SULFUR-BASED POLYMERS

Abstract

The present invention relates to curable compositions based on elemental sulfur and polymer components. The inventive composition cures in the presence of elemental sulfur, thus providing a novel composition with enhanced chemical and physical properties in particular useful for sealing and coating applications.

Claims

1. A curable composition, comprising: a) a multifunctional thioester; b) elemental sulfur; and c) at least one ethylenically unsaturated compound.

2. The composition of claim 1, wherein the at least one ethyl enically unsaturated compound is an activated ethylenically unsaturated compound.

3. The composition of claim 1, wherein the multifunctional thioester is selected from: (i) RCOSRSCOR, wherein R independently is, linear, branched or cyclic C.sub.1-C.sub.10 alkyl, aryl, heteroaryl; R is a linear, cyclic or branched C.sub.1-C.sub.10 alkyl, alkoxy, or a single bond; or (ii) a compound of formula I, II or III: ##STR00003## wherein: X independently is H or RCOSR.sup.1; or a polymer of formula HS[(CH.sub.2(R).sub.hCH.sub.2S.sub.a).sub.c(RS.sub.a).sub.d(SH).sub.f]CH.sub.2(R).sub.bCH.sub.2SH where a is 1-5, b is 0 or 1, c is 5-10, d is 0-0.05c and 0.05cfd, 1>f which is d times (number of free valencies in R-2), R is O, S or a divalent saturated organic radical consisting of C and H atoms and optionally O and/or S in COC, CS.sub.aC or OH links; R independently is C.sub.1-C.sub.20, optionally substituted, linear, cyclic or branched alkyl, aryl alkylaryl, aralkyl; R.sup.1 independently is C.sub.1-C.sub.20, optionally substituted, linear, cyclic or branched alkyl, aryl alkylaryl, or aralkyl, and R.sup.2 is either H or C.sub.1-C.sub.20 alkyl.

4. The composition of claim 1, wherein the multifunctional thioester component is selected from the group consisting of distearoyldisulfane, dibenzoyldisulfane, stearoyldiester of 1,4-butandithiol, adipate of 1,4-butandithiol, succinate of 1,4-butandithiol tetraacetate of pentaerithritol-tetrakis-mercaptopropionate, tetra-benzoate of pentaerithritol-tetrakis-mercaptopropionate, diacetate of poly(ethyleneglycol) dithiol, distearate of poly(ethylene glycol) dithiol, polymeric ester of adipate and poly(ethylene glycol) dithiol, diacetate of benzene dithioles, diacetate of toluene dithioles, triacetate of trime-thylolpropane tris(3-mercaptopropionate), and maleate of poly(ethylene glycol) dithiol.

5. The composition of claim 1, wherein the ethylenically unsaturated compound is an acrylate component selected from the group consisting of 1,4-butanedioldiacrylate, 1,6-hexanedioldiacrylate, trimethylolpropanetriacrylate, pentaerythrittetraacrylate, triacrylate of one to twenty fold ethoxylated trimethylolpropane and tetraacryl ate of one-to twenty fold ethoxylated pentaerythrit.

6. The composition of claim 1, further comprising at least one catalyst.

7. The composition of claim 6, wherein the at least one catalyst is selected from the group consisting of 1,4-diaza-bicyclo[2,2,2,]octane, 1,5-diazabicyclo[4.3.0]-non-5-en, 1,8-diazabicyclo[5.4.0]-undec-7-ene, N- methyldicyclohexylamine, quinuclidine, 3-aminoquinuclidine or 3-hydroxyquinuclidine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, dimethylphenylphosphine, Ti (IV) i sopropoxi de, Ti (TV) acetyl aceton ate, Ti(IV)-tetrachloride, Zr(IV)-acetate, Zr(IV)isopropoxide, Sn-chloride, Sn-nitrate, dibutyltinlaurate, and Zn(II)-chloride.

8. The composition of claim 1 further comprising a water-capturing agent or desiccant.

9. The composition of claim 5, wherein the ratio of thioester:sulfur:acrylate is in the range from 4:1: 4 to 1:2:1.

10. The composition of claim 1, comprising: 1-20 weight-% thioester; 1-70 weight-% sulfur; 10-50 weight-% ethylenically unsaturated compound, which is an acrylate and 0-5 weight-% additive.

11. A one-component curable polymer composition comprising the composition of claim 1.

12. An adhesive, sealant or coating material comprising the composition of claim 1.

13. A method of making a one-component curable composition of claim 11, the method comprising: mixing the a) multifunctional thioester, b) elemental sulfur, and c) at least one ethylenically unsaturated compound to obtain the composition.

14. The method of claim 13 wherein the thioester, sulfur and ethylenically unsaturated compound are mixed under water-free conditions to obtain a homogeneous paste, followed by addition of water capturing agent and catalysts and packing the resulting mixture into water and humidity proof containers.

15. A water and humidity proof container containing a one-component curable composition of claim 11.

16. The composition of claim 2, wherein the at least one ethylenically unsaturated compound is an acrylate compound.

17. The composition of claim 3, wherein R.sup.1 independently is (CH.sub.2).sub.1-5CO.

18. The composition of claim 3, wherein R.sup.1 independently is CH.sub.2CH.sub.2CO.

19. The composition of claim 7, wherein the at least one catalyst is selected from the group consisting of 1,8-diazabicyclo[5.4.0]-undec-7-ene and N-methyldicyclohexylamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0021] It was an object of the present invention to provide a novel curable composition that may be formulated as a one-component system with practically unrestricted shelf-life as long as water-free conditions are maintained. Additionally the novel curable composition is easy to use and is not associated with unpleasant or strong odor.

[0022] The problem is solved by the present inventive curable composition comprising at least one multithioester, sulfur and at least one ethylenically unsaturated component resulting in a water sensitive composition. By contact with water the thioester component hydrolyses and, in-situ, sets mercapto terminated components free. These immediately further react with the ethylenically unsaturated components present in the composition in a thiol-based Michael-like addition into the cured polymer product. Such a composition is easy to manufacture and, if kept under water- or moisture-free conditions, is extremely storage stable.

[0023] Thus, the invention provides a storage stable 1K polysulfide composition based on a water-triggered curing mechanism. A further benefit of the inventive composition is the non-oxidative and non-radical curing mechanism and its insensitivity towards atmospheric oxygen or any other oxidizing and reducing agents. This altogether significantly increases the shelf-life of the novel 1K curable composition.

[0024] The basic binder system comprises at least one multifunctional thioester compound, sulfur powder, a catalyst and at least one ethylenically unsaturated compound, particularly advantageously an acrylate compound that may be selected from mono-, di-, tri-, tetra- or penta-acrylate as cross-linker, as well as, optionally, as reactive thinning agent.

[0025] For the purpose of the invention the terms sulfur or elemental sulfur are understood to refer to the nonmetallic element sulfur in simple, uncompounded or native free and/or any allotropic forms known to the skilled person.

[0026] Acrylates are a family of polymers, which are a type of vinyl polymer made from acrylate monomers. Acrylate monomers are esters that contain vinyl groups directly attached to the carbonyl carbon. Preferably the acrylates are one to 20-fold ethoxylated or propoxylated or mixed ethoxylated or propoxylated or non-oxylated glycerol, trimethylolpropane, trimethylolethane or pentaerythrite.

[0027] Advantageous acrylate components may be selected from ethyleneglycoldiacrylate, 1,2-propanedioldiacrylate, 1,3-propanedioldiacrylate, 1,4-butanedioldiacrylate, 1,3-butanedioldiacrylate, 1,5-pentanedioldiacrylate, 1,6-hexanedioldiacrylate, 1,8-octanedioldiacrylate, neopentylglycoldiacrylate, 1,1-, 1,2-, 1,3- or 1,4-cyclohexanedimethanoldiacrylate, 1,2-, 1,3- or 1,4-cyclohexanedioldiacrylate, trimethylolpro-panetriacrylate, ditrimethylolpropanepenta- or hexaacrylate, pentaerythrittriacrylate, pentaeryth-rittetraacrylate, glycerindiacrylate, glycerintriacrylate, di- or polyacrylates of sugar alcohols, preferably of sorbit, mannit, diglycerol, threit, erythrit, adonit (Ribit), arabit (Lyxit), xylit, dulcit (Galactit), maltit, isomaltit, or polyesterpolyols, polyetherols, poly-THF, poly-1,3-propanediol, polyethyleneglycol, urethaneacrylates or polycarbonateacrylates.

[0028] If a methacrylate is used it usually functions as a solvent, i.e. a reactive thinner. Typically reactive thinners are esters of methacrylic acid with alcohols of 1-20 carbon atoms.

[0029] Preferred acrylates are trimethylolpropanetriacrylate, pentaerythritetetraacrylat, dipentaeryth-ritolpentaacrylate, glycerolformalmethacrylate, polypropyleneglycoldiacrylate.

[0030] Generally speaking thioesters are the product of the esterification reaction between a carboxylic acid and a thiol resulting in compounds with the functional group RSCOR. A dithioester resembles a bifunctional ester of the general formula RCOSRSCOR, wherein R is a hydro-carbon-group or a single bond. A multifunctional thioester is the product of the esterification reaction between carboxylic acids and a polythiol, resulting in compounds with two or multiples of the functional moietySCO.

[0031] A preferred group of multifunctional thioester compounds are derived from polyols. Polyols are compounds with multiple hydroxyl functional groups available for organic reactions. This includes compounds with two hydroxyl groups, a diol, with three hydroxyl groups, a triol, with four, a tetrol and so on. Monomeric polyols such as glycerin, pentaerythritol, ethylene glycol and sucrose are of particular interest, but polymeric polyols may also be utilized. Multifunctional thioester compounds may also be derived from polyalcohols, such as polyols, polyetherols, polyesterols or polyacrylate polyols with respective functionality, preferably with a functionality of at least two. Also advantageously adipate of 1,4-butandithiol, succinate of 1,4-butandithiol, tetraacetate of pentaerithritol-tetrakis-mercaptopropionate, tetrabenzoate of pentaerithritol-tetrakis-mercaptopropionate, diacetate of Poly(ethylene glycol) dithiol, distearate of Poly(ethylene glycol) dithiol, polymeric ester of adipate and Poly(ethylene glycol) dithiol, diacetate of benzene dithioles, diacetate of toluene dithioles, triacetate of Trimethylolpropane tris(3-mercaptopropionate) or maleate of Poly(ethylene glycol) dithiol may be utilized. A preferred multifunctional thioester is derived from pentaerythritol-tetramercaptopropionate. Difunctonal thioester derived from dimercaptanes may also be envisaged such as distearoyl-1,4-butanethiolate or based on disulfanes, such as distearoyldisulfane or dibenzoyldisulfane, i.e. thioester compounds of the general structure stearoyl-SS-stearoyl or benzoyl-SS-benzoyl. Further the multi-functional thioester may present 2-20 hydrolysable functional groups, preferably 2-6 and more preferred 4-6, where such functional groups may preferably also constitute branched moieties.

[0032] Multifunctional thioesters may also encompass the following compounds described by formula's I, II, and III.

##STR00001##

[0033] Wherein,

[0034] X independently is H, RCOSR.sup.1; or a polymer of the Formula HS[(CH.sub.2(R).sub.bCH.sub.2S.sub.a).sub.c(RS.sub.a).sub.d(SH).sub.f]CH.sub.2(R).sub.bCH.sub.2SH where a is 1-5, b is 0 or 1, c is 5-10, d is 0-0.05c and 0.05c fd, 1>f which is d times (number of free valencies in R-2), R is O, S or a divalent saturated organic radical consisting of C and H atoms and optionally O and/or S in COC, CS.sub.aC or OH links.

[0035] R.sup.1 independently is C.sub.1-C.sub.20, optionally substituted, linear, cyclic or branched alkyl, aryl alkylaryl, aralkyl;

[0036] R.sup.2 independently is C.sub.1-C.sub.20, optionally substituted, linear, cyclic or branched alkyl, aryl alkylaryl, aralkyl, preferably (CH.sub.2).sub.1-6CO, more preferred (CH.sub.2).sub.2-6CO and most preferred CH.sub.2CH.sub.2CO

[0037] R.sup.2 is either H or C.sub.1-C.sub.20 alkyl.

[0038] In a first step, the multifunctional thioester-compound hydrolyzes towards contact with water, either added to the mixture or simply derived from air humidity or environment moisture. This reaction is assisted by a catalyst such as an amine, phosphine, Lewis acids, carboxylates, organyls of tin (Sn), a lanthanide (Ln), zink (Zn), bismuth (Bi), titanium (Ti), zirconium (Zr), or any of the known catalysts used to increase the rate of reaction or in acceleration of addition reactions in coating and sealing compositions. Such catalysts may be selected from primary, secondary or tertiary amines as well as quarternary ammonium salts, imines or iminiumsalts. These may be aliphatic or aromatic, wherein aliphatic are preferred. Preferred tertiary amines may be selected from trimethylamine, triethylamine, tri-n-butylamine, ethyl-di-iso-Propylamine, methyl-di-iso-propylamine, N-methylmorpholine, N-methylpiperidine, tri-ethanolamine, N,N-dimethylethanolamine, N-methyldicyclohexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, 4-N,N-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]-non-5-en (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-en (DBU), tetramethyl-guanidine, pyrrocoline, quinuclidine, 3-aminoquinuclidine or 3-hydroxyquinuclidine. Catalysts of particular advantage are 1,4-diaza-bicyclo[2,2,2]octan (DABCO), 1,5-diazabicyclo[4.3.0]-non-5-en (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-en (DBU), N-methyldicyclohexylamine, quinuclidine, 3-aminoquinuclidine, 3-hydroxyquinuclidine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, dimethylphenylphosphine, Ti(IV) isopropoxide, Ti(IV) acetylacetonate, Ti(IV)tetrachloride, Zr(IV)acetate, Zr(IV)isopropoxide, Snchloride, Snnitrate, dibutyltinlaurate, Zn(II)chloride. The hydrolysis of the thioester releases terminal multifunctional thiols, at least a dithiol such as HSRSH. Subsequently the multifunctional thiol, at least a dithiol such as HSRSH reacts with elemental sulfur to form SH-terminated polysulfides HS(S.sub.x).sub.nRSH, wherein x may be any integer from 1-8, n any integer selected from 1-100, preferably 1-50 and in most cases may be an integer from 1-25. R is either a hydrocarbon-group or a single bond. The term polysulfide as used in the context of this invention is meant to describe a class of chemical compounds containing chains of sulfur atoms. Polysulfides above S5 are generally unstable, therefore it is believed that the resulting polysulfide will comprise a mixture containing S2, S3, S4, S5, S6, S7, S8 polysulfides and/or multiples thereof.

[0039] Within the formulation it is believed that the formed polysulfides subsequently react in the presence of alkaline catalysts (amine, phosphine, or any of the catalysts as listed above) in a Michael-type addition of the SH-group from the polysulfide to compounds with ethylenically unsaturated bonds. Particularly advantageous are olefinic, such as vinylic bonds and even more advantageous are activated ethylenically unsaturated compounds or double bonds such as in acrylate esters, acrolein, acrylamides, acrylonitriles and vinyl ketones, within the formulation to form a cross-linked polymer system. Activated ethylenically unsaturated compounds contain double bond groups that are activated by direct attachment to a electronegative group such as a halogen, CO, CN, CC, O or aryl. The adjacent groups increase the polarization of the double bond and so give rise to its reactivity or activation.

[0040] Via the addition of a certain amount of water capturing agent or desiccants (e.g. isocyanates, trialkoxysilanes, silazanes, molecular sieves) the shelf life, curing speed and pot life can be adjusted or tuned as may be required.

[0041] Preferably the ratio of thioester:sulfur:acrylate based on weight can range from 4:1:4 to 1:2:1, wherein the given ratio range is particularly suitable for the inventive curable composition.

[0042] The curable composition typically contains the individual components thioester in 1-20 weight-%, sulfur from 1 to 70, preferably 5-60, more preferred 10-50 weight-%, acrylate from 10-60 weight-% and up to 5 weight-% of additives, with weight-% being based on the total weight of the composition.

[0043] Typically the term acrylate component as used herein also is meant to encompass methacrylates. The acrylate component may present one or more acrylate groups of preferably up to 8. The acrylate component may be selected from an acrylic acid ester of polyalcohols, such as polyols, polyetherols, polyesterols, polyacrylate polyols and the like.

[0044] The acrylate component may be monomeric, oligomeric or polymeric. Suitable monomers include diethylenglycol dimethacrylate, tetraethylene glycol dimethacrylate, 2-ethyl-2 (hydroxymethyl) 1,3-propanediol trimethacrylate etc. By selection or combination of various acrylate components of varying lengths, a functional acrylate-mixture is provided with desired viscosity. The molecular weight of the acrylate component typically is from 72 to 2000 g/mol.

[0045] Since the curing of the mixture is activated by water, it is important that compounding of the present compositions be carried out in a water or moisture-free atmosphere and that the curable composition or mixture be maintained in such an atmosphere until used. This may be achieved by using desiccants. The desiccant may be for example a molecular sieve desiccant, but other water binding or capturing substances or agents may also be utilized. The obtained mixture can be filled into water and humidity-proof containers, collapsible containers, bags or cartridges and is storage stable for months provided the containment maintains exclusion of humidity. When the containers are opened after storage, also over prolonged periods of time and at a given temperature, the viscosity of the curable mixture will be similar to the viscosity of a freshly prepared curable mixture. Hence, such prepared and packaged curable compositions are characterized by outstanding storage stability. Storage temperature may vary from below 40 to 50 degrees Celsius. Curing of the curable composition or mixture after application to a surface or substrate is activated either by addition of water or merely by the humidity or moisture present in the environment. Once the mixture is utilized and after the water capturing agent, if present, is consumed, the binder system starts to crosslink and harden. It is contemplated that this process and chemical reaction is understood by the term to cure and believed to form a useful adhesive bond between substrates on to which the curable mixture is applied. The curing process is characterized by relatively rapid development of an essentially tack-free film or skin that toughens with age and by polymerization of the liquid material beneath the skin. Depending on the amount of water or moisture some skins develop almost instantly while others take as long as 24 hours. The curing period may be selected from within a range of minutes to several months and depends primarily on the amount of water or moisture available for the curing process or ambient temperature during curing and the ratio of exposed area of the curable composition used. The present curable composition also is particularly useful at low temperatures even at/or around 0 degrees Celsius conditions. Within a formulation ready for application, additional compounds, such as plasticizers, reactive thinners, pigments, fillers, such as calcium carbonate, barium sulfate, clay, titanium dioxide, soot, tertiary amines, thixotropic agents, accelerators, de-foaming agents, adhesion promoters etc. may be added. Depending on the components used for the curable composition the mechanical properties can be varied from hard and brittle to soft and elastic.

[0046] In general the present curable compositions can be used for all of the purposes for which prior 2K or conventional 1K polysulfide polymer compositions have been used, e.g. caulking, sealing, potting, coating, impregnation of porous materials and the like. The produced cured materials adhere tenaciously to clean surfaces of wood, glass, metal, building materials like concrete or stone, plastics, leather and so forth. Additionally the cured materials exhibit the well-known properties of the cured polysulfide polymers such as elasticity, tensile strength, low permeability to gases and resistance to degradation from sunlight, atmospheric oxidation, acids, caustics, solvents, fuels and oils. The present compositions are well suited for uses in which temperature extremes, chemically harsh environments and mechanical stress are experienced. Therefore the present compositions are particularly useful as high performance coating for primary containment, like chemical or fuel storage tanks and secondary containment like coating with crackbridging ability in concrete, earthen dikes or floors in process areas exposed to chemical or fuel spill etc. Uses may also be envisaged in aerospace applications as aerospace sealant, fuel tank sealant and the lining of fuselages and the like, coating for ship ballast and fuel tanks or railcar linings and so forth.

[0047] The invention of the present application may be partially characterized by reference to this non-exclusive list of exemplary items:

[0048] 1 A curable or polymerizable composition comprising a) a multifunctional thioester, b) elemental sulfur, and c) at least one ethylenically unsaturated compound.

[0049] 2 A composition of item 1, wherein the at least one ethylenically unsaturated compound is an activated ethylenically unsaturated compound, preferably an acrylate compound.

[0050] 3 A composition of either item 1 or 2, wherein the multifunctional thioester is selected from:

[0051] (i) RCOSRSCOR, wherein R independently is, linear, branched or cyclic C1-C10 alkyl, aryl, heteroaryl; R is a linear, cyclic or branched C1-C10 alkyl, alkoxy, or a single bond; or

[0052] (ii) a compound of the formula

##STR00002##

[0053] wherein

[0054] X independently is H or RCOSR1-; or a polymer of the Formula HS[(CH2(R)bCH2Sa)c(RSa)d(SH)f]CH2(R)bCH2SH where a is 1-5, b is 0 or 1, c is 5-10, d is 0-0.05c and 0.05cfd, 1>f which is d times (number of free valencies in R-2), R is O, S or a divalent saturated organic radical consisting of C and H atoms and optionally O and/or S in COC, CSaC or OH links.

[0055] R independently is C1-C20, optionally substituted, linear, cyclic or branched alkyl, aryl alkylaryl, aralkyl;

[0056] R1 independently is C1-C20, optionally substituted, linear, cyclic or branched alkyl, aryl alkylaryl, aralkyl, preferably (CH2)1-5-CO and most preferred CH2-CH2-CO, and

[0057] R2 is either H or C1-C20 alkyl.

[0058] 4 A composition of any of the items from 1-3, wherein the multifunctional thioester component are derived from polyols. Polyols are compounds with multiple hydroxyl functional groups available for organic reactions. This includes compounds with two hydroxyl groups, a diol, with three hydroxyl groups, a triol, with four, a tetrol and so on. Monomeric polyols such as glycerin, pentaerythritol, ethylene glycol and sucrose are of particular interest, but polymeric polyols may also be utilized. Multifunctional thioester compounds may also be derived from polyalcohols, such as polyols, polyetherols, polyesterols or polyacrylate polyols with respective functionality, preferably with a functionality of at least two. A preferred multifunctional thioester is derived from pentaerythritol-tetramercaptopropionate. Difunctonal thioester derived from dimercaptanes may also be envisaged such as distearoyl-1,4-butanethiolate or based on disulfanes, such as distearoyldisulfane or dibenzoyldisulfane, i.e. thioester compounds of the general structure stearoyl-SS-stearoyl or benzoyl-SS-benzoyl. Further the multifunctional thioester may present 2-20 hydrolysable functional groups, preferably 2- 6 and more preferred 4-6, where such functional groups may preferably also constitute branched moieties. Advantageous thioester compounds may be selected from distearoyldisulfane, dibenzoyldisulfane, stearoyldiester of 1,4-butandithiol or the adipate of 1,4-butandithiol, succinate of 1,4-butandithiol tetraacetate of pentaerithritol-tetrakis-mercaptopropionate, tetrabenzoate of pentaerithritol-tetrakis-mercaptopropionate, diacetate of poly(ethyleneglycol) dithiol, distearate of poly(ethylene glycol) dithiol, polymeric ester of adipate and poly(ethylene glycol) dithiol, diacetate of benzene dithioles, diacetate of toluene dithioles, triacetate of trimethylolpropane tris(3-mercaptopropionate) or maleate of poly(ethylene glycol) dithiol.

[0059] 5 A composition of any of the items above, wherein the acrylate component is selected from acrylates that are one to 20-fold ethoxylated or propoxylated or mixed ethoxylated or propoxylated or non-oxylated glycerol, trimethylolpropane, trimethylolethane or pentaerythrite. Advantageous acrylate components may further be selected from ethyleneglycoldiacrylate, 1,2-propanedioldiacrylate, 1,3-propanedioldiacrylate, 1,4-butanedioldiacrylate, 1,3-butanedioldiacrylate, 1,5-pentanedioldiacrylate, 1,6-hexanedioldiacrylate, 1,8-octanedioldiacrylate, neopentylglycoldiacrylate, 1,1-, 1,2-, 1,3- or 1,4-cyclohexanedimethanoldiacrylate, 1,2-, 1,3- or 1,4-cyclohexanedioldiacrylate, trimethylolpro-panetriacrylate, ditrimethylolpropanepenta- or hexaacrylate, pentaerythrittriacrylate, pentaeryth-rittetraacrylate, glycerindiacrylate, glycerintriacrylate, di-or polyacrylates of sugar alcohols, preferably of sorbit, mannit, diglycerol, threit, erythrit, adonit (Ribit), arabit (Lyxit), xylit, dulcit (Galactit), maltit, isomaltit, or polyesterpolyols, polyetherols, polytetrahydrofuran, poly-1,3-propanediol, polyethyleneglycol, urethaneacrylates or polycarbonateacrylates.

[0060] 6 A composition of any of the items above, wherein the acrylate component is selected from the preferred components 1,4-butanedioldiacrylat, 1,6-hexanedioldiacrylat, trimethylolpropane-triacrylate, pentaerythrittetraacrylate, triacrylate of one to twenty fold ethoxylated trimethylolpropane or tetraacrylate of one-to twenty fold ethoxylated pentaerythrit.

[0061] 7 A composition of any of any of the items above, further containing one or more catalysts.

[0062] 8 A composition of item 7, wherein the one or more catalyst is selected from amine, phosphine, Lewis acids, carboxylates, organyls of tin (Sn), a lanthanide (Ln), zink (Zn), bismuth (Bi), titanium (Ti), zirconium (Zr), or any of the known catalysts used to increase the rate of reaction or in acceleration of addition reactions in coating and sealing compositions. Such catalysts may be selected from primary, secondary or tertiary amines as well as quarternary ammonium salts, imines or iminiumsalts. These may be aliphatic or aromatic, wherein aliphatic are preferred. Preferred tertiary amines may be selected from trimethylamine, triethylamine, tri-n-butylamine, ethyl-di-iso-Propylamine, methyl-di-iso-propylamine, N-methylmorpholine, N-methylpiperidine, tri-ethanolamine, N,N-dimethylethanolamine, N-methyldicyclohexylamine, dimethylcyclohexyl-amine, diethylcyclohex-ylamine, methyldicyclohexylamine, ethyldicyclohexylamine, 4-N,N-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]-non-5-en (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-en (DBU), tetramethyl-guanidine, pyrrocoline, quinuclidine, 3-aminoquinuclidine or 3-hydroxyquinuclidine. Catalysts of particular advantage are 1,4-diaza-bicyclo[2,2,2]octan (DAB-CO), 1,5-diazabicyclo[4.3.0]-non-5-en (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-en (DBU), N-methyldicyclohexylamine, quinuclidine, 3-aminoquinuclidine or 3-hydroxyquinuclidine, trime-thylphosphine, triethylphosphine, tri-n-butylphosphine, dimethylphenylphosphine, Ti(IV) isopropoxide, Ti(IV) acetylacetonate, Ti(IV)tetrachloride, Zr(IV)acetate, Zr(IV)isopropoxide, Snchloride, Snnitrate, dibutyltinlaurate, or Zn(II)chloride.

[0063] 9 A composition of item 7, wherein the one or more catalyst is preferably selected from DABCO, DBN, DBU, N- methyldicyclohexylamine, quinuclidine, 3-aminoquinuclidine or 3-hydroxyquinuclidine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, dime-thylphenylphosphine, Ti(IV) isopropoxide, Ti(IV) acetylacetonate, Ti(IV)tetrachloride, Zr(IV)acetate, Zr(IV)isopropoxide, Snchloride, Snnitrate, dibutyltinlaurate, Zn(II)chloride most preferred are DBU or N-Methyldicyclohexylamine.

[0064] 10 A composition of any of the items above further containing a water-capturing agent or desiccant.

[0065] 11 A composition of any of the items above, wherein the ratio by weight of thioester:sulfur:acrylate is in the range from 4:1:4 to 1:2:1, preferably 1:1:1.

[0066] 12 A composition of any of the items above, comprising

[0067] 1-20 weight-% thioester,

[0068] 1-70 weight-% sulfur,

[0069] 10-50 weight-% acrylate,

[0070] 0-5 weight-% additive.

[0071] 13 A polymerizable composition as described in any of the items above.

[0072] 14 A polymer obtained by curing a composition as described in any of the items above.

[0073] 15 Use of a composition of any of the items above as a one-component curable polymer composition.

[0074] 16 Use of a composition of any of the items above as an adhesive, sealant or coating material.

[0075] 17 Method of making a one-component curable composition comprising the steps of mixing components of any item 1-12.

[0076] 18 Method of making one-component curable composition comprising the steps of combining selected components of claims 1-12, wherein the thioester, sulfur and ethylenically unsaturated compound are mixed under water-free conditions to give a homogeneous paste, followed by addition of water capturing agent and catalysts and packing the resulting mixture into water and humidity proof containers.

[0077] 19 A process for the preparation of a curable or polymerizable composition as in item 1-12 comprising the steps of mixing components according to any of the items 17 or 18.

[0078] 20 A process for the preparation of a curable or polymerizable composition as in item 1-12 comprising the steps of

[0079] (i) creating and maintaining a water-free environment,

[0080] (ii) mixing components (a), (b) and (c) according to any of the items 1-12,

[0081] (iii) continued mixing and grinding of the obtained mixture, optionally

[0082] (iv) under stirring addition of further additives, followed by,

[0083] (v) addition of a water-capturing agent, and

[0084] (vi) packaging the resulting mixture in a water- and moisture proof container.

[0085] 21 A water and humidity proof container containing a one-component curable composition of any of the items 1-12 or as obtained by a process according to item 19 or 20.

[0086] 22 A crosslinked polymer article obtained by curing a composition of any of the items 1-12 or obtained by a method either item 17 or 18 or by a process of items 19 or 20.

EXAMPLES

Example 1

[0087] 6.0 g sulfur powder and 1.2 g dibenzoyldisulphane were mixed with 2.0 g glycerolformalmethacrylate and 5.0 g dipentaerythritol pentaacrylate mixed and ground to give a homogeneous paste. Then 100 mg 4-toluolsulfonylisocyanate and 140 mg 1,8-diazabicycloundec-7-ene was added. The mixture was stirred and ready for application.

[0088] When exposed to humid environment (100% relative humidity, 23 C.), the pot life was approx. 60 min. The material was tack-free after 24 hours and a plate of 5 mm thickness was fully cured after 3 days. When not exposed to humidity or water, the mixture was stable for more than five months in a closed vessel. The fully cured material showed a hardness of 80 Shore A.

Example 2

[0089] 6.0 g sulfur powder and 1.2 g dibenzoyldisulphane were mixed with 2.0 g poly (propyleneglycol)-diacrylate (Mn=900 g/mol) and 5.0 g dipentaerythritol pentaacrylate, mixed and ground to give a homogeneous paste. Then 100 mg 4-toluolsulfonylisocyanate and 140 mg 1,8-diazabicycloundec-7-ene were added. The mixture was stirred and ready for application.

[0090] When exposed to humid environment (100% relative humidity, 23 C.), the pot life was approx. 60 min. The material was tack-free after 24 hours and a plate of 5 mm thickness was fully cured after 3 days. When not exposed to humidity or water, the mixture was stable for more than five months in a closed vessel. The fully cured material showed a hardness of 60 Shore A.

Example 3

[0091] 6.0 g sulfur powder and 1.2 g distearoyldisulphane were mixed with 2.0 g glycerolformalmethacrylate and 5.0 g dipentaerythritol pentaacrylate were mixed and ground to give a homogeneous paste. Then 100 mg 4-toluolsulfonylisocyanate and 140 mg 1,8-diazabicycloundec-7-ene were added. The mixture was stirred and ready for application.

[0092] When exposed to humid environment (100% relative humidity, 23 C.), the pot life was approx. 60 min. The material was tack-free after 24 hours and a plate of 5 mm thickness was fully cured after 3 days. When not exposed to humidity or water, the mixture was stable for more than five months in a closed vessel. The fully cured material showed a hardness of 55 Shore A.

Example 4

[0093] 6.0 g sulfur powder, 2 g of BaSO.sub.4 powder and 1.2 g dibenzoyldisulphane were mixed with 2.0 g glycerolformalmethycrylate and 5.0 g dipentaerythritol pentaacrylate were mixed and ground to give a homogeneous paste. Then 100 mg 4-toluolsulfonylisocyanate and 140 mg 1,8-diazabicycloundec-7-ene were added. The mixture was stirred and ready for application.

[0094] When exposed to humid environment (100% relative humidity, 23 C.), the pot life was approx. 60 min. The material was tack-free after 24 hours and a plate of 5 mm thickness was fully cured after 3 days. When not exposed to humidity or water, the mixture was stable for more than five months in a closed vessel. The fully cured material showed a hardness of 89 Shore A.

Example 5

[0095] 6.0 g sulfur powder and 1.2 g dibenzoyldisulphane were mixed with 1.0 g glycerolformal-methycrylate as reactive thinner, 1.0 g Liquid rubber LIR 30 (supplier: Kuraray, polyisoprene with Mn=30000 g/mol) 5.0 g dipentaerythritol pentaacrylate were mixed and ground to give a homogeneous paste. Then 100 mg 4-toluolsulfonylisocyanate and 140 mg 1,8-diazabicycloundec-7-ene were added. The mixture was stirred and ready for application.

[0096] When exposed to humid environment (100% relative humidity, 23 C.), the pot life was approx. 60 min. The material is tack-free after 24 hours and a plate of 5 mm thickness was fully cured after 3 days. When not exposed to humidity or water, the mixture was stable for more than five months in a closed vessel. The fully cured material showed a hardness of 30 Shore A.

Example 6

[0097] 29.9 g adipic acid dichloride were mixed with 33.0 g stearoyl chloride and 20.0 g 1,4-butanethiol under dry conditions and warmed to 30 C. for 1 h until a solid material, thiopolymer, was obtained.

[0098] 9.0 g sulfur powder and 1.8 g of thiopolymer were mixed with 3.0 g glycerolformalmethycrylate as reactive thinner, 7.5 g dipentaerythritol pentaacrylate were mixed and ground to give a homogeneous paste. Then 120 mg 4-toluolsulfonylisocyanate and 860 mg 1,8-diazabicycloundec-7-ene were added. The mixture was stirred and ready for application.

[0099] When exposed to humid environment (100% relative humidity, 23 C.), the pot life was approx. 60 min. The material was tack-free after 24 hours and a plate of 5 mm thickness was fully cured after 3 days. When not exposed to humidity or water, the mixture was stable for more than five months in a closed vessel. The fully cured material showed a hardness of 68 Shore A.