfacial preparation and properties of poly(tributyltin acrylate) and related polymers D. Oldfield, D. Oldfield Materials Research Laboratories, Department of Defence Maribyrnong, Victoria, 3032, AustraliaSearch for more papers by this author D. Oldfield, D. Oldfield Materials Research Laboratories, Department of Defence Maribyrnong, Victoria, 3032, AustraliaSearch for more papers by this author First published: October 1975 https://doi.org/10.1002/app.1975.070191026AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume19, Issue10October 1975Pages 2911-2912 ReferencesRelatedInformation

Polymers of tributyltin acrylate esters

Journal of Polymer ScienceVolume 32, Issue 125 p. 523-525 Letter to the Editor Polymers of tributyltin acrylate esters† J. C. Montermoso, J. C. Montermoso Chemicals & Plastics Division, QMR&E Command, Natick, MassachusettsSearch for more papers by this authorT. M. Andrews, T. M. Andrews Chemicals & Plastics Division, QMR&E Command, Natick, MassachusettsSearch for more papers by this authorL. P. Marinelli, L. P. Marinelli Chemicals & Plastics Division, QMR&E Command, Natick, MassachusettsSearch for more papers by this author J. C. Montermoso, J. C. Montermoso Chemicals & Plastics Division, QMR&E Command, Natick, MassachusettsSearch for more papers by this authorT. M. Andrews, T. M. Andrews Chemicals & Plastics Division, QMR&E Command, Natick, MassachusettsSearch for more papers by this authorL. P. Marinelli, L. P. Marinelli Chemicals & Plastics Division, QMR&E Command, Natick, MassachusettsSearch for more papers by this author First published: November 1958 https://doi.org/10.1002/pol.1958.1203212525Citations: 52 † Presented at the American Chemical Society Meeting (Polymer Division), San Francisco, California, April 1958. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume32, Issue125November 1958Pages 523-525 RelatedInformation