Moisture curable composition with improved UV resistance

Abstract

Disclosed is a moisture curable composition comprising a polyacrylate polymer, a silane modified polymer, an aminosilane, a moisture cure catalyst and optional additives, as well as cured reaction products of the composition providing good adhesion, elongation and weather exposure fade resistance, both being particularly suitable for exterior use.

Description

Moisture Curable Composition with Improved UV ResistanceFIELD OF THE INVENTION

[0001] The invention relates to moisture curable compositions. The moisture curable compositions provide good strength, elongation and weather exposure resistance and are particularly suitable for exterior use.BACKGROUND OF THE INVENTION

[0002] Curable adhesives and sealants are extensively used to seal building exteriors and building fenestrations from air, moisture and water infiltration. The sealants are applied on a surface and once cured the cured reaction products seal the surface from air, moisture and water infiltration.

[0003] Exterior sealants have been based on silicone, polyurethane and other curable polymer chemistries. However, curable polymers with desirable combinations of strength, elongation and weather resistance would be beneficial.

[0004] Curable polyacrylate polymers and compositions are used as adhesives, sealants, coatings, paintings, encapsulants, and the like, in a broad range of applications including packaging, automotive, highway, electronic device, appliance assembly and consumer uses. Polyacrylate polymers are an important class of polymers that are soft, tough and rubbery. Their glass transition temperature is well below room temperature. They are known for their high transparency, good impact toughness and elasticity, and have fairly good heat resistance up to 450 K under dry heat.

[0005] U.S. Pat. Nos. 7129294, 6274688, 6420492, 6441101 , 6667369, 4334036, 7439308, 7276574 and 5986014 disclose oil resistant (meth)acrylic polymers having alkenyl or curable silyl groups at the chain ends in high functionality ratios. These (meth)acrylic polymers are prepared by a process which comprises (i) preparing a (meth)acrylic polymer chain, i.e. polymer backbone, having halogen atoms at the chain ends, using an organohalogenated compound or a halosulfonyl compound as an initiator and a metal complex catalyst wherein the central metal atom is selected fromthe group consisting of the elements of Groups 8, 9, 10 and 11 of the periodic table; and (ii) transforming the halogen atom into an alkenyl group- or a curable silyl group- containing substituent. The obtained (meth)acrylic polymers form homogeneous curing materials. Methods for producing these (meth)acrylic polymer having crosslinkable silyl groups at the termini, comprising a step of adding a hydrosilane compound having a crosslinkable silyl group to an alkenyl-term inated (meth)acrylic polymer (A), which is prepared by atom transfer radical polymerization, in the presence of a platinum hydrosilylation catalyst. The amount of the platinum hydrosilylation catalyst is 0.1 to 10 mg on a platinum metal basis per kilogram of the alkenyl-term inated (meth)acrylic polymer (A). These moisture curable alkoxysilane terminated polyacrylate polymers are commercially available from Kaneka Corporation, Japan, which are currently prepared in a two-step process. In the disclosed processes, bromine substitution with an unsaturated carboxylic acid is followed by hydrosilation with an alkoxysilane. This two- step process can be expensive and time consuming for the manufacturer.

[0006] It would be desirable to provide a curable composition that can be applied to surfaces easily and when cured provides a desirable combination of strength, elongation and weather resistance.BRIEF SUMMARY OF THE INVENTION

[0007] One embodiment provides a moisture curable composition comprising a blend of (A) a polyacrylate polymer formed by random polymerization, (B) a silane modified polymer, (C) an aminosilane, (D) a moisture cure catalyst and optionally at least one additive. The composition can be applied to surfaces easily; when cured provides a desirable combination of strength, elongation and weather resistance; and is particularly suitable as construction sealants for exterior use.

[0008] Below described are various aspects of the invention. Aspect 1 . A moisture curable composition comprising a mixture of:(A) a polyacrylate polymer prepared by polymerizing: i. 30 to 90% by weight of a first acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR4, where R3is H or CH3 and R4is a C4-24 linear, branched or cyclic alkyl chain, or combination thereof, ii. 1 to 50% by weight of a second acrylic or methacrylic acid derivative having a structure of CH2=CR3COOZXR5, where R3is H or CH3; X is O, S, NR5or a covalent bond; Z is an optionally present C1-6 alkylene chain; and each R5is independently H, C1-2 alkyl chain or a combination thereof, and iii. 0.1 to 40% by weight of a third acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR6, where R3is H or CH3 and R6is a C7-20 fused or bridged ring system that can be substituted with one or more alkyl groups, and iv. 1 .0 to 5% by weight of a silane functional acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR7SiR83 -n Yn, where R3is H or CH3; R7is a Ci- 24 linear, branched or cyclic alkylene or arylene chain; R8is a C1-24 linear, branched or cyclic alkyl chain; Y is C1-3 alkoxy, aryloxy, acetoxy, oximino, enoxy, amino, ester, amide, lactate ester, lactate amide, H, OH, halogen, OCHCH3CON(CH3)2, OCHCH3COOCH2CH3, or combination thereof; n = 1 , 2, or 3;(B) a silane modified polymer (SMP) comprising at least one reactive silyl group of the general formula (II)B-Xo-R-Si(Rc)m(Rd)3-m (II), whereinB is a polymer backbone selected from polyethers, polyesters, polyurethanes, poly-a-olefins, or copolymers of at least two of said polymers;X is a divalent linking group containing at least one heteroatom;R is selected from divalent hydrocarbon residues containing 1 to 12 carbon atoms; each Rc is, independently of one another, selected from hydrocarbon residues containing 1 to 20 carbon atoms;each Rd is, independently of one another, selected from a hydroxyl group or hydrolysable groups, wherein Rc and Rd are substituents directly bound with the Si atom or the two of the substituents Rc and Rd form a ring together with the Si atom to which they are bound; m is 0, 1 , or 2; and, o is 0 or 1 ;(C) an aminosilane;(D) a moisture cure catalyst; and optionally one or more additives.

[0009] Aspect 2 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein the i. first acrylic or methacrylic acid derivative is selected from n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n- heptyl acrylate, and n-octyl acrylate, n-nonyl acrylate, lauryl methacrylate, cyclohexyl acrylate, and branched (meth)acrylic isomers, such as i-butyl acrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, isooctyl acrylate, or combination thereof.

[0010] Aspect 3 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein the ii. second acrylic or methacrylic acid derivative is selected from methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethyl methacrylate, methyl methacrylate, or combination thereof.

[0011] Aspect 4 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein the iii. third acrylic or methacrylic acid derivative is selected from isobornyl (meth)acrylate, ethylene glycol dicyclopentenylether (meth)acrylate, or combination thereof.

[0012] Aspect 5 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein the iv. silane functional acrylic or methacrylic acid derivative is selected from trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylethyl (meth)acrylate, methyldimethoxysilylpropyl (meth)acrylate, methacryloxypropyltrimethoxysilane, 3- (methacryloyloxy)propyltrimethoxysilane, (meth)acryloxypropylSi(OCHCH3CON(CH3)2)3, (meth)acryloxypropylSi(OCHCH3COOCH2CH3), or combination thereof.

[0013] Aspect 6 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein o is 1 and X comprises a urethane or urea.

[0014] Aspect 7 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein for the (B) silane modified polymer: the polymer backbone is a polyether, a polyester, a polyurethane, a poly-a-olefin or a copolymer of at least two of the polymers;R is a methylene, ethylene or n-propylene, and / orRc is a C1-10 alkyl group, a Ce- aryl group, or a C7-10 aralkyl group, and / orRd is a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy groups, and / or m is 0 or 1.

[0015] Aspect 8 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein for the (B) silane modified polymer: the backbone is a polyether or a polyurethane or a copolymer of a polyether and a polyurethane;R is a methylene or n-propylene, and / orRc is a methyl group or an ethyl group, and / orRd is an alkoxy group or an acyloxy group.

[0016] Aspect 9 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein for the (B) silane modified polymer, the silyl group -Si(Rc)m(Rd)3-m is selected from alkyldialkoxysilyl or trialkoxysilyl groups.

[0017] Aspect 10 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein for the (B) silane modified polymer the silyl group - Si(Rc)m(Rd)3-m is selected from a methyldimethoxysilyl, ethyldiethoxysilyl, trimethoxysilyl, or triethoxysilyl group.

[0018] Aspect 11 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, wherein for the (B) silane modified polymer, the silyl group - Si(Rc)m(Rd)3-m is selected from a methyldimethoxysilyl or trimethoxysilyl group.

[0019] Aspect 12 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, further comprising an additive selected from stabilizer, moisture scavenger, acid scavenger, moisture cure catalyst, filler, plasticizer, reactive diluent, solvent, adhesion promoter, dispersing agent, thickener.

[0020] Aspect 13 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, being substantially free of solvent.

[0021] Aspect 14 comprises the moisture curable polyacrylate polymer according to any of the foregoing aspects, having a UV weathering hours before fade of >750 hours.

[0022] Aspect 15 comprises cured reaction products of the moisture curable polyacrylate polymer according to any of the foregoing aspects.

[0023] Aspect 16. comprises a method of sealing a surface exposed to exterior use and / or weathering comprising applying the moisture curable polyacrylate composition according to any of the foregoing aspects, to the surface; and curing the composition on the surface thereby forming a cured sealant adhered to the surface, optionally the surface comprises a building exterior and / or building fenestration.DETAILED DESCRIPTION OF THE INVENTION

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0025] As used in the specification and in the claims, the term "comprising" may include the embodiments "consisting of and "consisting essentially of." The terms"comprise(s)," "include(s)," "having," "has," "can," "contain(s)," and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients / steps and permit the presence of other ingredients / steps. However, such description should be construed as also describing compositions or processes as "consisting of and "consisting essentially of the enumerated ingredients / steps, which allows the presence of only the named ingredients / steps, along with any impurities that might result therefrom, and excludes other ingredients / steps.

[0026] Numerical values in the specification and claims of this application, particularly as they relate to polymers or polymer compositions, reflect average values for a composition that may contain individual polymers of different characteristics. Furthermore, unless indicated to the contrary, the numerical values should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.

[0027] All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of "from 2 to 10" is inclusive of the endpoints, 2 and 10, and all the intermediate values). The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value; they are sufficiently imprecise to include values approximating these ranges and / or values. As used herein, approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," may not be limited to the precise value specified, in some cases. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. The modifier "about" should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression "from about 2 to about 4" also discloses the range "from 2 to 4." The term "about" may refer to plus or minus 10% of the indicated number. For example, "about 10%" may indicate a range of 9% to 11 ", and "about 1" may mean from 0.9-1.1. Other meaningsof "about" may be apparent from the context, such as rounding off, so, for example "about 1 " may also mean from 0.5 to 1 .4.

[0028] As used herein, a polymer or an oligomer is a macromolecule that consists of a plurality of monomer units greater than about one monomer unit. Polymer and oligomer, or polymeric and oligomeric, are used interchangeably here in the invention.

[0029] As used herein, the term "alkyl" refers to a monovalent linear, cyclic or branched moiety containing C1 to C24 carbon and only single bonds between carbon atoms in the moiety and including, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, and n-octadecyl.

[0030] As used herein, the term "aryl" refers to a monovalent unsaturated aromatic carbocyclic group of from 6 to 24 carbon atoms having a single ring (e.g., phenyl) or multiple condensed (fused) rings, wherein at least one ring is aromatic (e.g., naphthyl, dihydrophenanthrenyl, fluorenyl, or anthryl). Preferred examples include phenyl, methyl phenyl, ethyl phenyl, methyl naphthyl, ethyl naphthyl, and the like.

[0031] As used herein, the term "alkoxy" refers to the group -O-R, wherein R is alkyl as defined above.

[0032] As used herein, the above groups may be further substituted or unsubstituted. When substituted, hydrogen atoms on the groups are replaced by substituent group(s) that is one or more groups independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl)alkyl, hydroxy, protected hydroxyl, alkoxy, aryloxy, acyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O- thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C- carboxy, protected C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl, trihalomethanesulfonamido, and amino, including mono- and di-substituted amino groups, and the protected derivatives thereof. In case that an aryl is substituted, substituents on an aryl group may form a non-aromatic ring fused to the aryl group, including a cycloalkyl, cycloalkenyl, cycloalkynyl, and heterocyclyl.

[0033] The term, “polyacrylates” herein refers to acrylic polymers, acrylates, or acrylics, acrylic resins. They are used interchangeably here in the invention. A (meth)acrylate includes both acrylate and methacrylate

[0034] The term, “moisture cure” herein refers to hardening or vulcanization of the curable portion of the material or polymer by condensation crosslinking reaction of terminal functional group of polymer chains, brought about by water or moisture in the air and / or on a substrate, in the presence of a moisture curing catalyst.

[0035] One embodiment discloses a moisture curable composition comprising (A) a polyacrylate polymer formed by random polymerization and comprising pendant alkoxy or other moisture reactive silyl-functional groups bound to the polymer chain blended with (B) a silane modified polymer, (C) an aminosilane, (D) a moisture cure catalyst and optionally combined with other components and additives.(A) Polyacrylate Polymer

[0036] In one embodiment the polyacrylate polymer with pendant moisture curable functional groups is prepared by polymerizing: i. 30 to 90% by weight of a first acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR4, where R3is H or CH3 and R4is a C4-24 linear, branched or cyclic alkyl chain, or combination thereof, ii. 1 to 50% by weight of a second acrylic or methacrylic acid derivative having a structure of CH2=CR3COOZXR5, where R3is H or CH3; X is O, S, NR5or a covalent bond; Z is an optionally present C1-6 alkylene chain; and each R5is independently H, C1-2 alkyl chain or a combination thereof, and iii. 0.1 to 40% by weight of a third acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR6, where R3is H or CH3 and R6is a C7-20 fused or bridged ring system that can be substituted with one or more alkyl groups, and iv. 1 .0 to 5% by weight of a silane functional acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR7SiR83-n Yn, where R3is H or CH3; R7is a C1-24 linear, branched or cyclic alkylene or arylene chain; R8is a C1-24 linear,branched or cyclic alkyl chain; Y is C1-3 alkoxy, aryloxy, acetoxy, oximino, enoxy, amino, ester, amide, lactate ester, lactate amide, H, OH, halogen, OCHCH3CON(CH3)2, OCHCH3COOCH2CH3 or combination thereof; n = 1 , 2, or 3.

[0037] In one embodiment the polyacrylate polymer with pendant moisture curable functional groups can be prepared by polymerizing: i. 50 to 80% by weight of a first acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR4, where R3is H or CH3 and R4is a C4-24 linear, branched or cyclic alkyl chain, or combination thereof, ii. 3 to 30% by weight of a second acrylic or methacrylic acid derivative having a structure of CH2=CR3COOZXR5, where R3is H or CH3; X is O, S, NR5or a covalent bond; Z is an optionally present C1-6 alkylene chain; and each R5is H, C1-2 alkyl chain or a combination thereof, and iii. 5.0 to 12% by weight of a third acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR6, where R3is H or CH3 and R6is a C7-20 fused and / or bridged ring system that can be substituted with one or more alkyl groups, and iv. 1 .5 to 3% by weight of a silane functional acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR7SiR83-n Yn, where R3is H or CH3; R7is a C1-24 linear, branched or cyclic alkylene or arylene chain; R8is a C1-24 linear, branched or cyclic alkyl chain; Y is C1-3 alkoxy, aryloxy, acetoxy, oximino, enoxy, amino, ester, amide, lactate ester, lactate amide, H, OH, halogen, OCHCH3CON(CH3)2, OCHCH3COOCH2CH3, or combination thereof; n = 1 , 2, or 3.

[0038] The moisture curable polyacrylate polymer can be prepared by a method comprising:1 ) polymerizing with a reaction temperature of about 50 to about 120°C for about 4 to 24 hours of: a. 40 to 90% by weight of a mixture of:i. 30 to 90% by weight of a first acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR4, where R3is H or CH3 and R4is a C4-24 linear, branched or cyclic alkyl chain, or combination thereof, ii. 1 to 50% by weight of a second acrylic or methacrylic acid derivative having a structure of CH2=CR3COOZXR5, where R3is H or CH3; X is 0, S, NR5or a covalent bond; Z is an optionally present C1-6 alkylene chain; and each R5is independently H, C1-2 alkyl chain or a combination thereof, and iii. 0.1 to 40% by weight of a third acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR6, where R3is H or CH3 and R6is a C7-20 fused and / or bridged ring system that can be substituted with one or more alkyl groups, and iv. 1 .00 to 5% by weight of a silane functional acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR7SiR83-n Yn, where R3is H or CH3; R7is a C1-24 linear, branched or cyclic alkylene or arylene chain; R8is a C1-24 linear, branched or cyclic alkyl chain; Y is C1-3 alkoxy, aryloxy, acetoxy, oximino, enoxy, amino, ester, amide, lactate ester, lactate amide, H, OH, halogen, OCHCH3CON(CH3)2, OCHCH3COOCH2CH3, or combination thereof; n - 1 , 2, or 3, b. 10-60% by weight of an alcohol of the formula HOR9, where R9is C1-4 linear or branched alkyl chain, c. 0-60% by weight of an ester of the formula R9COOR9, where each R9is independently a C1-4 linear or branched alkyl chain, d. 0.01 to 5% of an azo or peroxide radical initiator, and2) removing the solvents and any volatile at the temperature from about 50 to about 120°C under a vacuum from about 0.2 to 200 mbar.

[0039] The free radical process can use 2,2 azobis- (2 - methyl propionitrile (AIBN) as an initiator and isopropyl alcohol as a chain transfer agent.

[0040] The monomers of components (i), (ii) (iii) and (iv) described above are converted by polymerization into the moisture curable polyacrylates.

[0041] Examples of the first acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR4include n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n- hexyl acrylate, n-heptyl acrylate, and n-octyl acrylate, n-nonyl acrylate, lauryl methacrylate, cyclohexyl acrylate, and branched (meth)acrylic isomers, such as i-butyl acrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, isooctyl acrylate, or combination thereof.

[0042] Examples of the second acrylic or methacrylic acid derivative having a structure CH2=CR3COOZXR5, include methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethyl methacrylate, methyl methacrylate, or combination thereof.

[0043] Examples of the third acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR6include isobornyl (meth)acrylate and ethylene glycol dicyclopentenylether (meth)acrylate,

[0044] Examples of the silane functional acrylic or methacrylic acid derivative having a formula CH2=CR3COOR7SiR83-n Yninclude trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylethyl (meth)acrylate, methyldimethoxysilylpropyl (meth)acrylate, methacryloxypropyltrimethoxysilane, 3- (methacryloyloxy)propyltrimethoxysilane, (meth)acryloxypropyl Si(OCHCH3CON(CH3)2)3, (meth)acryloxypropyl Si(OCHCH3COOCH2CH3), or combination thereof.

[0045] The polyacrylate polymers may be prepared by solution, emulsion, or bulk polymerization procedures using well-known polymerization techniques, such as free radical, anionic, and cationic techniques. The polymers can then be formed into a neat polymer after the removal of the solvent, coagulation of the latex or melt-processing.

[0046] The polymerization is prepared in the presence of one or more organic solvents. Suitable organic solvents or mixtures of solvents are alkanes, such as hexane, heptane, octane, and isooctane; aromatic hydrocarbons, such as benzene, toluene, and xylene; esters, such as ethyl, propyl, butyl and heptyl acetate; halogenated hydrocarbons, such as chlorobenzene; alcohols, such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol; ethers, such as THF, diethyl ether and dibutyl ether; or mixtures thereof.

[0047] In one advantageous embodiment of the process, the polymerization reactions proceed in isopropanol using AIBN as a radical initiator. In other variant, the polymerization reactions are conducted with a mixture of isopropanol and ethyl acetate. The acrylic polymers prepared will generally have a weight average molecular weight (Mw) of from 4,700 to 25,000 g / mol, preferably 10,000 to 20,000 g / mol and a number average molecular weight (Mn) of 4,500 to 8,000 g / mol. The Mw is determined by gel permeation chromatography (GPC) or matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS).

[0048] In one preferred embodiment the moisture curable polyacrylate polymer is prepared from the mixture shown in the table below. This embodiment provides good, cured strength and elongation properties while having superior UV weathering properties. The weight percent in each case is based on the total mixture of i+ii+iii+iv.

[0049] In one embodiment the moisture curable polyacrylate polymer comprises - Si(R5)3-n(Y)nmoieties pendant from the polyacrylate backbone. Since the polyacrylate polymer is a random copolymer location of these moieties will also be random. The alkoxy silane moieties provide moisture cure ability and amounts can be tailored to influence crosslinking and cure speed.

[0050] In one embodiment the moisture curable polyacrylate polymer when cured has the following properties:

[0051] Conventional silane polyacrylate polymers have poor miscibility with silane modified polyurethane polymers, especially silane modified polyurethane polymers based on polyether polyols making blending with silane modified polymers difficult or even not possible. The disclosed silane-modified polyacrylate polymers made by a free radical polymerisation process have increased miscibility with silane-modified polyurethane polymers.(B) Silane Modified Polymer

[0052] The disclosed composition comprises at least one silane modified polymer (SMP) comprising at least one reactive silyl group of the general formula (II)B-X0-R-Si(Rc)m(Rd)3-m (II), wherein polymer backbone B, is not polyacrylate but is selected from polyethers, polyesters, polyurethanes, poly-a-olefins, or copolymers of at least two of said polymers;X is a divalent linking group containing at least one heteroatom;R is selected from divalent hydrocarbon residues containing 1 to 12 carbon atoms; each Rc is, independently of one another, selected from hydrocarbon residues containing 1 to 20 carbon atoms and each Rd is, independently of one another, selected from a hydroxyl group or hydrolysable groups, wherein Rc and Rd are substituents directly bound with the Si atom or the two of the substituents Rc and Rd form a ring together with the Si atom to which they are bound;m is 0, 1 , or 2; and, o is 0 or 1 .

[0053] In this context, the divalent linking group (bonding group) X comprising at least one heteroatom is understood to be a divalent chemical group which links the polymer backbone of the silane modified polymer with the residue R of the general formula (II).

[0054] The index "o" corresponds to 0 (zero) or 1 , i.e. , the linking group X links the polymer backbone with the residue R (o = 1 ) or the polymer backbone is bound or linked directly with the residue R (o = 0).

[0055] In various embodiments, when o is 1 , the divalent linking group X in the general formula (II) is selected from -O-, -S-, -N(R”)-, -R”’-O-, a substituted or unsubstituted amide, carbamate, urethane, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group, wherein R” is a hydrogen or a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms; and R’” is a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms. The term “substituted” in relation to these groups means that a hydrogen atom present in these groups may be replaced by a nonhydrogen moiety, such as alkyl or aryl groups, preferably C1-12 alkyl or C6-14 aryl groups.

[0056] When o is 1 , in preferred embodiments, the linking group X is urethane or urea group, more preferably urethane group. Urethane group can be formed, for example, either when the polymer backbone comprises terminal hydroxy groups and isocyanatosilanes are used as a further component, or conversely when a polymer having terminal isocyanate groups is reacted with an alkoxysilane comprising terminal hydroxy groups. Similarly, urea group can be obtained if a terminal primary or secondary amino group - either on the silane or on the polymer - is used, which reacts with a terminal isocyanate group that is present in the respective reactant. This means that either an aminosilane is reacted with a polymer having terminal isocyanate groups or a polymer that is terminally substituted with an amino group is reacted with anisocyanatosilane. Urethane and urea groups advantageously increase the strength of the polymer chains and of the overall crosslinked polymer.

[0057] In preferred embodiments, the linking group X is selected from the group consisting of -O-C(=O)-N(R”)-, -N(R”)-C(=O)O-, -N(R”)-C(=O)-N(R”)-, -N(R”)-C(=O)-, - C(=O)-N(R”)-, -C(=O)-O- -O-C(=O)-, -O-C(=O)-O- -S-C(=O)-N(R”)-, -N(R”)-C(=O)-S- , -C(=O)-S- -S-C(=O)-, -S-C(=O)-S- , -C(=O)-, -S-, -O-, -NR”-, and -R”’-O-, wherein R” and R’” are as defined above. In more preferred embodiments, the linking group X is selected from -O-C(=O)-N(R”)-, -N(R”)-C(=O)O- , -N(R”)-C(=O)-N(R”)-, -S-, -O-, - N(R”)-, or -R”’-O-, wherein R” and R’” are as defined above. In particularly preferred embodiments, the linking group X is selected from -O-C(=O)-N(R”)-, -N(R”)-C(=O)- N(R”)-, -O-, or -R”’-O-, wherein R” and R’” are as defined above, more preferably -0- C(=O)-NH- or -NH-C(=O)-NH-, most preferably -O-C(=O)-NH-.

[0058] In other preferred embodiments, o is 0 (zero) and the reactive silyl group of the general formula (II) is directly bound to polymer backbone via the residue R.

[0059] The residue R is a divalent hydrocarbon residue having 1 to 12 carbon atoms. The hydrocarbon residue can be a linear, branched or cyclic alkylene residue and can be substituted or unsubstituted.

[0060] The hydrocarbon residue can be saturated or unsaturated. In preferred embodiments, R is a divalent hydrocarbon residue having 1 to 6 carbon atoms. The curing rate of the composition can be influenced by the length of the hydrocarbon residues which form one of the binding links or the binding link between polymer backbone and silyl residue. Particularly preferably, R is a methylene, ethylene or n- propylene, in particular a methylene or n-propylene.

[0061] Rc and Rd are substituents directly bound with the Si atom or the two of the substituents Rc and Rd can form a ring together with the Si atom to which they are bound. In preferred embodiments, Rc and Rd are the substituents directly bound with the Si atom.

[0062] Each Rc in the general formula (II) is, independently of one another, selected from hydrocarbon residues containing 1 to 20 carbon atoms; preferably selected fromC1 to C10 alkyl groups, C6 to C10 aryl groups, or C7 to C10 aralkyl groups; more preferably selected from C1 to C8 alkyl groups; most preferably is a methyl or an ethyl group.

[0063] Each Rd in the general formula (II) is, independently of one another, selected from a hydroxyl group or hydrolysable group(s); preferably selected from the group consisting of a hydrogen atom, a halogen atom, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups; more preferably selected from alkoxy or acyloxy groups; most preferably selected from C1 to C8 alkoxy groups or C1 to C8 acyloxy groups.

[0064] In particularly preferred embodiments, each Rd is, independently of one another, selected from C1 to C8 alkoxy groups, in particular selected from a methoxy, ethoxy, i-propyloxy or i-butyloxy group.

[0065] When m is 0 or 1 , combinations of more than one group are also possible. In preferred embodiments, m is 0 or 1.

[0066] In particularly preferable embodiments, the silyl group -Si(Rc)m(Rd)3-m is selected from alkyldialkoxysilyl or trialkoxysilyl groups, preferably selected from a methyldimethoxysilyl, ethyldiethoxysilyl, trimethoxysilyl, or triethoxysilyl group, most preferably selected from a methyldimethoxysilyl or trimethoxysilyl group.

[0067] The reactive silyl group of the general formula (II) can be a lateral group within the polymer chain of the silane modified polymer or a terminal group of the silane modified polymer. In preferred embodiments, the silyl group of the general formula (II) is a terminal group of the silane modified polymer.

[0068] In preferred embodiments, the silane modified polymer has at least two reactive silyl groups of the general formula (II). In this case, the silane modified polymer can have at least one lateral silyl group of the general formula (II) and at least one terminal silyl group of the general formula (II); or at least two lateral silyl groups of the general formula (II); or at least two terminal silyl groups of the general formula (II). In particularly preferred embodiments, the silane modified polymer has at least twoterminal silyl groups of the general formula (II). Then, each polymer chain comprises at least two linking points at which the condensation of the polymers can be completed, splitting off the hydrolyzed residues in the presence of atmospheric moisture. In this way, regular and rapid crosslinkability is achieved so that bonds with good strengths can be obtained. In addition, by means of the quantity and the structure of the hydrolyzable groups - for example by using di- or trialkoxysilyl groups, methoxy groups or longer residues - the configuration of the network that can be achieved as a long- chain system (thermoplastics), relatively wide-mesh three-dimensional network (elastomers) or highly crosslinked system (thermosets) can be controlled, so that inter alia the elasticity, flexibility and heat resistance of the finished crosslinked compositions can be influenced in this way.

[0069] The polymer backbone of the silane modified polymer is selected from polyethers, polyesters, polyurethanes, or poly-a-olefins, or copolymers of at least two of said polymers. Preferably, the polymer backbone is selected from polyethers or polyurethanes.

[0070] A “polyether”, “polyoxyalkylene”, or “polyalkylene glycol”, as used interchangeably herein, is understood to be a polymer in which the organic repeating units comprise ether functionalities C-OC in the main chain. Examples for such polymers are polypropylene glycol and polyethylene glycol and copolymers thereof. Polymers having lateral ether groups, such as cellulose ethers, starch ethers and vinyl ether polymers, as well as polyacetals such as polyoxymethylene (POM) are not included in the polyethers.

[0071] A “polyurethane" is understood to be a polymer which has at least two urethane groups -NH-CO-O in the main chain.

[0072] In particularly preferred embodiments, the polymer (B) has a polyether backbone. Polyethers have a flexible and elastic structure, with which compositions having excellent elastic properties can be produced. Polyethers are not only flexible in their backbone, but at the same time strong. Thus, for example, polyethers are not attacked or decomposed by water and bacteria, in contrast to, e.g., polyesters, for example.

[0073] The number average molecular weight Mn of the polyether on which the polymer is based is for preference 500 to 500,000 g / mol (Daltons), more preferably 500 to 60,000, particularly preferably 1 ,000 to 60,000 and in particular 2,000 to 40,000 g / mol, most preferably 8,000 to 35,000 g / mol.

[0074] Particularly advantageous viscoelastic properties can be achieved if polyethers having a narrow molecular weight distribution, and thus low polydispersity, are used. These can be produced, for example, by so-called double metal cyanide catalysis (DMC catalysis). Polyethers produced in this way are distinguished by a particularly narrow molecular weight distribution, by a high average molecular weight and by a very low number of double bonds at the ends of the polymer chains.

[0075] In a special embodiment of the present invention, the maximum polydispersity Mw / Mn of the polyether on which the polymer is based is therefore 2, particularly preferably 1.5 and most particularly preferably 1.3. The ratio Mw / Mn (polydispersity) indicates the width of the molecular weight distribution and thus of the different degrees of polymerization of the individual chains in polydisperse polymers. For many polymers and polycondensates, a polydispersity value of about 2 applies. Strict monodispersity would exist at a value of 1 . A low polydispersity of, for example, less than 1 .5 indicates a comparatively narrow molecular weight distribution, and thus the specific expression of properties associated with molecular weight, such as e.g., viscosity. In preferred embodiments, the polyether on which the silane modified polymer is based has a polydispersity (Mw / Mn) of less than 1.3.

[0076] The silane modified polymer can be obtained by various ways, which are known in the art, e.g., (i) by reacting at least one polyol and at least one isocyanatosilane; or (ii) by reacting at least one polyol with a stoichiometric excess of at least one polyisocyanate and reacting the obtained NCO-terminated polyurethane prepolymer with at least one aminosilane, such as 3-aminopropyltrimethoxysilane.

[0077] A “polyol” is understood to be a compound which contains at least two OH groups, irrespective of whether the compound contains other functional groups. However, a polyol used in accordance with the present invention preferably contains only OH groups as functional groups or, if other functional groups are present, none ofthese other functional groups is reactive at least to isocyanates under the conditions prevailing during the reaction of the polyol(s) and isocyanatosilane(s) or polyisocyante(s).

[0078] The polyols suitable for preparing said silane-term inated polymer are preferably polyether polyol.

[0079] The above descriptions about the molecular weight and polydispersity of the polyether apply to the polyether polyol. The polyether polyol is preferably a polyalkylene oxide, particularly preferably polyethylene oxide and / or polypropylene oxide. In preferred embodiments, a polyether or a mixture of two polyethers are used.

[0080] Besides the polyethers, the polyol mixture may contain other polyols. For example, it may contain polyester polyols with a molecular weight of about 200 to about 30,000.

[0081] The isocyanatosilane used in the above reaction is understood to have the general formula of 0CNR-Si(Rc)m(Rd)3-m, wherein R, Rc, Rd, and m are as defined for the general formula (II).

[0082] A “polyisocyanate” is understood to be a compound which has at least two isocyanate groups -NCO. This compound does not have to be a polymer, and instead is frequently a low molecular compound. The polyisocyanates suitable for preparing the polyurethane according to the invention include ethylene diisocyanate, 1 ,4- tetramethylene diisocyanate, 1 ,4-tetramethoxybutane diisocyanate, 1 ,6-hexamethylene diisocyanate (HDI), cyclobutane-1 ,3-diisocyanate, cyclohexane-1 ,3- and -1 ,4- diisocyanate, bis(2-isocyanatoethyl)fumarate, 1 -isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate, I P D I), 2,4- and 2,6- hexahydrotoluylene diisocyanate, hexahydro-1 ,3- or -1 ,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1 ,5-diisocyanate, 1 ,6-diisocyanato-2,2,4- trimethylhexane, 1 ,6-diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1 ,3- and 1 ,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'- diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate (MDI), and the isomeric mixtures thereof. Also suitable are partially or completely hydrogenatedcycloalkyl derivatives of MDI, for example completely hydrogenated MDI (H12-MDI), alkyl-substituted diphenylmethane diisocyanates, for example mono-, di-, tri-, or tetraalkyldiphenylmethane diisocyanate and the partially or completely hydrogenated cycloalkyl derivatives thereof, 4,4'-diisocyanatophenylperfluorethane, phthalic acid-bis- isocyanatoethyl ester, 1 chloromethylphenyl-2,4- or -2,6-diisocyanate, 1- bromomethylphenyl-2,4- or -2,6-diisocyanate, 3,3’-bis-chloromethyl ether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates such as those obtainable by reacting 2 moles diisocyanate with 1 mole thiodiglycol or dihydroxydihexyl sulfide, diisocyanates of dimer fatty acids, or mixtures of two or more of the named diisocyanates. The polyisocyanate is preferably IPDI, TDI or MDI.

[0083] Other polyisocyanates suitable for use in accordance with the invention are isocyanates with a functionality of three or more obtainable, for example, by oligomerization of diisocyanates, more particularly by oligomerization of the isocyanates mentioned above. Examples of such tri- and higher isocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof or mixed triisocyanurates thereof and polyphenyl methylene polyisocyanate obtainable by phosgenation of aniline / formaldehyde condensates.

[0084] Alternatively, the silane modified polymer can be obtained by the method as described in EP 2684690 A1 and EP2289997 A1 , the whole content of which is herein incorporated by reference.

[0085] With respect to the ratio between the polyacrylate polymer (PP) and the silane modified polymer (SMP) in the curable composition, the weight ratio (PP) / (SMP) is preferably in the range of 10 / 90 to 80 / 20, more preferably from 30 / 70 to 55 / 45 for good compatibility and viscosity, and good strength of a cured product to be provided. In some embodiments, the weight ratio can be 40 / 60 to 50 / 50.(C) Aminosilane

[0086] The curable composition comprises at least one aminosilane or a diaminosilane. Primary aminosilanes are preferred to accelerate cure speed. Secondary aminosilanes are possible but less preferred as they will incur longer curetimes. Tertiary aminosilanes should be avoided and may not cure at all. Some useful diamino silanes are Silquest A2120 from Momentive or Dynasylan AMMO from Evonik. Some useful secondary aminosilanes are Dynasylan 1189 from Evonik or N-(3- (Trimethoxysilyl)propyl)butan-1 -amine.(D) moisture cure catalyst

[0087] The curable composition comprises at least one curing catalyst. The catalysts that can be used are all known compounds that can catalyze hydrolytic cleavage of the hydrolysable groups of the silane groupings, as well as subsequent condensation of the Si-OH group to yield siloxane groupings (crosslinking reaction and adhesion promotion function).

[0088] Examples thereof are titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin octaoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethylmaleate, dioctyltin diisooctylmaleate, dioctyltin diacetate, dioctyltin diketanoate, and tin naphthenoate; tin alkoxides such as dibutyltin dimethoxide, dibutyltin diphenoxide, and dibutyltin diisoproxide; tin oxides such as dibutyltin oxide and dioctyltin oxide; reaction products between dibutyltin oxides and phthalic acid esters, dibutyltin bisacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octanoate; amine compounds or salts thereof with carboxylic acids, such as butylamine, octylamine, laurylamine, dibutylamines, monoethanolamines, diethanolamines, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamines, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6- tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4- methylimidazole, und 1 ,8-diazabicyclo-(5,4,0)-undecene-7 (DBU), a low-molecular-weight polyamide resin obtained from an excess of a polyamine and a polybasic acid, adducts of a polyamine in excess with an epoxy, silane adhesion promoters having amino groups, such as 3-aminopropyltrimethoxysilane and N-(beta- aminoethyl)aminopropylmethyldimethoxysilane. Mixtures of several catalysts can be used.Optional Additives

[0089] The moisture curable composition can optionally comprise one or more additives selected from stabilizer, moisture scavenger, acid scavenger, moisture cure catalyst, filler, plasticizer, reactive diluent, solvent, adhesion promoter, dispersing agent, thickener. Preferably the moisture curable adhesive composition or moisture curable sealant is free or substantially free of added solvents.

[0090] The curable composition can further comprise at least one stabilizer, selected from antioxidant, UV stabilizer and thermal stabilizer. All conventional antioxidants may be used as antioxidants in the composition. The composition can optionally comprise up to about 7% by weight, particularly up to about 5% by weight. The composition herein can comprise UV stabilizers, which are preferably used up to about 2% by weight, more preferably about 1 % by weight. The so-called hindered amine light stabilizers (HALS) are particularly suitable as UV stabilizers. It is preferred within the context of the present invention if a UV stabilizer is employed, which carries a silyl group and is incorporated into the end product during crosslinking or curing. The products Addworks 760 IBC and Hostanox P3P (Clariant); Lowilite 75 and Lowilite 77 (Great Lakes, USA) are suitable for this purpose. Further, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and / or sulfur can also be added. Conventional thermal stabilizers can be used in the composition.

[0091] To increase the shelf-life stability of the moisture curable composition antioxidants and moisture scavengers may be added. All compounds that react with water with the formation of a group inert to the reactive groups present in the preparation are suitable as drying agents and thereby undergo the smallest possible changes in their molecular weight. Furthermore, the reactivity of the drying agents to moisture penetrating into the curable composition must be higher than the reactivity ofthe groups of the silyl group-bearing polymer of the invention present in the preparation. Examples of the moisture scavenger include vinyltrimethoxysilane, vinylmethyldimethoxysilane, hexamethyldisilazane, methyltriethoxysilane, 3- vinylpropyltriethoxysilane, oxime silanes such as methyl-O,O',O"-butan-2- onetrioximosilane or O,O',O",O"'-butan-2-one-tetraoximosilane or benzamidosilanes such as bis(N-methylbenzamido)methylethoxysilane or carbamatosilanes such as carbamatomethyltrimethoxysilane; or combination thereof. The use of methyl, ethyl or vinyl trimethoxysilane, tetramethyl- or tetraethyl-ethoxysilane is also possible. Alkyl orthoformates or alkyl orthoacetates can also be used as drying agents, for example, methyl or ethyl orthoformate or methyl or ethyl orthoacetate, vinyltrimethoxysilane and tetraethoxysilane are particularly preferred in terms of cost and efficiency. The composition can optionally contain up to about 6% by weight.

[0092] The curable composition may optionally comprise one or more fillers. Suitable fillers include, for example, chalk, lime powder, silica, fumed silica, precipitated silica, zeolites, bentonites, magnesium carbonate, diatomaceous earth, alumina, clay, tallow, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground mineral substances. Organic fillers can also be used, such as, for example, carbon black, graphite, wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, and chaff. Short fibers such as glass fibers, glass filament, polyacrylonitrile, carbon fibers, Kevlar fibers, or polyethylene fibers may also be added. Aluminum powder is also suitable as a filler. Suitable further as fillers are hollow spheres having a mineral shell or a plastic shell. These can be, for example, hollow glass spheres which are obtainable commercially under the trade names Glass Bubbles®. Plastic-based hollow spheres, e.g., Expancel® or Dualite®, are described, for example, in EP 0 520 426 B1 . They are made up of inorganic or organic substances and each have a diameter of 1 mm or less, preferably 500 pm or less.

[0093] Fillers that impart thixotropy to the preparations may be used for some applications. Such fillers are also described as rheological adjuvants, e.g., hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC. In order to be readily squeezable out of a suitable dispensing device (e.g., a tube), such preparations possess a viscosity from 3000 to 15,000, preferably 40,000 to 80,000 mPas, or even 50,000 to60,000 mPas. The composition can optionally contain about 1 to 70% by weight, preferably 2 to 40% by weight. Mixtures of different fillers can also be used.

[0094] A “plasticizer” is understood as a substance that decreases the viscosity of the compositions and thus facilitates processability. Hydrophilic plasticizers serve to improve moisture uptake and thus to improve reactivity at low temperatures. Suitable as plasticizers are, for example, adipic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, acetic acid esters; esters of higher fatty acids having approximately 8 to approximately 44 carbon atoms, esters of OH-group-carrying or epoxidized fatty acids, fatty acid esters and fats, glycolic acid esters, phosphoric acid esters, phthalic acid esters of linear or branched alcohols containing 1 to 12 carbon atoms, propionic acid esters, sebacic acid esters, sulfonic acid esters, thiobutyric acid esters, trimellitic acid esters, citric acid esters, and esters based on nitrocellulose and polyvinyl acetate, as well as mixtures of two or more thereof.

[0095] In particularly preferred embodiments, the plasticizer comprises an ester of a polyol and an aliphatic monocarboxylic acid having 3 to 20 carbon atoms, preferably selected from triethylene glycol bis-2 -ethylhexanoate, tetraethylene glycol di-n- heptanoate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-n-heptanoate or tetraethylene glycol di-2-ethylhexanoate. In most preferred embodiments, triethylene glycol bis-2-ethylhexanoate is used as plasticizer.

[0096] The composition can optionally contain about 1 to 40% by weight, preferably about 15 to 35% by weight, particularly preferably about 20 to 30% by weight, based in each case on the total weight of the composition. If a mixture of plasticizers is used, the amounts refer to the total amount of plasticizers in the composition.

[0097] The curable composition can further optionally comprise an adhesion promoter different from the other components up to about 20% by weight. Suitable as adhesion promoters are, for example, resins, terpene oligomers, coumarone / indene resins, aliphatic petrochemical resins, and modified phenol resins. Suitable within the context of the present invention are, for example, hydrocarbon resins, as can be obtained by polymerization of terpenes, primarily a- or [3-pinene, dipentene, or limonene. These monomers are generally polymerized cationically with initiation usingFriedel-Crafts catalysts. The terpene resins also include, for example, copolymers of terpenes and other monomers, for example, styrene, a-methylstyrene, isoprene, and the like. The aforesaid resins are used, for example, as adhesion promoters for contact adhesives and coating materials. Also suitable are terpene-phenol resins, which are prepared by the acid-catalyzed addition of phenols to terpenes or rosin. Terpene-phenol resins are soluble in most organic solvents and oils and miscible with other resins, waxes, and natural rubber. Also suitable as an additive in the aforesaid sense within the context of the present invention are the rosin resins and derivatives thereof, for example, the esters thereof.

[0098] Also suitable are silane adhesion promoters, particularly alkoxysilanes, with a (further) functional group such as, e.g., an amino group, a mercapto group, an epoxy group, a carboxyl group, a vinyl group, an isocyanate group, an isocyanurate group, or a halogen. Examples are primary or secondary aminosilanes, y- mercaptopropyltrimethoxysilane, y-mercaptopropyltriethoxysilane, y- mercaptopropylmethyldimethoxysilane, y-glycidoxypropyltrimethoxysilane, y- glycidoxypropyltriethoxysilane, y-glycidoxypropylmethyldimethoxysilane, [3- carboxyethyltriethoxysilane, [3-carboxyethylphenylbis(2-methoxyethoxy)silane, N-|3- (carboxymethyl)aminoethyl-y-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, y-acroyloxypropylmethyltriethoxysilane, y- isocyanatopropyltrimethoxysilane, y-isocyanatopropyltriethoxysilane, y- isocyanatopropylmethyldiethoxysilane, y-isocyanatopropylmethyldimethoxysilane, tris(trimethoxysilyl)isocyanurate, and y-chloropropyltrimethoxysilane.

[0099] In some embodiments, the curable composition is substantially free from primary aminosilane. In the context of the present invention, "substantially free from primary aminosilane" is understood to mean that the curable composition does not contain said component or does not contain it as an intentionally added component. The amount of the primary aminosilane in the curable composition is therefore preferably less than 0.1 % by weight, more preferably less than 0.05% by weight, in particular less than 0.01 % by weight or below the detection limit.

[0100] The curable composition can further optionally comprise at least one dispersing agent, up to 3% by weight. For example, it is commercially obtainable under the trade name DISPERPLAST-P, DISPERPLAST-1142, DISPERPLAST® 1148, DISPERPLAST-I, DISPERBYK-2157, DISPERBYK-2155, or BYK-9076 by the company BYK-Chemie GmbH.

[0101] The curable composition can further optionally comprise at least one thickener (thixotropic agent), up to 5% by weight. Examples of the thickener include hydrogenated castor oils, micronized amide waxes. Some useful thickeners include Thixcin R (Elementis), Polluwax HCO3299 (Castor Products), EfkA® RM 1900 or Efka® RM 1920 (BASF), ALBERDINGK® Albothix 82-32 (Alberdingk Boley), LUVOTIX R (Lehmann & Voss & Co), DISPARLON® 6500 (Kusomoto Chemicals), or CRAYVALLAC® SLT, CRAYVALLAC® SLX, CRAYVALLAC® SL, or CRAYVALLAC® SLW (Arkema).

[0102] In some embodiments the curable composition can comprise:Amounts above are in wt.% wherein the total of all components in the curable composition is 100%.

[0103] Preparation of the curable composition can take place by simple mixing of the components and any optional additives. This can take place in suitable dispersing units, e.g., a dissolver mixer. In this case, preferably, care is taken that the mixture does not come into contact with moisture as far as possible, which could lead to an undesirable premature curing. Suitable measures are sufficiently known and comprise, for example, working in an inert atmosphere, possibly under a protective gas, and drying / heating of individual components before they are added.

[0104] In some embodiments the curable composition can have the following properties.PLI: Pounds / Linear Inch1QUV Specimen: 1 Mil Thickness, tested as described herein2James Hardie Building Products Inc. registered trademark

[0105] Bonding of at least two substrates can be done by applying the curable composition between the substrates. In some embodiments the substrate is selected from solid materials. Sone exemplary materials include ceramic tiles, glass, fiber cement materials, high-pressure laminate, untreated wood, painted / stained / varnished / glazed wood, concrete, non-ferrous metals, plastics such as vinyl and PVC (except PE, PP, PTFE, PS).

[0106] The disclosed components are surprisingly miscible when mixed, allowing the cured composition to achieve good (synergistic) performance. Cured reaction products of the curable compositions have higher elongation than conventional silane polyacrylate polymers, moderate to low tack, and UV / weather resistance.EXAMPLES

[0107] The following examples are provided for illustrative purposes only, without wishing to subject them to any unnecessary restriction.

[0108] All fillers and additives are commercially available from various suppliers. Samples were made by blending the listed components in the absence of moisture. After blending samples were stored with the exclusion of moisture to prevent unwanted curing.Elongation at Break and Tensile Stress Value Testing

[0109] The elongation at break, and tensile stress values (E modulus) were determined in accordance with ASTM D412 using a standard tensile test apparatus. The test took place after seven days of curing. A two mm thick film was drawn out of the material. The film was stored for 21 days under standard room conditions, and the dumbbells were then punched out. Five dumbbells were made for each test. The test was carried out under standard climatic conditions. The specimens were acclimatized to the test temperature (i.e. , stored) for at least 20 minutes before the measurement. Before the measurement, the thickness of the test specimens was measured at three places at room temperature using a vernier caliper; i.e., for the dumbbells, at the ends, and the middle within the initial gauge length. The average values were entered in the measuring program. The test specimens were clamped in the tensile testing machine so that the longitudinal axis coincided with the mechanical axis of the tensile testing machine and the largest possible surface of the grips was grasped, without the narrow section being clamped. At a test speed of 50 mm / min, the dumbbell tensioned to a preload of <0.1 MPa.QLIV Fade Resistance Testing

[0110] Weathering was tested using a Q-Labs QUV accelerated weathering vertical test chamber. The QUV cycle was about 6 hours exposure to 340 nm radiation at 0.89 W / M2 / nm irradiance with 60 degree C black panel temperature followed by five minutes of water spray. Samples were positionally rotated daily in the chamber. To accelerate test results a sample thickness of 1 mil (0.001 inches) was used in place of the standard 0.125 inch sample thickness. A 6 inch by 12 inch (15.2 cm by 30.5 cm) mylar sheet was placed on a hard surface. A 3 / 16 inch (4.8 mm) diameter bead of sample about 3 inches (6.6 mm) long on a Mylar sheet. The sample bead should be parallel to and about 1 inch (2.5 cm) away from the edge of the mylar sheet. The sample bead was drawn down to a thickness of 1 mil (0.001 inches, 0.025 mm) along the 12 inch length of the mylar film. The drawn down sample was allowed to fully cure on the mylar sheet for a minimum of 7 days at standard room conditions, about 20 ± 3 °C and 40 to 60% relative humidity. The mylar sheet and cured sample was then cut to fit the QUV holder, thickness was measured and the sample placed in the QUV sample holder so that halfof the sample was exposed and half of the sample was masked from exposure by the holder. The assembled sample was placed in the QUV test chamber and testing started. Samples were checked every 48 hours to document fading. The test was considered finished when the specification time was met or when the first white spot appears in the exposed sample.Polyacrylate Polymer preparation

[0111] A polyacrylate polymer was prepared and used in the following Examples. A 1 L 5-neck- round - bottom reaction flask was equipped with a temperature control device, a condenser, a mechanical stirrer, two addition funnels and nitrogen inlet / outlet. The set - up was purged with nitrogen gas for 15 min. To one of the addition funnels was charged a monomer mixture of methyl acrylate (60 g ), 2-ethylhexyl- acrylate (210 g ), isobornyl acrylate (24.0 g ), and Dynasylan (MEMO, 6 g ). To another funnel was charged the initiator solution of 2,2 azobis- (2 - methyl propionitrile) (AIBN , 0.4 g ) and isopropanol (IPA , 56g ) / ethyl-acetate (EA, 4g) . To the reaction flask was charged initiator 2,2 ' - azobis- (2 - methyl propionitrile) (AIBN , 0.116 g ); IPA (116.5 ). The reaction flask was heated to a reflux (about 85°C). Once the AIBN was dissolved then the monomer mixture in the funnel was added continuously over 2 hours at a constant rate. Simultaneously, the initiator solution in the funnel was added continuously over 3 hours at a constant rate. Upon complete addition, the mixture was stirred for an extra 1 hour at reflux. Monomer scavenger solution of t-APP (t-amyl peroxy pivalate, 0.5 g desolved in 20 g of isopropanol) were charged into the initiator funnel and then added into the reaction mixture over 1 hour and hold for 1 hour at reflux. The reaction solvent and any volatiles were stripped off under vacuum at the reflux temperature. The resulting polyacrylate polymer was cooled to room temperature under nitrogen.

[0112] The final obtained polyacrylate polymer had a weight average molecular weight (Mw) of 18,520 Da and polydispersity (PDI) of 2.1 determined by GPC. This polyacrylate polymer had a cured tensile strength of 160 psi, a cured elongation of 600%, QUV of 830 hours, a skin over time (SOT) of about 60 minutes with the skinned material being very tacky.EXAMPLE 1

[0113] A sample within the following parameters was prepared.1For Ex. 1 , 2, & 3: MA850 from Kaneka2For Ex. 1 , 2, & 3: Thixcin R from ElementisEXAMPLE 2

[0114] A sample within the following parameters was prepared.EXAMPLE 3

[0115] A sample within the following parameters was prepared.PERFORMANCE TESTING

[0116] Examples 1-3 and a Control were tested using test methods described herein.Results are shown in the Table below.1 QUADMAX sealant commercially available from Henkel Corporation.

[0117] The above results indicate significant improvement in QUV fade resistance for all Examples compared to the Control, while maintaining or improving elongation performance. Examples 1 and 2 showed ASTM 719 adhesion performance at the high end of the Control range and Example 3 performed more than three times better than the Control’s upper endpoint.

Claims

CLAIMSWe claim:1 . A moisture curable composition comprising a mixture of:(A) a polyacrylate polymer prepared by polymerizing: i. 30 to 90% by weight of a first acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR4where R3is H or CH3 and R4is a C4-24 linear, branched or cyclic alkyl chain, or combination thereof, ii. 1 to 50% by weight of a second acrylic or methacrylic acid derivative having a structure of CH2=CR3COOZXR5, where R3is H or CH3; X is 0, S, NR5or a covalent bond; Z is an optionally present C1-6 alkylene chain; and each R5is independently H, C1-2 alkyl chain or a combination thereof, and iii. 0.1 to 40% by weight of a third acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR6, where R3is H or CH3 and R6is a C 7-20 fused or bridged ring system that can be substituted with one or more alkyl groups, and iv. 1 .0 to 5% by weight of a silane functional acrylic or methacrylic acid derivative having a structure of CH2=CR3COOR7SiR83-n Yn, where R3is H or CH3; R7is a C1-24 linear, branched or cyclic alkylene or arylene chain; R8is a C1-24 linear, branched or cyclic alkyl chain; Y is C1-3 alkoxy, aryloxy, acetoxy, oximino, enoxy, amino, ester, amide, lactate ester, lactate amide, H, OH, halogen, OCHCH3CON(CH3)2, OCHCH3COOCH2CH3, or combination thereof; n = 1 , 2, or 3;(B) a silane modified polymer (SMP) comprising at least one reactive silyl group of the general formula (II):B-Xo-R-Si(Rc)m(Rd)3-m(II), wherein polymer backbone B is selected from polyethers, polyesters, polyurethanes, poly-a-olefins, or copolymers of at least two of said polymers;X is a divalent linking group containing at least one heteroatom;R is selected from divalent hydrocarbon residues containing 1 to 12 carbon atoms; each Rc is, independently of one another, selected from hydrocarbon residues containing 1 to 20 carbon atoms; each Rd is, independently of one another, selected from a hydroxyl group or hydrolysable groups, wherein Rc and Rd are substituents directly bound with the Si atom or the two of the substituents Rc and Rd form a ring together with the Si atom to which they are bound; m is 0, 1 , or 2; and, o is 0 or 1 ;(C) an aminosilane;(D) a moisture cure catalyst; and optionally one or more additives.

2. The moisture curable composition of claim 1 , wherein the i. first acrylic or methacrylic acid derivative is selected from n-butyl acrylate, n-butyl methacrylate, n- pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, and n-octyl acrylate, n-nonyl acrylate, lauryl methacrylate, cyclohexyl acrylate, and branched (meth)acrylic isomers, such as i- butyl acrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, isooctyl acrylate, or combination thereof.

3. The moisture curable composition of claim 1 , wherein the ii. second acrylic or methacrylic acid derivative is selected from methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethyl methacrylate, methyl methacrylate, or combination thereof.

4. The moisture curable composition of claim 1 , wherein the iii. third acrylic or methacrylic acid derivative is selected from isobornyl (meth)acrylate, ethylene glycol dicyclopentenylether (meth)acrylate, or combination thereof.

5. The moisture curable composition of claim 1 , wherein the iv. silane functional acrylic or methacrylic acid derivative is selected from trimethoxysilylpropyl(meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylethyl (meth)acrylate, methyldimethoxysilylpropyl (meth)acrylate, methacryloxypropyltrimethoxysilane, 3- (methacryloyloxy)propyltrimethoxysilane, (meth)acryloxypropylSi(OCHCH3CON(CH3)2)3, (meth)acryloxypropylSi(OCHCH3COOCH2CH3), or combination thereof.

6. The moisture curable composition of claim 1 , wherein o is 1 and X comprises a urethane or urea.

7. The moisture curable composition of claim 1 , wherein for the (B) silane modified polymer: the backbone is a polyether, a polyester, a polyurethane, a poly-a-olefin or a copolymer of at least two of the polymers;R is a methylene, ethylene or n-propylene, and / orRc is a C1-10 alkyl group, a Ce- aryl group, or a C7-10 aralkyl group, and / orRd is a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy groups, and / or m is 0 or 1.

8. The moisture curable composition of claim 1 , wherein for the (B) silane modified polymer: the backbone is a polyether or a polyurethane or a copolymer of a polyether and a polyurethane;R is a methylene or n-propylene, and / orRc is a methyl group or an ethyl group, and / or Rd is an alkoxy group or an acyloxy group.

9. The moisture curable composition of claim 1 , wherein for the (B) silane modified polymer, the silyl group -Si(Rc)m(Rd)3-mis selected from alkyldialkoxysilyl or trialkoxysilyl groups.

10. The moisture curable composition of claim 1 , wherein for the (B) silane modified polymer the silyl group -Si(Rc)m(Rd)3-m is selected from a methyldimethoxysilyl, ethyldiethoxysilyl, trimethoxysilyl, or triethoxysilyl group.11 . The moisture curable composition of claim 1 , wherein for the (B) silane modified polymer, the silyl group -Si(Rc)m(Rd)3-m is selected from a methyldimethoxysilyl or trimethoxysilyl group.

12. The moisture curable composition of claim 1 , further comprising an additive selected from stabilizer, moisture scavenger, acid scavenger, moisture cure catalyst, filler, plasticizer, reactive diluent, solvent, adhesion promoter, dispersing agent, thickener.

13. The moisture curable composition of claim 1 being substantially free of solvent.

14. The moisture curable composition of claim 1 , having a UV weathering hours before fade of >750 hours.

15. Cured reaction products of the moisture curable polyacrylate composition of claim 1.

16. A method of sealing a surface exposed to exterior use and / or weathering comprising applying the moisture curable polyacrylate composition of claim 1 to the surface; and curing the composition on the surface thereby forming a cured sealant adhered to the surface, optionally the surface comprises a building exterior and / or building fenestration.

17. The moisture curable polyacrylate polymer of claim 1 , wherein the i. first acrylic or methacrylic acid derivative is selected from n-butyl acrylate, n- butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, and n-octyl acrylate, n-nonyl acrylate, lauryl methacrylate, cyclohexyl acrylate, and branched (meth)acrylic isomers, such as i-butyl acrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, isooctyl acrylate, or combination thereof; the ii. second acrylic or methacrylic acid derivative is selected from methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethyl methacrylate, methyl methacrylate, or combination thereof; the iii. third acrylic or methacrylic acid derivative is selected from isobornyl (meth)acrylate, ethylene glycol dicyclopentenylether (meth)acrylate, or combination thereof; the iv. silane functional acrylic or methacrylic acid derivative is selected from trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, trimethoxysilylethyl (meth)acrylate, methyldimethoxysilylpropyl (meth)acrylate, methacryloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, (meth)acryloxypropyl Si(OCHCH3CON(CH3)2)3, (meth)acryloxypropylSi(OCHCH3COOCH2CH3), or combination thereof; o is 1 ;X comprises a urethane or urea; and wherein for the (B) silane modified polymer: the backbone is a polyether, a polyester, a polyurethane, a poly-a-olefin or a copolymer of at least two of the polymers;R is a methylene, ethylene or n-propylene, and / orRc is a C1-10 alkyl group, a Ce- aryl group, or a C7-10 aralkyl group, and / orRd is a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy groups, and / or m is 0 or 1.

18. The moisture curable polyacrylate composition of claim 17, wherein for the (B) silane modified polymer: the backbone is a polyether or a polyurethane or a copolymer of a polyether and a polyurethane;R is a methylene or n-propylene, and / orRc is a methyl group or an ethyl group, and / or Rd is an alkoxy group or an acyloxy group.

19. The moisture curable polyacrylate composition of claim 18, wherein for the (B) silane modified polymer, the silyl group -Si(Rc)m(Rd)3-m is selected from alkyldialkoxysilyl or trialkoxysilyl groups.

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