Moisture-curable polymerizable compositions including a polyurethane DIOL, tapes, polymerized compositions, articles, and methods

Abstract

The present disclosure provides a moisture-curable polymerizable composition including a reaction product of a polyurethane diol having a number average molecular weight of 20,000 grams per mole or greater and a multifunctional isocyanate, in the presence of a catalyst. A ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1. The composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater. A tape is also provided, including a liner and a layer of the composition disposed on at least a portion of the liner. Further, a polymerized composition is provided, including a moisture-cured crosslinked reaction product of the moisture-curable polymerizable composition. An article is provided including a substrate and a layer of the polymerized composition disposed on at least a portion of the substrate. Additionally, a method of making a moisture-curable polymerizable composition is provided, including reacting a diisocyanate with a polyol to form a polyurethane diol and reacting the polyurethane diol with a multifunctional diisocyanate in the presence of a catalyst.

Description

PA103027W002MOISTURE-CURABLE POLYMERIZABLE COMPOSITIONS INCLUDING A POLYURETHANE DIOL, TAPES, POLYMERIZED COMPOSITIONS, ARTICLES, AND METHODSField

[0001] The present disclosure generally relates to the field of polyurethane compositions.Background

[0002] Polyurethane adhesives generally provide a combination of high bond strength and high flexibility. Some poly(urethane-urea) materials can have extremely high flexibility and resilience, but these materials are often difficult to handle and typically require solvent processing as well as elevated curing temperatures.Brief Description of Drawings

[0003] FIG. 1 A is a schematic cross-sectional view of an exemplary tape, according to some embodiments of the present disclosure.

[0004] FIG. IB is a schematic cross-sectional view of an exemplary tape including two liners, according to some embodiments of the present disclosure.

[0005] FIG. 2A is a schematic cross-sectional view of an exemplary article, according to some embodiments of the present disclosure.

[0006] FIG. 2B is a schematic cross-sectional view of an exemplary article including two substrates adhered together, according to some embodiments of the present disclosure.

[0007] Repeated use of reference characters in the specification and drawings is intended to represent the same or analogous features or elements of the disclosure, ft should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the disclosure. The figures may not be drawn to scale.Summary

[0008] In a first aspect, a moisture-curable polymerizable composition is provided. The composition comprises a reaction product of a polyurethane diol having a number average molecular weight (Mn) of 20,000 grams per mole or greater and a multifunctional isocyanate, in the presence of a catalyst. A ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1. The composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.

[0009] In a second aspect, a tape is provided. The tape comprises a liner having a first major surface and a layer of the composition according to any embodiment of the first aspect disposed on at least a portion of the first major surface of the liner.

[0010] In a third aspect, a polymerized composition is provided. The polymerized composition comprises a moisture-cured crosslinked reaction product of the moisture-curable polymerizable composition according to any embodiment of the first aspect.

[0011] In a fourth aspect, an article is provided. The article comprises a substrate having a first major surface and a layer of the polymerized composition according to any embodiment of the third aspect disposed on at least a portion of the first major surface of the substrate.

[0012] In a fifth aspect, a method of making a moisture-curable polymerizable composition is provided. The method comprises: a) reacting a diisocyanate with a polyol to form a polyurethane diol having a Mn of 20,000 grams per mole or greater; and b) reacting the polyurethane diol with a multifunctional diisocyanate in the presence of a catalyst. A ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1. The moisture-curable polymerizable composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.Detailed Description

[0013] The terms “a”, “an”, “the”, “at least one”, and “one or more” are used interchangeably.

[0014] The term “and / or” means one or both such as in the expression A and / or B refers to A alone, B alone, or to both A and B.

[0015] The term “essentially” means 95% or more.

[0016] The term “equivalents” refers to the number of moles of a functional group (e.g., OH groups, isocyanate groups, etc.) per molecule of a polymer chain or per mole of a different functional group. The term “equivalent” means “moles” in this case, thus the isocyanate content in a material (in terms of equivalents / moles) is divided by the weight of the entire formulation to give a value of equivalents per kilograms.

[0017] The term “alkyl” refers to a monovalent radical of an alkane. Suitable alkyl groups can have up to 50 carbon atoms, up to 40 carbon atoms, up to 30 carbon atoms, up to 20 carbon atoms, up to 16 carbon atoms, up to 12 carbon atoms, up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, up to 4 carbon atoms, or up to 3 carbon atoms. The alkyl groups can be linear, branched, cyclic, or a combination thereof. Linear alkyl groups often have 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Branched alkyl groups often have 3 to 50 carbon atoms, 3 to 40 carbon atoms, 4 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms. Cyclic alkyl groups often have 3 to 50 carbon atoms, 5 to 40 carbon atoms, 6 to 20 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms.

[0018] The term “alkylene” refers to a divalent group that is a radical of an alkane. The alkylene can be straight-chained, branched, cyclic, or combinations thereof. The alkylene typically has 1 to 20 carbon atoms. In some embodiments, the alkylene contains 4 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. The radical centers of the alkylene can be on the same carbon atom (i.e., an alkylidene) or on different carbon atoms. In certain embodiments, the alkylene can be substituted with an OH group.

[0019] The term “hydroxyl group” means a monovalent group of formula -OH.

[0020] The term “isocyanate group” means a monovalent group of formula -N=C=O.

[0021] The term “carbamate ester” refers to a divalent group in a polyurethane having the general formula (-R-O-C(O)-NH-R’-).

[0022] The term “aryl” refers to a monovalent group that is radical of an arene, which is a carbocyclic, aromatic compound. The aryl can have one to five rings that are connected to or fused to the aromatic ring. The other ring structures can be aromatic, non-aromatic, or combinations thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.

[0023] The term “aralkyl” refers to a monovalent group of formula -R-Ar where R is an alkylene and Ar is an aryl group. That is, the aralkyl is an alkyl substituted with an aryl.

[0024] The term “aralkylene” refers to a divalent group of formula -R-Ar3- where R is an alkylene and Ar3is an arylene (i.e., an alkylene is bonded to an arylene).

[0025] The term “arylene” refers to a divalent group that is carbocyclic and aromatic. The group has one to five rings that are connected, fused, or combinations thereof. The other rings can be aromatic, non-aromatic, or combinations thereof. In some embodiments, the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromatic ring. For example, the arylene group can be phenylene. The term “alkarylene” refers to a divalent group that is an arylene group substituted with an alkyl group or an arylene group attached to an alkylene group. Unless otherwise indicated, the alkarylene group typically has from 1 to 20 carbon atoms, 4 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Unless otherwise indicated, for both groups, the alkyl or alkylene portion typically has from 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Unless otherwise indicated, for both groups, the aryl or arylene portion typically has from 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. In certain embodiments, the arylene group or the alkarylene group has 4 to 14 carbon atoms.

[0026] The term “diisocyanate” refers to a compound having the general formula O=C=N — R — N=C=O. Preferred R groups include alkylene and arylene groups.

[0027] The term “diol” refers to a compound with two OH groups.

[0028] The term “(meth)acrylate” means acrylate or methacrylate.

[0029] The term “triamine” refers to a compound with three amino groups.

[0030] The term “polyester” refers to repeating difunctional polymer wherein the repeat units are joined by ester linkages. Ester groups have the general formula -R — C(O) — OR’. The term “polyether” refers to repeating difunctional alkoxy radicals having the general formula -O-R-. Preferred R and R’ groups have the general formula -CJUn- and include, for example, methylene, ethylene and propylene (including n-propylene and i-propylene) or a combination thereof. Combinations of R and R’ groups may be provided, for example, as random or block type copolymers.

[0031] The term “polyol” refers to a compound with two or more hydroxyl (i.e., OH) groups.

[0032] The term “polymeric material” refers to any homopolymer, copolymer, terpolymer, and the like, as well as any diluent.

[0033] The term “ambient temperature” refers to a temperature in the range of 20 degrees Celsius to 25 degrees Celsius, inclusive.

[0034] The terms “cure” and “curable” refer to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably. A cured or crosslinked polymer is generally characterized by insolubility, but may be swellable in the presence of an appropriate solvent.

[0035] The term “backbone” refers to the main continuous chain of a polymer.

[0036] The term “substantially”, unless otherwise specifically defined, means to a high degree of approximation (e.g., within + / - 10% for quantifiable properties) but again without requiring absolute precision or a perfect match. Terms such as same, equal, uniform, constant, strictly, and the like, are understood to be within the usual tolerances or measuring error applicable to the specific circumstance rather than requiring absolute precision or a perfect match.

[0037] By definition, the total weight percentages of all ingredients in a composition equals 100 weight percent.

[0038] As used herein, “adjacent” encompasses both in direct contact (e.g., directly adjacent) and having one or more intermediate layers present between the adjacent materials.

[0039] The term “film” or “layer” refers to a single stratum within a multilayer film or article.

[0040] The term “substrate” encompasses films, layers, and articles.

[0041] As used herein, “thickness” refers to the smallest dimension of a film or layer, e.g., in a z-axis while a major surface of the film or layer is in the x- and y-axes. Thickness may be determined using a micrometer gauge or doing a microscopic analysis of a cross-sectional sample of a layer or an article.

[0042] Moisture-Curable Polymerizable Compositions

[0043] In a first aspect, a moisture-curable polymerizable composition is provided. The composition comprises a reaction product of a polyurethane diol having a number average molecular weight (Mn) of 20,000 grams per mole (g / mol) or greater and a multifunctional isocyanate, in the presence of a catalyst, wherein a ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1. When the catalyst, polyurethane diol, and multifunctional isocyanate are mixed, isocyanate groups will react with the available hydroxyl groups from the polyurethane diol, plus the catalyst may assist in catalyzing that reaction. Excess isocyanate groups remain available to react during subsequent moisture-curing of the polymerizable composition, and the catalyst is primarily present to catalyze reaction during the moisture-curing step. The composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method. The 180 Degree Peel Test Method is described in detail in the Examples.

[0044] In some embodiments, the moisture-curable polymerizable composition exhibits a 180 degree peel of 5.5 Newtons per centimeter (N / cm) or greater, as determined by the 180 Degree Peel Test Method, such as 6.0 N / cm, 6.5 N / cm, 7.0 N / cm, 7.5 N / cm, 8.0 N / cm, 8.5 N / cm, 9.0 N / cm, 9.5 N / cm, 10.0N / cm, 10.5 N / cm, 11.0 N / cm, 11.5 N / cm, 12.0 N / cm, 12.5 N / cm, 13.0 N / cm, 13.5 N / cm, 14.0 N / cm, 14.5 N / cm, 15.0 N / cm, 15.5 N / cm, 16.0 N / cm, 16.5 N / cm, 17.0 N / cm, 17.5 N / cm, 18.0 N / cm, 18.5 N / cm, 19.0 N / cm, 19.5 N / cm, or 20.0 N / cm or greater, as determined by the 180 Degree Peel Test Method.Typically, a maximum 180 degree peel exhibited by a tape according to various embodiments of the present disclosure is 40.0 N / cm.

[0045] It has been discovered that it is possible to provide a tacky, moisture-curing polyurethane adhesive without requiring a solvent or elevated temperatures for curing. After moisture curing, the adhesive exhibits high flexibility and elasticity with the capability to undergo high elongations while still returning to the original dimensions. Adhesives with these properties can be useful in assemblies that experience significant deformations in routine use, but that need to quickly recover their prior shape after the deformations. Examples could include, for instance, waistbands of garments and splices of abrasive belts.

[0046] Components of the moisture-curable polymerizable composition are described below.

[0047] Because the polymerizable composition is moisture-curable, absorption of moisture from the environment until a desired curing time should typically be minimized. Depending on storage conditions, in some cases the polymerizable composition is hermetically sealed in a package. Further, a desiccant is optionally present in the package or as a component of the package to further minimize absorption of moisture by the polymerizable composition during storage. A desiccant could be incorporated into the structure of the package, e.g., disposed within a polymeric film or wall that forms the package. The form of the package is not particularly limited and for instance can be a pouch, a bag, a box, etc.

[0048] Polyurethane Diol

[0049] Moisture-curable polymerizable compositions according to the present disclosure include a polyurethane diol having a Mn of 20,000 g / mol or greater. In some embodiments, the polyurethane diol comprises a reaction product of a diisocyanate and a polyol where the polyol is chosen to provide substantially no crystallinity in the resulting polyurethane. In some embodiments, the polyurethane diol comprises a reaction product of a diisocyanate and either a polypropylene glycol or a poly(tetramethylene ether) glycol. In some embodiments, the poly(tetramethylene ether) glycol polyol has an average molecular weight less than 3000 g / mol or less than 2100 g / mol or less than 1900 g / mol to limit crystallinity in the resulting polyurethane diol.

[0050] In some embodiments, the polyurethane diol comprises a reaction product of a diisocyanate and a polyester. Preferably, the polyester polyol is selected to provide substantially no crystallinity in the resulting polyurethane diol. In some such cases, the polyester comprises a reaction product of at least one diacid and at least two different diols. One suitable polyester that is a reaction product of at least one diacid and at least two different diols is poly(butylene-co-ethylene adipate). In other such cases, the polyester comprises a reaction product of at least two different diacids and at least one diol. Some suitable polyesters that are a reaction product of at least two different diacids and at least one diol include poly(ethylene adipate-co-phthalate), poly(butylene adipate-co-phthalate), or poly(hexamethylene adipate- co-phthalate).

[0051] In certain embodiments, the polyurethane diol comprises a reaction product of a diisocyanate and a polyol comprising one of a polypropylene glycol, a poly(tetramethylene ether) glycol, or a polyester, as noted above. Preferably, there are 1.01 to 1.25 hydroxyl groups present on the polyol for each isocyanate group. Stated another way, a ratio of equivalents of hydroxyl groups to isocyanate groups when forming the polyurethane diol may be 1.01 : 1 or greater, 1.02 : 1, 1.03 : 1, 1.04 : 1, 1.05 : 1, 1.06 : 1, 1.08 : 1, 1.10 : 1, 1.12 : 1, 1.14 : 1 , 1.16 : 1, 1.18 : 1, 1.20 : 1, 1.22 : 1, 1.24 : 1 or greater, or 1.25 : 1. In select embodiments, a ratio of equivalents of hydroxyl groups to isocyanate groups when forming the polyurethane diol may be 1.05 : 1 or 1.10 : 1. Using a slight excess of hydroxyl groups tends to assist in achieving a desirable length of the polyurethane diol.

[0052] Stated another way, in the polyurethane diol a ratio of equivalents of hydroxyl chain ends to equivalents of carbamate ester groups in the chain may be 0.01 : 1 or greater, 0.02 : 1, 0.03 : 1, 0.04 : 1, 0.05 : 1, 0.06 : 1, 0.08 : 1, 0.10 : 1, 0.12 : 1, 0.14 : 1 , 0.16 : 1, 0.18 : 1, 0.20 : 1, 0.22 : 1, 0.24 : 1 or greater, or 0.25 : 1.

[0053] The polyurethane diol has a number average molecular weight (Mn) that is 20,000 grams per mole (g / mol) or greater, such as 25,000 g / mol or greater, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, or 95,000 g / mol or greater; and 150,000 g / mol or less, 140,000 g / mol, 130,000 g / mol, 120,000 g / mol, 110,000 g / mol, 90,000 g / mol, 85,000 g / mol, 80,000 g / mol, 75,000 g / mol, 70,000 g / mol, 65,000 g / mol, 60,000 g / mol, 55,000 g / mol, 50,000 g / mol, 45,000 g / mol, 40,000 g / mol, 35,000 g / mol, 30,000 g / mol, or 25,000 g / mol or less. In certain cases, the polyurethane diol has a Mn of 20,000 g / mol to 80,000 g / mol. It was unexpectedly discovered that the Mn of the polyurethane diol has a significant impact on each of cohesive strength and elongation at break of the polymerizable composition and cured polymerized composition. More particularly, use of a polyurethane diol that has a Mn of less than 20,000 g / mol results in an uncured composition that has such a low cohesive integrity that it flows when removal of a liner is attempted (see, e.g., Comparative Examples 4 and 5 below).

[0054] In some embodiments, the polyurethane diol is present in an amount of at least 50 weight percent (wt.%), based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst, such as least 60 wt.%, 62 wt.%, 64 wt.%, 66 wt.%, 68 wt.%, 70 wt.%, 72 wt.%, 74 wt.%, 76 wt.%, 78 wt.%, 80 wt.%, 82 wt.%, 84 wt.%, 86 wt.%, 88 wt.%, or at least 90 wt.%; and 95 wt.% or less, 94 wt.%, 93 wt.%, 92 wt.%, 91 wt.%, 90 wt.%, 88 wt.%, 86 wt.%, 84 wt.%, 82 wt.%, 80 wt.%, 75 wt.%, or 70 wt.% or less, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst. In select embodiments, the polyurethane diol is present in an amount of 60 wt.% to 95 wt.%, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

[0055] Diisocyanate

[0056] Examples of diisocyanates include 4,4'-methylenediphenylenediisocyanate (MDI), 2,4- toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4'-diisocyanatodiphenylether, 3,3 '-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diphenyldiisocyanate, 4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'- diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanato diphenyl, 1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate, 4-chloro-l,2-naphthylene diisocyanate, 1,3 -naphthylene diisocyanate, and l,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5- trimethylcyclohexylisocyanate; 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aliphatic diisocyanates such as 1,6-hexamethylenediisocyanate, 2,2,4-trimethyl-l,6-hexamethylenediisocyanate, and 1,2-ethylenediisocyanate; cyclic diisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4'-diisocyanate.

[0057] In some embodiments, the diisocyanate can be provided in the form of an isocyanate prepolymer. The isocyanate prepolymer can be the reaction product of a diol with a molar excess of diisocyanate. In some embodiments, the prepolymer is the reaction product of a polyester diol with a diisocyanate. In some embodiments, the isocyanate prepolymer is the reaction product of a polyether diol with a diisocyanate. Preferably, the polyol used to make the isocyanate prepolymer is selected from a polypropylene glycol, a poly(tetramethylene ether) glycol, a polyester that is a reaction product of at least one diacid and at least two different diols, or a polyester that is a reaction product of at least one diol and at least two different diacids,

[0058] Polyester

[0059] Polyesters may be formed as the reaction product of diacids and diols. For example, terephthalic acid (a diacid) and ethylene glycol (a diol) can be reacted to form polyethylene terephthalate (PET).More generally, one or more diacids and one or more diols can be reacted, in equal molar portions of total diacids and total diols, to form a polyester comprising residues of the diacids and residues of the diols. The term residue when used in reference to the components of a polyester, refers to the moiety in the polyester resulting from the reaction of a corresponding monomer. In some cases, polyesters are formed from the reaction of diesters with diols by transesterification. In this reaction, instead of replacement of a hydrogen atom with a hydrocarbon group, it involves replacement of a hydrocarbon group (such as a methyl group) with a different hydrocarbon group (a diol).

[0060] A polyester can be prepared by preparing a reaction mixture, heating the reaction mixture with stirring, and removing the water byproduct of the condensation reaction. Typically, the water or alcohol byproduct is removed at a reduced pressure. In addition to the reactants noted above, the reaction mixture may contain optional reactive or non-reactive additives such as at least one catalyst selected from the acetate, phosphate, acid, or oxide form of antimony, zinc, cobalt, titanium, iron, potassium, calcium, and combinations thereof; or stabilizing agents selected from primary antioxidant, secondary antioxidant, antiozonant, UV absorber, hindered amine stabilizer, phosphate stabilizer, acid scavenger, heat stabilizer, and combinations thereof.

[0061] A wide range of diacids are suitable for use in a reaction mixture to form a polyester. In general, the diacids are of general Formula 1 below:

[0062] HO2C-A-CO2H Formula I

[0063] wherein A comprises a divalent group comprising an alkylene, arylene, heteroalkylene, heteroarylene, aralkylene, cyclic, branched, or a combination thereof. The selection of diacids depends upon the specific properties desired for the polyester copolymer.

[0064] In some embodiments, at least one of the diacids comprises an alkylene diacid of generalFormula 1A below:

[0065] HO2C-(CH2)„-CO2H Formula 1A

[0066] wherein n is an integer from 1-12. Examples of suitable alkylene diacids include: malonic acid (n =1); succinic acid (n = 2); glutaric acid (n = 3); adipic acid (n = 4); pimelic acid (n = 5); suberic acid (n = 6); azelaic acid (n = 7); sebacic acid (n = 8); undecanedioc acid (n = 9); and dodecanedioc acid (n = 10). Particularly suitable alkylene diacids include adipic acid, suberic acid and sebacic acid.

[0067] In some embodiments, at least one of the diacids is an arylene diacid, where the arylene is substituted or unsubstituted. Examples of suitable arylene diacids include: phthalic acid; terephthalic acid; isophthalic acid; dibenzoic acid; and 2,6-napththalenedicarboxylic acid.

[0068] A wide range of diols are suitable for use in a reaction mixture to form a polyester. In general, the diols are of general Formula 2 below:

[0069] HO-B-OH Formula 2

[0070] wherein B comprises a divalent group comprising an alkylene, arylene, heteroalkylene, heteroarylene, aralkylene, cyclic, branched, or a combination thereof. The selection of diols depends upon the specific properties desired for the polyester copolymer.

[0071] In some embodiments, at least one of the diols comprises an alkylene diol of general Formula 2 A below:

[0072] HO-(CH2)n-OH Formula 2A

[0073] wherein n is an integer from 2-12. Examples of suitable alkylene diols include: ethylene glycol (n = 2); 1, 4-butane diol (n = 4); 1,5-pentane diol (n = 5); 1,6-hexane diol ( n = 6); 1,8-octane diol (n = 8); and 1,10-decane diol (n = 10). Besides these straight chain diols, other 1, 2-diols, also called vicinal diols, are suitable such as are described by general Formula 2B below:

[0074] HO-(CRaH-CRbH)-OH Formula 2B

[0075] wherein each Raand Rbindependently comprises a hydrogen atom or an alkyl group with a 1-6 carbon atoms. In some embodiments, Rais H and Rbis a methyl group, and the compound is 1,2-propane diol. In other embodiments, Raand Rbare both methyl and the compound is 2,3 -butane diol.

[0076] In some embodiments, the diol of Formula 2 is a cycloalkylene diol. In these embodiments, the B group comprises a cycloalkylene group. Particularly suitable cycloalkylene diols are those with 6- membered cycloalkylene rings, such as CHDM (1,4-cyclohexane dimethanol. In some embodiments, the diol of Formula 2 is branched diol, such as neopentyl glycol (2,2-dimethylpropane-l,3-diol).

[0077] In some embodiments, at least one of the diols is an arylene diol, where the arylene is substituted or unsubstituted. Examples of suitable arylene diols include the isomers of dihydroxybenzenes: 1,2- dihydroxybenzene commonly referred to as catechol; 1,3 -dihydroxybenzene commonly referred to asresorcinol; 1,4 -dihydroxybenzene commonly referred to as hydroquinone; and chain extended phenols such as bisphenol A and bisphenol F.

[0078] Polypropylene Glycol and Poly(tetramethylene ether) Glycol

[0079] Examples of suitable polyoxyalkylene polyols, which may be used to form the polyurethane diol, include polyoxyalkylene polyols with an alkylene portion having from 1 to 6 carbons, and preferably from 2 to 4 carbons. In some cases, the molecular weight of the polyoxyalkylene polyol is preferably from 100 to 10000, or from 500 to 5000. As the polyoxyalkylene polyol, a polyoxyalkylene diol can be used, and a polyoxyalkylene diol having an alkylene portion with from 2 to 6 carbons is preferable. Examples of this type of compound include polyoxyethylene glycol (polyethylene glycol), polyoxypropylene glycol (polypropylene glycol), and polyoxytetramethylene glycol (poly(tetramethylene ether) glycol).

[0080] Multifunctional Isocyanate

[0081] The moisture-curable polymerizable composition includes a multifunctional isocyanate, which is a compound having two or more isocyanate groups (e.g., polyisocyanates). Polyisocyanates include diisocyanates, triisocyanates, and higher functional isocyanates, including polymeric isocyanates. They may be aliphatic (including alicyclic) and cyclic (including aromatic). Examples of diisocyanates include 4,4'-methylenediphenylenediisocyanate (MDI), 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4'-diisocyanatodiphenylether, 3,3'-dichloro-4,4'- diisocyanatodiphenylmethane, 4,4'-diphenyldiisocyanate, 4,4'-diisocyanatodibenzyl, 3, 3 '-dimethoxy -4,4'- diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'- diisocyanato diphenyl, 1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate, 4-chloro-l,2-naphthylene diisocyanate, 1,3 -naphthylene diisocyanate, and l,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; 3-isocyanatomethyl- 3,5,5-trimethylcyclohexylisocyanate; aliphatic diisocyanates such as 1,6-hexamethylenediisocyanate, 2,2,4-trimethyl-l,6-hexamethylenediisocyanate, and 1,2-ethylenediisocyanate; cyclic diisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4'-diisocyanate. Examples of triisocyanates include aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate and aromatic triisocyanates such as tri-(4-isocyanatophenyl)-methane. An example of a polymeric isocyanate includes polymethylenepolyphenylisocyanate (PAPI). An example of an aliphatic polyisocyanate is available under the tradename Desmodur N 100 from Bayer MaterialScience LLC, Pittsburgh, PA, which is based on hexamethylene diisocyanate (HDI). In some cases, suitable isocyanate containing compounds include prepolymers formed as the reaction product of multifunctional alcohols with an excess of diisocyanate monomers.

[0082] In some embodiments, the multifunctional isocyanate is present in an amount of at least 5 weight percent (wt.%), based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst, such as least 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, or at least 15 wt.%; and 30 wt.% or less, 27 wt.%, 25 wt.%, 23 wt.%, 20 wt.%, 18 wt.%, 16 wt.%, 14 wt.%, 12 wt.%, or 10 wt.% or less, based on a combined weight of the polyurethane diol, themultifunctional isocyanate, and the catalyst. In select embodiments, the multifunctional isocyanate is present in an amount of 5 wt.% to 25 wt.%, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

[0083] In some embodiments, the ratio of equivalents of isocyanate groups from the multifunctional isocyanate to the equivalents of hydroxyl groups from the polyurethane diol is greater than 3 : 1, 5 : 1, 10 : 1, 15 : 1, 25 : 1, 30 : 1, or greater than 50 : 1. Typically, a maximum ratio of equivalents of isocyanate groups from the multifunctional isocyanate to the equivalents of hydroxyl groups from the polyurethane diol is 100 : 1.

[0084] Catalyst

[0085] A catalyst is present in moisture-curable polymerizable compositions according to the present disclosure. In some embodiments, the catalyst comprises an amine catalyst or a metal catalyst. For example, suitable catalysts can include amines or organometallic catalysts such as tin compounds, bismuth compounds, zinc compounds, and zirconium compounds. Optionally, a bismuth carboxylate may be a suitable catalyst, for instance bismuth neodecanoate and / or bismuth ethylhexanoate. In select embodiments, the compositions are free of catalysts that contain tin. Suitable amine catalysts include cyclo hexyldimethylamine, 2-dimethylaminoethanol, 4-ethylmorpholine, N,N,4-trimethylpiperazine-l- ethylamine, 1,4-dimethylpiperazine, 3 -aminopropyldimethylamine, 2,2'-iminodiethanol, 1- methylimidazole, 1,2-dimethylimidazole, 2-propyl imidazole, 2-butyl imidazole, 2-benzyl imidazole, 2- benzyl-4-methyl imidazole, 2-butyl-4-methyl imidazole, imidazole, 2-methylimidazole, 2-ethyl-4- methylimidazole, 2-phenylimidazole, l-benzyl-2 -methylimidazole, 2,4-dimethylimidazole, 2,4,5- trimethylimiazole, 2-ethylimidazole, 2-[[2-(dimethylamino)ethyl]methylamino]ethanol, N-[3- (dimethylamino)propyl]-N,N’,N’-trimethylpropane-l,3-diamine, formic acid, compound with 2,2'- oxybis[N,N-dimethylethylamine] (2:1), l,r-[[3-(dimethylamino)propyl]imino]bispropan-2-ol, 2-[(2-[2- (dimethylamino)ethoxy]ethyl)methylamino] ethanol, benzyldimethylamine 4-methylmorpholine, N,N,N’,N’ -tetramethylhexamethylenediamine, 2-[2-(dimethylamino)ethoxy]ethanol, 1,4- diazabicyclooctane, bis(2-dimethylaminoethyl)(methyl)amine, N,N,N’,N’-tetramethyl-2,2'- oxybis(ethylamine, 2,2'-dimorpholinyldiethyl ether, l,8-diazabicyclo[5.4.0]undec -7-ene, N’-[3- (dimethylamino)propyl]-N,N-dimethylpropane-l,3-diamine, N,N,N’,N’,N”,N”-hexamethyl-l,3,5- triazine- 1 ,3 ,5(2H,4H,6H)-tripropanamine, N,N-bis[3 -(dimethylamino)propyl] -N’ ,N’ -dimethylpropane- 1,3 -diamine.

[0086] One or more catalysts may be present in the moisture-curable polymerizable composition in an amount of at least 0.02 wt.%, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst, such as at least 0.03 wt.%, 0.04 wt.%, 0.05 wt.%, 0.06 wt.%, 0.07 wt.%, 0.08 wt.%, 0.09 wt.%, 0.10 wt.%, 0.12 wt.%, 0.14 wt.%, 0.16 wt.%, 0.18 wt.%, 0.20 wt.%, 0.25 wt.%, 0.30 wt.%, 0.35 wt.%, 0.40 wt.%, 0.45 wt.%, or at least 0.50 wt.%; and 5 wt.% or less, 4.5 wt.%, 4 wt.%, 3.5 wt.%, 3 wt.%, 2.5 wt.%, 2 wt.%, 1.5 wt.%, 1 wt.%, 0.9 wt.%, 0.8 wt.%, 0.7 wt.%, 0.6 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, or 0.2 wt.% or less, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst. In select embodiments, the catalyst is present in an amountof 0.02 wt.% to 5 wt.%, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

[0087] Additives

[0088] The moisture-curable polymerizable composition may further comprise one or more additives, e.g., plasticizers, non-reactive diluents, toughening agents, fillers, flow control agents, colorants (e.g., pigments and dyes), adhesion promoters, UV stabilizers, flexibilizers, fire retardants, antistatic materials, thermally and / or electrically conductive particles, antioxidants, abrasive granules, thermal degradation stabilizers, light stabilizers, conductive particles, tackifiers, flow agents, bodying agents, flatting agents, inert fillers, binders, blowing agents, fungicides, bactericides, surfactants, thixotropic agents (e.g., ultrafine silica powder), surfactants, antifoamers, antistatic agents, metal deactivators, chemical blowing agents such as azodicarbonamide, or expandable polymeric microspheres containing a hydrocarbon liquid, such as those sold under the tradename EXPANCEL by Expancel Inc. (Duluth, GA). These additives, if present, are added in an amount effective for their intended purpose. The amount and type of such additives may be selected by one skilled in the art, depending on the intended end use of the composition.

[0089] Tapes

[0090] In a second aspect, a tape is provided. The tape comprises a liner having a first major surface and a layer of the moisture-curable polymerizable composition according to any embodiment of the first aspect disposed on at least a portion of the first major surface of the liner.

[0091] Referring to FIG. 1 A, a tape 100a comprises a liner 110 having a first major surface 112 and a layer of moisture-curable polymerizable composition 120 disposed on at least a portion of the first major surface 112 of the liner 110. A second major surface 114 of the liner 110 is also indicated in FIG. 1 A.

[0092] Referring to FIG. IB, a tape 100b comprises a liner 110 having a first major surface 112 and a layer of moisture-curable polymerizable composition 120 disposed on at least a portion of the first major surface 112 of the liner 110. The layer of moisture-curable polymerizable composition 120 has a first major surface 122 and an opposing second major surface 124. The tape 100b further comprises an optional second liner 130 attached to the layer of moisture-curable polymerizable composition 120 opposite the first liner 110. It is noted that the second major surface 124 of the layer of moisture-curable polymerizable composition 120 is adjacent to the first major surface 112 of the first liner 110. Additionally, the first major surface 122 of the layer of moisture-curable polymerizable composition 120 is adjacent to the second liner 130.

[0093] Liners

[0094] Suitable (e.g., release) liners may comprise flexible paper and polymeric films having sufficient dimensional stability to hold layers formed thereon in position without excessive stretching. Suitable paper liners include, but are not limited to, densified Kraft paper (commercially available from, for example, Loparex North America, Willowbrook, IL), poly -coated paper such as polyethylene coated Kraft paper, and the like. Suitable polymeric film / liners include, but are not limited to, thermoplastic polymer films including polyalkylenes, e.g., polyethylene and polypropylene; polybutadiene,polyisoprene; polyalkylene oxides, e.g., polyethylene oxide; polyesters, e.g., PET and PBT; polyamides; polycarbonates, polystyrenes, block copolymers of any of the proceeding polymers, and combinations thereof. Other suitable polymeric materials include polyimide, polysilicone, polytetrafluoroethylene, polyethylenephthalate, polyvinylchloride, or combinations thereof. Polymer blends of any of the above may also be employed, and nonwoven or woven liners may also be used.

[0095] The liner is preferably chosen to limit the amount of moisture that can be transferred from the liner to the moisture-curable polymerizable composition. Moisture transferred from the liner can prematurely cure the moisture-curable polymerizable composition and lead to poor shelf life of the tape. The moisture can be limited by drying the liner at elevated temperature before depositing the moisture- curable polymerizable composition to the liner. In some cases, it is preferrable to use a liner that inherently tends to hold negligible amounts of moisture, such as polyethylene liners and polypropylene liners.

[0096] In some embodiments, any or all of the major surfaces of a release liner may include a release coating, which may be the same or different, to tune or otherwise modify their release values. In various embodiments, which are not intended to be limiting, the release coatings applied to the major surfaces of the release liners may be selected from a fluorine-containing material, a silicone-containing material, a fluoropolymer, a silicone polymer, or a poly(meth)acrylate ester derived from a monomer including an alkyl (methjacrylate having an alkyl group with 12 to 30 carbon atoms. In one embodiment, the alkyl group on the alkyl (methjacrylate can be branched. Illustrative examples of useful fluoropolymers and silicone polymers can be found in U.S. Patent No. 4,472,480 (Olson), U.S. Patent No. 4,567,073 and U.S. Patent No. 4,614,667 (both Larson et al), incorporated herein by reference in their entireties. Illustrative examples of useful poly(meth)acrylate esters can be found in U.S. Patent Appl. Publ. No. 2005 / 0118352 (Suwa), incorporated herein by reference in its entirety.

[0097] Polymerized Compositions

[0098] In a third aspect, a polymerized composition is provided.

[0099] The polymerized composition comprises a moisture-cured crosslinked reaction product of the moisture-curable polymerizable composition of any embodiment according to the first aspect. For instance, exposure to ambient moisture in the environment may be sufficient to polymerize the moisture- curable polymerizable composition. In some cases, water vapor or liquid water is applied directly to at least a portion of the moisture-curable polymerizable composition to polymerize the moisture-curable polymerizable composition.

[0100] Articles

[0101] In a fourth aspect, an article is provided. The article comprises a substrate having a first major surface and a layer of the polymerized composition according to any embodiment of the third aspect disposed on at least a portion of the first major surface of the substrate.

[0102] Referring to FIG. 2A, an article 200a comprises a substrate 240 having a first major surface 242 and a layer of a polymerized composition 250 disposed on at least a portion of the first major surface 242 of the substrate 240. A second major surface 244 of the substrate 210 is also indicated in FIG. 2A.

[0103] Referring to FIG. 2B, an article 200b comprises a substrate 240 having a first major surface 242 and a layer of a polymerized composition 250 disposed on at least a portion of the first major surface 242 of the liner 240. The layer of polymerized composition 250 has a first major surface 252 and an opposing second major surface 254. The article 200b further comprises an optional second substrate 260 attached to the layer of polymerized composition 250 opposite the first substrate 240. In some cases, the layer of polymerized composition 250 adheres the first substrate 240 and the second substrate 260 together. It is noted that the second major surface 254 of the layer of polymerized composition 250 is adjacent to the first major surface 242 of the first substrate 240. Additionally, the first major surface 252 of the layer of polymerized composition 250 is adjacent to the second substrate 260.

[0104] In some embodiments, the polymerized composition may function as a structural adhesive, i.e., the moisture-curable polymerizable composition is capable of bonding a first substrate to a second substrate, after curing. Generally, the bond strength (e.g., peel strength, overlap shear strength, or impact strength) of a structural adhesive continues to build well after the initial cure time. Advantageously, in some embodiments, the article exhibits a T-peel of 6 Newtons per centimeter (N / cm) or greater, as determined by the T-Peel Test Method. The T-Peel Test Method is described in detail in the Examples below. In select cases, the article exhibits a T-peel of 8 N / cm or greater, 10 N / cm, 12 N / cm, 14 N / cm, 16 N / cm, 18 N / cm, or 20 N / cm or greater.

[0105] Substrates

[0106] Some suitable substrates include for instance a metal (e.g., steel), a glass, a wood, a ceramic, or a polymeric material. The polymerized composition may also be employed with one or more substrates that have moisture permeability, for instance but without limitation, woven materials, nonwoven materials, paper, foams, membranes, and polymeric films. The composition typically coats at least a portion of a substrate, and up to the entire surface of a substrate depending on the application.Optionally, the composition forms a discontinuous pattern on the substrate.

[0107] Useful substrates can be of any nature and composition, and can be inorganic or organic. Representative examples of useful substrates include ceramics, siliceous substrates including glass, metal (e.g., aluminum or steel), natural and man-made stone, woven and nonwoven articles, polymeric materials, including thermoplastic and thermosets, (such as polymethyl (methjacrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), silicones, paints (such as those based on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), and wood; and composites of the foregoing materials.

[0108] Methods of Making a Moisture-Curable Polymerizable Composition

[0109] In a fifth aspect, a method of making a moisture-curable polymerizable composition is provided.The method comprises:

[0110] a) reacting a diisocyanate with a polyol to form a polyurethane diol having a Mn of 20,000 grams per mole or greater; and

[0111] b) reacting the polyurethane diol with a multifunctional diisocyanate in the presence of a catalyst,

[0112] wherein a ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1, and wherein the moisture- curable polymerizable composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.

[0113] In some embodiments, operation a) further comprises catalyzing the reaction of the diisocyanate and the polyol. Any of the catalysts mentioned above may be employed when catalyzing the reaction of the diisocyanate and the polyol.

[0114] In certain embodiments, operation b) is advantageously performed a temperature of no greater than 180 degrees Celsius, 175 degrees Celsius, 170 degrees Celsius, 165 degrees Celsius, 160 degrees Celsius, or no greater than 155 degrees Celsius. Employing lower temperatures tends to result in desirably longer polymer chain lengths.

[0115] In some cases, operation b) optionally comprises mixing the polyurethane diol with the multifunctional diisocyanate and the catalyst to form a mixture; depositing the mixture on a first liner; and placing a second liner on the mixture opposite the first liner. The liners preferably protect the polymerizable composition from exposure to moisture before use, which may be particularly helpful when a moisture-curable polymerizable composition is prepared well in advance of its use.

[0116] In cases where the moisture-curable polymerizable composition will act as an adhesive, the substrate on which the composition is deposited optionally comprises a release liner. Other suitable substrates include for instance a metal (e.g., steel), a glass, a wood, a ceramic, or a polymeric material. The moisture-curable polymerizable composition may also be employed with one or more substrates that have moisture permeability, for instance but without limitation, woven materials, nonwoven materials, paper, foams, membranes, and polymeric films. The dispensed moisture-curable polymerizable composition typically coats at least a portion of a substrate, and up to the entire surface of a substrate depending on the application. Optionally, the adhesive forms a discontinuous pattern on the substrate.

[0117] The moisture-curable polymerizable composition may be deposited onto substrates at useful thicknesses ranging from 5 micrometers to 10000 micrometers, 25 micrometers to 10000 micrometers, 100 micrometers to 5000 micrometers, or 250 micrometers to 1000 micrometers. Useful substrates can be of any nature and composition, and can be inorganic or organic. Representative examples of useful substrates include ceramics, siliceous substrates including glass, metal (e.g., aluminum or steel), natural and man-made stone, woven and nonwoven articles, polymeric materials, including thermoplastic and thermosets, (such as polymethyl (meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), silicones, paints (such as those based on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), and wood; and composites of the foregoing materials.

[0118] It is expressly contemplated that the resulting moisture-curable polymerizable composition made according to such methods may be according to any embodiment of the first aspect described in detail above.

[0119] Select Embodiments of the Disclosure

[0120] In a first embodiment, the present disclosure provides a moisture-curable polymerizable composition. The composition comprises a reaction product of a polyurethane diol having a number average molecular weight (Mu) of 20,000 grams per mole or greater and a multifunctional isocyanate, in the presence of a catalyst, wherein a ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1. The composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.

[0121] In a second embodiment, the present disclosure provides a composition according to the first embodiment, wherein the multifunctional isocyanate is present in an amount of at least 5 weight percent (wt.%), based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

[0122] In a third embodiment, the present disclosure provides a composition according to the first embodiment or the second embodiment, wherein the multifunctional isocyanate is present in an amount of 5 wt.% to 25 wt.%, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

[0123] In a fourth embodiment, the present disclosure provides a composition according to any of the first through third embodiments, wherein the polyurethane diol comprises a reaction product of a diisocyanate and either a polypropylene glycol or a poly(tetramethylene ether) glycol.

[0124] In a fifth embodiment, the present disclosure provides a composition according to any of the first through third embodiments, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyester.

[0125] In a sixth embodiment, the present disclosure provides a composition according to the fifth embodiment, wherein the polyester comprises a reaction product of at least one diacid and at least two different diols.

[0126] In a seventh embodiment, the present disclosure provides a composition according to the sixth embodiment, wherein the polyester comprises poly(butylene-co-ethylene adipate).

[0127] In an eighth embodiment, the present disclosure provides a composition according to the fifth embodiment, wherein the polyester comprises a reaction product of at least two different diacids and at least one diol.

[0128] In a ninth embodiment, the present disclosure provides a composition according to the eighth embodiment, wherein the polyester comprises polyethylene adipate-co-phthalate), poly(butylene adipate- co-phthalate), or poly(hexamethylene adipate-co-phthalate).

[0129] In a tenth embodiment, the present disclosure provides a composition according to any of the fourth through ninth embodiments, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyol comprising one of the polypropylene glycol, the poly(tetramethylene ether) glycol, or the polyester, wherein there are 0.01 to 0.10 hydroxyl groups present for each carbamate ester group.

[0130] In an eleventh embodiment, the present disclosure provides a composition according to any of the first through tenth embodiments, wherein the catalyst comprises an amine catalyst or a metal catalyst.

[0131] In a twelfth embodiment, the present disclosure provides a tape. The tape comprises a liner having a first major surface and a layer of the composition according to any of the first through eleventh embodiments disposed on at least a portion of the first major surface of the liner.

[0132] In a thirteenth embodiment, the present disclosure provides a tape according to the twelfth embodiment, wherein the liner is a first liner and the tape further comprises a second liner attached to the layer of the composition opposite the first liner.

[0133] In a fourteenth embodiment, the present disclosure provides a polymerized composition. The polymerized composition comprises a moisture-cured crosslinked reaction product of the moisture- curable polymerizable composition according to any of the first through eleventh embodiments.

[0134] In a fifteenth embodiment, the present disclosure provides an article. The article comprises a substrate having a first major surface and a layer of the polymerized composition according to the fourteenth embodiment disposed on at least a portion of the first major surface of the substrate.

[0135] In a sixteenth embodiment, the present disclosure provides an article according to the fifteenth embodiment, exhibiting a T-peel of 8 Newtons per centimeter or greater, as determined by the T-Peel Test Method.

[0136] In a seventeenth embodiment, the present disclosure provides an article according to the fifteenth embodiment or the sixteenth embodiment, wherein the substrate is a first substrate and the article further comprises a second substrate bonded to the layer of the polymerized composition opposite the first substrate.

[0137] In an eighteenth embodiment, the present disclosure provides a method of making a moisture- curable polymerizable composition. The method comprises: a) reacting a diisocyanate with a polyol to form a polyurethane diol having a Mn of 20,000 grams per mole or greater; and b) reacting the polyurethane diol with a multifunctional diisocyanate, in the presence of a catalyst. A ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1. The moisture-curable polymerizable composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.

[0138] In a nineteenth embodiment, the present disclosure provides a method according to the eighteenth embodiment, wherein operation a) further comprises catalyzing the reaction of the diisocyanate and the polyol.

[0139] In a twentieth embodiment, the present disclosure provides a method according to the eighteenth embodiment or the nineteenth embodiment, wherein operation b) is performed at a temperature of no greater than 155 degrees Celsius.

[0140] In a twenty -first embodiment, the present disclosure provides a method according to any of the eighteenth through twentieth embodiments, wherein the polyurethane diol comprises a reaction product of a diisocyanate and either a polypropylene glycol or a poly(tetramethylene ether) glycol.

[0141] In a twenty-second embodiment, the present disclosure provides a method according to any of the eighteenth through twentieth embodiments, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyester.

[0142] In a twenty -third embodiment, the present disclosure provides a method according to the twenty- second embodiment, wherein the polyester comprises a reaction product of at least one diacid and at least two different diols.

[0143] In a twenty -fourth embodiment, the present disclosure provides a method according to the twenty -third embodiment, wherein the polyester comprises poly(butylene-co-ethylene adipate).

[0144] In a twenty -fifth embodiment, the present disclosure provides a method according to the twenty- second embodiment, wherein the polyester comprises a reaction product of at least two different diacids and at least one diol.

[0145] In a twenty-sixth embodiment, the present disclosure provides a method according to the twentyfifth embodiment, wherein the polyester comprises polyethylene adipate-co-phthalate), poly(butylene adipate-co-phthalate), or poly(hexamethylene adipate-co-phthalate).

[0146] In a twenty-seventh embodiment, the present disclosure provides a method according to any of the twenty -first through twenty-sixth embodiments, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyol comprising one of the polypropylene glycol, the poly(tetramethylene ether) glycol, or the polyester, wherein there are 0.01 to 0.10 hydroxyl groups present for each carbamate ester group.

[0147] In a twenty-eighth embodiment, the present disclosure provides a method according to any of the eighteenth through twenty-seventh embodiments, wherein operation b) comprises mixing the polyurethane diol with the multifunctional diisocyanate and the catalyst to form a mixture; depositing the mixture on a first liner; and placing a second liner on the mixture opposite the first liner.EXAMPLES

[0148] Unless otherwise noted or readily apparent from the context, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight. Table 1 (below) lists materials used in the examples and their sources. In the Tables, "NA" means not applicable. In the examples:TABLE 1. Materials List

[0149] Preparatory Example: PTMEG Prepolymer

[0150] An isocyanate prepolymer was made by mixing 105.1 grams of molten 4,4’ -MDI (105.1 grams(g)) with 50.6 g of PTMEG 650. The mixture was stirred with an overhead mixer for 3 hours while under a continuous purge of nitrogen.

[0151] Size Exclusion Chromatography (SEC) Method

[0152] Samples of polymer were dissolved in tetrahydrofuran at a concentration of 5 milligrams / gram (mg / g) and then subjected to SEC analysis. The SEC equipment consisted of a 1260 Infinity II liquid chromatography system (comprised of isocratic pump, autosampler, column compartment and variable wavelength UV / vis detector) from Agilent Technologies (Santa Clara, CA) operated at a flow rate of 1.0 milliliter / minute (mL / min). The SEC column set was comprised of two PLgel 5 micrometer MIXED-C (300 millimeter (mm) length x 7.5 mm internal diameter) and a PLgel 5 micrometer guard column (50 mm length x 7.5 mm internal diameter) all from Agilent Technologies. The detection consisted of aminiDAWN 3 angle Light Scattering detector and an OPTILAB differential refractive index detector, both from Wyatt Technology Corporation (Santa Barbara, CA). Data were collected and analyzed using software ASTRA version 8 from Wyatt Technology Corporation. The column compartment, UV / vis detector, and differential refractive index detector were set to 40 °C. The solvent and eluent (or mobile phase) consisted of tetrahydrofuran (stabilized with 250 parts per million of butylated hydroxytoluene) OMNISOLV grade from EMD Millipore Corporation, Burlington, MA.

[0153] 180 Degree Peel Test Method

[0154] The ability of the uncured tape to form a bond at room temperature was evaluated with a 180 degree peel test. The adhesive tape was allowed to rest for at least 24 hours at a temperature below 30 °C. The sample was cut in to strips 0.5 inches (1.27 centimeters (cm)) wide and 2 inches (5.08 cm) long. Pieces of woven polyester fiber tape (From Adirondack, product 5P-67, 7 mils (177.8 micrometers) thick, 1.5 inches (3.81 cm) wide) were cut to 6 inch (15.24 cm) lengths. The liner was removed from one face of the adhesive, and the exposed adhesive was laminated to the polyester tape. A steel roller weighing 7 kilograms (kg) was rolled over the tape four times. The liner was then removed from the other face of the adhesive and a second strip of polyester tape was placed over the adhesive. Four more passes with the steel roller were performed to complete the lamination. After a one-minute rest period, the polyester tapes were peeled apart in a 180 degree mode (Imass at 12” / min (30.48 cm / min) with 5 second averaging).Four replicate peel tests were performed, and the average observed peel value for the four tests is reported.

[0155] Tensile Test Method

[0156] The properties of the cured adhesive films were measured with a tensile test to failure. A sample of the adhesive (2 grams) was placed on silicone-treated polyester liner. The sample was sprayed with a mist of water. A second polyester liner was placed over the sample. The sample was pressed with 6000 pound-force (Ibf) for two minutes to cure the adhesive into an elastomeric film. After resting for three days, dogbone test specimens were cut from each sample (three replicates each, 5 mm width and 21 mm length in the gauge section). The dogbone specimens were tested to failure at 210 millimeters / minute (mm / min) (1000% / min) using an MTS load frame (1 kiloNewton (kN) load cell). The average tensile strength and elongation at break for the three replicates is reported.

[0157] T-Peel Test Method

[0158] The cured adhesive performance was characterized by a T-peel test. Strips of cotton knit fabric (TX309 Cotton Wipers from TexWipe, Kernersville, NC) were cut to 1 inch wide and 8.5 inches long. Adhesive tape was cut with a die to dimensions of 0.5” (1.27 cm) x 2.5” (6.35 cm) die. The liners were removed and the tape was laminated between two cotton strips. The test preparation could not be completed for Comparative Examples 4 and 5. With those samples, two liners could not both be removed because the cohesive integrity of the adhesive was too low to allow it to be peeled from the liner withoutflowing, and the adhesive bond to the cotton was too low to adhere to the cotton while the second liner is removed. Comparative Example 8 did not bond during this initial assembly, so the intermediate samples were handled carefully to prevent the adhesive from falling out of the assembly. The samples were then pressed with a hydraulic press at room temperature with 2500 Ibf for 10 seconds for each sample. The samples were allowed to cure in a 72 °F, 50% relative humidity (RH) environment for thirteen days. At that point, FTIR analysis confirmed that excess isocyanate was all substantially consumed. The samples were tested in T-Peel mode at a rate of 12” / min (30.48 cm / min) with an electromechanical test system (MTS Criterion Model 43, MTS Systems Corporation, Eden Prairie, MN). Three replicates were tested for each sample. For Comparative Examples, the specimens fell apart while loading into the grips, so the peel value was too low to measure. The peel strength was calculated by dividing the peel force by the width of bonded area, and the average peel strength over a 75 mm peel distance was calculated. The average value from the three replicates is reported.

[0159] Preparatory Examples 1-5

[0160] Polyurethane diols were prepared with a reactive compounding method. The formulations shown in Table 2 were mixed, and 15 mL of the reactive mixture was transferred to a microcompounder (MC-15 from Xplore Instruments, Sittard, The Netherlands) with a temperature setting of 180 °C and a screw speed of 100 RPM. The sample was allowed to react for at least three minutes, and it was then deposited onto a PTFE sheet. Two replicate batches were combined for each formulation. A portion of each sample was analyzed by SEC to characterize the molecular weight.Table 2. Formulations for PE 1 to PE 5, with amounts in parts by weight.

[0161] Preparatory Example 6

[0162] 5000P-30 (35.75 g) and DBTDL (0.004 g) were placed in a plastic cup and mixed for 4 minutes at 3250 RPM with a speedmixer (model DAC 330-100 SE from Flacktek, Landrum, SC). Rub 1234 (4.25 g) was then added, and the cup was mixed again for 4 minutes at 3250 RPM. The cup was then left in a 70 °C oven for 60 minutes to cure. The cup was removed, and FTIR analysis showed substantially no remaining isocyanate peak. SEC analysis showed an Mn value of 61 ,700 g / mol and an Mw value of 153,800 g / mol.

[0163] Examples 1, 2, 3, and Comparative Examples 4 and 5.

[0164] 15 grams of polyurethane diol from the corresponding Preparatory Example (i.e., Prep. Ex. 1-5, respectively) were added to the microcompounder at a temperature between 130 °C and 150 °C. The polymer was allowed to melt for at least five minutes before adding 2.46 grams of PAPI 94 and 0.07 grams of 33LV. This was allowed to continue mixing for 30-60 seconds and then dispensed between two polypropylene liners with silicone release treatment. The material was placed in a hydraulic press with platens at 250 °F and pressed into a film with a thickness between 0.012” (0.03 cm) and 0.019” (0.048 cm). The sample was then stored in a metallized bag with Drierite to limit moisture exposure. Samples were tested with the 180 degree peel test, the tensile test, and the T-peel test to characterize their performance.

[0165] Example 6.

[0166] 14.7 grams of the polyurethane diol from Preparatory Example 6 was added the microcompounder at 160 °C. The polymer was allowed to melt for two minutes before adding 2.21 grams of MLQ and 0.07 grams of 33LV. This was allowed to continue mixing for 30 seconds and then dispensed between two polypropylene liners with silicone release treatment. The material was placed in a hydraulic press with platens at 225 °F and pressed into a film with a thickness of about 0.007” (0.018 cm). The sample was then stored in a metallized bag to limit moisture exposure. Samples were tested with the 180 degree peel test, the tensile test, and the T-peel test to characterize their performance.

[0167] Example 7

[0168] In the MC-15 microcompounder, a polyurethane diol was prepared by adding a mixture of 222- 056 (12.5 g), DBTDL (0.001 g), and Isonate 181 (2.5 g) and compounded at a setting of 160 °C and 100 RPM for 3.5 minutes. The temperature setting was decreased to 150 °C and compounding continued for an additional 2 minutes. A small sample (approximately 0.3 grams) of the resulting polyurethane was removed from the microcompounder. This sample was shown by IR to have substantially no remaining isocyanate signal, and SEC analysis showed an Mn value of 64,000 g / mol and an Mw value of 212,300 g / mol. To the remaining material in the microcompounder, 33LV (0.08 g) and PAPI 20 (5.0 g) were added. This was allowed to mix at a temperature setting of 150 °C for about 1 minute, and it was then dispensed between polypropylene liners with silicone release treatment. The material was placed in a hydraulic press with platens at 250 °F and pressed into a film with a thickness of about 0.01” (0.025 cm). The sample was then stored in a metallized bag purged with nitrogen to limit moisture exposure. Samples were tested with the 180 degree peel test, the tensile test, and the T-peel test to characterize their performance.

[0169] Comparative Example 8. The method of Examples 1-5 was repeated using 15 grams of Des 176 as the polyurethane diol. The Des 176 had been measured by SEC to have Mn=54,000 and Mw=l 18,000. The 180 degree peel test was attempted, but no bond was formed and no value could be measured.Table 3.

[0170] Other modifications and variations to the present disclosure may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present disclosure, which is more particularly set forth in the appended claims. It is understood that aspects of the various embodiments may be interchanged in whole or part or combined with other aspects of the various embodiments. All cited references, patents, or patent applications in the above application for letters patent are herein incorporated by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. The preceding description, given in order to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.

Claims

What is claimed is:

1. A moisture-curable polymerizable composition comprising a reaction product of a polyurethane diol having a number average molecular weight (Mn) of 20,000 grams per mole or greater and a multifunctional isocyanate, in the presence of a catalyst, wherein a ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1, wherein the composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.

2. The composition of claim 1, wherein the multifunctional isocyanate is present in an amount of at least 5 weight percent (wt.%), based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

3. The composition of claim 1 or claim 2, wherein the multifunctional isocyanate is present in an amount of 5 wt.% to 25 wt.%, based on a combined weight of the polyurethane diol, the multifunctional isocyanate, and the catalyst.

4. The composition of any of claims 1 to 3, wherein the polyurethane diol comprises a reaction product of a diisocyanate and either a polypropylene glycol or a poly(tetramethylene ether) glycol.

5. The composition of any of claims 1 to 3, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyester.

6. The composition of claim 5, wherein the polyester comprises a reaction product of at least one diacid and at least two different diols.

7. The composition of claim 6, wherein the polyester comprises poly(butylene-co-ethylene adipate).

8. The composition of claim 5, wherein the polyester comprises a reaction product of at least two different diacids and at least one diol.

9. The composition of claim 8, wherein the polyester comprises polyethylene adipate-co-phthalate), poly(butylene adipate-co-phthalate), or poly(hexamethylene adipate-co-phthalate).

10. The composition of any of claims 4 to 9, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyol comprising one of the polypropylene glycol, the poly(tetramethylene ether) glycol, or the polyester, wherein there are 0.01 to 0.10 hydroxyl groups present for each carbamate ester group.

11. The composition of any of claims 1 to 10, wherein the catalyst comprises an amine catalyst or a metal catalyst.

12. A tape comprising a liner having a first major surface; and a layer of the composition of any of claims 1 to 11 disposed on at least a portion of the first major surface of the liner.

13. The tape of claim 12, wherein the liner is a first liner and the tape further comprises a second liner attached to the layer of the composition opposite the first liner.

14. A polymerized composition comprising a moisture-cured crosslinked reaction product of the moisture-curable polymerizable composition of any of claims 1 to 11.

15. An article comprising a substrate having a first major surface; and a layer of the polymerized composition of claim 14 disposed on at least a portion of the first major surface of the substrate.

16. The article of claim 15, exhibiting a T-peel of 6 Newtons per centimeter or greater, as determined by the T-Peel Test Method.

17. The article of claim 15 or claim 16, wherein the substrate is a first substrate and the article further comprises a second substrate bonded to the layer of the polymerized composition opposite the first substrate.

18. A method of making a moisture-curable polymerizable composition, the method comprising: a) reacting a diisocyanate with a polyol to form a polyurethane diol having a Mn of 20,000 grams per mole or greater; and b) reacting the polyurethane diol with a multifunctional diisocyanate in the presence of a catalyst, wherein a ratio of equivalents of isocyanate groups from the multifunctional isocyanate to equivalents of hydroxyl groups from the polyurethane diol is greater than 1:1, and wherein the moisture-curable polymerizable composition exhibits a 180 degree peel of 5.0 Newtons per centimeter or greater, as determined by the 180 Degree Peel Test Method.

19. The method of claim 18, wherein operation a) further comprises catalyzing the reaction of the diisocyanate and the polyol.

20. The method of claim 18 or claim 19, wherein operation b) is performed a temperature of no greater than 155 degrees Celsius.

21. The method of any of claims 18 to 20, wherein the polyurethane diol comprises a reaction product of a diisocyanate and either a polypropylene glycol or a poly(tetramethylene ether) glycol.

22. The method of any of claims 18 to 20, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyester.

23. The method of claim 22, wherein the polyester comprises a reaction product of at least one diacid and at least two different diols.

24. The method of claim 23, wherein the polyester comprises poly(butylene-co-ethylene adipate).

25. The method of claim 22, wherein the polyester comprises a reaction product of at least two different diacids and at least one diol.

26. The method of claim 25, wherein the polyester comprises polyethylene adipate-co-phthalate), poly(butylene adipate-co-phthalate), or poly(hexamethylene adipate-co-phthalate).

27. The method of any of claims 21 to 26, wherein the polyurethane diol comprises a reaction product of a diisocyanate and a polyol comprising one of the polypropylene glycol, the poly(tetramethylene ether) glycol, or the polyester, wherein there are 0.01 to 0.10 hydroxyl groups present for each carbamate ester group.

28. The method of any of claims 18 to 27, wherein operation b) comprises mixing the polyurethane diol with the multifunctional diisocyanate and the catalyst to form a mixture; depositing the mixture on a first liner; and placing a second liner on the mixture opposite the first liner.

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