WO2025111365A1

WO2025111365A1 - Method of preparing a moisture curable resin composition with a non-tin catalyst

Info

Publication number: WO2025111365A1
Application number: PCT/US2024/056716
Authority: WO
Inventors: Yoshiki Nakagawa; Jonathan BARRUS; Ruolei Wang; Shota KOYA
Original assignee: Kaneka Americas Holding Inc
Current assignee: Kaneka Americas Holding Inc
Priority date: 2023-11-20
Filing date: 2024-11-20
Publication date: 2025-05-30
Anticipated expiration: 2026-05-20

Abstract

A method includes combining at least one moisture curable resin and at least one plasticizer, thereby forming an initial mixture, removing moisture by mixing the initial mixture with a first dose of a dehydration agent, a primary dose of a dehydration catalytic component and an additive, thereby forming a reaction mixture and heating to a temperature of at least 60°C, and contacting the reaction mixture with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition, wherein the curable catalytic component is a non-tin complex.

Description

METHOD OF PREPARING A MOISTURE CURABLE RESIN COMPOSITION WITH A NON-TIN CATALYST

BACKGROUND

[0001] Moisture curable resin compositions are often used as a coating material to protect a structure. Such compositions may include a moisture curable resin, a catalytic component, and a plasticizer. Conventional methods have proven to be time consuming and utilize a one to two component moisture curable formulation. In the one component formulations, a vessel is charged with all required non-volatile components, however, ingredients containing water require dehydration and drying prior to use and a form of physical drying performed during mixing. In two component formulations, the catalyst is not added in the beginning formulation, but when long term storage of the final product is required, the ingredients must also be dried via chemical and physical means. Formulations involving solid ingredients call for heating for dehydration and drying purposes. When liquid ingredients are used, vacuum drying or the use of synthetic desiccants is preferred. However, in either of the two component cases, storage stability of the formulation requires improvement through the use of additional catalysts. Accordingly, there exists a need for continuing improvement in the method of forming moisture curable resin compositions.

SUMMARY

[0002] This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0003] Embodiments disclosed herein relate to a method including combining at least one moisture curable resin and at least one plasticizer, thereby forming an initial mixture; removing moisture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component and an additive, thereby forming a reaction mixture and heating to a temperature of at least 60°C, and contacting the reaction mixture with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition, wherein the curable catalytic component is a non-tin complex.

[0004] Other aspects and advantages of the claimed subject matter will be apparent from the following description and the appended claims.

DETAILED DESCRIPTION

[0005] The present disclosure relates to a one component method of formulating moisture curable resin compositions, where dehydration agents and catalysts are used to facilitate the chemical drying of the composition. In general, conventional methods of making moisture curable resins add a dehydration agent and a catalytic component only at the end of the process, to ensure that premature curing of the resin does not occur and that it has good shelf stability. However, the present disclosure provides advantages over conventional methods by including a plurality of additions of a dehydration agent and a catalytic component. These two steps improve the overall processing of the composition by reducing the amount of volatile components that must be removed during processing. Furthermore, surprisingly, the disclosed method also may improve mechanical properties of the cured resins made from the curable resin composition.

[0006] One or more embodiments of the present disclosure relate to a method of making a moisture curable resin. The method of forming a curable resin composition includes the steps of combining at least one moisture curable resin and at least one plasticizer to form an initial mixture. Moisture may be removed from the initial mixture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component and an additive to form a reaction mixture and heating to a temperature of 60°C or greater. The reaction mixture is subsequently contacted with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition, wherein the curable catalytic component is a non-tin complex.

[0007] Initially, the dehydration agent and the primary dose of the dehydration catalytic component are charged to a vessel with a moisture curable resin, prior to heating. The components are then treated with additional amounts of both the dehydration agent and the catalytic component, after cooling, to thereby form a curable resin composition. The addition of the dehydration agent and the catalytic component at two different points in time during the process results in sufficient chemical drying of the curable composition, thereby allowing for improved commercial scaling and processability of the curable resin formulations.

[0008] Thus, the present disclosure generally relates to a method of forming a curable resin composition, wherein a variety of components are combined to ultimately form the curable resin. The components used in the method include at least one moisture curable resin, at least one plasticizer, dehydration agents, and dehydration catalytic components. Each of these, as well as other optional components that may also be included, are described below.

[0009] The moisture curable resin used in the methods of the present disclosure may be a polymer containing functional group(s) reactive with moisture or water. In one or more embodiments, the moisture curable resin includes reactive silicone groups, such as silyl-terminated polyether and/or silane-terminated polyurethane.

[0010] A specific structure of the reactive silicon groups is not particularly limited, but may include reactive silicon groups represented by the general formula (1):

-SiCR^-a/Xa (1) where R¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; X represents a hydrolyzable group, wherein each X is the same or different when two or more X are present; and a is an integer from 1 to 3, wherein, when a is 1, each R¹ may be the same or different, and when a is 2 or 3, each X may be the same or different.

[0011] In one or more embodiments, the moisture curable resin includes trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, or methyldiethoxysilyl groups, or combinations thereof.

[0012] Specific examples of the moisture curable resin may include, but are not limited to, one or more of KANEKA MS POLYMER® S327, S227, S203H, and S303H, and KANEKA SILYL® MA904, SAX220, SAX350, SAX530, SAX400, SAX590, SAT145, and SAT115.

[0013] The moisture curable resin may have a number of the reactive silicone groups in a range of from about 0.5 to about 6 per single polymer chain, such as a lower limit selected from any one of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, and 1.1, to an upper limit selected from any one of 3, 4, 5, and 6, where any lower limit may be paired with any upper limit.

[0014] The moisture curable resin may have linear or branched structures, and the numberaverage molecular weight (Mn) may be in a range of from about 500 to about 100,000, such as a lower limit selected from any one of 500, 1000, 2000, and 3000, to an upper limit selected from any one of 10,000, 15,000, 50,000, and 100,000, where any lower limit may be paired with any upper limit. The Mn may be measured with the use of HLC-8120GPC (TOSOH CORPORATION) as a solution-sending system, TSK-GEL H type column (TOSOH CORPORATION), and THF solvent.

[0015] The moisture curable resin may have a molecular weight distribution (Mn/Mw), or a ratio of Mn and weight-average molecular weight (Mw), of 1.6 or less, such as 1.6 or less, 1.4 or less, or 1.2 or less.

[0016] The reactive silicone group of the moisture curable resin may be bonded to a terminal end of the polymer chain or along the polymer chain between the terminal ends, or a plurality of the reactive silicone groups may be bonded to both the terminal ends and along the polymer chain.

[0017] The number of the reactive silicon groups in a single polymer chain of the moisture curable resin may be 0.5 or more on average, or 1 or more on average; or they may be in a range of from about 0.5 to 6, such as in a range of from a lower limit selected from any one of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, and 1.1, to an upper limit selected from any one of 3, 4, 5, and 6, where any lower limit may be paired with any upper limit.

[0018] The curable resin composition of the present disclosure includes at least one plasticizer. Suitable plasticizer(s) may include, but are not limited to, benzoate, phthalates, cyclohexyl diesters, glycol diester, petroleum distillate, and combinations thereof. Benzoate plasticizers may include isodecyl benzoate (e.g., Jayflex™ MB 10 (“MB 10”) available from ExxonMobil), glycol diester plasticizers may include tri(ethylene glycol)bis(2-ethylhexanoate) “TEG-EH)” (e.g. Oxfilm 351 available from OQ Chemicals), phthalates may include diisononyl phthalates (e.g., Jayflex™ DINP), cyclohexyl diesters may include 1,2-cyclohexane dicarboxylic acid diisononyl ester (e.g. Hexamoll™ DINCH available from BASF), and petroleum distillate plasticizers may include Fluid D 170 LPP (available from TotalEnergies). [0019] In one or more embodiments, the plasticizer is used alone or used in combination with at least one higher viscosity plasticizer (plasticizer blend). The higher viscosity plasticizer refers to a plasticizer having a Brookfield viscosity of at least 25 cP at 23 °C. The plasticizer, or at least one plasticizer in the plasticizer blend, contained in the curable resin composition may have a dynamic viscosity of less than 25 cP at 23 °C, when measured with a rotational, or a Brookfield viscometer (“Brookfield viscosity”). In one or more embodiments, the plasticizer has a viscosity in a range of from about 1 cP to about 25 cP at 23 °C, such as a lower limit selected from any one of 1, 2, 4, and 5 cP, to an upper limit selected from any one of 15, 20, and 25 cP, where any lower limit may be paired with any upper limit. For example, MB 10, D 170 LPP, and TEG-EH may have a dynamic viscosity of 13 cP, 15 cP, and 17 cP respectively, when measured with a Brookfield LV viscometer with an RV-01 spindle at a temperature of 23 °C and at 12 revolutions per minute (rpm).

[0020] The dehydration agents used in the methods of the present disclosure may be independently selected from, but are not limited to, alkoxysilane compounds such as n-propyl trimethoxysilane, vinyl trimethoxy silane (VTMO), vinyl methyldimethoxylsilane, y-mercaptopropyl methyldimethoxysilane, y- mercaptopropyl methyldiethoxysilane, y-glycidoxypropyl trimethoxysilane, and octyl trimethoxy silane, and combinations thereof.

[0021] The dehydration catalytic components used in the methods of the present disclosure may be independently selected from, but are not limited to, silane coupling agents; reaction products of silane coupling agents, such as isocyanate-group-containing silanes, amino-group-containing silanes (aminosilane), mercapto-group-containing silanes, epoxy-group-containing silanes, vinylically unsaturated group containing silanes, and halogen-containing silanes; amino-modified- silyl polymers; unsaturated aminosilane complexes; phenylamino long chain alkyl-silanes; aminosilylated silicones; silylated polyesters, amine compounds such as aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and aliphatic unsaturated amines; nitrogen-containing heterocyclic compounds such as pyridine and imidazole; amidines such as 1,8-diazabicyclo (5,4,0) undecane - 7 (DBU); silanol condensation catalysts including titanium complexes such as organotins tetrabutyl titanate, tetrapropyl titanate, and titanium tetraacetryl acetonate, tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctoate, dibutyltin diethylhexanoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin dioctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctylmaleate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyltin oxide, dibutyltin diacetylacetonate, dibutyltin diethylacetoacetonate, and reaction products of dibutyltin oxide and phthalic esters; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, and tin versatate; inorganic tins; and aluminum complexes and organoaluminum compounds such as aluminum trisacetyl acetonate, aluminum trisethyl acetoacetate, and diisopropoxyaluminum ethylacetoacetate.

[0022] Non-tin catalysts, including non-tin complexes, such as zinc complexes, may also be used as catalyst. A “non-tin” catalyst refers to a catalyst which contains no tin or no compounds containing tin, such as organotin compounds. Non-tin complexes that may be used as curable catalytic components include but are not limited to carboxylic acid metal salt catalysts, zinc complexes, titanium complexes and their condensates, amidine structure-containing complexes and combinations thereof. The non-tin complex may also include complexes generated in situ from any of the above combinations. Suitable non-tin catalysts may include, but are not limited to, a carboxylic acid metal salt catalyst, such as potassium neodecanoate (e.g., “TIB KAT® K25” available from TIB Chemicals AG), a zinc complex (e.g. “K-KAT 670” available from King Industries), and a titanium complex, such as diisopropoxy- bisethylacetoacetatotitanate (e.g., “Tyzor® PITA” available from Dorf Ketal Chemical, LLC.).

[0023] Examples of other titanium complexes include but are not limited to complexes with the formula (I)

Ti(OR⁵)_dY₄-d (I)

[0024] where R⁵ is a substituted or unsubstituted hydrocarbon having 1 to 20 carbons, Y represents a chelate coordination compound and d represents 0 or an integer from 1 to 4.

[0025] The substituted or unsubstituted hydrocarbon group represented by R5 is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable. Examples of the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups. The saturated hydrocarbon group is preferably a straight chain or branched alkyl group. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Hydrocarbon groups represented by R⁵ include but are not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the substituent that the hydrocarbon group may have include, but are not limited to, a methoxy group, an ethoxy group, a hydroxyl group, and an acetoxy group. When multiple R5’s exist, they may be the same or different.

[0026] The chelate coordination compound represented by Y may be a compound known to coordinate to titanium. Examples include, but are not limited to, 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1- phenyl- 1 -aryl- 1 ,3-butanedione, 1 ,3-butanedione, 1 -(4-methoxyphenyl)- 1,3- butanedione, l,3-diphenyl-l,3-propanedione, 1,3 -bis(2-pyridyl)-l,3-propanedione, 1 ,3-diaryl- 1 ,3-propanedione, 1 ,3-bis(4- methoxyphenyl)- 1 ,3-propanedione.

[0027] Y may also be a diketone such as 3-benzyl-2,4-pentanedione; Ketoesters such as methyl acetoacetate, ethyl acetoacetate, butylacetoacetate, t-butylacetoacetate, ethyl 3-oxohexanoate; N,N-dimethyl ketoamides such as acetoacetamide, N,N- diethylacetoacetamide, acetoacetanilide; malonic acid esters such as dimethylmalonate, diethylmalonate, diphenylmal onate; N,N,N’,N Examples include malonic acid amides such as ‘-tetramethylmalonamide and N,N,N’,N’- tetraethylmalonamide. Among these, diketones and ketoesters are preferred.

[0028] When there are a plurality of chelate coordination compounds (Y’s), they may be the same or different. In formula (I) d represents 0 or an integer from 1 to 4. Since the curable resin composition according to the present disclosure exhibits better curability and improved elongation after curing, d preferably represents 0 or an integer from 1 to 3, and preferably from 1 to 3. It is more preferable to show an integer of 2. Specific examples of the titanium compound represented by the general formula (I) include but are not limited to tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium trimethoxybutoxytitanium, dimethoxydiethoxytitanium, and dimethoxydiisopropoxytitanium. Titanium, dimethoxy dibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxy

Triisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, tetratert-butoxytitanium, diisopropoxytitanium bis(acetylacetonate), diisopropoxy titanium bis (ethylacetoacetate), diisobutoxy titanium bis(ethylacetoacetate); condensates of titanium alkoxides such as tetrabutoxytitanium dimer and tetrabutoxytitanium tetramer. Only one type of titanium compound may be used, or two or more types may be used in combination. The titanium compound represented by general formula (I) is preferably a compound containing a chelate coordination compound represented by Y, since good curability can be obtained and improved elongation can be exhibited after curing. Specifically, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), and diisobutoxytitanium bis(ethyl acetoacetate) are particularly preferred.

[0029] The amidine structure-containing complexes are represented by general formula (II):

R²N=CR³-NR⁴2 (II)

[0030] where R², R³ and R⁴ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The two R⁴ groups may be the same or different. Any two or more of the R², R³ and two R⁴ may be bonded to form a cyclic structure.

[0031] In order to improve the curability of the resin composition, R² is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the carbon atom adjacent to the nitrogen atom has an unsaturated bond. More preferably R² is a hydrocarbon group that contains the number 1 to 10 carbons, more preferably 1 to 6 because of easy availability.

[0032] R³ is preferably a hydrogen atom or an organic group represented by — NR⁶2, and more preferably an organic group represented by — NR⁶2, since it increases the curability of the curable resin composition. However, the two R⁶ groups each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. In this case, the compound represented by general formula (II) is a guanidine compound. [0033] Furthermore, R³ may be an organic group represented by -NR⁷-C(=NR⁸)-NR⁹2 or by — N=C(NR¹⁰2)-NR^U2, since good physical properties of the obtained cured product are preferred. However, R⁷, R⁸ and two R⁹s each independently represent a hydrogen atom or an organic group having 1 to 6 carbon atoms. Two R¹⁰s and two Rⁿs each independently represent a hydrogen atom or an organic group having 1 to 6 carbon atoms. In this case, the compound represented by general formula (II) is called a biguanide compound. The two R⁴s in general formula (II) are hydrogen atoms or hydrocarbons having 1 to 20 carbons atoms because they are easily available and improve the curability of the curable resin composition. It preferably represents a group, and more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0034] The number of carbon atoms contained in the amidine structure-containing compound is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 10,000 or less. Furthermore, the molecular weight of the amidine structure-containing compound is preferably 60 or more, more preferably 120 or more, and particularly preferably 130 or more. The upper limit of the molecular weight is not particularly limited, but is preferably 100,000 or less. The amidine structure-containing compound (bl) is not particularly limited, but includes, for example, pyrimidine, 2-aminopyrimidine, 6-amino-2,4-dimethylpyrimidine, 2- amino-4,6-dimethylpyrimidine, 1 ,4,5,6-tetrahydropyrimidine, 1 ,2-dimethyl- 1 ,4,5,6- tetrahydropyrimidine, 1 -ethyl-2-methyl- 1 ,4,5,6-tetrahydropyrimidine, 1 ,2-diethyl- 1,4,5,6-tetrahydropyrimidine, l-n-propyl-2-methyl-l,4,5,6-tetrahydropyrimidine, 2- hydroxy-4,6-dimethylpyrimidine, 1 ,3-diazanaphthalene, 2-hydroxy-4- aminopyrimidine, etc. pyrimidine compounds; 2-imidazoline, 2-methyl-2- imidazoline, 2-ethyl-2-imidazoline, 2-propyl-2-imidazoline, 2-vinyl-2-imidazoline, l-(2-hydroxy ethyl)-2-Imidazoline compounds such as methyl-2-imidazoline, 1,3- dimethyl-2-iminoimidazolidine, 1 -methyl-2-iminoimidazolidin-4-one; 1,8- diazabicyclo[5.4.0] undec-7-ene (DBU), l,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2,9-diazabicyclo[4.3. 0] Amidine compounds such as nona-l,3,5,7-tetraene, 6- (dibutylamino)-l,8-diazabicyclo[5,4,0]undecene-7 (DBA-DBU); guanidine, dicyandiamide , 1 -methylguanidine, 1 -ethylguanidine, 1 -cyclohexylguanidine, 1- phenylguanidine, l-(o-tolyl)guanidine, 1,1 -dimethylguanidine, 1,3- dimethylguanidine, 1,2- Diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3- trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2 Ethyl- 1 , 1 ,3,3-tetramethylguanidine, 1 , 1 ,3,3-tetramethyl-2-npropylguanidine,

1 , 1 ,3,3-tetramethyl-2-isopropylguanidine, 2-n-butyl- 1 , 1 ,3,3-tetramethylguanidine, 2- tert-butyl- 1,1,3,3-tetramethylguanidine, 1,2,3-tricyclohexylguanidine, 1 -benzyl-2,3- dimethylguanidine, l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl- 1,5,7- triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n- propyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isopropyl- 1,5,7- triazabicyclo[4.4.0]dec-5-ene, 7-nbutyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7- cyclohexyl- 1,5,7 -triazabicyclo[4.4.0]dec-5 -ene, 7 -n-octyl- 1,5,7- triazabicyclo[4.4.0]dec-5- Guanidine compounds such as biguanide, 1- methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, l-(2-ethylhexyl)biguanide, 1-noctadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1- cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, l-(o-tolyl)biguanide, 1- morpholinobiguanide, l-n-butyl-N2-ethylbiguanide, l,l'-ethylenebisbiguanide, 1,5- ethylenebiguanide, l-[3-(diethylamino)propyl]biguanide, l-[3-

(dibutylamino)propyl]biguanide, N',N"-dihexyl-Biguanide compounds such as 3,12- diimino-2,4,l l,13-tetraazatetradecanediamidine; and the like. As the amidine structure-containing compound, only one type may be used, or two or more types may be used in combination. The amidine structure-containing compound is preferably an amidine compound or a guanidine compound, more preferably DBU, DBA-DBU, DBN, or phenylguanidine, because the curability is improved, DBA-DBU, or DBN are more preferred, and DBU is particularly preferred.

[0035] Examples of other catalytic components may include, but are not limited to, phenol and epoxy resins, sulfur, alkyl titanates, and aromatic polyisocyanates, used alone or in combination. As will be appreciated by those skilled in the art, while referred to as a “catalytic component” herein, the above-mentioned exemplary catalytic components may serve a variety of purposes in the composition, particularly when employed in the catalytic doses as explained below. For example, some of the aforementioned components may be employed as an adhesion promoter.

[0036] The additives used in the methods of the present disclosure may include stabilizers, fillers, rheology modifiers, pigments, and combinations thereof. Other suitable additives include, but are not limited to, thixotropic agents (anti-sagging agents), UV inhibitors/absorbers, antioxidants, flame retardants, curability modifiers, lubricants, antifungal agents, and combinations thereof.

[0037] Examples of the fillers may include, but are not limited to, ground and precipitated calcium carbonate (CaCCE), magnesium carbonate, diatomite, calcined clay, clay, and bentonite; reinforcing fdlers such as fumed silica, precipitated silica, and crystalline silica; and fibrous fillers such as glass fibers and filaments.

[0038] Examples of pigments may include, but are not limited to, titanium dioxide (TiCE) and carbon black.

[0039] Examples of thixotropic agents may include, but are not limited to, hydrogenated castor oil, organic amid wax, organic bentonite, and calcium stearate.

[0040] Examples of UV inhibitors/absorbers may include, but are not limited to, benzophenone compounds, benzotriazole compounds, triazine compounds, salicylate compounds, substituted tolyl compounds, and metal chelate compounds.

[0041] Examples of stabilizers may include, but are not limited to, hindered amine light stabilizer (HALS), benzotriazole compounds, and benzoate compounds.

[0042] Examples of antioxidants may include, but are not limited to, hindered phenolic antioxidants such as Irganox®245, 1010, and 1076 (available from BASF).

[0043] As mentioned above, the present disclosure primarily relates to a method of forming a curable resin composition comprising the steps of combining at least one moisture curable resin and at least one plasticizer, thereby forming an initial mixture, removing moisture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component to form a reaction mixture and heating to a temperature of 60°C or more and contacting the reaction mixture with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition. Furthermore, the method of forming a curable resin composition may be advantageously conducted at atmospheric pressure. Removing the need for vacuum pumps can greatly simplify the process, thereby reducing time and cost associated with preparing the curable resin as compared to conventional preparation methods. However, the method may also be conducted under reduced pressure, such that the method steps may be performed, in part, under reduced pressure, or as a whole. [0044] In one or more embodiments, at least one moisture curable resin and at least one plasticizer are combined in a vessel, thereby forming an initial mixture. The at least one moisture curable resin and at least one plasticizer may be any of the curable resins and plasticizers described above. The initial mixture is wetted throughout to form an initial mixture. This wetting is to ensure there are no visible powder ingredients, reaching an initial degree of homogeneity to form an initial mixture, but not necessarily reaching the required degree of powder agglomerate breakdown to be achieved via higher shear mixing. The mixer is not particularly limited, and any suitable mixer known in the art may be used. In one or more particular embodiments, a planetary or multi- shaft mixer may be used. While shear mixing is not required for the initial wetting step, it may be employed for this step, as it is useful for subsequent mixing steps, as explained below. The initial wetting may be conducted at room temperature and pressure. In some embodiments, a vacuum may be applied during the wetting step.

[0045] In one or more embodiments, the amount of the moisture curable resin in the initial mixture is in a range of from about 10 wt% to about 70 wt% of the initial mixture, such as a lower limit selected from any one of 10, 20, and 30 wt%, to an upper limit selected from any one of 50, 60, and 70 wt%, where any lower limit may be paired with any upper limit.

[0046] In one or more embodiments, the amount of the plasticizer in the initial mixture is in a range of from about 5 wt% to about 50 wt% of the initial mixture, such as a lower limit selected from any one of 5, 10, and 20 wt%, to an upper limit selected from any one of 30, 40, and 50 wt%, where any lower limit may be paired with any upper limit.

[0047] In one or more embodiments, a content of the moisture curable resin and the plasticizer in the initial mixture is in a range of about 20 wt% to about 90 wt% of the initial mixture, such as a lower limit selected from any one of 20, 30, and 40 wt%, to an upper limit selected from any one of 70, 80, and 90 wt%, where any lower limit may be paired with any upper limit. Other components making up the remainder of the initial mixture are as follows.

[0048] As mentioned above, the curable resin composition may also include additives. Thus, the step of combining the moisture curable resin with the plasticizer may further comprise contacting the initial mixture with additives such as stabilizers, fillers, rheology modifiers, pigments, thixotropic agents (anti-sagging agents), UV inhibitors/absorbers, antioxidants, flame retardants, curability modifiers, lubricants, and antifungal agents, and combinations thereof. Additionally, those skilled in the art will recognize that many of these types of additives may serve a variety of purposes in the composition and may also be used in method steps involving the reaction mixture. For example, UV absorbers and antioxidants may be used as stabilizers. In one or more embodiments, the amount of the additives present in the initial mixture is in a range of from about 5 wt% to about 80 wt% of the initial mixture, such as a lower limit selected from any one of 5, 10, 15, and 20 wt%, to an upper limit selected from any one of 50, 60, 70 and 80 wt%, where any lower limit may be paired with any upper limit.

[0049] In one or more embodiments in which a stabilizer is included, the amount of the stabilizer in the initial mixture is in a range of from about 0 wt% to about 3 wt% of the initial mixture, such as a lower limit selected from any one of 0, 0.1, and 0.2 wt%, to an upper limit selected from any one of 0.5, 1, 2, and 3 wt%, where any lower limit may be paired with any upper limit.

[0050] In one or more embodiments in which a filler is included, the amount of the filler in the initial mixture is in a range of from about 0 wt% to about 75 wt% of the initial mixture, such as a lower limit selected from any one of 0, 1, 5, and 10 wt%, to an upper limit selected from any one of 55, 65, and 75 wt%, where any lower limit may be paired with any upper limit.

[0051] In one or more embodiments in which a pigment is included, the amount of the pigment in the initial mixture is in a range of from about 0 wt% to about 10 wt% of the initial mixture, such as a lower limit selected from any one of 0, 0.1, 0.2, 0.3, 0.4, and 0.5 wt%, to an upper limit selected from any one of 6, 7, 8, 9, and 10 wt%, where any lower limit may be paired with any mathematically compatible upper limit.

[0052] In one or more embodiments in which a thixotropic agent is included, the amount of the thixotropic agent in the initial mixture is in a range of from about 0 wt% to about 4 wt% of the initial mixture, such as a lower limit selected from any one of 0, 0.1, and 0.2 wt%, to an upper limit selected from any one of 1, 1.5, 1.7, 2, 3, 3.9, and 4 wt%, where any lower limit may be paired with any upper limit. [0053] Following the formation of the initial mixture, the initial mixture may be mixed with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component, thereby forming a reaction mixture. In one or more embodiments, these components may be slowly added to the vessel such that no visible liquid remains, and then the mixture may be mixed using a high shear mixer. In some embodiments, the reaction mixture is heated to a temperature of at least 60°C, either via external heating or shear friction, to promote dehydration as explained in greater detail below.

[0054] The combination of the primary dose of the dehydration catalytic component with first dose of the dehydration agent, acting as a moisture scavenger, promotes the chemical drying of the initial mixture as opposed to relying heavily on physical drying methods, such as drying under vacuum and at elevated temperatures. Volatile components in the reaction mixture can cause damage to vacuum pumps, therefore, utilizing chemical drying methods can significantly improve processing of the resins.

[0055] The first dose of the dehydration agent used may be in an amount ranging from about 0.1 wt% to about 3 wt% of the reaction mixture, such as a lower limit selected from any one of 0.1, 0.2, and 0.3 wt%, to an upper limit selected from any one of 0.5, 1, 2 and 3 wt%, where any lower limit may be paired with any upper limit. Generally, the initial loading of the dehydration agent may be stoichiometrically similar to the theoretical moisture level of the formulation, based on individual component moisture specifications. Thus, as will be appreciated by those skilled in the art, the amount of dehydration agent may be appropriately selected to be suitable for a given formulation.

[0056] The amount of the primary dose of the dehydration catalytic component should be optimized to ensure adequate chemical processing of the mixture without causing excessive premature curing of the resin. As such, the content of the primary dose of a catalytic component in the reaction mixture may be in an amount ranging from about 0.1 wt% to about 3 wt% of the reaction mixture, such as a lower limit selected from any one of 0.1, 0.15, 0.2, 0.5, and 1 wt%, to an upper limit selected from any one of 0.5, 1.0, 1.5, 2, 2.5, and 3 wt%, where any lower limit may be paired with any upper limit.

[0057] Following the addition of the first dose of the dehydration agent and the primary dose of the dehydration catalytic component, the reaction mixture is heated. The mixing step is conducted at a temperature ranging from about 60°C to about 120°C, such as in a range from a lower limit selected from any one of 60, 70, 80 and 90°C to an upper limit selected from any one of 100, 110 and 120°C, where any lower limit may be paired with any upper limit. The heat may be applied externally, such as by using jacketed vessels with external heating, or by friction supplied by mixer geometries that provide sufficiently high shear rates, such as cowles dispersers.

[0058] In one or more embodiments, the reaction mixture is initially held at about 80°C for at least 15 minutes to allow the initial condensation of the dehydration agent. After the initial condensation, reduced pressure may be applied to the reaction mixture to supplement the chemical drying of the reaction mixture. The reduced pressure may be applied using a vacuum pump such as, but not limited to, a diaphragm pump, or any other equipment that may be used to reduce pressure and facilitate the physical removal of moisture or water. However, as an alternative to applying reduced pressure, the mixing step may be performed at atmospheric pressure.

[0059] In one or more embodiments, the mixing step is conducted for an amount of time ranging from at least 15 minutes to 4 hours, such as in the range from a lower limit selected from any one of 15, 30, and 60 minutes, to an upper limit selected from any one of 2, 3, and 4 hours, where any lower limit may be paired with any upper limit.

[0060] After the mixing step is conducted, the reaction mixture is cooled and contacted with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form the curable resin composition. In one or more embodiments, the contacting step is conducted at a temperature ranging from 20 to 50°C whereby allowing the reaction mixture to be cooled to the target temperature range, such as in the range from a lower limit selected from any one of 20, 22.5, 25, and 30°C, to an upper limit selected from any one of 40, 45 and 50°C, where any lower limit may be paired with any upper limit. The reaction mixture may be cooled using either external chilling medium through jacketed vessels, or by allowing a period of time to pass for the reaction medium’s heat to dissipate over time.

[0061] The dehydration agent of the second dose of a dehydration agent may be any dehydration agent as above described. The second dose of the dehydration agent used may be present in an amount ranging from about 0.1 wt% to about 3 wt% of the curable resin composition, such as a lower limit selected from any one of 0.1, 0.2, and 0.3 wt%, to an upper limit selected from any one of 0.5, 1, 2, and 3 wt%, where any lower limit may be paired with any upper limit.

[0062] The catalytic component of the secondary dose of a dehydration catalytic component may be any catalytic component as above described. The content of the secondary dose of a dehydration catalytic component may be present in an amount ranging from about 0.1 wt% to about 20 wt% of the curable resin composition, such as a lower limit selected from any one of 0.1 , 0.5, and 1 wt%, to an upper limit selected from any one of 4, 4.5, and 5 wt%, where any lower limit may be paired with any upper limit. In embodiments involving a non-tin catalyst complex as the curable catalytic composition, where the non-tin catalyst complex includes an amidine structure-containing compound and a titanium complex or its condensate, the weight ratio of the titanium compound or its condensate to the amidine structure-containing compound is in the range of about 0.1 to 20.

[0063] Following the addition of the second dose of dehydration agent and the secondary dose of a dehydration catalytic component of the contacting step, the curable resin composition may be treated with additional additives, including any of the additives above described, any volatile components, and/or an additional catalyst. While the primary and secondary doses of the catalytic components are used to assist in the chemical drying process while forming the curable resin composition, an additional amount of a final dose of a catalytic component may be added once the curable resin composition is formed, to facilitate in its ability to cure upon exposure to moisture. Therefore, the final dose of the catalytic component may be added immediately before packaging into moisture proof packaging. The catalyst of the final dose of the catalytic component may be any of the catalysts above described. The amount of the final dose of the catalytic component may be present in an amount ranging from about 0.01 wt% to 1.0 wt % of the curable resin composition, such as a lower limit selected from any one of 0.01, 0.03, and 0.5 wt%, to an upper limit selected from any one of 0.7, 0.85, and 1.0 wt %, where any lower limit may be paired with any upper limit. Thus, a total amount of the catalytic component, comprising the first, second, and final doses of the catalytic components, provide sufficient catalytic activity such that the compound will have desirable skin time and overall curing characteristics once introduced to ambient moisture. In one or more embodiments, the total amount of the catalytic component in the curable resin composition is in a range of from about 0.1 wt% to about 5.2 wt%, such as a lower limit selected from any one of 0.2, 1, and 2 wt%, to an upper limit selected from any one of 3, 4, 5, and 5.1 wt%, where any lower limit may be paired with any upper limit.

[0064] Once the aforementioned method steps are completed and the composition is packaged into moisture proof packaging, a shelf-stable curable resin composition is formed. The curable resin composition may have suitable properties for various applications. For example, the viscosity of the curable resin composition may be within suitable ranges for its intended commercial application. As noted above, said viscosities may be achieved through simpler processing with less need for reduced pressures.

[0065] That is, the present invention relates to the following: (1) A method for preparing a moisture curable resin composition comprising the following steps: the step of combining at least one moisture curable resin and at least one plasticizer thereby forming an initial mixture; the step of removing moisture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component and an additive, thereby forming a reaction mixture and heating to a temperature of at least 60°C; and the step of contacting the reaction mixture with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition, wherein the at least one moisture curable resin comprises reactive silicon groups represented by the general formula (1):

[0066] -Si(R* ₃-a)Xa (1)

[0067] wherein R¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; wherein X represents a hydrolyzable group, wherein each X is the same or different when two or more X are present; wherein a is an integer from 1 to 3, when a is 1, each R¹ may be the same or different, and when a is 2 or 3, each X may be the same or different; and wherein the curable catalytic component is a non-tin complex.

[0068] (2) The method according to (1), wherein the additive is selected from the group consisting of a stabilizer, a filler, a rheology modifier, a pigment, and combinations thereof. [0069] (3) The method according to (1) or (2), wherein the mixing is conducted at atmospheric pressure.

[0070] (4) The method according to any one of (1) to (3), wherein the at least one moisture curable resin is selected from the group consisting of trimethoxy silyl, methyldimethoxysilyl, triethoxysilyl, and methyldiethoxy silyl groups, and combinations thereof.

[0071] (5) The method according to any one of (1) to (4), wherein the at least one moisture curable resin comprises a silyl-terminated polyether.

[0072] (6) The method according to any one of (1) to (5), wherein the at least one plasticizer is selected from the group consisting of a benzoate, a phthalate, a cyclohexyl diester, a glycol diester, a petroleum distillate, and combinations thereof.

[0073] (7) The method according to any one of (1) to (6), wherein the first dose of the dehydration agent is present in a range of 0.1 to 3 wt%.

[0074] (8) The method according to any one of (1) to (7), wherein the second dose of the dehydration agent is present in a range of 0.1 to 3 wt%.

[0075] (9) The method according to any one of (1) to (8), wherein the dehydration agents of the first and second doses are independently selected from the group consisting of n-propyl trimethoxysilane, vinyl trimethoxysilane, vinyl methyldimethoxylsilane, y- mercaptopropyl methyldimethoxysilane, y-mercaptopropyl methyldiethoxysilane, y- glycidoxypropyl trimethoxysilane, and combinations thereof.

[0076] (10) The method according to any one of (1) to (9), wherein a content of the moisture curable resin and the plasticizer in the reaction mixture is in an amount ranging from 20 to 90 wt%.

[0077] (11) The method according to any one of (1) to (10), wherein a content of the primary dose of the dehydration catalytic component in the reaction mixture is in an amount ranging from 0.1 to 3 wt%.

[0078] (12) The method according to any one of (1) to (11), wherein a content of the primary dose of the dehydration catalytic component in the reaction mixture is in an amount ranging from 0.1 to 0.5 wt%. [0079] (13) The method according to any one of (1) to (12), wherein a content of the secondary dose of the dehydration catalytic component in the reaction mixture is in an amount ranging from 0.1 to 5 wt%.

[0080] (14) The method according to any one of (1) to (13), wherein the non-tin complex is selected from the group consisting of carboxylic acid metal salt catalysts, zinc complexes, titanium complexes and their condensates, amidine structure-containing complexes and combinations thereof.

[0081] EXAMPLES

[0082] The following examples are provided to illustrate embodiments of the present disclosure. The Examples are not intended to limit the scope of the present invention, and they should not be so interpreted.

[0083] “SAX350” (MS Polymer) and “SAX220” (MS Polymer) of Tables 1-10 are moisture curable resins available from Kaneka Corporation. The plasticizer, diisononyl phthalate (DINP), is a non-benzoate plasticizer with a boiling point greater than 400 °C. DINP has a dynamic viscosity of 86 cP when measured with a Brookfield LV viscometer with RV-01 spindle at a temperature of 23 °C at 6 rpm. UltraPflex is available from Specialty Minerals. Hubercarb® Q3T is available from Huber Corporation. Ti-Pure™ R902+ is available from Chemours. CRAYVALLAC® SLT is available from Arkema. Eversorb® HP6 is available from Everlight Chemical. VTMO, DAMO-T, and Dynasylan 1146 and 6490 are available from Evonik. NEOSTANN U-220H organotin catalyst is available from Nitto Kasi Co., Ltd. Tyzor® PITA and Tyzor® TPT are available from Dorf Ketal Chemicals, LLC. TIB KAT® K25 is available from TIB Chemicals AG.

[0084] Moisture curable resin compositions Examples 1-6 (Ex 1-9) and Comparative Examples 1-2 (Comp Ex 1-2) were produced by mixing moisture curable resin(s), plasticizer(s), catalytic component(s), and various additives as shown in Tables 1-3.

[0085] Comparative Examples 1-2 and Examples 1-9

[0086] For Comp Ex 1-2 and Ex 1-9, the MS Polymer and plasticizer diisononyl phthalate (DINP) were initially combined in a vessel with varying amounts of the additives calcium carbonate (UltraPflex, Q3T), Titanium oxide (Ti-Pure R902+), Crayvallac SLT, and HP6, as shown in Tables 1-3. These components were wetted throughout then mixed and heated at 60°C. A first dose of VTMO and primary dose of DAMO- T, as indicated in Tables 1-3, if applicable, were added and mixed with heat. Comp Ex 1 used a hot process. The removal of moisture was facilitated using solely chemical drying from the VTMO and catalytic component for Comp Ex 2 and Examples 1-4 and 6-9. The mixture was allowed to cool then the second dose of dehydration agent (VTMO or Dynasylan 6490), secondary dose of catalytic component (DAMO-T or Dynasylan 1146), and the organotin or non-tin complex (U- 220H, Tyzor PITA, Tyzor TPT and/or DBU) were added in the amounts as indicated in Tables 1-3 with no vacuum. The mix time for Comp Ex 2 and Ex 2-3, 6 and 8-9 was 90 minutes, while that of Ex 1, 4-5-6 and 7 was 30 minutes.

Table 1

Table 2

Table 3

PHYSICAL PROPERTIES

[0087] Dynamic viscosities of the resin compositions were measured by a Brookfield rotational viscometer (“HA” or “Brookfield” viscosity) with a 07 spindle. The viscosity was measured at a frequency of 1 rpm, 2 rpm, and 10 rpm. The Brookfield Thixotropic Index value of each resin composition was determined by dividing the HA viscosity at 2 rpm by the HA viscosity of the same resin composition at 10 rpm. The viscosity increase was measured as the difference between (i) the dynamic viscosity of the resin composition after the components were mixed and (ii) the dynamic viscosity of the resin compositions after 4 weeks of storage at 50°C.

[0088] A skin time of the resin composition was determined by placing the resin composition in a container and measuring the time required for a skin to form under 23°C and 50% relative humidity (RH) conditions. The skin time test was conducted on the resin compositions immediately after the components were mixed.

[0089] The curable compositions each were extruded from the cartridge and filled in a molding frame of about 5 mm in thickness with a spatula; the surface of each of the filled compositions was fully flattened, and the planarization completion time was set as the curing starting time. Every one minute, the surface of each of the compositions was touched with a spatula, and the skin formation time was measured as the time when the composition no longer stuck to the spatula.

[0090] Cure in depth was determined as the thickness in mm of the composition, when cured to an elastomeric state during aging at ambient temperature and humidity for a specified period of time.

[0091] Residual tack was observed after 1 and 7 days, by finger touch, and was measured on a scale of 1 to 8, where 8 represents no residual tack and 1 represents very tacky.

[0092] Shore A durometer hardness refers to the indentation hardness. The hardness referred to herein was measured according to ASTM C661 standard.

[0093] Tensile properties were measured according to ASTM D412. A Japanese Industrial Standards No. 3 dumbbell specimen punched out from the sheet was used. The modulus at 100% elongation (Ml 00) at a tensile rate of 200 mm/min, tensile strength, and the elongation at break of this specimen were measured with a universal testing machine.

[0094] The curable compositions each were extruded from the cartridge so that the compositions each were adhered to different substrates and were aged at 23° C for 7 days. Thereafter, the compositions were subjected to a 90 degree hand peel test. The breakdown conditions of the cured substances were observed, and the cohesion and adhesion failure rates (CF rates) were investigated.

[0095] Various physical properties of the resin compositions of Examples 1-9 and Comparative Examples 1-2 were measured as described below.

[0096] Tables 4-7 exemplify the changes in the physical properties of the composition made when both dehydration agent and catalytic component are used in the formulation and are supplemented with physical drying. The inventive examples 1-9 employ a combination of non-tin catalyst (titanium compounds Tyzor PITA or Tyzor TPT and K25) and amidine structure (DBU), which provides enough catalytic activity to see the improvement to the tensile and elongation properties, compared to Comparative Example 2, which employs only an organotin catalyst. Specifically, a comparison between that of Comp Ex 2 and Ex 2 shows that the use of the non-tin complex shows improvements in the tensile strength, elongation at break and viscosity increase. Ex 1 shows that use of a different secondary dehydration agent and catalytic component with the non-tin catalyst still shows improvements in elongation at break. Ex 3 shows that using 1 phr as the primary dose and 2 as the secondary dose of the catalytic components showed further improved tensile and elongation properties, as well as lower viscosity increases, when the compositions are stored long term. A similar effect is shown between Ex 2 and Ex 6 where only the mixing time is reduced (to 30 minutes) for the latter example yet improved the viscosity increase. Ex 4 and 5 compare physical properties from use of just chemical drying versus chemical and physical drying. While the tensile properties are still improved in Ex 4 and 5 compared to Comp Ex. 2, the viscosity increases are more pronounced. Overall, the examples demonstrate that in- situ oligomers of VTMO/DAMO-T, which are likely products of the chemical dehydration facilitated by the unique inclusion of moisture scavenger and catalytic component before the main mixing step, can be used to enhance skin times in finished goods even with non-tin curing catalysts. Table 4

Table 5

Table 6

Table 7

[0097] While the scope of the methods will be described with several embodiments, it is understood that one of ordinary skill in the relevant art will appreciate that many examples, variations, and alterations to the composition and methods described here are within the scope and spirit of the disclosure. Accordingly, the embodiments described are set forth without any loss of generality, and without imposing limitations, on the disclosure. Those of skill in the art understand that the scope includes all possible combinations and uses of particular features described in the specifications.

[0098] Although only a few example embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from this invention. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function, and not only structural equivalents, but also equivalent structures. Thus, although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooden parts together, whereas a screw employs a helical surface, in the environment of fastening wooden parts, a nail and a screw may be equivalent structures.

Claims

CLAIMS What is claimed is:

1. A method for preparing a moisture curable resin composition comprising the following steps: the step of combining at least one moisture curable resin and at least one plasticizer thereby forming an initial mixture; the step of removing moisture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component and an additive, thereby forming a reaction mixture and heating to a temperature of at least 60°C ; and the step of contacting the reaction mixture with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition, wherein the at least one moisture curable resin comprises reactive silicon groups represented by the general formula (1):

-SiCR¹ 3-a)X_a (l), wherein R¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; wherein X represents a hydrolyzable group, wherein each X is the same or different when two or more X are present; wherein a is an integer from 1 to 3, when a is 1, each R¹ may be the same or different, and when a is 2 or 3, each X may be the same or different; and wherein the curable catalytic component is a non-tin complex.

2. The method of claim 1, wherein the additive is selected from the group consisting of a stabilizer, a filler, a rheology modifier, a pigment, and combinations thereof.

3. The method of claim 1, wherein the mixing is conducted at atmospheric pressure.

4. The method of claim 1, wherein the at least one moisture curable resin is selected from the group consisting of trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, and methyldiethoxy silyl groups, and combinations thereof.

5. The method of claim 1, wherein the at least one moisture curable resin comprises a silyl-terminated polyether.

6. The method of claim 1, wherein the at least one plasticizer is selected from the group consisting of a benzoate, a phthalate, a cyclohexyl diester, a glycol diester, a petroleum distillate, and combinations thereof.

7. The method of claim 1, wherein the first dose of the dehydration agent is present in a range of 0.1 to 3 wt%.

8. The method of claim 1, wherein the second dose of the dehydration agent is present in a range of 0.1 to 3 wt%.

9. The method of claim 1, wherein the dehydration agents of the first and second doses are independently selected from the group consisting of n-propyl trimethoxysilane, vinyl trimethoxysilane, vinyl methyldimethoxylsilane, y-mercaptopropyl methyldimethoxysilane, y-mercaptopropyl methyldiethoxysilane, y-glycidoxypropyl trimethoxysilane, and combinations thereof.

10. The method of claim 1, wherein a content of the moisture curable resin and the plasticizer in the reaction mixture is in an amount ranging from 20 to 90 wt%.

11. The method of claim 1, wherein a content of the primary dose of the dehydration catalytic component in the reaction mixture is in an amount ranging from 0.1 to 3 wt%.

12. The method of claim 1, wherein a content of the primary dose of the dehydration catalytic component in the reaction mixture is in an amount ranging from 0.1 to 0.5 wt%.

13. The method of claim 1, wherein a content of the secondary dose of the dehydration catalytic component in the reaction mixture is in an amount ranging from 0.1 to 5 wt%.

14. The method of claim 1, wherein the non-tin complex is selected from the group consisting of carboxylic acid metal salt catalysts, zinc complexes, titanium complexes and their condensates, amidine structure-containing complexes and combinations thereof.