WO2011072056A2

WO2011072056A2 - Cure rate control for alkoxysilyl-end-blocked polymers

Info

Publication number: WO2011072056A2
Application number: PCT/US2010/059536
Authority: WO
Inventors: Loren Lower; Timothy B. Lueder
Original assignee: Dow Corning Coporation
Priority date: 2009-12-08
Filing date: 2010-12-08
Publication date: 2011-06-16
Also published as: WO2011072056A3

Abstract

A method for modifying cure speed of a condensation reaction curable involves converting the higher alkoxy groups on ingredient (A) to lower alkoxy groups (such as methoxy groups) using ingredients (B) and (C). Ingredient (A) is a substrate (polymer) having an average, per molecule, of at least two higher alkoxy group functionalized silyl end-blocking groups. Ingredient (B) is a reactant having lower alkoxy groups bonded to silicon. Ingredient (C) is a transesterification catalyst. It is thought that the higher alkoxy groups on ingredient (A) cure too slowly to be practical for many moisture curable sealants and adhesives. As used herein, the term higher alkoxy group means an alkoxy group having more carbon atoms than the lower alkoxy group on ingredient (B). By exchanging some or all of the higher alkoxy groups on ingredient (A) with lower alkoxy groups from ingredient (B), it is thought that cure speed of a sealant or adhesive composition can be increased. Furthermore, it may be possible to control cure speed of the composition by varying the amount of lower alkoxy groups present. And, it may be possible to control physical properties, such as modulus, by varying the amounts of ingredients (A) and (B) relative to each other.

Description

CURE RATE CONTROL FOR ALKOXYSILYL-END-BLOCKED POLYMERS CROSS-REFERENCE TO RELATED APPLICATIONS [0001] None.

BACKGROUND OF THE INVENTION

TECHNICAL FIELD

[0002] A moisture curable composition contains a polymer having alkoxysilyl end- blocking groups. The composition is useful for making and curing sealants and adhesives.

BACKGROUND

[0003] Organic polymers having alkoxysilyl end-blocking groups are useful in the preparation of moisture curable sealants and adhesives. The organic polymer backbones are exemplified by polyacrylates, polybutadienes, polyethers, and polyolefins. Certain polymers having higher alkoxysilyl end-blocking groups suffer from the drawback of having cure time too long to be practical for use in sealant and adhesive compositions. However, compositions containing polymers having lower alkoxysilyl, e.g., methoxysilyl, end-blocking groups may suffer from the drawback of instability, or insufficient shelf life for some applications.

BRIEF SUMMARY OF THE INVENTION

[0004] A transesterified polymer may be prepared by mixing ingredients comprising: (A) a polymer selected from organic polymers and silicone-organic block copolymers, wherein said polymer has an average, per molecule, of at least two alkoxy group functionalized silyl end-blocking groups;

(B) a reactant having alkoxy groups bonded to silicon, where at least a portion of the alkoxy groups of ingredient (B) differ from the alkoxy groups of ingredient (A);

(C) a transesterification catalyst, with the proviso that the alkoxy groups on ingredient (B) are more reactive than the alkoxy groups on ingredient (A). "More reactive" means that when a polymer is formulated into a condensation reaction curable composition, a polymer with the alkoxy groups of ingredient (B) will cure faster than a polymer with the alkoxy groups of ingredient (A) would cure in the same composition.

DETAILED DESCRIPTION OF THE INVENTION

[0005] All amounts, ratios and percentages are by weight unless otherwise indicated. The following definitions apply to terms as used herein. The articles "a", "an", and "the" each refer to one or more, unless otherwise indicated.

TRANSESTERIFIED POLYMER

[0006] The transesterified polymer may be prepared by mixing ingredients comprising (A), (B), and (C), described above. Ingredient (A) is a polymer selected from organic polymers and silicone-organic block copolymers. Ingredient (A) has an average, per molecule, of at least two alkoxy group functionalized end-blocking groups. Suitable polymers for ingredient (A), and methods for their preparation, are known in the art.

[0007] For example, an organic polymer having OH end-groups (terminal or pendant), such as a polyether glycol or poly(propylene glycol), may be reacted with an isocyanate- functional alkoxysilane, such as isocyanatopropyltriethoxysilane in the presence of a tin catalyst, such as dibutyl tin dilaurate. Alternatively, an alkenyl functional organic polymer may be reacted with a dialkoxysilane or trialkoxysilane having a silicon bonded hydrogen atom via a hydro silylation reaction. For example, an allyl functional organic polymer may be reacted with methyldiethoxysilane in the presence of a platinum group metal hydrosilylation catalyst.

[0008] Such polymers for ingredient (A), and methods for their preparation, are known in the art. For example, the organic polymers modified to include alkoxy groups on their chain terminals disclosed in U.S. Patent 6,168,253 at col. 4, line 1 to col. 5, line 50 are suitable for use herein when the alkoxy groups have two or more carbon atoms.

EP 1 746 133 A 1 at paragraphs [0036] to [0040], [0044] to [0045], [0050] to [0052], [0054] to [0066], [0075] to [0076] discloses methods of preparing silicone modified organic polymers; and paragraphs [0025] to [0035], [0043], [0047] to [0049], [0053], [0074], disclose the silicone modified organic polymers. US 4,291,316 discloses alkoxysilane modified alkylene alkylacrylate copolymers. And, US 4,889,903 discloses alkoxysilane modified polyurethanes. Suitable organic polymers for use in preparing ingredient (A) are known in the art and are commercially available. For example, the organic polymer can be a polyacrylate, polybutadiene, polyether, polyisobutylene, polyolefin, or polyurethane, as disclosed in the patent publications cited above.

[0009] Alternatively, ingredient (A) may be a silicone-organic block copolymer. Exemplary silicone organic block copolymers include polyorganosiloxane-polyether block copolymers, polyorganosiloxane-polyoxyalkylene block copolymers such as those disclosed in WO2008/132236; crosslinked polyorganosiloxane-polyoxyalkylene block copolymers such as those disclosed in WO2008/132237; polyorganosiloxane- polyorganoamine block copolymers such as those disclosed in U.S. Patent 5,489,622; polyorganosiloxane-polyurethane block copolymers such as those disclosed in WO1990/06958 and W01999/65966; and polycarbosiloxanes such as those disclosed in European Patent Application EP09306051.5 filed on 3 November 2009.

[0010] Suitable polycarbosiloxanes may be prepared by a process comprising: a) ring opening polymerization of a cyclic monomer of the structure

where X' is selected from

(i) a linear or branched alkylene group having from 1 to 14 carbon atoms;

and

(ii) an aromatic group having from 6 to 20 carbon atoms; each R is the same or different and is selected from H, OH, a monovalent organic group having from 1 to 18 member atoms, and subscript n is an integer having a value ranging from 1 to 6 in the presence of an acidic or basic ring opening polymerisation catalyst; b) removing linear oligomer prepared in step (a) optionally using a suitable solvent; and

c) removing the aforementioned solvent, when present.

Alternatively, each R may be a hydrocarbon group having from 1 to 18 carbon atoms or a hydrocarbonoxy group having 1 to 18 carbon atoms.

[0011] The alkoxy end-blocking groups of ingredient (A) may have formula 0R1, alkoxy groups bonded to ingredient (B) and other ingredients of the composition may have formula OR^, and at least 60 mol % of the R^ groups differ from the R1 groups. Each of the alkoxy groups on ingredient (A) may have at least two carbon atoms, and at least a portion of the alkoxy groups on ingredient (B) have fewer carbon atoms than the alkoxy groups on ingredient (A). Alternatively, each alkoxy group of ingredient (A) may be an ethoxy group. The alkoxy end-blocking groups on ingredient (A) may be terminal or pendant. Alternatively, the alkoxy groups of ingredient (B) may be methoxy.

Alternatively, when each of the R1 groups are ethyl, at least 60 mol % of R2 groups are methyl. [0012] Alternatively, each alkoxy group of ingredient (A) may have at least two carbon atoms, and the composition may further comprise at least one other ingredient having alkoxy groups (i.e. , in addition to ingredients (A) and (B)), and at least 60 mol % of all the alkoxy groups on the ingredients in the composition are methoxy groups. At least 60 % of the alkoxy groups in the composition which are not bonded to ingredient (A) may be methoxy.

Ingredient (B) [0013] Ingredient (B) is a reactant having alkoxy groups bonded to silicon, where at least a portion of the alkoxy groups of ingredient (B) differ from the alkoxy groups of ingredient (A). Ingredient (B) may be a silane. The alkoxy groups of ingredient (A) differ from at least a portion of the alkoxy groups of ingredient (B) and any other alkoxy groups in the composition (e.g. , in the transesterification catalyst and any additional ingredients of the composition, if present).

[0014] The exact amount of ingredient (B) depends on various factors including the alkoxy groups on each of ingredients (A) and (B) and the structures of ingredients (A) and (B), however, the amount of ingredient (B) may range from 0.5 to 15 parts based on 100 parts by weight of ingredient (A). The relative amounts of ingredients (A) and (B) may be varied to change the modulus and/or cure rate of a sealant prepared containing ingredients (A) and (B). Ingredient (B) may comprise a silane crosslinker having alkoxy groups or partial or full hydrolysis products thereof. Examples of suitable silane crosslinkers may have the general formula (III) R^_cSi(R^)(4-c)' where each R4 is independently a monovalent hydrocarbon group such as an alkyl group; each is an alkoxy group having at least one carbon atom fewer than the alkoxy groups on ingredient (A); and subscript c is 0, 1, 2, or 3. [0015] Ingredient (B) may comprise an alkoxysilane exemplified by a dialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, such as an alkyltrialkoxysilane; a tetraalkoxysilane; or partial or full hydrolysis products thereof, or another combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combination thereof, and alternatively methyltrimethoxysilane or isobutyltrimethoxysilane. Examples of suitable tetraalkoxysilanes include trimethoxyethoxysilane, tetramethoxysilane and tetraethoxysilane. The amount of the alkoxysilane used to prepare the transesterified polymer may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (A). Examples of alkoxysilane crosslinkers are disclosed in U.S. Patents 4,962,076; 5,051,455; and 5,053,442.

(C) Transesterification catalyst

[0016] Ingredient (C) is a transesterification catalyst. Ingredient (C) may be selected from alumina compounds, titanate compounds, and zirconate compounds. Alternatively, ingredient (C) may be a titanate compound. Suitable compounds for ingredient (C) include a compound of formula (V): M(0R3) , where M is Al, Ti, or Zr and each is an organic group. For example, OR^ may represent an alkoxy group of 1 to 20 carbon atoms or an acyloxy group. Each OR^ may be the same or different. Alternatively, M may be Ti.

[0017] Examples of aluminates represented by general formula (V) include aluminum trimethoxide, aluminum triethoxide, aluminum triallyloxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide, aluminum tri-t-butoxide, aluminum tri-n-pentyloxide, aluminum tricyclopentyloxide, aluminum trihexyloxide, aluminum tricyclohexyloxide, aluminum tribenzyloxide, aluminum trioctyloxide, aluminum tris(2-ethylhexyloxide), aluminum tridecyloxide, aluminum tridodecyloxide, aluminum tristearyloxide, aluminum tributoxide dimer, aluminum tris(8-hydroxyoctyloxide), aluminum isopropoxide-bis(2- ethyl- 1 ,3-hexanediolate), aluminum diisopropoxide(2-ethyl- 1 ,3-hexanediolate), aluminum(2-ethylhexyloxy)bis(2-ethyl-l,3-hexanediolate), aluminum bis(2- ethylhexyloxy)(2-ethyl-l,3-hexanediolate), aluminum tris(2-chloroethoxide), aluminum tris(2-bromoethoxide), aluminum tris(2-methoxyethoxide), aluminum tris(2- ethoxyethoxide), aluminum butoxidedimethoxide, aluminum methoxidedibutoxide, aluminum butoxidediethoxide, aluminum ethoxidedibutoxide, aluminum butoxidediisopropoxide, aluminum isopropoxidedibutoxide, aluminum triphenoxide, aluminum tris(o-chlorophenoxide), aluminum tris(m-nitrophenoxide), aluminum tris(p- methylphenoxide) and combinations thereof. [0018] Examples of titanates represented by general formula (V) include titanium tetraethoxide, titanium tetraallyloxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-sec- butoxide, titanium tetra-t-butoxide, titanium tetra-t-amyloxide, titanium tetra-n- pentyloxide, titanium tetracyclopentyloxide, titanium tetrahexyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetraoctyloxide, titanium tetrakis(2-ethylhexyloxide), titanium tetradecyloxide, titanium tetradodecyloxide, titanium tetrastearyloxide, titanium tetrabutoxide dimer, titanium tetrakis(8- hydroxyoctyloxide), titanium diisopropoxidebis(2-ethyl-l,3-hexanediolate), titanium bis(2-ethylhexyloxy)bis(2-ethyl-l,3-hexanediolate), titanium tetrakis(2-chloroethoxide), titanium tetrakis(2-bromoethoxide), titanium tetrakis(2-methoxyethoxide), titanium tetrakis(2-ethoxyethoxide), titanium butoxidetrimethoxide, titanium dibutoxidedimethoxide, titanium butoxidetriethoxide, titanium dibutoxidediethoxide, titanium butoxidetriisopropoxide, titanium dibutoxidediisopropoxide, titanium tetraphenoxide, titanium tetrakis(o-chlorophenoxide), titanium tetrakis(m- nitrophenoxide), titanium tetrakis(p-methylphenoxide), titanium tetrakis(trimethylsilyloxide), and combinations thereof.

[0019] Alternatively, examples of titanates of formula (V) include tetrabutyl titanate (TTBT), titanium chelates such as dialkoxytitanium-bis-(acetylacetonates), dialkoxytitanium-bis-(alkylacetonates), and dialkoxytitanium-bis-(alkylacetoacetonate). Examples of dialkoxytitanium-bis-(acetylacetonates) include diisopropoxytitanium-bis- (acetylacetonate), isopropoxyethoxytitanium-bis-(acetylacetonate). Examples of dialkoxytitanium-bis-(alkylacetoacetates) include dialkoxytitanium-bis- (methylacetoacetate) and dialkoxytitanium-bis-(ethylacetoacetate).

[0020] Examples of zirconates of formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraallyloxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-sec-butoxide, zirconium tetra-t-butoxide, zirconium tetra-pentyloxide, zirconium tetracyclopentyloxide, zirconium tetrahexyloxide, zirconium tetracyclohexyloxide, zirconium tetrabenzyloxide, zirconium tetraoctyloxide, zirconium tetrakis(2-ethylhexyloxide), zirconium tetradecyloxide, zirconium tetradodecyloxide, zirconium tetrastearyloxide, zirconium tetrabutoxide dimer, zirconium tetrakis(8- hydroxyoctyloxide), zirconium diisopropoxidebis(2-ethyl-l,3-hexanediolate), zirconium- bis(2-ethylhexyloxy)bis(2-ethyl- 1 ,3-hexanediolate), zirconium tetrakis(2- chloroethoxide), zirconium tetrakis(2-bromoethoxide), zirconium tetrakis(2- methoxyethoxide), zirconium tetrakis(2-ethoxyethoxide), zirconium butoxidetrimethoxide, zirconium dibutoxidedimethoxide, zirconium butoxidetriethoxide, zirconium dibutoxidediethoxide, zirconium butoxidetriisopropoxide, zirconium dibutoxidediisopropoxide, zirconium tetraphenoxide, zirconium tetrakis(o- chlorophenoxide), zirconium tetrakis(m-nitrophenoxide), zirconium tetrakis(p- methylphenoxide) and combinations thereof.

[0021] Examples of zirconium acylates of formula (V) include zirconium acrylate triisopropoxide, zirconium methacrylate triisopropoxide, zirconium dimethacrylate diisopropoxide, zirconium isopropoxide trimethacrylate, zirconium hexanoate triisopropoxide, zirconium stearate triisopropoxide and combinations thereof.

[0022] Other transesterification catalysts may be selected from acids and bases. Catalyst selection depends on various factors including the alkoxy group being transesterified and the substrate to which the alkoxy group is bonded. For example, an amino containing alkoxy-end-blocked polymer may be transesterified with a basic catalyst such a metal alkoxide, e.g., sodium alkoxide (such as sodium ethoxide or sodium methoxide). An alkoxy-end-blocked polymer containing non-functional or base sensitive alkyl or alkoxy group could be transesterified with an acid catalyst, such as para- toluenesulfonic acid. The transesterification catalysts can be heterogeneous, such as in the form of pellets or beads, or homogenous (i.e., soluble). The amount of transesterification catalyst depends on the type of catalyst selected, the groups to be transesterified, and the desired rate of transesterification, however the amount may range from 0.001 % to 1 % based on the combined weights of ingredients (A), (B), and (C). Process

[0023] The transesterification method comprises: 1) in a polymer selected from silicon modified organic polymers and silicone-organic block copolymers, wherein said polymer has an average, per molecule, of at least two alkoxy group functionalized end-blocking groups, converting at least 60 % of the alkoxy groups on the polymer to different alkoxy groups. Thereafter, the product of step 1) may be cured in combination with a crosslinker and a condensation reaction catalyst.

[0024] Alternatively, the method may comprise:

(1) reacting the composition comprising ingredients (A), (B) and (C) described above to form ingredient (Α'), a polymer in which at least a portion of the alkoxy groups from ingredient (A) have been replaced with alkoxy groups from ingredient (B); and

(2) combining ingredients comprising:

(Α') the polymer prepared in step (1);

crosslinker having an average, per molecule, of at least two condensation reaction curable groups;

condensation reaction catalyst other than ingredient (C); and optionally

(D) a plasticizer. The method may optionally further comprise a step of pre-treating the product of step (1) and/or reacting the product of step (1) with a catalyst deactivating agent, thereby deactivating ingredient (C) before step (2). [0025] In step (1), alkoxy groups bonded to ingredient (A) are replaced with different alkoxy groups, which are initially bonded to reactant (B). The reactant may be a silane, such as an alkoxysilane or a different polymer from the substrate, such as a polyorganosiloxane, a different organic polymer, or a different silicone-organic block copolymer. The end-blocking groups on ingredient (A) may be alkoxy groups having two or more carbon atoms, and the reactant (B) may have alkoxy groups, at least some of which differ from the alkoxy groups bonded to ingredient (A). Ingredient (A) may have alkoxy groups of two or more carbon atoms and the reactant (B) may have methoxy groups. Alternatively, ingredient (A) may have ethoxy groups and ingredient (B) may have methoxy groups. Without wishing to be bound by theory, it is thought that methoxy groups will cure faster in step (2) than alkoxy groups having two or more carbon atoms, and the process can be used to prepare a composition with a controlled cure rate.

[0026] In step (1), at least 60 mol % of the alkoxy groups on ingredient (A) may be replaced, alternatively at least 70 mol %, alternatively 60 mol % to 100 mol %, alternatively 60 mol % to 90 mol %, alternatively at least 80 mol %, and alternatively, 70 mol % to 80 mol %. The amount of end -blocking groups replaced will depend on various factors including the end-blocking groups on the substrate, the groups that will replace the end-blocking groups on the substrate, the relative amounts of ingredients (A) and (B) (and other alkoxy containing ingredients, if any), and the end use of the product of step (1), ingredient (Α').

[0027] After step (1), an optional step may be added to the method. The method may optionally further comprise a step of pre-treating the product of step (1) and/or reacting the product of step (1) with a catalyst deactivating agent thereby deactivating ingredient (C) before step (2). The product of step (1) may optionally be pre-treated (for example, by stripping or distillation to remove remaining reactants and/or transesterification catalyst). The catalyst deactivating agent may be selected from a glycol, an alcohol such as methanol, a catechol, and a combination thereof.

[0028] Ingredient (Α') prepared in step (1) is reacted (e.g. , cured) in step (2). Ingredient (Α') may be formulated into a composition with other ingredients before or during step (2). In step (2), the alkoxy groups, which were reacted onto ingredient (A) in step (1), are reacted with other ingredients. The other ingredients may comprise: (C) a condensation reaction catalyst, , (Β') a crosslinker e.g. , an alkoxysilane or alkoxy functional polyorganosiloxane, where the crosslinker has alkoxy groups which are the same as at least 60 mol % of the alkoxy groups bonded to ingredient (Α'). The condensation reaction catalyst (C) may differ from the transesterification catalyst used in step (1). Alternatively, the condensation reaction catalyst (C) may be the same as the transesterification catalyst (C), described above. When the condensation reaction catalyst is the same as the transesterification catalyst, such as when a titanate is used, it is not necessary to deactivate transesterification catalyst and/or add a separate condensation reaction catalyst, such as a tin catalyst. Ingredient (Β') Crosslinker

[0029] Ingredient (Β') is a crosslinker. Ingredient (Β') may comprise a silane of formula

where each R6 is independently a monovalent hydrocarbon group

(such as an alkyl group); each is a hydrolyzable group selected from a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, and a methylacetamido group; and subscript a is 0, 1, 2, or 3. [0030] Ingredient (Β') may comprise an acyloxysilane, such as an acetoxysilane. Acetoxysilanes include a tetraacetoxysilane, an organotriacetoxysilane, a diorganodiacetoxysilane, or a combination thereof. The acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3- trifluoropropyl. Alternatively, ingredient (Β') may comprise organotriacetoxysilanes, for example mixtures containing methyltriacetoxysilane and ethyltriacetoxysilane. The amount of the acetoxysilane in the composition may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (A'); alternatively 3 to 10 parts by weight of acetoxysilane per 100 parts by weight of ingredient (Α').

[0031] Other crosslinkers include alkoxysilanes, oximeosilanes, enoxysilanes, and combinations thereof. Akoxysilane crosslinkers include dialkoxysilanes and trialkoxysilanes. Examples of trialkoxysilanes include methyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, or aminoethylaminopropyltrimethoxysilane. Dialkoxysilanes may also be used, such as methylvinyldimethoxysilane. The amount of crosslinker may range from 0.5 parts to 15 parts, alternatively 2 parts to 8 parts, per 100 parts by weight of ingredient (Α').

Ingredient (C) Condensation Reaction Catalyst [0032] Ingredient (C) is a condensation reaction catalyst capable of curing the composition comprising ingredients (Α') and (Β'). Examples of condensation reaction catalysts include a carboxylate, a carboxylic acid, a carboxylic acid salt of metal, a tin compound, a titanium compound, or a zirconium compound, or a combination thereof. Alternatively, ingredient (C) may be a carboxylate, a carboxylic acid, a carboxylic acid salt of metal, a tin compound, a chelated titanium compound, a titanate, or a combination thereof.

[0033] Ingredient (C) may comprise carboxylic acid salts of metals, ranging from lead to manganese inclusive, in the electromotive series of metals. Suitable tin catalysts for ingredient (C) include tin (IV) compounds and tin (II) compounds. Examples of tin (IV) compounds include dibutyl tin dilaurate (DBTDL), dimethyl tin dilaurate, di-(n-butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin di acetylacetonate, dibutyl tin dimethoxide carbomethoxyphenyl tin tris-uberate, isobutyl tin triceroate, dimethyl tin dibutyrate, dimethyl tin di-neodeconoate (DMDTN), triethyl tin tartrate, dibutyl tin dibenzoate, butyltintri-2-ethylhexoate, a dioctyl tin diacetate, tin octylate, tin oleate, tin butyrate, tin naphthenate, dimethyl tin dichloride, and a combination thereof. Tin (IV) compounds are known in the art and are commercially available, such as METATIN® 740 and FASCAT® 4202.

[0034] Examples of tin (II) compounds include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate, stannous salts of carboxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, and a combination thereof.

[0035] Examples of organofunctional titanates include 1,3-propanedioxytitanium bis(ethylacetoacetate); 1,3-propanedioxytitanium bis (acetylacetonate); diisopropoxytitanium bis(acetylacetonate); 2,3-di-isopropoxy-bis(ethylacetate)titanium; titanium naphthenate; tetra-propyl titanate; tetrabutyltitanate; tetra-ethylhexyl titanate; tetraphenyltitanate; tetra-octadecyl titanate; tetra-butoxy titanium; tetra-isopropoxy titanium; ethyltriethanolaminetitanate; a betadicarbonyltitanium compound such as bis(acetylacetonyl)di-isopropyl titanate; or a combination thereof. Siloxytitanates are exemplified by tetrakis(trimethylsiloxy)titanium, bis(trimethylsiloxy)bis(isopropoxy)titanium, or a combination thereof. Examples of condensation reaction catalysts are disclosed in, for example, U.S. Patents 4,962,076; 5,051,455; and 5,053,442 and EP 1 746 133 paragraphs [0086] to [0122] for examples of condensation reaction catalysts.

[0036] The amount of ingredient (C) is sufficient to cure the composition. The amount of ingredient (C) will vary depending on the selection of ingredients (Α'), (Β'), and (C), however, the amount of ingredient (C) may range from 0.001 parts to 3 parts, alternatively 0.005 parts to 2 parts, based on the weight of the composition. Ingredient (C) may be one condensation reaction catalyst. Alternatively, ingredient (C) may comprise two or more different condensation catalysts.

[0037] The composition may optionally further comprise one or more additional ingredients. These additional ingredients may be selected from (D) a plasticizer, (E) a stabilizer, (F) a filler, (G) a filler treating agent, (H) an adhesion promoter, (I) a fungicide, (J) a rheological additive, (K) a flame retardant, (L) a pigment, (M) a co- catalyst, and a combination thereof.

Ingredient (D) Plasticizer

[0038] Ingredient (D) is a plasticizer, which may be added to the composition to adjust the viscosity and slump properties of the composition and the mechanical properties, such as tensile strength and elongation, of a product obtained by curing the composition.

[0039] The plasticizer may have an average, per molecule, of at least one group of formula (V). (V) o

where R represents a hydrogen atom or a monovalent organic group. Alternatively, R may represent a branched or linear monovalent hydrocarbon group. The monovalent organic group may be a branched or linear monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms. Suitable plasticizers may be selected from the group consisting of adipates, carboxylates, phthalates, and a combination thereof.

[0040] Alternatively, the plasticizer may have an average, per molecule, of at least two groups of formula (V) bonded to carbon atoms in a cyclic hydrocarbon. The plasticizer may have general formula (VI):

(VI)

In formula (VI), group X represents a cyclic hydrocarbon group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms. (Subscript x may have a value ranging from 1 to 12.) Group X may be saturated or aromatic. Each R" is independently a hydrogen atom or a branched or linear monovalent organic group. The monovalent organic group for R" may be an alkyl group such as methyl, ethyl, or butyl. Alternatively, the monovalent organic group for R" may be an ester functional group. Each R' is independently a branched or linear monovalent hydrocarbon group, such as an alkyl group of 4 to 15 carbon atoms.

[0041] Examples of organic plasticizers of formula (VI) may have a formula (VII), (VII), (IX), or (X) set forth below.

II) (VIII)

In formulae (VII), (VII), (IX), or (X), R' is as described above. Formulae (VII) and (VIII) represent the cases where the cycloalkyl group in formula (VII) and the aryl group in formula (VIII) are unsubstituted. Formulae (IX) and (X) show that the cycloalkyl group in formula (IX) and the aryl group in formula (X) may be replaced with organic groups in which one or more of the hydrogen atoms bonded to the member atoms, in the cycloalkyl group of formula (VII) or in the aryl group of formula (VIII), shown is replaced with another monovalent organic group represented by R'. Each R' may be an alkyl group such as methyl, ethyl, or butyl. Alternatively, the monovalent organic group for R' may be an ester functional group. [0042] Suitable plasticizers are known in the art and are commercially available. The plasticizer may comprise a phthalate, such as: dibutyl phthalate, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, bis(2-propylheptyl) phthalate, di(2-ethylhexyl) phthalate, dimethyl phthalate; diethyl phthalate; dibutyl phthalate, and bis(2-ethylhexyl) terephthalate; a cadicarboxylate such as 1,2, 4-benzenetricarboxylic acid, bis(2-ethylhexyl)-l,4- benzenedicarboxylate; 2-ethylhexyl methyl- 1,4-benzenedicarboxylate; 1,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear; diisononyl adipate; trimellitates such as trioctyl trimellitate; triethylene glycol bis(2-ethylhexanoate); triacetin; nonaromatic dibasic acid esters such as dioctyl adipate, bis (2-ethylhexyl) adipate, di-2-ethylhexyladipate, dioctyl sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl recinolate; phosphates such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; tris (2-ethylhexyl) ester; a fatty acid ester; and a combination thereof. Examples of suitable plasticizers and their commercial sources include those listed below in the table below. [0043] Alternatively, a polymer plasticizer can be used. Examples of the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polyethers

including polyether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha-methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile, and polychloroprene.

Table of Plasticizers

[0044] The plasticizers may be used either each alone or in combinations of two or more thereof. A low molecular weight plasticizer and a higher molecular weight polymer plasticizer may be used in combination. The amount of plasticizer may range from 5 to 150 parts by weight based on the combined weights of all ingredients in the composition. Plasticizers are known in the art and are exemplified by those disclosed in EP 1 746 133 at paragraphs [0154] to [0161].

Ingredient (E) Stabilizer

[0045] Optional ingredient (E) is a stabilizer. Stabilizers include ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted tolyl compounds, and metal chelate compounds; photostabilizers such as benzotriazole compounds, hindered amine compounds, benzoate compounds; and antioxidants such as hindered amines, hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, and polyphenol antioxidants. Examples of suitable stabilizers are disclosed in EP 1 746 133 at paragraphs [0170] to [0173]. Suitable stabilizers are known in the art and are commercially available. For example, suitable stabilizers include Irganox® 1010, Irganox® 245, Irgafos® 168 and 126, EB 50-866, and Tinuvin® 5060, all of which are commercially available from BASF Corporation of Florham Park, New Jersey, USA. The exact amount of stabilizer depends on various factors including the type of stabilizer selected and the reactivity of the composition, however, the amount of stabilizer, when present, may range from 0.2 parts to 5 parts, per 100 parts by weight of ingredient (Α').

Ingredient (F) Filler [0046] Ingredient (F) is a filler, such as reinforcing filler, an extending filler, or a combination thereof. A reinforcing filler, when present, may be added in an amount ranging from 1% to 35%, alternatively 1% to 15%, based on the weight of the composition. Examples of suitable reinforcing fillers include reinforcing silica fillers such as fume silica, silica aerogel, silica zerogel, and precipitated silica. Fumed silicas are known in the art and commercially available; fumed silica is sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts.

[0047] The extending filler, when present, may be used in an amount ranging from 1% to 60%, alternatively 1% to 20%, based on the weight of the composition. Examples of extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof. Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV. One skilled in the art would recognize that the amounts of fillers disclosed are exemplary and not limiting. More or less filler may be used depending on the end use of the composition. Semi- reinforcing fillers, such as precipitated calcium carbonate fillers, may be used alone or in combination with other fillers. Ingredient (G) Filler Treating Agent

[0048] A filler treating agent, when present, may be used in an amount ranging from 0.1 % to 15 %, alternatively 0.5 % to 5 %, based on the weight of the composition. The filler (F) may optionally be surface treated with ingredient (G). Ingredient (F) may be treated with ingredient (G) before being added to the composition, or in situ. Ingredient (G) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl- functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid. Examples of stearates include calcium stearate. Examples of suitable filler treating agents and methods for their use are disclosed in, for example, EP 1 101 167 A2 and U.S. Patents 5,051,455, 5,053,442, and 6,169,142 (col. 4, line 42 to col. 5, line 2). (H) Adhesion Promoter

[0049] Suitable adhesion promoters may comprise alkoxysilanes of the formula R9qSi(ORlO)(4_q), where subscript q is 1, 2, or 3, alternatively q is 3. Each R9 is independently a monovalent organofunctional group. R^ can be an epoxyfunctional group such as glycidoxypropyl or (epoxycyclohexyl)ethyl, an amino functional group such as aminoethylaminopropyl or aminopropyl, a methacryloxypropyl, or an unsaturated organic group.

Each RIO is independently a saturated hydrocarbon group of at least 1 carbon atom. RIO may have 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. RIO is exemplified by methyl, ethyl, n-propyl, and iso-propyl.

[0050] Examples of suitable adhesion promoters include glycidoxypropyltrimethoxysilane or hydrolysis products thereof. When the adhesion promoter is present, the composition may comprise 2 % to 5 % of adhesion promoter based on the weight of the composition. One skilled in the art would recognize that this description of adhesion promoters and their amounts is exemplary and not limiting.

(I) Fungicide [0051] Any suitable fungicide may be utilized as component (I). Examples include, but are not limited to methyl benzimidazol-2-ylcarbamate (carbendazim), ΙΟ,ΙΟ'-oxybisphenoxarsine, 2-(4- thiazolyl)-benzimidazole, N-(fluorodichloromethylthio)phthalimide, diiodomethyl p-tolyl sulfone, if appropriate in combination with a UV stabilizer, such as 2,6-di(tert-butyl)-p-cresol, 3- iodo-2-propinyl butylcarbamate (IPBC), zinc 2-pyridinethiol 1 -oxide, triazolyl compounds such as [alpha] - [2-(4-chlorophenyl)ethyl] - [alpha] -( 1 , 1 -dimethylethyl)- 1 H- 1 ,2,4-triazole- 1 -ethanol (tebuconazole), 3-(benzo[b]thien-2-yl)-5,6-dihydro-l,4,2-oxathiazine 4-oxide and benzothiophene-2-cyclohexylcarboxamide S,S-dioxide, and also isothiazolinones, such as 4,5- dichloro-2-(n-octyl)-4-isothiazolin-3-one (DCOIT), 2-(n-octyl)-4-isothiazolin-3-one (OIT) and n-butyl-l,2-benzisothiazolin-3-one (BBIT). (J) Rheological Additive

[0052] The rheological additives include polyamides, silicone organic co-polymers based on polyols of polyethers or polyesters; non-ionic surfactants such as polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers or ethylene oxide (EO) and propylene oxide (PO), and silicone polyether copolymers; as well as silicone glycols. For some systems rheological additives, particularly copolymers of ethylene oxide (EO) and propylene oxide (PO), and silicone polyether copolymers may enhance the adhesion of a sealant to substrates, particularly plastic substrates. Suitable rheological additives are known in the art and are exemplified by those in EP 1 746 133 at paragraph [0165]. These include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof.

(K) Flame Retardant

[0053] Flame retardants may include for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds.

(L) Pigment

[0054] Pigments include carbon black, titanium dioxide, and PolyOne Stan-Tone Green, which is commercially available from PolyOne.

(M) Co-Catalvst

[0055] Ingredient (M) is a co-catalyst that may be added to the composition. Suitable co- catalysts include but are not limited to lauryl amine, aminoethylaminopropyltrimethoxysilane, and combinations thereof. One skilled in the art would recognize that aminoethylaminopropyltrimethoxysilane may be both a co-catalyst and a crosslinker. When present, the amount of ingredient (M) may range from 0.05 to 3 % based on the weight of the composition.

[0056] One skilled in the art would recognize that certain ingredients may be added in addition to, or instead of each other, when the ingredient may serve more than one purpose. For example, certain alkoxysilane adhesion promoters may also function as filler treating agents and/or crosslinkers. Certain rheological additives may function as polymers for use as ingredient (A). Certain flame retardants may also function as pigments and/or fillers and/or rheological additives. Certain co-catalysts may also function as crosslinkers. One skilled in the art would be able to select appropriate ingredients and amounts based on the desired end use of the composition. [0057] The compositions described above are useful in various applications such as sealant and adhesive applications. For example, a sealant may be prepared by a method comprising: i) preparing a sealant composition using the method and ingredients described above, and ii) curing the sealant composition. Alternatively, an adhesive may be prepared by a method comprising: i) preparing an adhesive composition using the method and ingredients described above, and ii) curing the adhesive composition.

EXAMPLES

[0058] The following examples are included to demonstrate the invention to those of ordinary skill in the art. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention set forth in the claims. All amounts, ratios, and percentages are by weight unless otherwise indicated. Reference Example 1 - Swell Gel Test

[0059] Resistance to a solvent, toluene, commonly used to dissolve the materials in the uncured state was used to determine completion of cure. A sample was allowed to cure for 5 days after which a known weight was placed into a bottle with toluene. Every few days the toluene was replaced with fresh toluene. After one week the sample was removed decanting off the bulk of solvent and then placing it into a pre-weighed dish for drying. The amount left after drying to a stable level was measured and compared to the weight of original sample to determine the amount of cured network of polymer, fillers and other curable materials.

Reference Example 2 - Preparation of an ethoxy-end-blocked organic polymer

[0060] The following ingredients were reacted to produce an ethoxy-end-blocked organic polymer:

• 200 grams (g) of a poly(propylene glycol) from Aldrich having a number average molecular weight (Mn) of 3500, OH content of 28 mg KOH/g , and viscosity of 1280 centiPoise (cps) at 25°C (values provided by the supplier); 26 g of N≡C-0- (CH₂)3Si(OCH₂CH3)3 (silane) from Gelest; and

• 0.02 g of dibutyltin dilaurate (DBTDL) as catalyst.

[0061] The procedure was to add 200 g of polymer to a round bottom flask, equipped with heating mantle, dropping funnel for the alkoxysilane, overhead mixer and nitrogen bleed. The DBTDL was then added. The silane was added over a few minutes. The mixture was heated gently for 6 hours at 70 °C.

[0062] To effect the in situ conversion of ethoxy to methoxy functionality, in examples 1-4, the ethoxy end-blocked polymer prepared in reference example 2 was exposed to a mixture of isobutyltrimethoxysilane (IBTMS) and a titanate transesterification catalyst . After the titanate/ IBTMS exposure, cure rate was gauged by addition of DBTDL and an amine (either lauryl amine or aminoethylaminopropyltrimethoxysilane). The resulting mixture was then exposed to moisture for cure. The compositions and results are in examples 1-4 below.

Example 1

[0063] The following ingredients were mixed at room temperature (RT): · 1 weight part of the ethoxy-end-blocked organic polymer prepared in reference example

2,

• 0.25 weight part isobutyl-trimethoxysilane (IBTMS),

• 0.002 weight part tetrabutyl titanate (TTBT) as transesterification catalyst,

• weight part DBTDL, and

· 0.005 weight part lauryl amine (LA).

(all weight part values being per 1 weight part of the ethoxy-end-blocked organic polymer prepared in reference example 2). The resulting composition gelled within 20 hours. Example 2

[0064] The following ingredients were mixed at RT:

• 1 weight part of the ethoxy-end-blocked organic polymer prepared in reference example 2,

• 0.25 weight part IBTMS,

• 0.002 weight part TTBT as transesterification catalyst,

• weight part DBTDL, and

• 0.005 weight part aminoethylaminopropyltrimethoxysilane. (all weight part values being per 1 weight part of the ethoxy-end-blocked organic polymer prepared in reference example 2). The resulting composition gelled within 60 minutes. Example 3

[0065] The following ingredients were mixed and heated at 50 °C for 20 hours:

• 0.25 weight part IBTMS,

• 0.002 weight part TTBT as transesterification catalyst,

• weight part DBTDL, and

• 0.005 weight part lauryl amine (LA).

(all weight part values being per 1 weight part of the ethoxy-end-blocked organic polymer prepared in reference example 2). The resulting composition gelled within 60 minutes.

Example 4

[0066] The following ingredients were mixed and heated at 50 °C for 20 hours:

· 0.25 weight part IBTMS,

• 0.002 weight part TTBT as transesterification catalyst,

• weight part DBTDL, and

• 0.005 weight part aminoethylaminopropyltrimethoxysilane. (all weight part values being per 1 weight part of the ethoxy-end-blocked organic polymer prepared in reference example 2). The resulting composition cured to form a cured elastomer having a dry surface within 45 minutes. Example 5 (comparative)

[0067] Example 1 was repeated, except that TTBT was eliminated. The composition did not cure after 24 hours. Example 6 (comparative)

[0068] Example 2 was repeated, except that TTBT was eliminated. The composition did not cure after 24 hours. [0069] Examples 3-4 show that the composition cures when a transesterification catalyst is added and the composition is aged to allow transesterification to occur. Examples 5 and 6 show that cure takes too long for the composition to be commercially viable when the transesterification catalyst is omitted, indicating that the ethoxy groups on the ethoxy-end- blocked organic polymer remain on the polymer (i.e., transesterification to a methoxy-end- blocked organic polymer does not take place).

Reference Example 3 - Preparation of a methoxy-end-blocked organic polymer

[0070] The following ingredients were reacted to produce a methoxy-end-blocked organic polymer:

• 200 grams (g) of poly(propylene glycol) from Aldrich having Mn of 3500, OH content of 28 mg KOH/g , and viscosity of 1280 cps at 25°C (values provided by the supplier);

• 21.6 g of N≡C-0-(CH₂)3Si(OCH₃)3 from Gelest; and 0.02 g of DBTDL as catalyst.

[0071] The ingredients were reacted under the following conditions. The polyl (pro ylene glycol) was weighed in a 3 neck flask with a dry nitrogen blanket. DBTDL was added and mixed for 15 minutes. The end blocker, N≡C-0-(CH2)3Si(OCH3)3 was added drop wise. After all the end blocker was added, the flask was heated. The contents of the flask were kept at 70 °C for 5 hours.

Examples 7-14

[0072] The ingredients in Table 1, below, were mixed under the following conditions:

The methoxy- or ethoxy- end-blocked polymer, IBTMS, and TTBT when used, were mixed and stored at 50 °C for 16 hours. Diisodecyl phthalate (DIDP) plasticizer was then added, and the resulting mixture was stored at 50 °C for another 16 hours. The mixture was a combination of DBTDL with aminoethylaminopropyltrimethoxysilane in a weight ratio 1.5 parts DBTDL to 1 part aminoethylaminopropyltrimethoxysilane. The amounts of each ingredient were in weight parts per 10 weight parts of polymer used from Example 2 or Example 3. The samples were evaluated for cure time and for swell gel according to reference example 1. The results are also in Table 1.

Table 1

[0073] Examples 10 and 14 show that the ethoxy-end-blocked polymer can be cured to a similar extent as a corresponding methoxy-end-blocked polymer according to the transesterification process described herein.

Reference Example 4 - Preparation of an ethoxy-end-blocked organic polymer [0074] The following ingredients were reacted to produce an ethoxy-end-blocked organic polymer:

• 50 grams (g) of poly(propylene glycol) from Bayer having a number average molecular weight (Mn) of 8200 (value provided by the supplier);

· 3.24 g of N≡C-0-(CH2)3Si(OCH₂CH₃)3 from Gelest; and

• 0.02 g of DBTDL as catalyst. [0075] The ingredients were reacted under the following conditions. The polyl (pro ylene glycol) was weighed in a 3 neck flask with a dry nitrogen blanket. DBTDL was added and mixed for 15 minutes. The end-blocker, N≡C-0-(CH2)3Si(OCH3)3 was added drop wise. After all the end-blocker was added, the flask was heated. The contents of the flask were kept at 70 °C for 5 hours.

Reference Example 5 - Preparation of a methoxy-end-blocked organic polymer [0076] The following ingredients were reacted to produce a methoxy-end-blocked organic polymer:

• 50 grams (g) of poly(propylene glycol) from Bayer having Mn of 8200 (value provided by the supplier);

· 2.69 g of N≡C-0-(CH₂)3Si(OCH₃)3 from Gelest; and

• 0.02 g of DBTDL as catalyst.

[0077] The ingredients were reacted under the following conditions. The polyl (propylene glycol) was weighed in a 3 neck flask with a dry nitrogen blanket. DBTDL was added and mixed for 15 minutes. The end-blocker, N≡C-0-(CH2)3Si(OCH3)3 was added drop wise. After all the end-blocker was added, the flask was heated. The contents of the flask were kept at 70 °C for 5 hours.

Examples 15 - 21

[0078] Samples were prepared by mixing the ingredients in Table 2 under the following conditions. The methoxy- or ethoxy- end-blocked polymer was mixed with IBTMS and stored at RT or 50 °C for 24 hours. The amounts of each ingredient were in weight parts per 10 weight parts of polymer used from Example 3, 4 or 5. After storage, a mixture of DBTDL and aminoethylaminopropyltrimethoxysilane was mixed therewith. The mixture contained 2 parts DBTDL per 1 part aminoethylaminopropyltrimethoxysilane and was added in an amount of 0.15 g mixture per 10 grams end-blocked polymer. IBTES was isobutyltriethoxysilane and Tyzor 9000 was titanium tetra-t-butoxide, Ti(OtBu)4, where tBu represents a tert-butyl group. The samples were evaluated for cure time and for swell gel according to reference example 1. The results are also in Table 2.

Table 2

[0079] Example 21 shows that transesterification occurs upon heating in this example, as evidenced by the comparable cure to the methoxy-end-blocked polymers in examples 15 and 16 when a transesterification catalyst and methoxysilane are used with the ethoxy-end-blocked polymer.

Industrial Applicability

[0080] The inventors found that, when subjected to moisture, curable compositions containing methoxy capped organic polymers typically cured at a faster rate as compared to a similar composition containing an organic polymer capped with ethoxy groups (or other alkoxy groups having more than one carbon atom). Without wishing to be bound by theory, it is thought that the present composition and method may provide the advantages of improved stability of the higher alkoxy functional organic polymer as compared to the same polymer with methoxy groups; ability to handle the higher alkoxy-end-blocked polymer at higher temperatures and/or for longer times in processing to allow for moisture removal from other sealant and/or adhesive ingredients such as precipitated CaC03, higher flash points for the higher alkoxy silanes and polymers end-blocked therewith, and improved availability of the ethoxy silane precursors, for example, for isocyanto silane preparation.

Claims

1. A composition prepared by combining ingredients comprising:

(A) a polymer selected from organic polymers and silicone-organic block copolymers, wherein said polymer has an average, per molecule, of at least two alkoxy group functionalized end-blocking groups;

(C) a transesterification catalyst, with the proviso that the alkoxy groups on ingredient (B) are more reactive than the alkoxy groups on ingredient (A).

2. The composition of claim 1, where each of the alkoxy groups on ingredient (A) has at least two carbon atoms, and at least a portion of the alkoxy groups on ingredient (B) are methoxy.

3. The composition of claim 1, where the alkoxy groups of ingredient (A) have formula

OR1, alkoxy groups bonded to other ingredients of the composition have formula OR2, and at least 60 mol % of the R2 groups differ from the Rl groups.

4. The composition of claim 3, where each of the Rl groups are ethyl and the at least 60 mol % of R2 groups are methyl.

5. The composition of claim 1 where each alkoxy group of ingredient (A) has at least two carbon atoms, the composition comprises at least one other ingredient having alkoxy groups in addition to ingredients (A) and (B), and at least 60 mol % of all the alkoxy groups on all ingredients in the composition are methoxy groups.

6. The composition of claim 1, where ingredient (B) is a silane.

7. The composition of claim 1, where the alkoxy groups of ingredient (A) differ from at least a portion of the alkoxy groups of ingredient (B) and any other alkoxy groups in the composition.

8. The composition of claim 1, where the polymer is an organic polymer.

9. The composition of claim 8, where the organic polymer is selected from a polyacrylate, polybutadiene, polyether, polyisobutylene, polyolefin, or polyurethane, or a combination thereof.

10. The composition of claim 1, where the polymer is a silicone-organic block copolymer.

11. The composition of any one of the preceding claims, where each alkoxy group of ingredient (A) is an ethoxy group.

12. The composition of any one of the preceding claims, where at least 60 % of the alkoxy groups in the composition which are not bonded to ingredient (A) are methoxy.

13. The composition of any one of the preceding claims, where ingredient (B) comprises is obutyltrimethoxy silane .

14. The composition of any one of the preceding claims, where ingredient (C) is selected from the group consisting of alumina compounds, titanate compounds, and zirconate compounds.

15. The composition of any one of the preceding claims, where ingredient (C) is tetra-t- butyl titanate.

16. A method comprising:

1) in a polymer selected from organic polymers and silicone-organic block copolymers, wherein said polymer has an average, per molecule, of at least two alkoxy group functionalized end-blocking groups, converting at least 60 % of the alkoxy groups to different alkoxy groups; and thereafter

2) curing the product of step 1) in combination with a crosslinker and a condensation reaction catalyst.

17. A method comprising:

1) reacting the composition of any one of claims 1 to 15 to form ingredient (Α'), a polymer in which at least a portion of the alkoxy groups from ingredient (A) have been replaced with alkoxy groups from ingredient (B); and optionally

2) reacting the product of step 1) with a catalyst deactivating agent; and

3) combining ingredients comprising:

(Α') the polymer prepared in step 1);

(Β') a crosslinker having an average, per molecule, of at least two condensation reaction curable groups;

(C) a condensation reaction catalyst other than ingredient (C); and optionally

(D) a plasticizer.

18. The method of claim 17, where the catalyst deactivating agent is selected from the group consisting of a glycol, an alcohol, water, a catechol, a chelating group, and a combination thereof.

19. The method of claim 17 or claim 18, where the polymer is an organic polymer.

20. The method of any one of claims 16 to 19, where the polymer is an organic polymer selected from a polyacrylate, polybutadiene, polyether, polyisobutylene, polyolefin, or polyurethane, or a combination thereof.

21. The method of any one of claims 16 to 19, where the polymer is a polyorganosiloxane.

22. The method of any one of claims 16 to 19, where the polymer is a silicone-organic block copolymer.

23. The method of any one of claims 16 to 22, where each alkoxy group of ingredient (A) is an ethoxy group.

24. The method of any one of claims 16 to 23, where each alkoxy group of ingredient (B) is a methoxy group.

25. The method of claim 24, where ingredient (B) is isobutyltrimethoxysilane.

26. The method of any one of claims 16 to 25, where ingredient (C) is selected from alumina compounds, titanate compounds, and zirconate compounds.

27. The method of claim 26, where ingredient (C) is tetrabutyl titanate.

28. The method of any one of claims 16 to 27, where ingredient (Β') comprises a silane of formula R6aSi(R7)4-a, where each R6 is independently a monovalent hydrocarbon group (such as an alkyl group); each R7 is a hydrolyzable substituent selected from the group consisting of a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, and a methylacetamido group; and subscript a is 0, 1, 2, or 3.

29. The method of claim 28, where ingredient (Β') comprises methyltrimethoxysilane.

30. The method of any one of claims 16 to 29, where ingredient (C) is selected from the group consisting of a carboxylate, a carboxylic acid, a carboxylic acid salt of metal, a tin compound, or a combination thereof.

31. The method of any one of claims 16 to 30, where the ingredients combined in step (3) further comprise an additional ingredient selected from (D) a plasticizer, (E) a stabilizer, (F) a filler, (G) a filler treating agent, (H) an adhesion promoter, (I) a fungicide, (J) a rheological additive, (K) a flame retardant, (L) a pigment, (M) a co-catalyst, and a combination thereof.

32. A sealant prepared by a method comprising: i) preparing a sealant composition using the method of any one of claims 16 to 31, and

ii) curing the sealant composition.

33. An adhesive prepared by a method comprising: preparing an adhesive composition using the method of any one of claims 16 to 31, and

curing the adhesive composition.