Organotin Monomers Research Articles

Synthesis, Characterization and Transesterification Activity of Cross-Linked Styrenic Resins Containing the Triphenyltincarboxylate Moiety Spaced by a Dimethylene from the Aromatic Ring

An organotin monomer, triphenyltin 3-(4-styryl)-propionate (TPTSPr) has been synthesized and copolymerized in different ratios with styrene and 1,4-divinylbenzene in order to obtain resins with catalytic activity in transesterification reactions. The resins and a low molecular weight model compound, triphenyltin 3-(4-ethylphenyl)-propionate (TPT-C2-Pr), mimicking the catalytic co-unit, have been characterized by FT-IR and NMR spectroscopy, with particular attention paid to the coordination at tin and how it correlates to the catalytic activity. The activity of both the resins and of the model compound have been tested in a transesterification model reaction between ethyl acetate and primary alcohol. All the resins show catalytic activity that decreases with increasing content of the active co-unit in the resins, owing to the interaction of the active sites among themselves.

Synthesis, Characterization and Reactivity Ratio Study of Poly(di(tri-n-butyltin) citraconate-co-N-vinylimidazole)

The organotin monomer di(tri-n-butyltin) citraconate (DTBTC, I) was synthesized. Subsequently this monomer was copolymerized with N-vinylimidazole (VI) using a free radical technique. The overall conversion was kept low (≤14% wt/wt) for all studied samples and the copolymer composition was determined from tin analysis using the Gilman and Rosenberg method. The synthesized monomer and copolymer were further characterized by elemental analysis, 1H- and 13C-NMR, and FTIR spectroscopy.

Reactivity Ratios for Organotin Copolymer Systems

Di(tri-n-butyltin) itaconate (DTBTI) and monoethyl tributyltin fumarate (METBTF) were synthesized as organotin monomers. The organotin monomers were copolymerized with styrene (ST) and methyl methacrylate (MMA) via a free radical polymerization technique. The overall conversion was kept low (°15% wt/wt) for all studied samples and the copolymer composition was determined from tin analysis. The synthesized monomers and copolymers were characterized by elemental analysis, 1H- and 13C-NMR, and FTIR spectroscopy.

Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

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.

Synthesis and copolymerization reactions of p‐acryloyloxybenzoic acid with organotin monomers

Abstractp‐Acryloyloxybenzoic acid (PAB) was prepared by the reaction of p‐hydroxybenzoic acid and acryloyl chloride in the presence of triethylamine. Triphenyltin acrylate (TPTA), triphenyltin methacrylate (TPTMA), p‐acryloyloxytriphenyltin benzoate (TPTB) and triphenyltin itaconate (TPTI) monomers were prepared by the reactions of acrylic, methacrylic, p‐acryloyloxybenzoic and itaconic acids, respectively, with triphenyltin hydroxide in the presence of dicyclohexylcarbodiimide (DCCI) as a dehydrating agent. Binary copolymerizations of PAB with TPTA, TPTMA, TPTB and TPTI were performed in dimethylformamide (DMF) using 1 mol% azobisisobutyronitrile (AIBN) as initiator at 65 °C. The structures of the monomers and copolymers were investigated by IR and 1H NMR spectrometry. The composition of the copolymers was determined by tin analysis. Copolymerization parameters for each system were calculated by both the Fineman–Ross and Kelen–Tüdös methods. The monomer reactivity ratios for the four systems studied, PAB‐TPTA, PAB‐TPTMA, PAB‐TPTB and PAB‐TPTI, were found to be r1 = 0.468, r2 = 2.096; r1 = 0.435, r2 = 2.292; r1 = 0.449, r2 = 2.225 and r1 = 0.416, r2 = 4.526, respectively. The average Q and e values for the prepared organotin monomers were calculated. Copyright © 2004 Society of Chemical Industry

Synthesis and characterization of novel organotin monomers and copolymers and their antibacterial activity

Two novel organotin monomers, (N-tri-n-butyltin) maleimide and m-acryloylamino-(tri-n-butyltin benzoate), were synthesized. Copolymerization of these two monomers with styrene was carried out in the bulk at 65°C using asobisisobutyronitrile as the free radical initiator. The monomers and copolymers were characterized by elemental analysis; the molecular weights of the copolymers were determined by GPC, solubility, IR, and 1H-NMR spectral studies. The antibacterial activities of the synthesized organotin monomers and copolymers toward various types of bacteria were also reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 740–745, 2000

Synthesis and characterization of novel organotin monomers and copolymers and their antibacterial activity

Two novel organotin monomers, (N-tri-n-butyltin) maleimide and m-acryloylamino-(tri-n-butyltin benzoate), were synthesized. Copolymerization of these two monomers with styrene was carried out in the bulk at 65°C using asobisisobutyronitrile as the free radical initiator. The monomers and copolymers were characterized by elemental analysis; the molecular weights of the copolymers were determined by GPC, solubility, IR, and 1H-NMR spectral studies. The antibacterial activities of the synthesized organotin monomers and copolymers toward various types of bacteria were also reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 740–745, 2000

Preparation and reactivity of a macroporous polymer-supported organotin hydride catalyst

Macroporous beads bearing organotin moieties have been synthesized by suspension copolymerization of a convenient organotin monomer with styrene and a crosslinking agent in the presence of a porogen. The influence of the nature and amount of the crosslinking agent on the properties of the resulting materials are discussed in terms of their permanent porosity, their swelling in solvents and their average pore diameter. The catalytic activity of the polymer-supported organotin chloride obtained has been tested in the reduction of 1-bromoadamantane by the sodium tetrahydroborate. The results are comparable with those observed with soluble tributyltin hydride. The good stability of the grafted tin functionality was demonstrated by performing several successive batches with constant activity without the need of a regeneration step.

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.

Plasma surface modification of polyethylene with organosilicon and organotin monomers

Plasmochemical modification of a polyethylene (PE) film surface by several selected silicon and tin containing monomers, such as vinyltriethoxysilane (VTES), hexamethyldisiloxane (HMDS), 3-aminopropyltriethoxysilane (APTS), tetraethylstannane (TES) and hexabutyldistannoxane (HBDS) were all examined. The structure and properties of plasma polymers obtained and plasma modified PE film surfaces were studied by FTIR, photoacoustic FTIR spectroscopies and by using surface energy and swelling measurements. It is shown that the structure of plasma polymers formed either on the inorganic non-active or on the organic active (PE films) surfaces do not differ much from each other. In the structure of the organosilicon surface plasma polymers, mainly polysiloxane type fragments emerge; while for the organotin analogs primarily carboxylate fragments predominate. The plasma of organosilicon and organotin compounds were used to modify PE film surfaces to produce thin hydrophobic, biologically active and inactive surfaces. The results of surface energy studies as followed by the interaction with methylene iodide (non-polar) and ethylene glycol (polar components), and degree of swelling studies for both unmodified as well as plasma modified PE films, in xylene showed decrease in the latter and an increase of hydrophobic components as expected.

Organotin polymers—XIX. Copolymerization parameters of p-acryloyloxy-tri-N-butyltin benzoate with allyl methacrylate, N-vinylpyrrolidone and vinyl acetate

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.

Effect of substitution on the reactivity of some new p‐phenylacrylamide derivatives with organotin monomers

AbstractThree new monomers of p‐phenylacrylamide derivatives were prepared by either the reaction of p‐methyl‐, p‐nitro‐, and p‐chloroaniline with acryloyl chloride or with acrylic acid in the presence of dicyclohexyl carbodiimide (DCCI). The prepared monomers were copolymerized with each of tri‐n‐butyltinacrylate and tri‐n‐butyltinmethacrylate. Copolymerization reactions were carried out in dioxane at 70°C using 1 mol % azobisisobutyronitrile as a free radical initiator. The structure of the new monomers and the prepared copolymers were investigated by IR and 1H‐NMR spectroscopy. The monomer reactivity ratios for the copolymerization of p‐chlorophenylacrylamide (M1) with each of tri‐n‐butyltinacrylate (TBTA) and tri‐n‐butyltinmethacrylate (TBTMA) (M2) were found to be r1 = 2.6; r2 = 0.83 and r1 = 1.3; r2 = 1.71, respectively. In case of p‐tolyacrylamide (M1) with TBTA and TBTMA (M2) r1 = 0.35, r2 = 1.03 and r1 = 1.38, r2 = 0.366 respectively. The Q and e values for the prepared p‐tolyl‐ and p‐chlorophenylacrylamide were calculated © 1993 John Wiley & Sons, Inc.

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.

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.

Ecotoxicity studies of some organotin monomers and polymers

Ecotoxicity data are reported for α‐substituted tributyltin monomers and polymers against two species of bacteria viz. Pseudomonas aeruginosa and Sarcina hutea and a crustacean specie Artemia salina larva. The results show that the toxicity of the compounds increased with the increase in tributyltin contents in the polymers. The homopolymers were most toxic towards the larvae amongst the polymers. Uncured polymers were found to be more toxic than cured polymers. It was not possible to correlate the biotoxicity with the chemical structure of the polymer.

Synthesis, polymerization and copolymerization of a new organotin monomer. Application of a copolymer as catalyst for reductive dehalogenation of alkyl halides

AbstractA new organotin monomer, N‐[3‐(tributylstannyl)propyl]methacrylamide (5) was synthesized in 49% yield by hydrostannylation of acrylonitrile with tributyltin hydride and subsequent reduction of the resulting 3‐tributylstannylpropionitrile (3) with lithium aluminium hydride into 3‐tributylstannylpropylamine (4) which reacted with methacryloyl chloride to afford 5. Polymerization of 5 and copolymerization of 5 with styrene gave homopolymer 6 and copolymer 7, respectively. In a model study on the stability toward solvolysis, N‐(3‐tributylstannylpropyl)propionamide (8) showed no reactivity, whereas the corresponding ester derivative, 3‐tributylstannylpropyl propionate (9), easily reacted with ethanol to release the tin moiety. Monobromostannyl derivative 10, formed by the reaction of 7 with bromine, showed the catalytic activity in the reductive debromonation of dodecyl bromide with sodium borohydride under photoirradiation conditions at room temperature.

Organotin polymers XIV. Synthesis and copolymerization reactions of p‐acryloyloxy‐tri‐n‐butyltin benzoate with some vinyl monomers

Abstractp‐Acryloyloxy‐tri‐n‐butyltin benzoate (ABTB) was prepared by the reaction of p‐hydroxy‐tri‐n‐butyltin benzoate and acrylic acid in the presence of dicyclohexylcarbodiimide. The monomer reactivity ratios for the copolymerizations of ABTB (M1) with methyl acrylate (M2), ethyl acrylate (M2), n‐butyl acrylate (M2), methyl methacrylate (M2), styrene (M2) and acrylonitrile (M2) have been found to be r1 = 0.080, r2 = 1.046; r1 = 0.039, r2 = 1.585; r1 = 0.019, r2 = 2.076; r1 = 0.150, r2 = 1.710; r1 = 0.113, r2 = 1.339 and r1 = 0.007, r2 = 2.853, respectively. The Q and e values for the prepared organotin monomer were calculated. Copolymerization reactions were carried out in solution at 70°C using 1 mol‐% azobisisobutyronitrile. The structure of the ABTB monomer and the prepared copolymers was investigated by IR and 1H‐NMR spectroscopy.

Deposition of conducting thin films of organometallic monomers by plasma polymerization

There has been a growing interest in depositing metal-containing thin films by plasma polymerization for various applications. These films have been deposited by two methods (a) by plasma polymerization of volatile organometallic monomers, and (b) by simultaneous plasma etching and polymerization in the same system, resulting in metal-containing fluoropolymers. Heretofore, most films so deposited have had low metal to carbon ratios and are insulating in nature. In our laboratories, we have been working on the plasma polymerization of volatile organometallic monomers with an aim to producing conducting films. We have observed that there is a critical threshold value of metal to carbon composition above which the films become electrically conductive. The key to depositing films having higher metal to carbon ratios is the plasma conditions. In this paper, we will review the work in our laboratories on plasma polymerization of organometallic monomers and discuss the preparation and properties of organotin monomers with various tin to carbon ratios. We will also discuss some of our recent results on plasma polymerization of an organoiron monomer. These films have been characterized by ESCA, IR, SEM, TEM, and x-ray diffractograms.

Organotin polymers: 6. Copolymerization parameters for tri-n-butyltin maleate, acrylate and methacrylate with some vinyl monomers

The monomer reactivity ratios for the copolymerization of methyl methacrylate (M 1), styrene (M 1), butyl acrylate (M 1) and acrylamide (M 1) with tri-n-butyltin maleate (M 2) have been found to be r 1 = 15.40, r 2 = 0.01; r 1 = 6.70, r 2 = 0.05; r 1 = 9.39, r 2 = 0.11; and r 1 = 122.44, r 2 = 0.06, respectively. Also, the copolymerization parameters of acrylamide (M 1) with tri-n-butyltin acrylate (M 2) or methacrylate (M 2) were as follows: r 1 = 0.11, r 2 = 0.82; and r 1 = 1.46, r 2 = 0.85, respectively. The Q and e values for the organotin monomers (tri-n-butyltin maleate, acrylate and methacrylate) were calculated from the monomer reactivity ratios determined in the present and previous studies. Copolymerization reactions were carried out in solution at 70°C using 1 mol% AIBN, and the copolymer compositions were determined by tin analysis. The structure of the tri-n-butyltin maleate and the prepared copolymers was investigated by i.r. spectroscopy.

Organotin monomers and polymers—V. The dependence of the formation of organotin polymers upon the polymerization conditions and some physicochemical properties of organotin copolymers : M. F. Shostakovskii, V. N. Kotrelev, G. I. Kuznetsova, S. P. Kalinina, L. V. Laine, A. I. Borisova, Vysokomol. soedin. 3: No. 8, 1131–1134, 1961

Organotin monomers and polymers—V. The dependence of the formation of organotin polymers upon the polymerization conditions and some physicochemical properties of organotin copolymers : M. F. Shostakovskii, V. N. Kotrelev, G. I. Kuznetsova, S. P. Kalinina, L. V. Laine, A. I. Borisova, Vysokomol. soedin. 3: No. 8, 1131–1134, 1961