WO2025076244A1

WO2025076244A1 - Moisture curable acrylic polymer compositions

Info

Publication number: WO2025076244A1
Application number: PCT/US2024/049827
Authority: WO
Inventors: Mohsen SOLEIMANI; Timothy Klots; Armin A. Burghart; Sridhar G. Iyer
Original assignee: BASF SE; BASF Corp
Current assignee: BASF SE; BASF Corp
Priority date: 2023-10-06
Filing date: 2024-10-03
Publication date: 2025-04-10
Anticipated expiration: 2026-04-06

Abstract

The present disclosure provides the synthesis, formulation, and application of an isocyanate-functional polyacrylate polymer optimized for the development of tensile strength and elongation for moisture-cure. The isocyanate-resin can be formulated into a one pack moisture cure system capable of transforming into an elastomeric material for applications in construction, coatings, and adhesives.

Description

MOISTURE CURABLE ACRYLIC POLYMER COMPOSITIONS

CROSS-REFERENCE TO RELATED APPLICATION

[001] The present application claims priority to U.S. Provisional Application No. 63/542,848, filed on October 6, 2023, and entitled “MOISTURE CURABLE ACRYLIC POLYMER COMPOSITIONS,” the entire disclosure of which is expressly incorporated by reference herein.

FIELD OF THE DISCLOSURE

[002] The present disclosure is related generally to acrylic polymer compositions for construction materials and, more specifically, a self-cross-linking moisture-curable isocyanate-functional polyacrylate, its methods of making, and its uses in various applications.

BACKGROUND OF THE DISCLOSURE

[003] Construction materials need to adapt to changes in building codes, consumer taste and building methods. The construction industry is facing skilled labor shortages and need innovative material solutions that enable inherent safe handling, faster return to service while extending the application window. At the same time, the desire is to maintain ease of use in the field while providing performance attribute needed as described by building codes and to withstand environmental elements over the building lifetime. Moisture curable polymers are an attractive solution for many applications such as elastomeric coatings, adhesives, sealants, and air-weather barrier. A wide range of technologies exist for producing moisture curable polymers. Alkoxy silane terminated poly ethers are widely used in such applications. The cure reaction in such systems results in undesired byproducts such as methanol, ethanol. In addition, there is a need to improve barrier properties of such material toward ingress of moisture and liquid water as well as their weatherability for outdoor applications. These limitations restrict the use of such chemistries in building envelop and when ultimate moisture barrier properties are needed. Another class of moisture curable polymers rely on reaction of isocyanate groups with ambient moisture and release carbon dioxide as byproduct. There polymers are commonly made by reacting a polyisocyanate with hydroxy terminated polymers such as polyethers and polyesters. However, these formulations contain excessive amounts of free-isocyanate monomers

1

SUBSTITUTE SHEET (RULE 26) which creates labeling requirements that leads to special safe-handling considerations in the field. The unreacted isocyanate moieties not only pose a health-hazard but also detract from mechanical performance of the final product. Moreover, the use of polymer backbones such as polyesters and polyethers; create similar hydrolytic stability, water susceptibility and poor outdoor weathering resistance challenges to those common for the alkoxy silane class.

[004] This invention discloses a novel chemistry based on a modified acrylic or styrenic-acrylic backbone that addresses such performance and regulatory challenges. The compositions described here enable combining ease of field application of moisture curable technologies with outstanding weathering, barrier and adhesion properties of acrylic backbone.

SUMMARY OF THE DISCLOSURE

[005] Disclosed herein is the synthesis, formulation, and application of an isocyanate- functional polyacrylate capable of transforming into an elastomeric material upon completion of a moisture cure reaction as demonstrated by tensile strength and elongation at break development. The isocyanate-resin can be stored as a one-pack system and then undergo self-cure when exposed to moisture under ambient conditions.

[006] In one form thereof, the present disclosure provides a moisture curable composition comprising an isocyanate-functional polyacrylate polymer and a catalyst that promotes an isocyanate- water reaction.

BRIEF DESCRIPTION OF THE DRAWINGS

[007] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the disclosure and together with the description, serve to explain the principles of the disclosure.

[008] Figure 1 is a graph showing the flow curve for Examples 6 and 7 showing neat resin viscosity < 60 Pa. sec at 25 °C.

[009] Figure 2 is a graph showing the tensile and elongation of films made from Example 6 and 7 in formulations A and B with 1 wt.% Polycat 5 as catalyst compared to commercial control.

[0010] Figure 3 is a graph of the tensile strength and elongation of Example 7 in formulation C.

2

SUBSTITUTE SHEET (RULE 26) [0011] Figure 4 is a graph of the tensile and elongation of films made from Example 7 in formulations C with 0.5, 1 and 1.5 wt.% of Polycat 5 as catalyst.

[0012] Figure 5 is a graph of the lap shear and failure mode when elastomeric materials were used to create Oak/Oak assemblies; control = 40 psi-adhesive.

[0013] Figure 6 is a chart of the water uptake after 12 hours immersion for Example 7 films in formulation C cured for 7 days with 0.5, 1, 1.5 and 2 wt.% Polycat 5 as catalyst.

Control = 12%.

DETAILED DESCRIPTION

I. Definitions

[0014] The term “comprising,” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of’ and “consisting of’ can be used in place of “comprising” and “including” to provide for more specific embodiments and are also disclosed. As used in this disclosure and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise. The disclosure of percentage ranges and other ranges herein includes the disclosure of the endpoints of the range and any integers provided in the range.

II. Isocyanate-Functional Polyacrylate Compositions

[0015] Provided herein are moisture curable resins that comprise an isocyanate- functional polyacrylate composition. The polymer compositions comprise an isocyanate functionality which is polymerized with an acrylate co-monomer to form the desired product. A key advantage of the compositions disclosed herein is that they may be formulated into one-pack with self-cross-linking only occurring once the formulation is applied to the desired substrate. In addition, the formulations disclosed herein do not emit any toxic or VOC by-products (such as methanol) during the curing process, thereby making them safer and easier to use.

[0016] The source of the isocyanate functionality may be any isocyanate containing monomer. A particularly preferred example is 3-isopropenyl-a,a-dimethylbenyzl isocyanate (TMI). Other suitable examples include 2-isocyanatoethyl acrylate, 2-

3

SUBSTITUTE SHEET (RULE 26) acryloyloxyethylisocyanate available under trade name AOI-VM from SDK corporation, and allyl isocyanate.

[0017] The isocyanate containing monomer may also be any monomer with the following general structure:

[0018] Where Ri is a hydrogen or methyl group and R2 may be an aliphatic, aromatic, heteroaliphatic, or heteroaromatic radical with 0 to 40 carbon-carbon bonds. Suitable heteroatoms for R include oxygen and nitrogen.

[0019] Acrylate co-monomers are preferred to make up the remaining bulk of the polymer because of their low T_g, high conversion, and low cost. Particularly preferred acrylate-commoners include butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), ethyl acrylate (EA), lauryl acrylate and 2-propylheptyl acrylate (2PHA). Other suitable examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl (meth)acrylate, n- hexyl (meth) acrylate, n-heptyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n- decyl (meth) acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth) acrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy (meth)acrylate, 2-(2- ethoxyethoxy)ethyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, polypropyleneglycol mono methyl (meth)acrylate, polyethyleneglycol mono methyl (meth)acrylate, benzyl (meth)acrylate, methylpolyglycol (meth)acrylate, and combinations thereof.

[0020] The structure of the isocyanate- functional polyacrylate polymer may be represented by Formula (I) below.

SUBSTITUTE SHEET (RULE 26)

[0021] wherein R1 can be a hydrogen atom or a methyl group and R2 can be an alkane radical with 0 to 40 carbon-carbon bonds. Non limiting examples of R2 include methyl, ethyl, butyl, isopropyl, hexyl, pentyl, 2-ethyl hexyl, and octyl. In some embodiments, R2 may comprise a urethane or urea based-linkage. R3 can be a single or double carbon-carbon bond such that the NCO group is directly bonded to the polymer backbone. R3 can also an aliphatic, aromatic, heteroaliphatic or heteroaromatic radical with 0 to 40 carbon-carbon bonds or an aromatic group. In particular, R3 can for example be 1- tert-butylene 4-mthylene benzene, ethylene methoxy carbonyl, or methylene. In all cases, R3 contains no urethane or urea based-linkage. R4 can be a hydrogen or methyl group. In some embodiments, the isocyanate-functional polyacrylate polymer is free from urethane or urea linkages. Structures with urethane or urea linkages in the side chains are possible but may have undesirable side effect of high viscosity due to strong hydrogen bonding between the urethane groups. The monomer enclosed between the brackets denoted by “ran” in formula 1 may be randomly organized throughout the polymer molecule. That is, the isocyanate- functional polyacrylate polymer may be a random polymer which lacks a specific regular or repeating pattern in its molecular structure. The number of monomer residues in each polymer molecule may be any integer from 1 to 1000.

[0022] In some embodiments, a fraction of isocyanate functionalities of the isocyanate- functional polyacrylate polymer may be further reacted with telechelic polymers carrying isocyanate reactive groups at terminal positions. Such groups may include but are not limited to amines and hydroxyl functionalities. The polymer backbone can be poly ethers, poly dimethyl siloxanes, poly esters, or polyamides. The hybrid system synthesized this way can be formulated into moisture curable systems in similar manner as described in this disclosure.

SUBSTITUTE SHEET (RULE 26) [0023] The number average molecular weights for the polymers may be as high as 1 kDa or higher, 2 kDa or higher, 3 kDa or higher, 4 kDa or higher, 5 kDa or higher, 6 kDa or higher, 7 kDa or higher, 8 kDa or higher, 9 kDa or higher, 10 kDa or higher, or within any range encompassed by any two of the foregoing endpoints.

[0024] The polymers disclosed herein may have a low glass transition temperature (T_g) such as -10°C or lower, - 15°C or lower, -20°C or lower, -25°C or lower, -30°C or lower, -35°C or lower, -40°C or lower, -45°C or lower, -50 °C or lower, -55°C or lower, - 60°C or lower -65°C or lower, or within any range encompassed by any two of the foregoing values as endpoints.

[0025] The polymers disclosed herein may contain, on average, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 isocyanate groups per chain.

In some embodiments, the isocyanate-functional polyacrylate polymer may be further reacted with a silicone polymer and a silane crosslinker. The silicone polymer and silane crosslinker may react directly or via a crosslinking agent with the isocyanate-functional polyacrylate polymer to form an isocyanate-functional silicone-acrylate polymer. The isocyanate-functional silicone-acrylate polymer may comprise a covalently bonded silicone polymer and the acrylate copolymer through -Si — X — Si linkages, where X is either O or NH bonds.

[0026] Other suitable additives that can optionally be incorporated into the composition include fillers, rheology modifiers, wetting and spreading agents, leveling agents, conductivity additives, adhesion promoters, anti-blocking agents, anti-cratering agents and anti-crawling agents, corrosion inhibitors, anti-static agents, flame retardants and intumescent additives, dyes, optical brighteners and fluorescent additives, UV absorbers and light stabilizers, chelating agents, cleanability additives, crosslinking agents, flatting agents, flocculants, humectants, insecticides, lubricants, odorants, oils, waxes, stain resisting agents, and combinations thereof.

III. Synthesis of Isocyanate-Functional Polyacrylate Compositions

[0027] The present disclosure also provides synthesis methods to produce moisture curable resins.

[0028] Polymerization of the isocyanate- functional polyacrylate compositions may be done in a continuous or batch process. The radical chain polymerization technique is

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SUBSTITUTE SHEET (RULE 26) preferred for direct incorporation of isocyanate moieties into the acrylic backbone as described in “principles of polymerization” George Odian, Chapter 3. Such polymerizations can be conducted in batch mode such as the one described in US7173084B2 which is herein incorporated by reference in its entirety or continuous mode such as the one described in US4414370 & US6552144B1 which is herein incorporated by reference in its entirety. An example of such technique applied in a continuous manner is solid grade oligomer (SGO) process capable of making low T_g, isocyanate functional resins for moisture cure. Free radical initiators are commonly used in solution polymerization process. These are compounds that decompose to generate free radicals and thus can control and govern the polymerization of vinylic monomers, such as butyl acrylate. For the current discussion, only so-called “oil-soluble” initiators are suitable. Often, these initiating chemicals are carbon- containing peroxides which decompose into to two radicals by thermal cleavage. These peroxides have been designed to yield useful decomposition rates across a range of temperatures. Suitable higher temperatures initiators are typically simple dialkyl peroxides such as di-tert-butyl (DTBP), di-tert-amyl peroxide, or dicumyl peroxide. Decomposing at slightly lower temperatures are alkyl peroxyesters such as t-amyl peroxyacetate, t-butyl peroxybenzoate. Diacyl peroxides, such as dilauroyl peroxide, are another class which actively decompose at even lower temperatures. Other sub-classes of peroxide initiators are peroxy carbonates and diperoxy ketals. It should be noted that of the initiators mentioned, DTBP has the highest 1-hour half-life temperature at 149 °C.

[0029] A non-peroxide class of initiators contains the azo functionality, which cleaves similarly, releasing nitrogen and generates alkyl radicals. The most common such initiator here is azobisisobutyronitrle (AIBN), which has a 1-hour half-life temperature at 82°C. Typically decomposing at lower temperatures, a range of suitable azo initiators have also been developed according to trade names VAZO™, Iniper™, and WAKO™. There is therefore a wide range of suitable molecular species for initiating controlled free-radical polymerization which is by no means limited to the chemicals referred to above.

[0030] Other suitable examples include 3-hydroxy-l,l-dimethylbutyl peroxyneodecanoate, a-cumyl peroxyneodec anoate, 2 -hydroxy- 1,1 -dimethylbutyl peroxyneoheptanoate, a -cumyl peroxyneoheptanoate, t-amyl peroxyneodecanoate, t-butyl peroxyneodecanoate, di(2-ethylhexyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, t-butyl peroxyneoheptanoate, t-amyl peroxypivalate, t-

7

SUBSTITUTE SHEET (RULE 26) butyl peroxypivalate, diisononanoyl peroxide, didodecanoyl peroxide, 3 -hydroxy- 1,1 dimethylbutylperoxy-2-ethylhexanoate, didecanoyl peroxide, 2,2’-azobis(isobutyronitrile), di(3-carboxypropionyl) peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, dibenzoyl peroxide, t-amylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy-(cis-3-carboxy)propenoate, 1, l-di(t- amylperoxy)cyclohexane, l,l-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,l,l-di(t- butylperoxy)cyclohexane, OO-t-amyl O-(2-ethylhexyl) monoperoxycarbonate, OO-t-butyl O-isopropyl monoperoxycarbonate, OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate, polyether tetrakis(t-butylperoxycarbonate), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t- amyl peroxyacetate, t-amyl peroxybenzoate, t-Butyl peroxyisononanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butyl diperoxyphthalate, 2,2-di(t butylperoxy )butane, 2,2-di(t-amylperoxy)propane, n-butyl 4,4-di(t-butylperoxy)valerate, ethyl 3,3-di(t-amylperoxy)butyrate, ethyl 3,3-di(t-butylperoxy)butyrate, dicumyl peroxide, a,a'-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di(t- amyl) peroxide, t-butyl a-cumyl peroxide, and di(t-butyl) peroxide.

[0031] Isocyanate functionality may be introduced to the compositions using 3- isopropenyl-a,a-dimethylbenyzl isocyanate also known as TMI. TMI may be copolymerized with butyl acrylate (BA) as shown in Scheme 1 below.

Scheme 1. SGO synthesis of co-polymer of BA and TMI.

[0032] Suitable solvents for the polymerization reaction include solvents that are typically anhydrous and also alcohol free. Examples of suitable solvents include toluene, xylene, Aromatic 100™ (trimethyl benzenes) and MAK (methyl amyl ketone), as well as MEK (methyl ethyl ketone). Such low boiling point solvents that are used in the process are typically removed after polymerization. As described herein, “low boiling point solvents”

SUBSTITUTE SHEET (RULE 26) refers to those with boiling point below 200°C at atmospheric pressure. Optionally, high boiling point solvents can be used during the polymerization process. These solvents can remain in the final product to reduce the final viscosity. Examples of such solvents include diisooctyl diphtalate, Eastman TXIB, and Loxanols from BASF.

[0033] Solvent loading can be as low as 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.% or as high as 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, or within any range encompassed by any two of the foregoing values as endpoints based on the total weight of the feed composition.

[0034] An initiator may be used in the polymerization reaction. Particularly preferred initiators include di-tert-amyl peroxide (DTAP) and di-tert-butyl peroxide (DTBP).

[0035] The polymerization reaction may be conducted at a temperature as low as 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140 °C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, or as high as 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, or within any range encompassed by any two of the foregoing endpoints.

[0036] If a continuous process is used, the residence time for the polymerization reaction may be little as 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, or as high as 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, or within any range encompassed by any two of the foregoing endpoints.

IV. Addition of a Silicone Polymer

[0037] A silicone polymer and a silane crosslinker may react with the isocyanate- functional acylate polymer forming an isocyanate-functional silicone- acrylate polymer. [0038] The silicone polymers can include a reactive functional group, such as a hydroxyl functional group, an amine functional group, a thiol functional group, an alkoxy functional group, a hydride functional group, a vinyl functional group, or a mixture thereof. In some embodiments, the silicone polymer is end-capped with the functional group. For example, the silicone polymer can be end-capped with the hydroxyl, alkoxyl, hydride, or vinyl functional group. Preferably, the silicone polymer includes a hydroxyl functional group. In this embodiment, the silicone polymer may be terminated by a silanol group ( - Si-O-H).

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SUBSTITUTE SHEET (RULE 26) [0039] In other embodiments, the silicone polymer includes a non-hydroxy- terminated silicone polymer or a mixture of hydroxy-terminated and non-hydroxy- terminated silicone polymers.

[0040] In some embodiments, the silicone polymer may include a poly siloxane backbone. The polysiloxane can include an organo-containing substituent such as an alkyl substituent. For example, the polysiloxane can include a dimethyl, methylvinyl, methylphenyl, diphenyl, methylethyl, or 3, 3, 3 -trifluoropropyl substituent. Preferably, the silicone polymer includes a polydialkylsiloxane backbone, more preferably a polydimethylsiloxane backbone.

[0041] The silicone polymer may include a polysiloxane having a structure according to the formula:

R¹ "R¹ R¹

1

HO — R²— Si — O — -S 1i— O- — S 1i— ²— OH

1 1 1

R¹ R¹ n R¹ wherein R¹, independently for each occurrence, is independently selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, and heterocyclylalkyl; R², independently for each occurrence, is independently selected from alkyl, aryl, arylalkyl and a bond; and n ranges from 10 to 1,000, from 50 to 800, from 100 to 500, or from 150-250, wherein the alkyl, alkenyl, alkynyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, and heterocyclylalkyl are each independently, at each occurrence, unsubstituted or substituted with one or more suitable substituents. In some embodiments, R¹, independently for each occurrence, is independently selected from Cl to C40 alkyl, C2 to C40 alkenyl, C2 to C40 alkynyl, C6 to C40 aryl, C3 to C40 heteroaryl. In some embodiments, R¹, independently for each occurrence, is independently selected from Cl to CIO alkyl, C2 to CIO alkenyl, or C2 to CIO alkynyl. In some embodiments, R², independently for each occurrence, is independently selected from Cl to Cao alkyl or a bond. In some embodiments, R², independently for each occurrence, is independently selected from Cl to CIO alkyl or a bond. In some example, R¹ is methyl at each occurrence. In certain embodiments, R¹ is methyl at each occurrence and R² is a bond at each occurrence. In certain embodiments, the polysiloxane is a hydroxy-terminated polydimethylsiloxane having formula:

SUBSTITUTE SHEET (RULE 26)

[0042] Suitable silicone polymers may include silanol terminated silicone polymers such as Andisil 750, Andisil 6000.

[0043] In certain embodiments, the silicone polymer may have a weight average molecular weight of 3,000,000 Da or less (e.g., 2,000,000 Da or less, from 10,000 Da to 2,000,000 Da, or from 500,000 Da to 2,000,000 Da.

[0044] In certain embodiments, the silicone polymer has a viscosity of greater than 100 cps, greater than 200 cps, or greater than 600 cps or less than 10,000 cps, less than 6,000 cps, or less than 750 cps, or any range using any of the foregoing values as endpoints, such as 100 cps to 10,000 cps, 200 cps to 6,000 cps, and 600 cps to 750 cps.

[0045] The silicone polymer may be present in the isocyanate-functional polyacrylate composition in a total amount from 15 wt.%, 25 wt. %, 35 wt. %, or 45 wt. % to 55 wt. %, 65 wt. %, 75 wt. %, or 85 wt. %, or any range using any of the foregoing values as endpoints, such as 15 wt.% to 85 wt. %, 25 wt. % to 75 wt. %, 35 wt. % to 65 wt. %, or 45 wt. % to 55 wt. %.

[0046] Suitable silane crosslinkers may include an acetoxy silane crosslinker, an oximino silane based crosslinker, a methylethylketoxime (MEKO) based crosslinker, a methylisobutylketoxime (MIBKO) based crosslinker, an acetoxime based crosslinker, an alkoxy silane based crosslinker, or a combination thereof. In some examples, the silane crosslinker includes a methyl tris(MEKO)silane, a tetra(MEKO)silane, a vinyl tris(MEKO)silane, a methylvinyl di(MEKO)silane, a phenyl tris(MEKO)silane, a methyl tris(MIBKO)silane, a tetra(MIBKO)silane, a vinyl tris(MIBKO)silane, a methyl tris(acetoxime)silane, a vinyl tris(acetoxime)silane, or a mixture thereof.

[0047] The silane crosslinker may be present in the isocyanate-functional polyacrylate composition in a total amount from 1.5 wt. %, 3 wt. %, or 5 wt. % to 7 wt. %, 9 wt. %, or 11 wt. %, or any range using any of the foregoing values as endpoints, such as 1.5 wt. % to 11 wt. %, 3 wt. % to 9 wt. %, or 5 wt. % to 7 wt. %.

V. Applications of Isocyanate-Functional Polyacrylate Compositions

SUBSTITUTE SHEET (RULE 26) [0048] The compounds described herein may be used in a variety of applications including, for example one pack moisture cure systems suitable for applications in construction, coatings, adhesives, potting compounds, caulks, mold making, structural sealants, acoustic insulation, foamed materials, paints, spraying materials, waterproofing compositions, roofing formulations, coatings in sanitary rooms, glazing, prototyping, joint seals between different materials, e.g. sealants between ceramic or mineral surfaces and thermoplastics, paper releases, impregnates, and the like. Furthermore, the copolymer composition when used, for example, as a coating or adhesive, can adhere onto a broad variety of metal, wood, mineral, ceramic, silicone, vinyl, rubber or plastic surfaces.

[0049] In some embodiments, the copolymer can be used in adhesive formulations. This can include flooring adhesives, roofing adhesives, industrial adhesives, automotive adhesives, elastic adhesives, contact-type adhesives, tiling adhesives, medical adhesives, adhesives for interior panels, adhesives for exterior panels, stone finishing adhesives, ceiling finishing adhesives, wall finishing adhesives, vehicle paneling adhesives, and electric or electronic or precision equipment assembly adhesives. The adhesive formulations can further include one or more additives such as one or more on enhancers (also referred to as adhesion promoters), coalescing aids/agents (coalescents), film forming aids (i.e., plasticizers), water scavengers, defoamers, fillers, pigments, thickeners, biocides, crosslinking agents, flame retardants, stabilizers, moisture cure catalysts, and corrosion inhibitors.

[0050] These one-pack moisture cure systems may comprise the polymers as described herein combined with a catalyst, optional inorganic fillers, moisture scavengers and plasticizers.

[0051] The one-pack moisture cure systems may comprise the polymers described in Sections II and III in an amount as low as 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, or as high as 30 wt.%, 32.5 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the adhesive composition. For example, the one-pack moisture cure system may comprise the polymers in an amount of from 1 wt.% to 40 wt.% or from 1 wt.% to 80 wt.%.

[0052] The catalyst may promote the reaction between the isocyanate functionality and water, forming polyurea and carbonic gas. Suitable catalysts include non-sterically

12

SUBSTITUTE SHEET (RULE 26) hindered tertiary amines such as N,N-dimethylethanolamine (DMEA), diaminobicyclooctane (DABCO), triethylene diamine (TEDA), bis(2- dimethylaminoethyl)ether (BDMAEE), N-ethylmorpholine, N'N'-dimethylpiperazine,

N,N,N’,N’,N”-pentamethyl-diethylene-triamine (PMDETA), N,N- dimethylcyclohexylamine (DMCHA), N,N-dimethylbenzylamine (DMBA), N,N- dimethylcethylamine, N,N,N’ ,N”,N”-pentamethyl-diproylene-triamine (PMDPTA), triethylamine, and l-(2-hydroxypropyl) imidazole. Additionally, a wide range of organic metal catalysts can be used to promote the reaction; examples include but are not limited to dibutyl tin dilaurate (DBTL), dioctyl tin diacetate (DOTA), dibutyl tin diacetyl acetonate (DBTAcAc), etc.

[0053] Suitable catalysts may also include pentamethylenediethylenetriamine (Polycat 5), l,3,5-tris[3-dimethylamino)propyl]hexahydro-l,3,5-triazine, bis-[2- dimethylamino-ethyl]ether (DABCO BL-19), N,N-dimethylaminopropyl-N’-methyl-N’-(2- hydroxy ethyl) amine (Polycat 17), N,N-dimethylcyclohexane (Polycat 8), triethylenediamine, (DABCO-TEDA), 2- [[2-(dimethylamino)ethyl]methylamino]ethanol (DABCO-T), dimethylethanolamine (DABCO DMEA), bis-(dimethylaminopropyl) methylamine (Polycat 77), l,8-diazabicyclo[5.4.0]undec-7-ene (Polycat DBU), and N,N- dicyclohexylmethylamine (Polycat 12).

[0054] The catalyst can be present at an amount of 0.1 - 5 wt.% in the formula.

[0055] Inorganic fillers also known as pigments can be selected from a variety of compounds including but not limited to TiOi (anatase or rutile), calcium carbonates (ground, precipitated, treated and nontreated grades), clay, talc, bentonite, barytes, feldspar, mica, wollastonite, nepheline syenite, and the like. Particle size of such fillers can be from

O.005 to 100 microns. The inorganic fillers can be presented at an amount of 0 wt.% to 85 wt.% of the total formula.

[0056] Plasticizers are fluid compounds that are miscible with the copolymer and are anhydrous. A class of plasticizers are based on alkyl phthalates for example diisooctyl di phthalate (DIDP). Other suitable plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, butyl benzyl phthalate, or a combination thereof. Plasticizers can be present from 0 wt.% to 40 wt.% of the formulation weight.

13

SUBSTITUTE SHEET (RULE 26) [0057] As described herein, the composition can include a water scavenger. Suitable water scavengers can include trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, organosilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, a-functional silanes such as N-(silylmethyl)-O-methyl-carbamates, in particular N-30 (methyldiethoxysilylmethyl)-O-methyl-carbamate, p-Tolenesulfonyl isocyanate, oxazolidine compounds such as 3-ethyl-2-methyl-2-(3-methylbutyl)-l,3- oxazolidine, (methacryloxymethyl) silanes, ethoxymethylsilanes, N-phenyl-, N-cyclohexyl- and N-alkylsilanes, p-Toluenesulfonyl isocyanate, orthoformic acid esters, calcium oxide, molecular sieves, or mixtures thereof. The water scavenger can be present in an amount of from 0% to 5% by weight, based on the weight of the composition.

[0058] The source of water for the curing reaction of the isocyanate functionality may be ambient moisture. The present disclosure encompasses a one-pack and self-curing system which requires no mixing and may cure upon exposure to the atmosphere. The copolymer may be produced under anhydrous conditions. In some instances, a water scavenger can be included during or after polymerization to capture rogue water. In some embodiments, the compositions comprise less than 0.1% by weight water, preferably less than 0.05% by weight water, more preferably the composition is anhydrous.

[0059] The one-pack and self-curing adhesive compositions may be substantially free of tin-based catalysts.

[0060] Unlike one-pack self-curing technologies that rely on alkoxy silane moieties and release methanol and(or) ethanol (VOCs) to the environment; the one-pack and selfcuring adhesive compositions described here releases only carbon dioxide, a non-VOC gas, as byproduct of curing reaction.

[0061] Coating or adhesive formulations can be applied to a surface by any suitable application technique, including troweling, spraying, rolling, brushing, or spreading. The coating or adhesive compositions can be applied in a single coat, or in multiple sequential coats (e.g., in two coats or in three coats) as required for a particular application. Generally, the formulation is allowed to cure under ambient conditions.

[0062] The coating or adhesive formulations can be applied to a variety of surfaces including, but not limited to metal, asphalt, concrete, stone, ceramic, wood, plastic, silicone, vinyl, polyurethane foam, glass, wall board coverings (e.g., drywall, cement board, etc.), roof materials, and combinations thereof. The formulations can be applied to interior or

14

SUBSTITUTE SHEET (RULE 26) exterior surfaces. In certain embodiments, the surface is an architectural surface, such as a roof, wall, floor, or combination thereof. The architectural surface can be located above ground, below ground, or combinations thereof.

[0063] When cured, the adhesive formulations of the present disclosure may form a film. The film may have advantageous structural properties such as high tensile strength and elongation.

[0064] In some embodiments, the film may have a tensile strength of as low as 70 psi, 75 psi, 80 psi, 90 psi, 100 psi, 110 psi, 120 psi, 130 psi, 140 psi, 150 psi, 160 psi, or as high as 170 psi, 180 psi, 190 psi, 200 psi, 210 psi, 220 psi, 230 psi, 240 psi, 250 psi, 260 psi, 270 psi, 280 psi, 290 psi, 300 psi, or within any range encompassed by any two of the foregoing values as endpoints. For example, the film may have a tensile strength of 75 to 150 psi, or from 75 to 300 psi.

[0065] In some embodiments, the film may have an elongation of as low as 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, 200%, 250%, 300%, 350%, 400%, 450%, 500%, 550%, 600% or within any range encompassed by any two of the foregoing values as endpoints. For example, the film may have an elongation of from 90% to 140%, or from 90% to 600%.

[0066] In another embodiment, the present disclosure provides a process for bonding two substrates together including applying the moisture cure adhesive composition of the invention on at least one surface of a first substrate and contacting the adhesive bearing surface of the first substrate with a second substrate to form a laminate.

[0067] In yet another embodiment, the present disclosure features an assembly comprising a first substrate, a second substrate and the adhesive composition of the invention sandwiched between the first substrate and the second substrate.

[0068] In some embodiments, the first and the second substrates are wood such as natural soft wood or hard wood, e.g., pine, fir, maple, oak, aspens, ash, etc., or synthetic wood, or wood/plastic materials.

[0069] In another embodiment, the first substrate is roofing gravel, and the second substrate is roofing materials such as silicone, TPO membrane, EPDM membrane, roofing asphalt, PVC.

15

SUBSTITUTE SHEET (RULE 26) [0070] In yet another embodiment, the first substrate is cement, such as, a cement floor, and the second substrate is a flooring material, such as vinyl tile, wood, synthetic wood, or wood/plastic materials.

[0071] In another embodiment, the first substrate is silicone roofing substrate, the second substrate is a roof coating, and the adhesive composition (the isocyanate-functional silicone-acrylic polymer) is a primer sandwiched between the silicone roofing substrate and the roofing coating.

[0072] The article includes such as structural beam, laminated veneer lumber (LVL), I-joint, finger-joint studs, and plywood.

EXAMPLES

[0073] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions and/or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the scope of the disclosure. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

[0074] Examples 1-7: Synthesis of TML Functional Resins

[0075] The TMLfunctional resins were synthesized in accordance with a high temperature, continuous polymerization process as described in U.S. Pat. Nos. 5,461,60;

4,414,370; and 4,529,787 which are all incorporated by reference herein. Monomers were fed near bulk into a continuous stirred tank reactor at a temperature of 175-190°C and polymerized at a relatively short residence time of around 12 minutes. At steady state, the fresh feed rate matched the reactor content removal rate and composition inside the reactor was invariant with time and space. Removed reactor contents traveled to a separate process area and were devolatilized, with neat resin exiting the reactor and unreacted monomer and solvent collected for potential recycle and or analyses.

[0076] Representative examples of polymer resins prepared using the procedure outlined above are provided in Table 1 below.

TABLE 1

TMI-Functional Resins

16

SUBSTITUTE SHEET (RULE 26)

[0077] In addition to the monomer content, key choices in the continuous polymerization process are the operating temperature (up to 280 °C), the residence time (usually 12 to 15 minutes), solvent selection and initiator level. Reaction temperature plays a critical role in the process efficiency and polymer MW (molecular weight). For the ranges of MW of interest to the moisture curable resins described herein, lower reaction temperatures are warranted (170 to 190 °C).

[0078] Residual TMI was measured for example 6 and 7 via GC and was found to be 0.09 wt.% and 0.13 wt.% respectively. A flow curve for Examples 6 and 7 showing neat resin viscosity is provided in FIG. 1

[0079] Example 8 - 14: filled systems containing moisture curable polymers [0080] Polymers depicted in Table 1 were turned into filled composite systems according to the formula depicted in Table 2. Polymer and DIDP (solvent) were combined followed by addition of the filler package which consist of different calcium carbonate grades. The mixture was combined using a bladeless FlackTek Speed mixer. The catalyst was introduced last followed by mixing under vacuum via the speed mixer.

[0081] The formulations were then drawn down on Teflon lined boards using a 20 mil Dow gap applicator. Films were allowed to mature in a controlled temperature humidity (CTH) room and at 25 °C and 50% relative humidity (RH). Films were tested after 7 days in CTH conditions unless specified otherwise. The final thickness of the films were measured prior to Tensile measurement and found to be 22-32 mills.

[0082] Bostik Green Force was used a control which is a moisture curable premium product based on alkoxy silane technology.

SUBSTITUTE SHEET (RULE 26) [0083] Tensile and elongation was measured on an Instron 3345 machine with elongation rate of 7.9 in/min.

TABLE 2

Formulations for Making Filled Moisture Curable Systems

[0084] In Table 2, the amount of PolyCat5 catalyst is reported as an amount added to 100 g of other ingredients.

[0085] Figure 2 shows Tensile and Elongation for films made from example 6 and 7 in both formulations A &B with 1 wt.% Polycat 5 as catalyst. Cured films could be made with superior tensile and elongation performance compared to the control.

[0086] Formulations with lower resin content can also be made with good mechanical properties. Figure 3 shows example 7 in formulation C with 1 wt.% Poly cat 5 as catalyst. Even at 25% polymer content the film can still cure to form an elastic composite with good mechanical properties.

[0087] The type of crosslinked network formed, and hence the mechanical properties of the final composite, can be further controlled by the type and amount of catalyst. Figure 3 shows example 7 in formulation C cure with different catalysts, namely 0.5 wt.% DBTL (dibutyl tin dilaurate), 0.5 wt.% DBTA (dibutyl tin diacetate) and 0.5 wt.% DBTAcAc (Dibutyl Tin diacetyl acetonate). Figure 3 also demonstrates that DBU (1,8- Diazabicyclo(5.4.0)undec-7-ene) is not an efficient catalyst for this system and does not promote the moisture cure reaction.

[0088] Figure 4 show the evolution of Tensile strength and elongation and break for example 7C formulated with different amounts of Polycat 5 as moisture cure catalyst. It is known in the art that as cure reaction proceeds and crosslinking continues to take place, tensile strength increases and elongation decreases. Figure 4 shows that cure reaction is complete for all cases after 7 days and the composite mechanical properties does not change

18

SUBSTITUTE SHEET (RULE 26) significantly upon further aging. The results suggest that higher levels of catalyst resulted in higher tensile strength without significant compromise in elongation.

[0089] The composite material formed in this way can adhere to a variety of substrates. Figure 5 shows performance of example 7C with 0.5, 1, 1.5 and 2 wt.% of Polycat 5 as catalyst when used as adhesive for Oak, a common wood used as flooring material. The Oak/Oak assemblies were made using 1 -inch- wide stripes of Oak. Adhesive was applied on a 1-inch square area and another stipe was firmly pressed on the adhesive to create an adhesive bond. The adhesive thickness was adjusted by a shim and was 1/16 inch. The assemblies were allowed to cure in CTH room for 7 days after which they were tested for lap sheer strength with a tensile machine at a displacement rate of 2 inch/min. 3 assemblies were tested for each formulation. Figure 5 shows that the elastomeric composite formulated has strong adhesion to wood. Lap sheer strength is > 50 psi and >100 psi for the formulation with lowest catalyst content. Moreover, in all cases, the failure mode is cohesive signifying strong adhesive forces between the composite and wood surface.

[0090] Figure 6 shows the water uptake after 12 hours for the Example 7C films after being cured for 7 days with 0.5, 1, 1.5 and 2 wt.% Polycat 5 as catalyst. The control had 12 wt.% of catalyst.

[0091] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

[0092] Examples 15-22: Synthesis of moisture curable isocyanate-siloxane resins [0093] The isocyanate silicone- acrylate compositions were synthesized in accordance to Table 3. Each component was blended at ambient conditions.

19

SUBSTITUTE SHEET (RULE 26) [0094] Inventive (Inv.) isocyanate silicone-acrylate examples 15-18 and comparative (Comp.) isocyanate silicone-acrylate examples 19-22 were prepared using the procedure outlined above are provided in Table 3 below.

TABLE 3

Isocyanate-functional acylate coating compositions with silicone polymers (wt.%)

'CAS 70131-67-8 Silanol terminated polymer 6,000 cP

²CAS 70131-67-8 Silanol terminated polymer 750 cP

³CAS 22984-54-9 Methyl tris(MEKO) silane

[0095] Examples 15-22 were applied to a Henry Silicone roof coating and were allowed to cure for 2 weeks.

[0096] Inventive examples 15-18 adhered to a fresh Henry Silicone roof coating after 2 weeks cure time.

[0097] Comparative examples 19 and 20 had only 1 wt. % of the silane crosslinker, outside the inventive range of 1.5 wt. % to 11 wt. % and did not have good adhesion after 2 weeks of cure time.

[0098] Comparative example 21 a silicone polymer added in an amount of 5 wt. % and did not show good adhesion after 2 weeks of cure time.

[0099] Comparative example 22 did not have any silicone polymer added and did not show good adhesion after 2 weeks of cure time.

SUBSTITUTE SHEET (RULE 26)

Claims

WHAT IS CLAIMED IS

1. A moisture curable composition comprising an isocyanate-functional poly acrylate polymer and a catalyst that promotes the isocyanate-water reaction.

2. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer does not have a urethane or urea bond.

3. The composition of claim 1 wherein the isocyanate functionality is incorporated into the acrylic polymer via radical chain polymerization of monomers with the following structure:

wherein Ri is a hydrogen or methyl group; and

R2 is an aliphatic, aromatic, heteroaliphatic, or heteroaromatic radical with 0 to 40 carbon-carbon bonds.

4. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer comprises a 3 -isopropenyl- a, a-dimethylbenyzl isocyanate, 2-isocyanatoethyl acrylate, allyl isocyanate monomer.

5. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer comprises a 3 -isopropenyl- a, a-dimethylbenyzl isocyanate.

6. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer comprises styrene monomers.

7. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer comprises alpha methyl styrene monomers.

8. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer

21

SUBSTITUTE SHEET (RULE 26) comprises methacrylate monomers.

9. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer comprises 2-ethylhexyl acrylate monomers.

10. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer is further reacted with telechelic polymers carrying isocyanate reactive groups at terminal locations.

11. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer has the following structure:

wherein n = 1 to 1000;

R1 is a hydrogen atom or methyl group;

R2 is an alkane radical with 0 to 40 carbon-carbon bonds;

R3 is a single or double carbon-carbon bond, an alkane radical with 0 to 40 carboncarbon bonds, a nitrogen, an oxygen, or an aromatic group with the proviso that R3 contains no urethane or urea based-linkage; and

R4 is a hydrogen or methyl group.

12. The composition of claim 11, wherein R2 comprises a urethane or urea based- linkage.

13. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer is a random polymer.

SUBSTITUTE SHEET (RULE 26)

14. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer comprises an isocyanate selected from the group consisting of 1,6- hexamethylene diisocyanate (HDI), 2,4- and 2,6-toluene diisocyanate (TDI), 4,4' diphenylmethane diisocyanate (MDI), methylene bis (4-cyclohexylisocyanate) (HMDI), isophorone diisocyanate (IPDI), and 1,5-naphthalene diisocyanate (NDI).

15. The composition of claim 1, wherein the composition comprises less than 0.1 wt.% non-bonded isocyanate moieties, based on the total weight of the composition.

16. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer has a glass transition temperature of 0°C or lower.

17. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer has a viscosity of 100,000 cP or lower at 25°C.

18. The composition of claim 1, wherein the isocyanate-functional polyacrylate polymer has a number average molecular weight of 2 kDa or greater.

19. A method of forming the composition of claim 1 comprising:

(i) feeding a monomer composition into a continuous stirred tank reactor at a constant temperature

(ii) polymerizing the monomers in the reactor

(iii) removing and devolatilizing the reactor contents

(iv) collecting the neat resin.

20. The method of claim 19, wherein the polymerization is a continuous process.

21. The method of claim 19, wherein the polymerization is a batch process.

22. The method of claim 19, wherein the monomer composition comprises 3- isopropenyl-a,a-dimethylbenyzl isocyanate, 2-isocyanatoethyl acrylate, butyl acrylate, styrene, methacrylate, alpha methylstyrene, or combinations thereof.

23

SUBSTITUTE SHEET (RULE 26)

23. A one-pack adhesive composition comprising the composition of claim 1.

24. The adhesive composition of claim 23, wherein the composition of claim 1 is present in an amount of from 1 wt.% to 80 wt.%, based on the total weight of the adhesive composition.

25. The adhesive composition of claim 23, further comprising a catalyst selected from the group consisting of N,N-dimethylethanolamine (DMEA), diaminobicyclooctane (DABCO), triethylene diamine (TEDA), bis(2-dimethylaminoethyl)ether (BDMAEE), N- ethylmorpholine, N'N'-dimethylpiperazine, N,N,N’,N’,N”-pentamethyl-diethylene-triamine (PMDETA), N,N-dimethylcyclohexylamine (DMCHA), N,N-dimethylbenzylamine (DMB A), N,N-dimethylcethylamine, N,N,N’ ,N”,N”-pentamethyl-diproylene-triamine (PMDPTA), triethylamine, l-(2 -hydroxypropyl) imidazole, pentamethylenediethylenetriamine (Polycat 5), l,3,5-tris[3- dimethylamino)propyl]hexahydro-l,3,5-triazine, bis-[2-dimethylamino-ethyl]ether (DABCO BL-19), N,N-dimethylaminopropyl-N’ -methyl-N’ -(2-hydroxyethyl)amine (Polycat 17), N,N-dimethylcyclohexane (Polycat 8), triethylenediamine, (DABCO-TEDA), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (DABCO-T), dimethylethanolamine (DABCO DMEA), bis-(dimethylaminopropyl) methylamine (Polycat 77), 1,8- diazabicyclo[5.4.0]undec-7-ene (Polycat DBU), and N,N-dicyclohexylmethylamine (Polycat 12).

26. The adhesive composition of claim 23, wherein the adhesive composition is capable of self-curing when exposed to ambient moisture.

27. The adhesive composition of claim 23, wherein the composition is substantially free of tin-based catalysts.

28. A cured film composition comprising the adhesive composition of claim 23.

29. The film of claim 28, wherein the film has a tensile strength of 50 to 500 psi.

24

SUBSTITUTE SHEET (RULE 26)

30. The film of claim 28, wherein the film has an elongation of from 60% to 600%.

31. A moisture curable composition comprising an isocyanate-functional poly acrylate polymer; a silicone polymer, a silane crosslinker; and a catalyst that promotes the isocyanate- water reaction.

32. The composition of claim 31 , wherein the silicone polymer is present in an amount from 15-85 wt. % and the silane crosslinker is present in an amount from 1.5-11 wt. %, based on a total weight of the composition.

33. The composition of claim 31, wherein silanol end groups of each of the at least two silicone polymers react with the isocyanate-functional polyacrylate.

34. The composition of claim 31, wherein the composition adheres to at least one of a silicone substrate, a roofing material, a vinyl substrate, and a wood substrate.

35. The composition of claim 31, wherein the isocyanate-functional polyacrylate polymer does not have a urethane or urea bond.

36. The composition of claim 31, wherein the isocyanate functionality is incorporated into the acrylic polymer via radical chain polymerization of monomers with the following structure:

wherein Ri is a hydrogen or methyl group; and

37. The composition of claim 31, wherein the isocyanate-functional polyacrylate

25

SUBSTITUTE SHEET (RULE 26) polymer comprises a 3-isopropenyl-a,a-dimethylbenyzl isocyanate, 2-isocyanatoethyl acrylate, allyl isocyanate monomer.

38. The composition of claim 31, wherein the isocyanate-functional polyacrylate polymer comprises a 3-isopropenyl-a,a-dimethylbenyzl isocyanate.

39. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer comprises styrene monomers.

40. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer comprises alpha methyl styrene monomers.

41. The composition of claim 31 , wherein the isocyanate-functional polyacrylate polymer comprises methacrylate monomers.

42. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer comprises 2-ethylhexyl acrylate monomers.

43. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer is further reacted with telechelic polymers carrying isocyanate reactive groups at terminal locations.

44. The composition of claim 31 , wherein the isocyanate-functional poly acrylate polymer has the following structure:

wherein n = 1 to 1000;

SUBSTITUTE SHEET (RULE 26) R1 is a hydrogen atom or methyl group;

R2 is an alkane radical with 0 to 40 carbon-carbon bonds;

R4 is a hydrogen or methyl group.

45. The composition of claim 44, wherein R2 comprises a urethane or urea based- linkage.

46. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer is a random polymer.

47. The composition of claim 31, wherein the isocyanate-functional polyacrylate polymer comprises an isocyanate selected from the group consisting of 1,6- hexamethylene diisocyanate (HDI), 2,4- and 2,6-toluene diisocyanate (TDI), 4,4' diphenylmethane diisocyanate (MDI), methylene bis (4-cyclohexylisocyanate) (HMDI), isophorone diisocyanate (IPDI), and 1,5-naphthalene diisocyanate (NDI).

48. The composition of claim 31 , wherein the composition comprises less than 0.1 wt. % non-bonded isocyanate moieties, based on the total weight of the composition.

49. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer has a glass transition temperature of 0°C or lower.

50. The composition of claim 31, wherein the isocyanate-functional poly acrylate polymer has a viscosity of 100,000 cP or lower at 25°C.

51. The composition of claim 31 , wherein the isocyanate-functional poly acrylate polymer has a number average molecular weight of 2 kDa or greater.

52. A method of forming the composition of claim 31 comprising:

27

SUBSTITUTE SHEET (RULE 26) (i) feeding a monomer composition into a continuous stirred tank reactor at a constant temperature

(ii) polymerizing the monomers in the reactor

(iii) reacting the polymerized monomers with the silicone polymer and silane crosslinker;

(iv) removing and devolatilizing the reactor contents

(v) collecting the neat resin.

53. The method of claim 52, wherein the silicone monomer is present in an amount from 15-85 wt. % and the silane crosslinker is present in an amount from 1.5-11 wt. %, based on a total weight of the neat resin.

54. The method of claim 52, wherein the polymerization is a continuous process.

55. The method of claim 52, wherein the polymerization is a batch process.

56. The method of claim 52, wherein the monomer composition comprises 3- isopropenyl-a,a-dimethylbenyzl isocyanate, 2-isocyanatoethyl acrylate, butyl acrylate, styrene, methacrylate, alpha methylstyrene, or combinations thereof.

57. A roof adhesive, comprising: an isocyanate monomer; an acrylate copolymer, the acrylate copolymer polymerizing with the isocyanate monomer to form an isocyanate-functional acrylate polymer; a silicone polymer; a silane crosslinker; and a catalyst; wherein the silicone polymer and the silane crosslinker react with the isocyanate-functional acrylate polymer and the catalyst to form the roof adhesive.

58. The roof adhesive of claim 57, wherein the silicone monomer is present in an amount from 15-85 wt. % and the silane crosslinker is present in an amount from 1.5-11 wt.

28

SUBSTITUTE SHEET (RULE 26) %, based on a total weight of the roof adhesive.

59. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer comprises a 3-isopropenyl-a,a-dimethylbenyzl isocyanate, 2-isocyanatoethyl acrylate, allyl isocyanate monomer.

60. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer comprises a 3-isopropenyl-a,a-dimethylbenyzl isocyanate.

61. The roof adhesive of claim 57, wherein the isocyanate-functional polyacrylate polymer comprises styrene monomers.

62. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer comprises alpha methyl styrene monomers.

63. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer comprises methacrylate monomers.

64. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer comprises 2-ethylhexyl acrylate monomers.

65. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer has the following structure:

wherein n = 1 to 1000;

R1 is a hydrogen atom or methyl group;

29

SUBSTITUTE SHEET (RULE 26) R2 is an alkane radical with 0 to 40 carbon-carbon bonds;

R4 is a hydrogen or methyl group.

66. The roof adhesive of claim 57, wherein the isocyanate-functional poly acrylate polymer comprises an isocyanate selected from the group consisting of 1,6- hexamethylene diisocyanate (HDI), 2,4- and 2,6-toluene diisocyanate (TDI), 4,4' diphenylmethane diisocyanate (MDI), methylene bis (4-cyclohexylisocyanate) (HMDI), isophorone diisocyanate (IPDI), and 1,5-naphthalene diisocyanate (NDI).

67. The roof adhesive of claim 57, wherein the silicone polymer has a viscosity of 6000 cP or lower at 25°C.

68. The roof adhesive of claim 57, wherein the catalyst is present in an amount from 0.5-5 wt. %.

69. The roof adhesive of claim 57, wherein the roof adhesive adheres to at least one of silicone, a TPO membrane, an EPDM membrane, roofing asphalt, PCV, and metal.

30

SUBSTITUTE SHEET (RULE 26)